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By W. G. Woolf, A. Y. Bethune

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process' for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt's earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.'s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By N. J. Grant, Per Knudsen, J. T. Blucher

The fatigue behavior of three SAP alloys was studied in ternzs of strain rate and temperature, at high strains. The k values in the modified Manson-Coffin equation, Nk4 = C, were less than 0.5 under all test conditions, and change with strain amplitude for the lower-oxide alloys at about 2 pct strain. Lowest k values were near 0.25. Strain rate had no effect on life at 80 F, but had an increasingly greater effect with increasing temperature above 500". Life decreased with decreasing strain rate, above 500"F, and with increasing temperature. Ductility at fracture in a tension test was indicated to be an important factor in determining 1ife in these big+-strain tests with the SAP alloys. INEVITABLY, in the course of mechanical tests at elevated temperatures, particularly if significant time at temperature is involved, there are large changes in structure; these changes make it difficult to relate behavior patterns over ranges of temperature or strain rates at high temperatures. Such changes are to be expetted in low cycle fatigue at low strain rates and high temperatures. Accordingly, it was of great interest to examine the low cycle fatigue behavior of SAP / an aluminum oxide dispersion-strengthened aluminum, a type of alloy which had shown unusual structure stability to temperatures as high as 1000" to 1150°F and resisted recrys-tallization essentially to the melting temperature.'j3 Since the matrix is pure aluminum, there are no complications of averaging, agglomeration, or phase solution. It was also desirable to check the Manson-Coffin equation4?' for the SAP alloys, namely N~E~ = , where ep is the total plastic strain amplitude, k and C are constants, and N is the number of cycles to failure. Here, too, was an opportunity to check the roles of temperature and strain rate with a very stable material. Tavernelli and coffin6 had concluded that k had a value of about 0.5 for many alloys and C was equal to ~/2, where E is the fracture ductility determined from a static tension test. The results were obtained from low-temperature tests where creep and diffusion processes are unimportant. Manson7 found k = 0.6 fitted his data reasonably well; however, in later analyses of a large amount of low cycle fatigue data generated at room temperat~re@"~ he found k to vary from 0.6 for short lives to 0.21 for long-life fatigue tests. In the latter studies,89g Manson separated the total strain range into elastic and plastic components when he found that k was influenced by the nature of the strain. The use of EL (total strain) instead of EP (total plastic strain)4'5 makes a difference in the resultant k value. The ratio of changes with temperature, strain rate, and strain; further, there are the problems in the determination of the elastic strain. Based on these considerations, and the improved fit of points in a plot of by Wells and Sullivan,' is also utilized in these studies. Anderson and wahl,14 using commercial 1100 aluminum, and Blucher and Grant,15 using 99.99 pct pure aluminum, found an increase in life with increasing test temperature. Anderson and Wahl were the first to report low cycle fatigue results from SAP materials. With increasing temperature, the role of strain rate becomes more important. In this regard, care must be exercised to differentiate between frequency (wherein strain rate may vary from zero to a maximum in each cycle, sinusoidally, for example), and constant strain rate, as used in the present study, in a saw-tooth type cycle; in the latter case, the frequency is not specified but can easily be calculated from the strain and strain rate data. It has generally been found that life in low cycle fatigue tests decreases with decreasing frequency16 or with decreasing strain rate at elevated temperatures.15 Coffin,17 reviewing Eckel's work,16 also reported that k increased with decreasing frequency for acid lead, yielding values from 4.0 at a frequency fo 6.6 cycles Per day to 1-46 at a frequency of 7440 cycles per day; the value of k decreased to 0.58 at a frequency of 2.38 x lo6 cycles per day. EXPERIMENTAL PROCEDURE Three SAP alloys, of two nominal compositions, were tested. Alcoa supplied XAP 005 as 2-in.-diam extruded bar, of nominal composition A1-7 wt pct A1203. The Danish Atomic Energy Commission supplied SAP 930 (A1-7 wt ~ct Ala3) and SAP 865 (A1-13 wt pct Al&) manufactured by Swiss Aluminium Ltd., in the form Of $-in.-diam extruded rod. Metallographic comparison of the structures of XAP 005 and SAP 930 showed the former to have a more uniform oxide distribution. Button-head specimens were machined in the longitudinal direction of the bar with 0.4 in. gage length by 0.2 in. diameter, with a fillet radius of j-B in. After machining, the specimens were electropolished in a 1 to 4 mixture of perchloric acid to methanol to remove all machining marks. All test bars were in the as-extruded condition. The fatigue tests were performed on a hydraulically activated, axial strain machine, with complete reversal of strain.15 Test conditions were:

Jan 1, 1969

By C. L. Sollenbeger, R. B. Greenwalt

PERHAPS the most widely used dispersants or gangue depressants in nonmetallic flotation are sodium silicates, which vary in silica-to-soda ratio from 1 to 3.75. Typical manufactured silicates in order of decreasing solubility and increasing amounts of silica are Metso, silica-to-soda ratio of 1.00; D, 2.00; RU, 2.40; K, 2.90; N, 3.22; and S-35, 3.75.* References in flotation literature1,2 to the use of sodium silicates are often weak because they fail to mention the type of silicate used. Metso and silicate N have occasionally been mentioned, but when the type of silicate is not mentioned, it is usually assumed to be N, the cheapest of the soluble silicates and the one recommended by sodium silicate manufacturers as a flotation agent. In the All is-Chalmers Research Laboratories a systematic study was made of the effect of different alkali-silica ratios on the concentration by flotation of two scheelite ores. One of these was a high grade ore from the Sang Dong mine in Korea. The effect of such factors as pH; addition agents; and conditioning time, temperature, and pulp density on the flotation efficiency of this ore have been described previously. The other ore was a low grade ore from Getchell Mines Inc., Nevada. The mineralogy and techniques of concentrating this ore have been described by Kunze. Hereafter these ores will be referred to as the Korean and Nevada ores. Experiments were made with both to determine the effect of three factors—-type of silicate, concentration of silicate, and pH of the pulp—on recovery and grade of tungsten in a rougher concentrate. Average WO, content of the Korean ore was 1.50 pct and of the Nevada ore 0.27 pct. The predominant tungsten mineral in both ores was scheelite, which was accompanied by a small amount of powellite. The powellite and scheelite were finely disseminated through both ores and required a —200 mesh grind for liberation. Major gangue minerals in the Korean ore, in decreasing order of abundance, were amphi-boles, quartz, biotite, garnet, fluorite, and calcite. Bulk sulfides composed about 3 pct of the total weight. Gangue in the Nevada ore, in descending order of abundance, was garnet, alpha quartz, calcite, phlogopite, wollastonite, and amphiboles. Sulfide minerals were 3 to 4 pct of total weight. Batch flotation experiments were made with 500-g samples of ore, each sample wet-ground to 90 pct passing 200 mesh. The finely ground ore was floated in a Fagergren batch cell at 25 pct solids. The natural pH of the Nevada ore was 8.9 and of the Korean ore, 8.5. The D, RU, K, N, and S-35 sodium silicates were obtained in colloidal dispersions with varying amounts of water. The most alkaline, Metso, was in dry powdered form. For convenience in addition, 5 pct solutions by weight were prepared from each of the silicates, on the basis of dry sodium silicate dissolved in the correct amount of distilled water. Chemical analyses of the various silicates are given in Table I, together with the pH of the 5 pct solutions. A preliminary bulk sulfide float was made with secondary butyl xanthate as the collector and pine oil as the frother. The WO] analysis of the sulfide concentrate was nearly 1 pct for the Korean ore and about 0.1 pct for the Nevada ore. The tungsten contained in the sulfide concentrate constituted about 3 pct of the total tungsten in each ore. No effort was made to recover these tungsten values. The scheelite was floated with oleic acid. Adjustments in pH were made with sulfuric acid or sodium carbonate. A 1 pct solution of 85 pct Aerosol OT was sprayed on the froth and sides of the cell during the scheelite float to aid in dispersing the minerals and to decrease the entrapment of gangue particles. Six tests were planned for each of the six types of silicate in which concentrations of 1, 2, and 4 1b of silicate per ton of dry ore were investigated at both 6.5 and 10 pH. All tests were made at room temperature. The performance of each silicate was judged from the grade and recovery of WO, in the scheelite rougher concentrate. Tungsten recovery was calculated on the basis of the scheelite remaining in the ore after the preliminary sulfide float. Testing of each silicate at three levels of concentration and two levels of pH required 36 tests with each scheelite ore. Variance analyses were performed on the concentrate grades and recoveries to determine whether or not the type of sodium silicate, the concentration of sodium silicate, or the pH significantly affected recovery or grade. Results Concentrate Grade: A variance analysis of the concentrate grades for the Korean ore showed that concentration of the silicate and pH of the ore pulp were major factors in producing a high grade concentrate. Also, the silica- to-so da ratio was important as an interaction with pH. The concentrate grade vs silica-to-soda ratio is plotted in Fig. 1. The curves show that the concentrate grade improved with an increase in concentration of sodium silicate and also

