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By Olav Mellgren

Part I. The interaction between potassium ethyl xanthate and lead salts has been studied thermo-chemically. It is shown that ethyl xanthate reacts with lead carbonate, basic carbonate, thiosulfate and sulfate according to principles of simple chemistry, whereas reactions with lead sulfite, metasulfite, basic thiosulfate and hydroxide at high pH are associated with secondary reactions. A new compound "xanthogen thiosulfate" is postulated. Part 11. Adsorption of ethyl xanthate on galena has been studied quantitatively and thennochemi-cally. It is shown that an ion-exchange mechanism governs the adsorption process and that the heat of adsorption of xanthate on galena is equivalent to the heat of reaction of ethyl xanthate with bulk lead salts. It is concluded that the entropy content of the surface "compound" on galena is different from that of a corresponding bulk lead salt. Alkali depression is in part shown to be due to the instability of the xanthate-galena system at high pH and to the formation of basic lead salts. Sulfate and carbonate ions are shown to have a stabilizing effect on the xanthate-galena system. PARTI. THERMOCHEMISTRY OF ETHYL XANTHATE AND OF ITS REACTION WITH LEAD SALTS In the past little attention has been paid to the chemistry of lead xanthate. It is known that xan-thates form slightly soluble compounds with lead and that suspensions of lead xanthates in alkaline solution decompose rather readily.' The solubility of lead ethyl xanthate is of the order of 2.6 x 10-6 moles per 1. At increasing pH the xanthate concentration of a saturated solution contains more xanthate. Thus at pH 11 this xanthate content is about 100-fold larger than at pH 7.1 Xanthates are known to be consumed when added to a suspension of slightly soluble lead salts such as lead sulfate and lead carbonate. It is unknown to what extent this xanthate consumption is due to a simple chemical reaction because, frequently, observations are made which reveal secondary reaction products in such reactions. Thermochemical study of the reaction between xanthate and lead salts offers a means to clarify the significance of these reactions as the enthalpy changes can be accurately predicted from heat of formation of lead salts in pure solution reactions. In the present work the heats of formation of lead ethyl xanthate from potassium ethyl xanthate and lead salts are determined and some thermochemical aspects of xanthate in solution are studied. The results of these investigations are presented in Part I. In Part II the heat of adsorption of ethyl xanthate on galena surfaces is presented. All enthalpy changes were measured directly in a microcalorimeter. Calorimeter: The calorimeter used for measuring enthalpy changes was similar to that used by Redinha and Kitchener2 which was based on a description by Derbyshire and Marshall.3 Other useful references4,5 are listed. A sketch of the calorimeter

Jan 1, 1967

By H. W. Fleming, R. R. Brooks

The Clearwater Deposit, a small occurrence of massive-sulphide mineralization enclosed in an envelope of disseminated-sulphide mineralization, was discovered as a result of an aeroelectromagnetic survey in New Brunswick in 1955. Subsequently, additional flights were made over the deposit and various ground follow-up methods were employed to ascertain the nature of their response. All methods proved to be capable of indicating the occurrence with varying degrees of precision. This paper is a presentation and a discussion of the magnetic and electromagnetic data, both airborne and ground, and the self-potential data obtained over this deposit. The attention of Canadian mining exploration companies was initially focussed on New Brunswick by the discovery, in 1953, of the Brunswick ore body. Ground electromagnetic surveys were of considerable assistance in locating and developing this deposit. In the following year, 1954, the Heath Steele base-metal deposits were discovered by employing an airborne electromagnetic device and ground electromagnetic surveys to follow-up the airborne indications. These discoveries demonstrated clearly that both airborne and ground electromagnetic techniques were applicable for locating the near-surface deposits of massive sulphides present in this region. Airborne electromagnetic equipment became available on a contract basis through Aeromagnetic Surveys Limited early in 1955 and was used extensively thereafter throughout a large portion of northern New Brunswick. It was as a result of one of these surveys with Aeromagnetic Surveys Limited equipment in the summer of 1955 that the Clearwater Deposit was detected. The airborne anomaly was located on the ground by means of an electromagnetic survey using a Swedish Slingram unit. During 1956, the region was investigated more thoroughly- in the hope that other sulphide bodies might be located. Airborne electromagnetic coverage was extended and the Clearwater Deposit itself was used as a testing ground for the various methods and types of equipment currently in use in New Brunswick. In this paper com prative data are presented for the airborne magnetic, airborne electromagnetic, ground magnetic and ground electromagnetic surveys over this deposit. The ground electromagnetic instruments used were the McPhar vertical-loop unit and the Slingram and Boliden horizontal-loop units. Self-potential surveys were carried out with a McPhar unit. From the geophysical point of view, all ground electrical methods employed indicated the presence and the extent of the massive-sulphide mineralization with a good degree of accuracy. The horizontal-loop methods however, defined the contacts more precisely as is to be expected when dealing with a flatly-dipping

Jan 1, 1961

By R. H. Atkinson, R. N. Rhoda

An improved technique has been developed for the deoxidation of palladium with aluminum which is especially suitable for use in making small castings with an induction-melting and casting machine. The effect of various crucible linings on the efficiency of the residual deoxidizer and accompanying oxide film in protecting palladium against oxidation during remelting also has been examined; the preferred crucible lining consists of zirconia cement. THE objective of this work was to develop a simple method of deoxidizing induction-melted palladium which would be suitable for use by manufacturers of jewelry and other small castings. In a common method of deoxidizing torch-melted palladium a piece of aluminum foil is dropped on the surface of the molten metal. If a film is present, which is usually the case, it must first be removed by oxidizing the molten metal thoroughly because it would interfere with the entry of the aluminum into the melt. Removal of the film is probably facilitated by a mild fluxing action of the silica crucibles which are used for torch-melting. However, removal of an alumina film from molten palladium in the crucibles normally used for induction melting is a much slower process and it became necessary to modify the de-