Jan 1, 1959

By J. A. Berger, G. W. Wiener

Several transition metal nitrides have been prepared and their saturation magnetization determined. On the basis of an atomic model of ferromagnetism involving a consideration of nearest neighbor interactions and the assumption that all atomic moments of the metal point in the same direction, it appears that the nitrogen interacts with d-shell of the transition metal in such a way as to reduce the magnetic moment. THERE is a large class of materials having metallic properties which are formed by a combination of hydrogen, boron, carbon, oxygen, or nitrogen with the transition metals. Several attempts have been made to establish the type of metal-nonmetal bonding in these interstitial alloys because it is believed that many of the physical properties of these materials are determined by the characteristics of this bond. Several of these alloys are ferromagnetic, and thus a powerful method is available for investigating the structures in a direct manner by measuring the saturation magnetization. The latter is a fundamental property of ferromagnetic metals and alloys which depends primarily on the electron distribution surrounding the atom. For the first row of transition metals, this refers specifically to the 3 d-shell. Since bonding involves the electronic configuration between atoms, there is reason to suppose that a relationship exists between ferromagnetism and bond type. In the case of the interstitial structures studied in this work, bonding will refer to the distribution of electrons between the transition metal and the nonmetal. Since these alloys have metallic properties, it is further proposed that any bonding interactions will involve the outer p-shell of the interstitial element and the incomplete d-shell of the transition metal. If this is the case, then the relationship between ferromagnetism and metal-non-metal bonding is established qualitatively. In order to investigate the subject quantitatively, certain transition metal nitrides were chosen because they have simple crystal structures, are ordered alloys, and are ferromagnetic. They also have sufficiently high saturation magnetization to be of technical interest. Currently there are two major theories of ferromagnetism, each of which has been applied to the interpretation of the saturation magnetization in terms of atomic structure. They are usually referred to as the band theory and the atomic theory. The former has found widespread application to the study of pure metals and certain solid-solution allays. However, it has not been applied to the interstitial structures or ordered alloys because it does not interpret the properties directly in terms of the crystal structure. The atomic theory on the other hand is especially suited to the study of interstitial structures because it permits an interpretation of ferromagnetic phenomena in terms of the crystal geometry. As has been pointed out previously, the nitrides have simple ordered crystal structures and, therefore, the choice of the atomic theory for the interpretation of the data is a natural one. One of the prime difficulties with the atomistic theory is that its mathematical justification is much more difficult, and for this reason its general acceptance will depend to a large extent on the value it has in explaining and predicting the results of experiment. Before the presentation of the theoretical basis for understanding the metal-nonmetal bond, it is useful to review the ideas existing prior to this work. Four different interpretations have been given to the metal-nonmetal bond. These are summarized as follows: 1—acceptance of electrons by the nonmetal from the incomplete d-shell of the transition metal, 2—transfer of electrons from the nonmetal to the incomplete shell of the transition metal, 3—no exchange of electrons between the two atoms, and 4— a resonating type of bond involving the p electrons of the interstitial atom giving rise to half bonds. Zener'-4 in a recent series of papers has proposed a new theory of ferromagnetism and has developed an explanation of the observed saturation magnetization of iron nitride (Fe,N) using the concept that nitrogen accepts electrons from the 3d-shell of iron. Jack," on the basis of atom size considerations in iron carbonitrides, has proposed that nitrogen transfers or donates electrons to the inner 3d-shell. He found that the effective size of the carbon atom was less than that of nitrogen and thus suggested that the interstitial atoms give up electrons. Kiessling" has studied the borides of several transition metal atoms and proposed that boron loses one p electron to the transition metal. He postulated that the additional electron added to the metal lattice compensates for the loss in metallic properties which results from the increased metal-metal atom separation. GuillaudT3" has proposed similar arguments from some recent magnetic studies he had made on manganese nitride. However, he did not base his conclusions on a quantitative argument. Pauling," in a recent paper, discussed electron transfer in in-termetallic compounds. He classified nitrogen as a hyperelectronic atom which can increase its valence by giving up electrons. He classified the transition metals as buffer atoms which are capable of either accepting or giving UP an electron. He pointed out that two factors are operating which promote electron transfer because they lead to increased stability. The first is an increase in the number of bonds, and the second is a decrease in the electric charges on the atoms. These ideas when applied to the interstitial nitrides would indicate a viewpoint favoring electron transfer by nitrogen to the transition metal. Hagg7s arguments in favor of no exchange are adequately summarized by Wells." Implicitly, Hagg

Jan 1, 1956

By William M. Boorstein, Robert D. Pehlke

The rates of solution (of hydrogen in liquid pure iron and in several liquid binary iron alloys were meas-ured using a constant volume technique. The rates of absorption and desorption were found to be equal un-der all experimental conditions. increasing concen-trations of S, Si, or Te decrease the rate of hydrogen uptake but additions of Al, B, Cr, Cu, or Ni have no measurable effect up to concentrations normally en-countered in steelmaking practice. No relation ship was found between the effect of an alloying element on the equilibrium solubility of hydrogen in liquid iron and its effect on the solution rate constant. Mathe-rnatical analysis of the data indicates that under the present experimental conditions the rate of reaction of hydrogen with liquid iron is controlled by transport of gas solute atoms in the metal phase. Comparison of the present resuts with data on nitrogen taken un der similar conditions establishes that the hydrody-nurnic conditions which exist near the surface of a metal bath are best approximated mathematically by a surface renewal model for the case of rapid in-ductive stirring and by a boundary layer model for more quiescent melts. HYDROGEN has long been recognized as being a detrimental constituent in steel. If dissolved in the molten metal in excess of its solid solubility, hydro-gen can be evolved during solidification and cause bleeding or porosity in ingots and castings. In the solid metal, lesser amounts play a definite role in causing other defects such as hairline cracks, blisters, and embrittlement. For significant refinements to be made in metallurgical procedures designed to control or eliminate hydrogen from liquid iron or steel dur-ing processing, available equilibrium solubility data must be supplemented with reliable fundamental in-formation pertaining to the kinetic factors involved in the transfer of hydrogen to or from the metal. The scarcity of such information in the literature prompted the present investigation. PREVIOUS RESEARCH Whereas much of the existing data on the solution kinetics of gases such as nitrogen were obtained during the course of thermodynamic investigations, the solu-tion rate of hydrogen has been found too rapid to be accurately determined by conventional solubility meas-urement techniques. Consequently, little work on hy-drogen solution kinetics has been reported in the lit-erature. Carney, Chipman, and crant1 attempted to study the rate of solution and evolution of hydrogen from liquid iron by employing a newly devised sampling method. Although no significant quantitative data could be obtained, it was observed that the rate of solution was approximately equal to the rate of evolution of hy-drogen from the melt. Karnaukov and Morozov2 stud-ied the rate of absorption and Knuppel and Oeters3 the rate of desorption of hydrogen from molten iron by measuring pressure changes with time in a constant volume system. Karnaukov and Morozov determined the hydrogen pressures over their inductively stirred melts with the aid of a McLeod gage and therefore, were forced to work at pressures not in excess of 40 mm of Hg. Their experimental data conformed to a mathematical correlation based on diffusion control: and the rate coefficients calculated on this basis were shown to be independent of the initial absorption pres-sure. These authors reported the solution rate of hy-drogen to be eight-to-ten times higher than they had found for nitrogen in a previous study. They also re-ported that under identical conditions, hydrogen dis-solves somewhat more slowly in iron-columbium alloys than in pure iron. Knuppel and Oeters found that the desorption of hydrogen from pure iron at 1600°C was controlled in all cases investigated by diffusion in the metal bath as long as bubble formation was sup-pressed. This was substantiated by Levin, Kurochkin, and umrikhin4 who studied the kinetics of hydrogen evolution from liquid (technical) iron while applying a vacuum. Salter5 measured the rate of hydrogen ab-sorbed by iron buttons, arc-melted by direct current, as a function of hydrogen partial pressure in a hy-drogen-argon atmosphere. A carrier gas technique was used for analysis of the hydrogen absorbed. The initial rate of absorption was found to increase di-rectly with the square root of the partial pressure of hydrogen. EXPERIMENTAL METHOD Because of the rapid uptake and evolution of hydro-gen by iron-base melts, a constant volume technique was devised in order to obtain meaningful kinetic data over the entire course of the solution process. Apparatus. A schematic view of the experimental apparatus is given in Fig. 1. The hydrogen-liquid iron reaction system consisted of a gas storage bulb con-nected to a meltcontaining reaction chamber through a normally-closed solenoid valve. The gas storage bulb, an inverted 250 ml round-bottomed Pyrex flask was joined to the inlet port of the solenoid valve by a glass-to-metal seal. A more detailed illustration of the reaction chamber is shown in Fig. 2. The design of the Vycor reaction bulb was essentially that de-scribed by Weinstein and Elliott6 with the exception of a shorter, larger diameter gas inlet for this kinetic study. In position, the reaction bulb was closely by an eight-turn coil of water-cooled copper tubing which, when energized by a 400-kc oscillator, provided the inductive heating source. The walls of the bulb were maintained relatively cool by circulating cold water along their outer surface, thus preventing

Jan 1, 1970

By R. F. Dickerson, D. A. Vaughan, A. F. Gerds

ALTHOUGH the metallurgy of uranium has been under intensive study since the early 1940's, no systematic effort has been made to identify the non-metallic inclusions in uranium. Uranium carbide (UC), which is probably the most common inclusion found in graphite-melted metal, has been tentatively identified by previous investigators, but the other nonmetallic inclusions have received little attention. Since metallography is a valuable tool in metallurgical studies, the metallographic identification of the nonmetallic inclusions in uranium is important. Such an investigation has been completed and the identification of slag-type inclusions and of uranium monocarbide, uranium hydride, uranium dioxide, uranium monoxide, and uranium mononitride is described. Metallographic Preporation It is often possible to prepare specimens for metal-lographic examination equally well by several methods. The specimens which were examined in this work were prepared by one of two acceptable methods. For the convenience of the reader, both methods will be discussed in detail and will be referred to simply as Method I or Method II in the subsequent sections. For both Methods I and 11, specimens for microscopic examination usually were mounted either in bakelite or in Paraplex room temperature mounting plastic. Method I—Specimens were ground in a spray of water on a revolving disk covered successively with 120-, 240-, and 600-grit silicon carbide papers. It was necessary to perform the final grinding operation carefully on worn 600-grit paper to keep the scratches as fine as possible. After washing and drying, the specimens were polished for 3 to 4 min on a slow speed wheel (250 rpm) covered with a medium nap cloth. Diamet Hyprez Blue diamond polishing paste, Grade 00, 0 to 2 µ, was used as abrasive with kerosene as lubricant on the wheel. Specimens were washed thoroughly in alcohol and final polished electrolytically in an electrolyte composed of 1 part stock solution (118 g CrO, dissolved in 100 cm3 H2O) with 4 parts of glacial acetic acid. A stainless steel cathode was used. At an open circuit potential of 40 v dc, a polishing time of 2 sec retained inclusions well with the bath at room temperature. If additional etching was required to sharpen the interface between the metal and the inclusions, an electrolyte composed of 1 part stock solution (100 g CrO3 and 100 cm8 H20) and 18 parts glacial acetic acid was used at room temperature. Best results were obtained by etching for from 10 to 15 sec at 20 v dc in the open circuit. Surfaces obtained by this method are suitable for microscopic examination. However, if desired, they may be etched further with other chemicals. Method 11—Rough grinding was done on a wet 180- or 240-grit continuous grinding belt. The specimen was then ground by hand successively on 240-, 400-, and 600-grit silicon carbide papers in a stream of water. Final polishing was accomplished on a 4 in. high speed wheel (3400 rpm) covered with Forstmann's cloth. Linde B levigated alumina, suspended in a 1 volume pet chromic acid solution, was the abrasive. Specimens usually were polished in 5 min or less by this technique. Often the inclusions present in the metal were identified in the mechanically polished condition. When etching was required to outline inclusions more sharply, one of the two following methods was used. In the first method, the specimen is etched lightly while electropolishing in the chromic-acetic acid solution described above (1 part of stock solution to 4 parts of acetic acid). The electrolyte was refrigerated in a dry ice-ethyl alcohol bath and specimens were etched at 60 v dc on the open circuit for 2 or 3 cycles of 3 to 4 sec each. The second technique utilizes electrolytical etching at about 10 v dc (open circuit) in a 10 pet citric acid solution at room temperature. X-Ray Diffraction Technique The major problem in the identification of inclusions in metals by X-ray diffraction techniques is the extraction of a sufficient amount of each type of inclusion to obtain an X-ray diffraction pattern. In the present study, X-ray diffraction patterns were obtained from individual inclusions of the order of 10 µ diam. The polished and etched samples shown in the micrographs were examined at a magnification of X54 or XI00 with a binocular microscope. This allowed sufficient working distance to extract the inclusions with a needle probe for powder X-ray diffraction analysis. Friable inclusions such as MgF2, CaF2, UO2, and UH3 could be freed from the metal by probing the as-polished and etched surface. The fine particles then were picked up on the end of a Vistanex-coated glass rod (0.002 in. diam) which was held in a brass adapter made to fit the powder X-ray diffraction camera. The end of the glass rod was centered in the path of the X-ray beam. In the case of the UC, UO, and UN inclusions which are smaller in size, more metallic in appearance, and less friable than the other inclusions, it was necessary to etch the inclusion in relief before extraction. UN inclusions etched sufficiently in relief in the electrolytic polishing solution described in Methods I and II by increasing the polishing time. UN inclusions were relief etched by extending the

Jan 1, 1957

By J. B. Clark

The oil industry has long recognized the need for increasing well productivity. To meet this need, a process is being developed whereby the producing formation permeability is increased by hydraulically fracturing the formation. The "Hydrafrac" process, as it is now being used, consists of two steps: (1) injecting a viscous liquid containing a granular material, such as sand for a propping agent, under high hydraulic pressure to fracture the formation; (2) causing the viscous liquid to change from a high to a low viscosity so that it may be readily displaced from the formation. To date the process has been used in 32 jobs on 23 wells in 7 fields, resulting in a sustained increase in production in 11 wells. INTRODUCTION Need For Process Although explosives, acidizing, and other methods have long been used, there still exists a need for artificial means of improving the productive ability of oil and gas wells, particularly for wells which produce from formations which do not react readily with acids. This paper discusses the development of a hydraulic fracturing process, "Hydrafrac", which shows distinct promise of increasing production rates from wells producing from any type of formation. The method is also considered applicable to gas and water injection wells, wells used for solution mining of salts and, with some modification, to water wells and sulphur wells. Requirements of Process In considering such a possible process, it appeared that certain requirements must be met. Some of these are as follows: A. The hydraulic fluid selected must be sufficiently viscous that it can be injected into the well at pressure high enough to cause fracturing. B. The hydraulic fluid should carry in suspension a propping agent, such as sand, so that once a fracture is formed, it will be prevented from closing off and the fracture created will remain to serve as a flow channel for oil and gas. C. The fluid should be an oily one rather than a water-base fluid, because the latter would be harmful to many formations. D. After the fracture is made, it is essential that the fracturing fluid be thin enough to flow hack out of the well and not stay in place and plug the crack which it has formed. E. Sufficient pump capacity must be available to inject the fluid faster than it will leak away into the porous rock formation. F. In many instances, formation packers must be used to confine the fracture to the desired level, and to obtain the advantages of multiple fracturing. Development of Process As a necessary step in the development of this process, it was deemed advisable to determine if the Hydrafrac fluids were actually fracturing the formation or whether these special fluids were merely leaking away into the surrounding formation. To determine this, a shallow well, 15 feet deep, was drilled into a hard sandstone. Casing was set, the plug drilled, and the well deepened in the conventional manner. A fracturing fluid dyed a bright red was used to break down the formation. Sand mixed with distinctively colored solids was injected into the well with the fracturing fluid to prop open any fracture made in the formation. A simulated gel breaker solution dyed a bright blue was then pumped into the well to determine if the gel breaker would follow the first solution. The results are shown in Figure 1. It was noted that a fracture was formed about the well bore, that the propping agent was transported back into the break, and that the breaker solution did actually follow the fracturing gel out into the fracture. While it is realized that this shallow well test is probably not exactly equivalent to a deep test, the results were interpreted as being a definite indication of what happens down the hole during a Hydrafrac job. Of interest in this connection is an investigation reported by S. T. Yuster and J. C. Calhoun, Jr.' This study, re~orted after the Hydrafrac work was under way, presents some excellent field data supporting the theory of fracturing a formation with hydraulic pressure. METHOD Steps of Hydrafrcu: Process Figure 2 shows a simplified cross-sectional view of a well treated by one version of the process. The first step, formation breakdown, is done with a viscous fluid, usually consisting of an oil such as crude oil or gasoline, to which has been added a bodying agent. Due to availability and price, war-surplus Napalm has been used in the majority of experiments to date. Napalm is the soap which was used in the war to make "jellied gasoline". The next step consists of breaking down the viscosity of the gel by injecting a gel-breaker solution and then after several hours, putting the well back on production. Figure 3 shows diagram-matically, a typical field hookup. The oil or gasoline is unloaded into the 10 bbl. tank shown on the left rear of the truck. This base fluid is picked up by the mixing pump and pumped through the jet mixer, where the granular soap is added. Next it goes into a small mixing tub, from which the high-pressure pump takes suction. The solution is then pumped into the well. The breaker solution is then taken from an extra tank and is displaced into the well immediately following the gel. When required, additional trucks may

Jan 1, 1949

By M. Deighton, R. N. Parkins

The metals Cd, ,Wg-, Sn, TI, Zn, and Zr reach a peak hardness after a criticfir1 deformation by rolling- and then soften with fwther rolling-, thereby exhibiting wovk softening. Optical metallography on Cd, Mg, and Zn shows that work softening is accompanied by a change in grain size occurring during deformation. The creep of zinc from -1l° to +60°C at stresses in the range of 7.9 to 17.3 kg per sq mm is given by € = e0 -t- Bt + Kt +at6. The third and second rate constcints are related by the equation a = K~ K6 and their stress and temperature dependence can be represented by the equations K = A, . exp - (u, - Bu)/kT. A model based upon the stress activated glide of sub-boundaries is proposed which qualitatively accounts for the metallog-raphic observations. Expressions, which are in reasonable quantitative agreement with the ex-pe~inzental observations, are derived for the creep of zinc. THE term "work softening" has been used previously by Polakowski1 and by Cottrell and stokes2 to describe phenomena where further strain of a deformed material leads to a decrease in flow stress. In both cases, however, the conditions were changed for the second straining. Here, the term "work softening" is intended to refer to a decrease in flow stress after continued straining in the same direction at the same temperature: work softening is the antithesis of "work hardening". Work softening of zinc was reported by chadwick3 and in discussion of that paper Jenkins4 indicated that cadmium also work softens. More recently work softening has been reported5 in two magnesium alloys, -99.5 pct Mg. Chadwick found that the hardness, 0.2 pct Proof Stress and the UTS of electrolytic zinc all increased with progressive cold reductions up to 30 pct and then progressively decreased with further rolling. Gay and Kelly6 used a back-reflection X-ray technique to study the effect of cold rolling zinc and found that although deformations greater than 2 to 5 pct reduction in thickness produced some recrystallized grains, deformations greater than 40 pct caused com-plete spontaneous recrystallization. At deformations greater than 60 pct the material was found to consist solely of recrystallized grains, -20 pm diam, the size of which decreased with increasing reduction and was much less than the initial grain size of the annealed material (-300 pm diam). Similar results were also reported for cadmium, tin, and lead.6 Gay, Hirsch, and Kelly' suggest that these experiments indicate recrys-tallization takes place when the dislocation density exceeds a certain value. However, no measurements of MATERIALS AND EXPERIMENTAL PROCEDURE The purity of the metals used in this work is indicated by the following figures: Zn (99.99); Cd (99.94); Mg (99.95); T1 (99.99). The zirconium was iodide crys tal bar with a probable purity of about 98 pct. The metals were obtained in the form of 0.25 in. thick strip or 0.425 in. diam rod by various fabrication methods and then annealed to ensure complete re-crystallization. Hardness-deformation curves were obtained at room temperature by rolling 4 in. thick strip under conditions which left a surface adequate for diamond pyramid hardness tests immediately after rolling. The hardness was taken as the niean of five impressions made using a 5 kg load and the time elapsing between rolling and making the last impression never exceeded 5 min. The zinc specimens for creep testing were from 3 by 3 by 4 in. cast slabs which were rolled to 0.10 in. thickness starting at 350°C and finishing cold. The resulting strip was cut into pieces 1 in. wide and annealed in batches. With suitable choices of annealing temperature between 100" arid 400°C five different grain sizes varying from 4.54 x 10' to 3.03 x l05 grains per sq cm (530 to 20 um diam) were obtained. Creep tests were done in compression using a sub-press, based on a design after Ford,8 in which the strip is compressed between dies 0.100 in. wide under conditions of plane strain. Since there is no lateral spread of the material, the area of contact between the dies and strip remains constant throughout the test and the application of a constant load, using the load maintaining device of a hydraulic testing machine, resulted in a constant stress. Covering the dies with strips of P.T.F.E. reduced frictional effects to a minimum. The creep strain was obtained by measuring the travel of the crosshead of the testing machine to a sensitivity of 0.1 pct reduction in thickness. The complete subpress assembly was contained in a steel box and for tests above the ambient this was filled with liquid paraffin and heated electrically. Temperatures below the ambient were obtained with a cooling mixture of acetone and solid carbon dioxide in the box. The liquids were stirred and the temperature of the specimen, which was controlled to ±0.5"C dur-ing a test, was measured by a thermocouple placed near the dies. Compression testing of cylindrical specimens was also carried out in the subpress using hardened flat discs separated from the test material by P.T.F.E. sheets which obviated barrelling of the specimens. Various initial strain rates were supplied by the hydraulic testing machine, and the deformation was measured by a clock dial gage resting on the cross-

Jan 1, 1970

By B. W. Roberts, V. A. Phillips

A copper alloy containing- 25.5 at, pct Zn and 19.0 at. pct Ni, which was previously found to show an anoma1old.s hardening effect on quenching- from 600 "C and aging- at 400oc, has now been examined by neutron diffraction. No evidence of long-range order was found. The aged sample showed diffuse scattering- consistent with clustering. The anomalous hardening effect is now attributed to lattice strains caused by clustering rather than (long-range) order hardening. SOLID-solution Cu-Ni-Zn alloys (the commercial 'nickel silvers") have been reported to show anomalies in: change of resistivity on cold working,1-6 temperature coefficient of resistance,2-12 resistivity at low temperatures,13,14 parameter (vs temperature),2"4 calorimetric data,2,4 specific heat,15,16 dilation,2-4 and elastic modulus.17 The structure responsible for the anomalies is produced by annealing typically near 400°C and is rather loosely referred to as the ('K-Zustands" (K state), a term coined by Thomas1' who apparently meant simply that the arrangement of atoms on the sites deviated from that expected statistically. Thomas proposed that the K state occurred in a variety of (solid-solution) alloys such as Cu-Ni-Zn, Ni-Cr, Ni-A1, Ni-Cu, Fe-A1, and Fe-Si and is recognized because its formation is strongly temperature-dependent and results in an increase in electrical resistance which can then be decreased by cold working. Later workers on ('nickel silver" have interpreted the K state variously as short-range order, long-range order. or a combination. The present work was prompted by the discovery by Phillips and Jones19 of a substantial hardening effect when an 18 pct "nickel silver" alloy which is fairly close to the Cu2NiZn composition, was reheated in the range 150" to 450 C after previously quenching from 600°C or, alternatively. was slow-cooled from 600°C or above. The phenomenon was attributed to (long-range) order hardening. Due to the similarity in the atomic scattering factors of copper. nickel, and zinc atoms, the ''nickel silvers" are unfavorable for X-ray diffraction studies aimed at detecting ordering. Nevertheless Bialas et a1.,20 using a powder sample containing 47.96 wt pct Cu, 24.03 wt pct Ni, and 27.98 wt pct Zn, slow-cooled from 400" to 200°C taking 500 hr, observed weak super lattice lines. Further unpublished work" using an anomalous dispersion X-ray technique indicates that zinc atoms are regularly ordered at the corner points of the lattice cell, while the nickel and copper atoms are statistically distributed on the remaining sites. Köster 17 also observed X-ray superlattice lines, for example, in an alloy containing 43.5 wt pct Cu, 28.6 wt pct Ni, and 27.9 wt pct Zn superimposed on the basic fcc cell with a = 3.62 kX. He proposed a Cu3Au-type superlattice with the Ll2 structure in which the A sites were statistically occupied by copper and nickel atoms and the B sites by zinc. He adds that substitution must be possible so that zinc atoms partly occupy A sites. Below about 35 pct Cu, Koster had some evidence for a CuAu-type superlattice with the Llo tetragonal fcc structure with a = 3.82 kX, c/a = 0.88 which could be preserved by quenching. This is suggested17722 to correspond to CuNiZn. While the present work was in progress Hirabaya-shi et a1.23 made an independent comprehensive neutron-diffraction study of a single crystal containing 50.05 at. pct Cu, 26.57 at. pct Ni, 0.25 at. pct Mn, 0.13 at. pct Fe, balance zinc. The presence of manganese and iron is surprising since the crystal was supposedly grown from high-purity metals. The homogenized crystal showed evidence of long-range ordering after an anneal of 5 months at about 300°C. Three possible crystal models were proposed. A curious feature of their results23 is that they could not find any neutron-diffraction evidence of ordering in a powdered polycrystalline near-stoichiometric Cu2NiZn alloy. There appears to be some essential difference between a near-stoichiometric Cu2NiZn alloy and one somewhat further off stoichiometry as used by the present authors. Thus Sato14 was able to reproduce the low-temperature resistivity anomaly reported by one of the authors13 on the present alloy if he used a similar composition, but found the normal behavior of the residual resistivity in a near-stoichiometric alloy. satol2 found that the resistivity of a cold-drawn slightly off-stoichiometric alloy increased to a maximum on isothermally annealing at 300°C and then decreased ("over-aged"). Since he could not explain this on the basis of ordering phenomenon, he proposed that zinc atoms were segregating to stacking faults (Suzuki effect) and found etching bands on the surface by replication which were attributed to the widening of faults. Sato suggested14 that the hardening effect observed by Phillips and Jones19 is partly due to the Suzuki effect. EXPERIMENTAL The starting material was 1/4-in.-diam hard-drawn rod of a commercial 18 pct "nickel silver" alloy identical with that used in a previous study by Phillips

Jan 1, 1967

By G. Nabi, W-K. Lu

Cylindrical specimens of natural dense hematite were reduced to magnetite at atmospheric pressure in H2-H2O mixtures of known composition over the temperature range 1084° to 1284°K. The rate of reduction was measured by the rate of movement of the interface between hematite and magnetite. The diffusion of gases through the gaseous boundary layer, the magnetite layer, and the interfacial chemical reaction were all considered in the interpretation of experimental data. The mass transfer coefficient through the boundary layer was calculated using accepted correlations. Values of the chemical reaction rate constant and the diffusivity of hydrogen in the magnetite phase were determined. THE present investigation is concerned with the reduction kinetics of natural hematite to magnetite by H2-H2O mixtures in the temperature range 1084" to 1284°K at atmospheric pressure. This reaction is the first step in the series of topochemical reactions in the process of reducing hematite to iron. Kinetic information of the simple steps such as hematite-magnetite transformation is necessary in order to have a better understanding of the complex processes of hematite reduction in iron-making. It also has direct industrial significance because magnetic roasting is one of the most important methods in benefication of lean ore.&apos; Although many technical papers have been published on the process of magnetic roasting and iron oxide reduction, very little information is available in the literature concerning the fundamental nature of hematite reduction to magnetite by reducing gases. Hansen et al.2 reduced the dense synthetic pellets of high-purity oxide in CO-CO2 mixtures and determined the reaction rate by weight-loss method. They were able to interpret most of their results by applying the interfacial area control theory developed by Mckewan.3 In contrast, Wilhelm and St. Pierre,4 who studied reduction of hematite to magnetite in H2-H2O mixtures by weight-loss method, stressed that the resistance of the porous magnetite layer to the diffusion of gases cannot be neglected in consideration of the overall reaction rate. In the present study the contributions of interfacial chemical reaction, diffusion of gases through the magnetite phase, and the gaseous boundary layer to the overall reaction rate will be considered. APPARATUS AND PROCEDURE Hematite Specimens Preparation. Natural hematite ore from Vermillon range of Northern Minnesota was selected for the present investigation because of its high purity and thermal stability. Chemical analysis of five samples gave the following average values: 67.52 pct total iron (96.62 pct Fe2O3, 0.28 pct FeO, 0.03 pct metallic iron), 2.53 pct SiO2, <0.07 pct MgO, 0.03 pct CaO, 0.05 pct combined mixture, 0.07 pct loss on ignition, and 0.34 pct other. Cylindrical specimens of 0.93 cm in diam and 2.7 cm in length were drilled from slabs of ore with a water-cooled diamond core drill. These specimens were heated to 1000°C and furnace-cooled. Specimens with silica pockets developed large cracks. The uncracked specimens were heated a second time, and their surfaces were carefully examined with a microscope. Those with hairline cracks or surface inhomoaenitv-- were rejected. Preparation of H2-H2O Mixtures. H2-H2O mixtures were prepared by the combustion of H2-O2, mixtures in a pyrex glass chamber in the presence of a catalyst. Alumina pellets coated with palladium, supplied by Englehard Industries, were used as the catalyst. Purified grades of hydrogen and oxygen were used which were repurified by usual techniques. Hydrogen before entering the combustion chamber was passed through an activated alumina H2O absorption bulb, with copper turning at the top. The cover of this bulb was not made pressure-tight so that any pressure development in the hydrogen line would cause the cover to blow off and also the copper turnings would act as a flame arrester in the case of a flashback from the combustion flame. Oxygen flow rates were measured with a bubble flow meter after purification with 1 pct accuracy. Hydrogen flow rates were measured by "precision wet test meter" and the amount of unburnt hydrogen was accurately measured by a bubble flow meter, after condensing water vapor in the gaseous stream. The Pyrex glass bulb contained concentric Vycor glass tubes as shown in Fig. 1. Oxygen was prevented from diffusing into the hydrogen line by threading platinum wire through pores at the combustion end of gas inlet tube. The glass bulb was heated with a Kanthal heating wire pasted in asbestos paper. The surface temperature of the bulb was measured with a thermocouple and adjusted to remain at approximately 350°C. The gaseous reaction chamber also served as a preheater for gases to avoid thermal segregation. The following sequence of operation was adopted. 1) Nitrogen was passed through the outer concentric tube to purge the catalyst bulb of oxygen. 2) Hydrogen was introduced through the inner tube until a steady flow was obtained. 3) Oxygen was then introduced into the nitrogen stream passing through the outer tube. 4) When combustion had commenced and a flame was visible over the platinum wire, the N2 was turned off.

Jan 1, 1969

By J. E. Lawver, J. D. Raulerson, Charles C. Cook

The agriculture industry has made great strides during the past decade to increase agriculture yields through increased use of fertilizers. Increased use of fertilizers may prevent, or at least delay, mass starvation due to the alarming increase in world population. Phosphate was added to soil as a plant nutrient in the form of calcined bones at least 2000 years ago (Anon., 1964), and man has used phosphate minerals as a source of fertilization in one form or another for at least 100 years. During 1977 the world produced about 116 Mt of phosphate rock, with about 86% used for fertilizers and another 4% for animal feed supplements. More than three-fourths of the total production comes from the United States, Morocco, and the Soviet Union. From a mineral beneficiation point of view, the major sources of phosphate rock and the methods of beneficiation can be classified as follows: marine deposits not containing appreciable carbonate minerals, marine deposits requiring a francolite carbonate mineral separation, igneous deposits not containing appreciable carbonate minerals, and igneous deposits requiring apatite carbonate mineral separation. [ ] Guano, mostly from Chile and Peru, accounts for 0.1% of the total world production, and the calcium phosphates from Ocean, Nauru, and Christmas Islands and the aluminum and iron phosphates from Brazil and Aruba account for less than 4% of the world production and are thus not considered in this classification (Lawver, et al.). At present, marine phosphorite deposits account for about 75% of the world&apos;s production; the igneous deposits account for 20%. The igneous deposits low in carbonate minerals are easily concentrated by crushing, grinding, and apatite flotation. The most important igneous deposits are those of the Kola Peninsula, USSR (Woodrooffe, 1972). The igneous deposits high in carbonate materials are of corn appreciably more difficult to beneficiate, but they have been concentrated by froth flotation for a number of years. An interesting but rather complicated flowsheet of this type is at Phalabonva, in the Republic of South Africa (Lovell, 1976). The Phalaborwa deposit is an igneous complex of pyroxenite with a central core of carbonatite surrounded by a serpentine- magnetite-apatite rock called phoscorite. The phoscorite containing about 10% P2O5, 35% magnetite, and 35% calcium magnesium carbonate is currently being processed. The process involves comminuting the material for fiberation and subjecting it to a copper float using a potassium amyl xanthate as collector and triethoxybutane as a frother followed by a magnetic separation of the tailings to produce a feed for phosphate flotation. This process produces a phosphate concentrate containing greater than 36% P2O5 at a P2O5 recovery ranging from 75 to 80%. Considerable success has been claimed for recovering apatite from carbonate-bearing ores at the Jacupiranga Mine of Serrana S/A (Silva and Andery, 1972). The carbonatite currently being mined contains an average of only 5% P205 and is concentrated using a unique flotation process (Andery, 1968) to yield 96% P205 concentrates. The ore contains about 12% apatite, 5% magnetite, 80% calcite plus dolomite, and minor amounts of phlogopite, olivine, zircon, ilmenite, and pyrochlore. Feed preparation consists of crushing to -31.75 mm (-1 M in.), rod milling in closed circuit with hydrocyclones to about 92% (-50 mesh), and two-stage cyclone desliming of the -50 mesh sands at 20 m. Weight recovery in the deslimed feed is normally 85 to 88% and the corresponding P2O5 recovery is usually about 90%. The deslimed feed is conditioned at 60 to 70% solids for 15 min at pH = 8-10 with 0.6 kg/t of causticized starch for iron oxide and calcite-dolomite depression. The conditioned slurry is diluted to 20 to 30% solids, about 0.2 kg/t of fatty acid or soap collector is added to the conditioner discharge, and the reagentized ore is subjected to rougher-scavenger flotation with additional fatty acid added to the scavenger float. The scavenger concentrate is returned to rougher circuit distributor, and the rougher concentrate froth is subjected to two stages of cleaner flotation to yield a final apatite concentrate analyzing 36 to 38% P205. Flotation recovery of P205 is, in general, above 90% when treating fresh carbonatite. The high-carbonate flotation tails normally analyze 1 % P2O5 or less and are suitable for portland cement production. The marine deposits. Types 1 and 2 of central Florida are representative of enormous reserves of phosphate rock that will undoubtedly account for much of the world&apos;s production in the near future. Until very recently the sedimentary deposits high in carbonate minerals (Type 2) have not been considered reserves due to the difficulty in making a francolite-carbonate separation. Although no commercial plant has yet been built to beneficiate Type 2 ore, laboratory and pilot plant data indicate the process is viable. If so, the reserves of Florida and similar deposits throughout the world will be substantially increased. A discussion of the beneficiation of these two types of sedimentary deposits and the relation of the resulting concentrates to the fertilizer industry of the United States is the subject of this paper.

Jan 1, 1981

By C. S. Sivaramakrishnan, Manjit Singh, Rajendra Kumar

Regarding liquid nzetals structurally as a suspm-sion of clusters , having derivated solid-state coordination, in truly liquid atoms, the recently developed Kuvlar-Samarin technique of centrifuging- in liquid state enabled the determination of the cluster sizes inAl-Cu mid Pb-Sn systems. It is shown that the colutne fraction of the clusters does not exceed 9 pct and the energy of their formation in Al-Cu is about 5.5 kcal per g-atom and in Pb-Sn eutectic alloys about 25 kcal per y-atoni. STRUCTURAL investigations of liquid state have principally followed the following three courses: i) studies with X-ray, electron, or neutron diffraction; these investigations have shown that there is a certain amount of regularity in the structure of liquid metals which can be defined by a coordination number and that the structure is a derived function of that in the solid state; ii) thermodynamical investigations which are based on the concept of ideal behavior; these describe the liquid state in terms of free-energy values and other thermodynamic functions; although these investigations are of help in the study of the general effects of alloying, they do not provide any structural insight into the precise atomic distribution in liquid state; iii) measurements of surface tension and viscosity; although it is natural to expect that the viscosity is related to the structure in liquid state, these investigations have so far only provided information which can be used by the foundry technologists and has been little utilized in formulating models of the structure of liquid state. As it happens, investigators in the three groups have worked almost independently of each other and there is practically no structural correlation between the results of one group with those of another. The purpose of the present paper is to indicate that the experimentally measured parameters of these three groups of research are closely related to the structure in the liquid state. STRUCTURE OF LIQUID METALS Although atomic distribution in solid and gaseous states is rigorously known, that of the liquid state is only appreciated on the fringes. There is no universal model of atomic distribution in liquid state, but two diverse models are at present hotly contested. The first, largely expounded by ~ildebrand,&apos; regards the liquids as condensed gas since many of their properties and much of their behavior can be adequately described by regarding them as fluids. The second mode12j3 considers that some form of near-solid as- sociation of large number of atoms exists in the liquid state. On the other hand, ~ernal&apos; was able to predict rather precisely the radial distribution functions in liquids on the basis of statistical geometric approach which considered that liquids are "homogeneous, coherent, and essentially irregular assemblage of molecules containing no crystalline regions or holes large enough to admit another molecule". He introduced the concept of pseudonuclei in the otherwise random structure as aggregates of closely packed tetrahedra which gradually merge into irregularity and continually replace each other. To what extent the pseudonuclei can be regarded as regions of near-solid association is indefinite but Bernal suggested that the concept of pseudonuclei can be compromised with the latter model if the near-solid associations are regarded as extremely dense and not necessarily crystalline. The difficulty in projecting the structure of liquid metals arises because they exhibit duplicity of character as some of their properties are closer to those of crystalline solids and others to fluids. There is an increasing tendency to discuss the structure of liquid metals in terms of the second concept according to which the structure of liquid metals may be conceived as consisting of i) clusters of atoms where the aggregation is a close derivative of that in the crystalline state, ii) individual atoms which behave like true liquids in respect to degrees of freedom and iii) excess number of vacancies. It is noteworthy that the introduction of only 5 pct vacancies is sufficient to transform crystalline matter into the liquid state. At any instant of time thermodynamic equilibrium exists between i, ii, and iii, but the relative proportion of the clusters and random atoms is not known. That this is so can be appreciated by the fact that, when liquid metal is rapidly cooled, liquid state vacancies may condense in the form of dislocation loops and vacancies in excess of their equilibrium number in solid state. These dislocation loops have been observed in thin foils of aluminum prepared from rapid cooled aluminum. As temperature increases above melting point the number and volume fraction of clusters decrease but those of vacancies and random atoms increase. Clusters are transient in nature. In pure metals the cluster is an aggregation of the metal itself. In alloys, however, the nature of the cluster largely depends on the interaction between solvent and solute atoms. If the interaction between unlike atoms is greater than between like atoms: the clusters are then aggregates of unlike atoms. Examples of this kind of system are A1-Cu, Mg-Pb, and so forth, i.e., systems which exhibit negative departures from the Raoult&apos;s law. In systems where the interaction between unlike atoms is smaller than be-

Jan 1, 1968

By K. S. Benson

DEPLETION is a subject of vital importance to the mining industry. Yet, in spite of its importance, its significance is not generally understood. The purpose of this discussion is to clarify the main aspects of the subject from the viewpoint of a metal mine taxpayer. To define the term depletion, it is necessary to distinguish among its various uses. In the economic or geological sense, depletion means the exhaustion of a natural resource. A mineral deposit is a wasting asset and once exhausted is nonrenewable. Millions of years were needed to produce an ore deposit, which may be consumed in a few years and which cannot be replaced except by the discovery of new sources of supply. The wasting asset feature of the mining industry has a vital bearing on the impact of the Federal Income Tax Law on this industry. This is recognized in the law by the various provisions dealing with the depletion allowance, and in this sense the term depletion has an income tax meaning. Depletion from the tax viewpoint means the statutory deduction from gross income designed to permit the return to the taxpayer of the capital consumed in the production and sale of a natural resource. The mining enterprise realizes income on the extraction and sale of minerals and a portion of the income realized represents capital consumed. As the resource is exhausted, the mining enterprise approaches the end of its existence unless new sources of supply can be acquired. Depletion from the tax viewpoint is a creature of statute with limited meaning and application and, in essence, is a method for amortizing the value of the primary asset of a mining enterprise. An example can best illustrate the significance of depletion from the tax viewpoint. Compare a manufacturing concern with a mining company. In computing taxable income of a manufacturing concern, consideraion is given to the cost of producing such income, the principal costs being capital investment for plant and equipment, labor, and raw materials going into the products produced. A mining enterprise, on the other hand, is faced with a different problem because its principal asset is the natural resource which it is producing. In computing its taxable income, consideration is given also to its capital investment for plant and equipment and the cost of labor; but in addition, recognition must be given to the fact that a portion of the proceeds realized on the sale of mineral represents capital. Without such recognition, the mining company would be taxed not on income but on capital and income, and Congress has never intended that capital be taxed as income. Thus, when depletion allowable is referred to in the mining industry, it means the statutory deduction allowable in computing taxable income of a mining enterprise. For guidance the appropriate provisions of the Internal Revenue Code, Income Tax Regulations, and the judicial decisions interpreting and construing them must be examined. It is important to identify and distinguish three methods of determining the allowance for depletion: 1—Cost depletion, 2—Discovery depletion, and 3—Percentage depletion. The basic method is cost depletion and in addition some taxpayers may be entitled to use discovery depletion and other taxpayers may be entitled to use percentage depletion. Discovery depletion and percentage depletion, however, are mutually exclusive and if a taxpayer is entitled to percentage depletion, he is not entitled to discovery depletion. By statute, a metal mine taxpayer is entitled to use cost depletion or percentage depletion, whichever produces the highest deduction. Thus, discovery depletion is merely of academic interest to such taxpayers and to most others. Briefly and broadly speaking, these methods of determining depletion may be described as follows: 1—Cost Depletion: Under this method, the allowable deduction for depletion is based upon the cost of the particular deposit to the taxpayer, unless the deposit was owned prior to Mar. 1, 1913, in which case the taxpayer may use the fair market value of the deposit on that date or actual cost, whichever is higher. This method is sometimes described as basis depletion or adjusted basis depletion, but in this discussion it will be referred to as cost depletion. 2—Discovery Depletion: Under this method, the allowable deduction for depletion is based on the fair market value of the deposit at the date of discovery or within 30 days thereafter and was originally designed to take into account deposits discovered subsequent to Feb. 28, 1913. 3—Percentage Depletion: Under this method, the allowable deduction for depletion is based on a specified percentage of the income realized during the taxable year from a particular property. As stated, the concept of depletion is based upon the exhaustion of a natural resource as distinguished, for example, from the concept of depreciation based on the exhaustion of property used in trade or business. From the tax viewpoint, depletion first became important in the administration of the Corporation Tax Act of 1909, which provided for an excise tax on net income. As soon as this act went into effect, mining taxpayers attempted to claim a deduction for depletion in computing net income although there was no specific mention of a deduction for depletion in the statute. The courts in these cases uniformly held that the statute did not permit an allowance for depletion in computing net income and also held that the provision permitting a reasonable allowance for depreciation did not include depletion. These early cases are quite significant because they establish the principle that the

Jan 1, 1952

By R. L. Fullman

IN the investigation of metallurgical transformations and the relationships between microstructure and properties of metals, it frequently is desirable to obtain a measurement of the relative amounts of the various phases present and of the mean size of particles into which each phase is dispersed. The relative amounts of the phases can be measured by the classical methods of area, lineal, and point analysis,1-5 in accordance with the principle that the volume fraction of a phase, the fraction of a polished cross section occupied by the phase, the fraction of a random line occupied by the phase, and the fraction of randomly arrayed points occupied by the phase are all equal. The validity of this relationship depends only on the attainment of a truly random sample of area, length, or points, and not on the size, shape, or distribution of the particles constituting the phase. Smith and Guttman8 have derived a relationship between the interface area per unit volume S, and the measurable quantities L., the interface length per unit area on a cross section, and NL, the number of interfaces per unit length intersected by a random line. Their equation, Sv = — L8 = 2NL is also valid regardless of the distribution of particle sizes and shapes. In contrast to the situation concerning measurement of relative fractions of phases and of interface area, the measurement of particle sizes in opaque samples has not been subjected to a complete analysis. It has been common to measure some lineal or area dimension of particles on a polished cross section and to use the mean value as a qualitative measure of particle size. In the present paper, quantitative relationships are established among the various mean dimensions on a polished cross section and the actual dimensions of the particles present. Particles of Uniform Size Spheres: If a metal sample contains particles of a phase a dispersed in the form of spheres of uniform size, a polished cross section through the sample will reveal circular areas of phase a with radii from 0 to ?, the radius of the spheres. Consider a cube of unit dimensions to be cut from the sample. If a cross section parallel to one of the cube faces is examined, the average number of particles per unit area (N,) equals the number of particles per unit volume (Nv) times the probability p1 that the plane would intersect a single sphere positioned at random within the unit cube. Since, of the various possible positions for the cross-sectional plane over the unit length from top to bottom of the cube, only those positions existing over the length 2r would lead to the plane intersecting the sphere, the probability of intersecting a single sphere is just 2r. N8= Nvp1 = Nd-2r [1] Applying the equality of area and volume fractions, the relationship is found between sphere size and average area s of uniform spheres intersected by a random cross section, 4 - f = NV V = Nr . — pra = N s = Nd . 2rs S = —pr2 [2] A similar analysis reveals the average traverse length across spheres of uniform size when random lines are passed through the sample. If a randomly oriented unit cube is cut from the sample and a randomly positioned line is passed through the cube parallel to a cube edge, the number of spheres intersected by the line (Nl) equals the number of spheres per unit volume times the probability p1 of the line hitting a single randomly placed sphere in the cube. Since possible positions of the line occupy unit area, and possible positions for which it will pass through the sphere occupy an area of pr2, the probability of the line hitting a randomly placed single sphere is pr2. NL = Nv p1 = Nvpr2 [3] Combining this relationship with the equality of volume and lineal fraction, the desired relationship is obtained between radius and mean lineal traverse length -i, for spheres of uniform size. 4 - - 3 l=4/3r [4] Circular Plates: Consider a sample containing particles of a phase a in the form of circular plates of uniform radius r and thickness t, where r >> t. If the plates are randomly oriented, as in a sufficiently large sample of a fine grained polycrystalline material, area and lineal analysis may be carried out with parallel cross-sectional planes and lineal traverses. If the plates are not randomly oriented, it is necessary to randomize the orientation of the cross-sectional planes and traverse directions. Let a unit cube be cut from the sample, and a cross-section plane be passed through the cube parallel to one of the cube faces. The number of plates cut by the cross-sectional plane per unit area is equal to the number of plates per unit volume times the probability of a plate intersecting a single randomly positioned and randomly oriented plate in the cube. If J is the component of the plate diameter in the direction normal to the cross-sectional planes, the probability of a plane cutting a single randomly oriented plate is equal to J, the mean value of J for all possible orientations of the plate. Let 4 be the dihedral angle between a plate and the cross-sectional plane, and let p?, d? be the probability that a plate makes an angle between 4 and ? + d? with the cross-sectional plane. Then for ran-

Jan 1, 1954

By J. D. Livingston, H. E. Cline

The lamellar-dendritic transition in Sn-Pb alloys near the eutectic composition has been studied at high growth rates. Lamellar structures were found over a substantial range of tin-rich compositions, and this range extended to increasingly tin-rich concentrations as growth rate increased. These results are discussed in terms of stability and competitive-growth arguments. Various experimental and structural limitations to the rate of directional solidification are discussed. The rate of heat removal at the heat sink is the major experimental limitation. ReCENT interet1,2 in the use of fine composite structures produced by directional solidification of eutectic alloys makes it important to determine the range of composition and growth conditions that yield such microstructures. Because increasing growth velocities produce increasingly finer microstructures, it is particularly significant to determine the factors limiting the rate of solidification. Mollard and Flemings3 have shown that composite structures, free of primary dendrites, can be obtained in Sn-Pb alloys of off-eutectic composition. The composition range of composite structures was found to increase with increasing values of G/V, where G is the temperature gradient and V is the growth velocity. These results are in good quantitative agreement with an analysis of the stability of a planar eutectic interface.4 This analysis specifically predicts that over a small range of compositions stable lamellar structures will be obtained even for G/V = 0, hence, even at very high growth rates. The lamellar-dendritic transition in Sn-Pb alloys has also been analyzed with a model based on competitive growth between dendrites and the composite structure.576 This treatment, based on earlier work on organic eutetics,7 predicts that the composition range yielding composite structures in Sn-Pb will increase rapidly at high growth rates. An increase in the composition range of composite structures at high growth rates was recently observed in Cu-Pb alloys near the monotectic composition.8 In view of these results, and the predictions of the stability and competitivegrowth analyses, it was decided to study the lamellar-dendritic transition in Sn-Pb alloys at high growth rates. EXPERIMENTAL Using 99.999 pct pure materials, a series of Sn-Pb alloys were prepared containing 16.8 at. pct to 27.6 at. pct lead. (Eutectic composition is 26.1 at. pct Pb.) Ingots were extruded to 0.175 in. rod, and some rod was drawn to 0.070-in. wire. Directional solidification was accomplished in two different ways, Fig. 1. For growth rates up to 2 x 10-1 cm per sec, a 0.175 in. diam sample was placed in a graphite crucible 5 in. long with 0.250 in. OD and 0.035 in. walls. Samples were melted under flowing argon in a vertical, platinum-wound furnace, and solidified by driving the crucible downwards through a \ in. hole in a water-cooled copper toroid, Fig. l(a). An insulated chromel-alumel thermocouple was imbedded in the center of a representative sample, and moved with the sample during solidification. The local temperature is plotted against the distance travelled by the sample in Fig. 2. As the growth rate increased, the solid-liquid interface moved closer to the water-cooled toroid and the temperature gradient increased. At growth rates above 10-1&apos; cm per sec, heat was not removed fast enough and the sample moved into the toroid in the liquid state. The curve for V = 2 x 10-1 cm per sec shows a plateau caused by incomplete removal of latent heat from the interface, a problem which will be discussed later. To improve the heat removal, the toroid was cooled by nitrogen gas precooled in liquid nitrogen. This allowed successful solidification at rates up to 2 x 10-1cm per sec. Higher solidification rates required still more effective heat removal. Samples 0.070 in. in diam were placed in graphite tubes 0.125 in. in diam with 0.020 in. walls. Instead of cooling by sliding contact with a cooled toroid, these thinner samples were sprayed or directly immersed into water, Fig. l(b). After solidification, samples were stored in liquid nitrogen until they could be examined metallographic-ally. The surface was prepared with a diamond-knife microtome, followed by a light etch. The presence or absence of tin dendrites, Fig. 3, or lead dendrites, Fig. 4, was noted by optical microscopy, usually of a transverse section near the center of the sample. Replicas of the surface were prepared and examined in an electron microscope to resolve the fine lamellar structures, Fig. 5. The structures observed at various compositions and growth rates are summarized in Fig. 6. Composite structures were observed at increasingly cin-rich compositions as growth rate increased. This transition from dendritic to composite structure with increasing growth rate was also demonstrated by solidifying half a sample at a slow rate and then suddenly increasing the growth rate by lifting the furnace and quenching the sample with a water spray. A longitudinal section of this sample, Fig. 7, shows that the tin dendrites, which extended ahead of the slow-moving composite interface, were bypassed by the composite when the growth rate was increased. The range of composite structures at high growth rates was limited by the appearance of primary lead dendrites on the tin-rich side of the eutectic composition. Observation of representative longitudinal

Jan 1, 1970

By L. R. Shoenberger

Boron has been used to produce nonaging low-carbon sheet steel. Retention of the necessary minimum amount of about 0.006 pet partially killed the steel. Amounts exceeding about 0.012 pet increased the degree of deoxidotion, piping tendencies, and possibility of hot tearing in primary rolling. Semikilled practice resulted in good ingot yields and satisfactory surface quality. Aluminum added with the boron provided a protective de-oxidizer. Good drawobility was indicated by performances of the steel in a limited number of deep-drawing trials. Some problems with hot-tearing and boron-analysis procedures were overcome. Metal lographically, the boron semikilled steels revealed some structures not usually found in plain low-carbon steels. IN 1943 Low and Gensamer1 reported that strain aging, which hardens and embrittles ordinary low-carbon rimmed steel, was due to nitrogen and carbon, and that oxygen played a relatively unimportant role. Since then, many investigators have substantiated their findings and indicated that nitrogen is particularly potent. Commercially, today&apos;s most widely produced non-aging sheet steels for deep drawing are either aluminum killed or vanadium rimmed types. The difference in deoxidation practice, alone, is evidence that oxygen is apparently not an important consideration in control of strain aging. The fact that nitrogen is important is apparent in the consideration that has been given, knowingly or unknowingly, to the amount combined with aluminum and vanadium. Patents were granted to Hayes and Griffis2 for the processing of aluminum-killed steel, and to Epstein" for the manufacture of vanadium rimmed material. Certain prescribed steps in producing these steels can be correlated with the formation of the respective nitrides within certain temperature ranges below the usual hot-finishing temperatures. The potential nonaging properties of either type can be reduced or suppressed by cooling too rapidly to permit the aluminum or vanadium to combine with nitrogen. Subsequent suberitical annealing of the cold-rolled strip, however, normally forms the nitrides and produces the resistance to strain aging. Titanium-killed nonaging steel, described by Comstock,1 forms a nitride in the molten state and is essentially nonaging throughout its processing. Zirconium-killed steel, which was investigated briefly by the author,* appeared to have similar nitride- forming characteristics. It is known" that chromium can produce nonaging rimmed steel, but relatively little is known of the potentialities of some of the other nitride-forming elements such as boron, silicon, columbium, and cerium. In attempting to develop a new nonaging cold-rolled sheet steel with good drawability, the following factors were considered pertinent. Such a steel would necessarily have a low carbon content and therefore have a relatively high degree of oxidation when made in a basic open-hearth furnace. If the denitriding element were also a deoxidizer, a part of the addition would be lost as oxide. The degree of deoxidation would determine whether the steel is rimmed, semikilled or killed, and also could be expected to have an important bearing on ingot yields and ultimate surface quality. Assuming that the pattern for the production of cold-rolled sheets would not be changed to any great extent, the nitride must form in the molten steel, in hot rolling, in subsequent cooling, or in annealing. The nitride, once formed, should resist dissociation and be stable in the final product. Usually an excess of the nitride-forming element is required to combine with sufficient nitrogen. If the element used is a strong ferrite strengthener, a small excess may markedly decrease drawability. With aluminum and vanadium, about 0.03 to 0.05 pct in the steel is preferred. Epstein has said" that about 0.30 pct chromium is required. Titanium nonaging steels are hard unless a sufficient amount (about 0.30 pct) is added also to combine with the carbon. The cost of the necessary amounts of these latter two elements discourages commercial acceptance. Silicon was considered as a possible nitride former, but since amounts up to 0.10 pct in rimmed and semikilled steels do not induce marked resistance to strain aging, larger amounts are apparently required, which would tend to harden and strengthen the ferrite. Of the other elements mentioned, all but boron are expensive heavy-metal elements. Stoichi-ometrically, almost an equal weight of boron would be required to combine with the nitrogen—-ordinarily about 0.003 to 0.006 pct in scrap-practice open-hearth steels. Boron is a slightly stronger deoxidizer than carbon but is less powerful than zirconium, aluminum, or titanium. Thus a rimmed-steel practice might be possible. There is much in the technical literature concerning the hardenability effects of minute amounts of boron in killed steels but very little about its behavior in low-carbon material—particularly as a ferrite strengthener. The available data indicated a need for better information concerning the effects of boron in low-carbon strip steels. Experimental Work Development of a Boron-Treated Nonaging Strip Steel—Initial attempts to produce a boron-rimmed strip steel employed 3-ton basic open-hearth heats which could be teemed into molds large enough to sustain a normal rimming action. Boron as ferro-boron was added to the ladle in small amounts because of the reported hot-short character of aluminum-killed heat-treating grades containing more than about 0.005 pct boron. Actually, the amounts used, i.e., 1/8 and 1/4 lb per ton, would be large for

Jan 1, 1959

By R. F. Krueger

Results are presented from tests of dynamic fluid-loss rates to cores from clay-gel water-base drilling fluids containing different commercial fluid-loss control agents (CMC, polyacrylate or smt,ch), organic viscosity reducers (quebracho and complex metal lignosulfonate) and oil at several different levels of concentration. In the dynamic system the most effective individual additives to the clay-gel drilling fluid, based on cost-equalized concentrutiom, were found to be starch and the viscosity reducers. These results do not conform with the rankings determined by API fluid-loss rests, which indicate CMC, polyacrylate and starch to be the most effective and comparable. Generally, minimum dynamic fluid-losr rates were attained at cost-equalized concentrations of additive (including thinner) of about $1.00/ bbl, or less. For chernically treated clay-gel drilling fluids, both the standard and the high-pressure API filter-loss tests were found to he inaccurate indicators of trends in dynamic fluid-loss rates under the test conditions used, particulurly for drilling muds containing viscosity reducers. From a practical field viewpoint, restrictions on the applicability of the API fluid-loss test are such that it is open to question whether or not results of this test can be used routinely with confidence as an indicator of control of down-hole fluid loss under field treating conditions. INTRODUCTION The petroleum industry spends large sums of money during drilling operations to control the fluid-loss properties of drilling fluids based on the standard API filter-loss test,&apos; which is a static filtration system. Laboratory studies&apos; &apos; of dynamic filtration have shown that in a given time period filtrate loss from a circulating mud stream is greater than from a static system and that it is a function of linear mud velocity, pressure and the properties of the drilling fluid. Ferguson and Klotz&apos; and Horner, et al," observed that (I) the dynamic fluid-loss rates for the drilling fluids used were not related to the extrapolated API filter loss and (2) the drilling fluids with the lowest API filter losses did not have the lowest dynamic fluid-loss rates. However, there has been no published information on the relative effects on dynamic fluid-loss rate as a given drilling fluid is treated with increasing amounts of chemical additive to reduce the API filter loss. Such information is economically important because drilling-fluid costs rise rapidly as chemical requirements increase. This paper presents the results of a study of dynamic filtratioi rates to cores from a clay-gel water-base drilling fluid treated with various commercial viscosity reducers and chemical fluid-loss control agents. The dynamic fluid-. loss rates to cores are compared with the standard API filter-loss values at several different levels of additive concentration. Dynamic filtration rates were obtained in each experiment under two different simulated wellbore conditions: (1) filtration just above the bit through a new mud cake laid down dynamically on a freshly drilled formation and (2) filtration up-hole through a mud cake formed by deposition of a static filter cake on top of the initial dynamically formed cake. The latter case corresponds to the bottom-hole conditions existing above the bit when mud circulation is restarted after a stand of pipe has been added or a round trip has been made to change the bit. Except for the short-duration, high-rate filtration beneath the bit where no mud cake can form, these two conditions probably represent the two extremes of dynamic filtration. Because thickness of a dynamic mud cake formed on freshly exposed formation is limited by the shearing action of the mud stream, the filtration rate for this condition is high. On the other hand, once circulation is stopped and a static mud cake forms on top of the dynamic cake, re-starting circulation has only a small effect on the cake properties and filtration rate is much lower thereafter. A discussion of the mechanics of mud-cake deposition and dynamic filtration is outside the scope of this paper but may be found in more detail in publications by prior investigators. APPARATUS AND EXPERIMENTAL CONDITIONS The test equipment used to simulate the dynamic flow conditions existing during drilling was a modification of that described previously by Krueger and Vogel: A schematic flow diagram is shown in Fig. 1. In general, a power-driven, high-pressure mud pump capable of delivering up to 60 gallmin was used to circulate drilling fluid parallel to the faces of 1-in. diameter sandstone cores mounted in a 2 3/4-in. ID high-pressure test cell. Pump rates were controlled by means of a magnetic clutch to maintain an average axial fluid velocity of 110 ft/min in the annular space between the cell wall and a 1 1/2-in. rod positioned on the center line of the cell. The core specimens were Berea sandstone plugs sealed with plastic inside 1 1/8-in. OD tubes and were fluid-saturated prior to use. Burettes were used to accumulate fluid discharged from the cores. The mud sump shown was used for treatment and storage of the drilling-fluid samples during a particular test. The valve arrangement permitted either (1) circulating drilling fluid through the by-pass line while treating with

By James W. Dally, William L. Fourney, Anders Ladegaard Peterson

For the past 3 years, the authors have been conducting research sponsored by the National Science Foundation (RANN) to improve the process of excavation by drilling and blasting. The approach followed has been experimental where the development of stress waves and fractures initiated at the bore hole have been investigated in order to obtain a complete understanding of the dynamic fracture process. The second step in the approach has been to introduce modifications in the drill and blast procedure which will permit closer control of the fracture process. The laboratory investigations involve high speed photography where the dynamic fracture process is recorded with a Cranz-Schardin 1, 2 multiple-spark camera. The camera is equipped with 16 spark gaps which are pulsed at 25 K volts to produce an intense but very short (0.5 sec) flash of light. The camera is capable of recording 16 photographs of a dynamic event at framing rates which can be varied from 30,000 to 1,500,000 frames per second. The exposure time is sufficiently short to stop motion associated with detonating explosive charges and to make visible the details of the fracture process at a bore hose. The bore hole in a massive intact rock formation is modelled with a two dimensional plate containing a circular hole to represent the bore hole. The model material employed is a transparent polyester known commercially as Homalite 100.* This polymeric material is extremely brittle as evidenced by its extremely low fracture toughness of [ ]. The fracture toughness is a measure of the ability of a material to resist the propagation of flaws or small cracks. In comparison, Schmidt3 has recently measured the fracture toughness of Salem limestone and determined [ ]. Thus, the Homalite 100 should closely model the brittle nature of rock where fractures occur at small flaws and propagate without any apparent plastic deformation. Homalite 100 is also birefringent, which indicates that it becomes optically anisotropic when subjected to either static or dynamic loads. Circularly polarized light is transmitted through the loaded Homalite 100 model in a polariscope4 and the birefringence produces an optical interference pattern which is called a fringe pattern. For dynamic photoelasticity, the multiple-spark camera is equipped with polaroid filters to produce the circularly polarized light required to generate the photoelastic fringe patterns. An example of a singlespark frame showing a fringe pattern from a typical experiment is presented in [Fig. 1]. The photograph was taken 0.000072 sec (72 sec) after the detonation of the explosive charge. The circular fringes are due to the outgoing dilatational or P type stress wave and travel with a velocity of 85,000 in. per sec (2260 m/sec) in the Homalite 100. The P wave is followed by a second lower velocity stress wave known as the shear or S type wave which propagates at a velocity of 49,000 in. per sec (1245 m/sec). In the local neighborhood of the bore hole, several radial cracks are visible. These cracks propagate at essentially a constant velocity of 15,000 in. per sec (380 m/sec) prior to arrest. The fringes about the crack tips and in the local region of the bore hole are primarily due to the residual gases contained in the bore hole after the explosive charge was detonated. Sixteen frames similar to this one are recorded during the experiment to give full field visualization of the dynamic event at 16 discrete times over its duration. The fringe order number N is related to the difference in the principal stresses of and 02 according to a stress optic law4: [ ] where f0 = material fringe value, and h = model thickness. The wholefield dynamic-fringe patterns provide a basis for simultaneously observing the interaction between propagating cracks and the stresses which drive these cracks. Fracture Control Experiments Improvements in the efficiency of the drill and blast procedures must involve close control of the fracture process following the detonation of an explosive charge in a bore hole. By control it is implied that the number of cracks initiated and the location of each crack on the wall of the bore hole can be specified. Control also, involves orienting each crack and maintaining the crack path and velocity until the specified crack length is achieved. If the entire fracture process can be controlled, then rounds can be designed to optimize volume removed. fragment size and minimize costs. One area of blasting where fracture control is vitally important is in underground excavation where the strength and stability of the rock walls must be maintained and smoothness and precision of the walls must be achieved. The smooth blasting method is one of the most commonly employed procedures for achieving some degree of fracture control. In smooth blasting, the central region of material is first removed, and then the final row of closely spaced undercharged or cushioned holes are fired to remove the final volume and produce a smooth wall. In some instances, unloaded or dummy holes between the loaded holes are recommended to guide the fracture plane. This investigation pertained to an evaluation of 3 features of the smooth blasting process. These included (a) the effect of stress reinforcement on fracture by simultaneously firing 2 charges; (b) the influence of a dummy hole on control of the fracture planes between 2 simultaneously fired charge holes; and (c) the influence of dummy hole spacing on fracture plane control.

Jan 1, 1979

By C. H. Curtis

HE valuable mineral content of the current feed -*- to the Miami concentrator is as follows: copper, 0.7 pct total; molybdenum, 0.01. Flotation of this ore yields a sulphide concentrate containing: chalco- cite, 44 pct; molybdenite, 0.5; pyrite, 50.0; insol, 5.5. A combination of potassium ethyl xanthate and pentasol amyl xanthate as collectors, and pine oil as frother, are used in this flotation. Rejection of pyrite is encouraged by holding the amount of collectors used to the minimum consistent with copper recovery and by operating at high alkalinity (equivalent to 0.35-0.40 lb CaO per ton solution of pH 11.0). The molybdenum recovery in the sulphide concentrates under the above flotation conditions is approximately 50 pct of that originally present in the ore. Taking into account the acid soluble molybdenum, indicated molybdenite recovery is 75 to 80 pct. The attempt to separate the molybdenite into an acceptable molybdenum product begins with the bulk sulphide flotation concentrate just described. This concentrate is composed of chalcocite, whose floatability has been promoted to the fullest extent possible for the sake of its recovery from the ore, together with the pyrite which has been activated along with the copper mineral. The problem is to deaden the copper and iron minerals, and to float the molybdenite. Obviously in the accomplishment of this end, conditioning and preparation of the pulp, prior to flotation, plays an all important role. The first step is thickening to 50 to 60 pct solids, with milk of lime added to the thickener feed to maintain an alkalinity of the pulp equivalent to a pH of 8.5 to 8.8 during its residence in the thickener. The purpose of the thickening is primarily to reduce the volume of pulp for subsequent treatment. However, the relatively prolonged retention of the pulp in the thickener at the desired alkalinity is known to have a favorable depressing effect upon pyrite. There is a limit for this alkalinity above which a depressing effect upon molybdenite occurs. The thickened pulp (alkalinity: 0.015 lb CaO per ton, pH 8.8), discharges into an agitator, retention time approximately 2 hr, to which additional lime is added to raise the alkalinity to 0.35 to 0.40 lb CaO per ton solution, pH 11.6. This additional lime is required for pyrite depression and can be tolerated without loss of molybdenite because of the limited time of contact in the conditioner tank. The pulp leaving the lime conditioner passes through two successive steaming tanks, which are mechanically agitated, and into which live steam is admitted directly into the pulp near the bottom of the tanks. The temperature of the pulp is maintained as near boiling as possible. The steaming time is approximately 4 hr. The pulp leaving the last steamer has an alkalinity of about 0.04 lb Cao per ton solution, pH 8.7. It is believed that oxidation of the copper and iron sulphides occurs during steaming, the resulting sulphates reacting the calcium hydroxide to calcium sulphate and thus reducing the alkalinity. Since the steamer-feed solution is already saturated with calcium sulphate, the calcium sulphate produced during steaming is precipitated. It is believed that this calcium sulphate is precipitated preferentially on copper and iron mineral surfaces thus decreasing their floatability. Aside from the "lime chemistry" during steaming, pine oil is displaced from the pulp and xanthate decomposed, which has a major effect upon the deadening of the copper and iron sulphides. Following steaming, the hot pulp is admitted to another conditioning tank wherein it is aerated, primarily for cooling, but incidentally for additional oxidation of the copper and iron sulphides. The resulting "deadened" pulp is then diluted to 20 pct solids, a specific collector for molybdenite, ordinary stove oil, is added and the separation of the molybdenite by flotation is undertaken at a pH of 8.5 to 8.8 in standard Miami air-flotation ma-chines. B-22 frother is used when necessary. A re-grind of the thickened rougher concentrates is made prior to the first cleaning operation chiefly for rejection of insoluble in subsequent flotation. The cleaner concentrate is then stepped up to 90 pct MoS, in an 8-cell Denver flotation machine No. 18. Sodium silicate is added to the cleaner circuit. Its effect is to flocculate molybdenite and stabilize the froth. In summary, it may be stated: 1. Separation of molybdenite into an acceptable product from sulphide copper concentrates by flotation involves preliminary preparation and conditioning of the pulp, which is of major importance. 2. This preparation and conditioning consists of several successive steps: (A) Thickening to 50 to 60 pct solids at controlled alkalinity to reduce volume of pulp and to contribute to depression of pyrite. (B) Agitation at high-pulp density for limited time with additional lime to provide for depression of pyrite. (C) Steaming at high-pulp density for decomposition of xanthate and xanthate surface films, evolution of pine oil, and oxidation of sulphide minerals other than molybdenite. The latter involves sulphating of lime with probable precipitation of calcium sulphate preferentially on copper and iron minerals. (D) Aeration at high-pulp density for cooling, and for further oxidation of copper and iron sulphide minerals. (E) Dilution of pulp to 20 pct solids and addition of specific collector for molybdenite, common stove oil. It is hardly necessary to point out that this rather drastic procedure for depression of previously activated copper and iron sulphide minerals, without at the same time depressing molybdenite, is possible due to the inherently high floatability and refractory nature of molybdenite. However, molybdenite is susceptible to depression by excessive lime which must therefore be limited to the amount consistent with satisfactory molybdenite recovery. The steaming procedure is being carried on at Miami Copper Co. under license agreement with Janney, Nokes, and Johnson, holders of letters patent on the process.

Jan 1, 1951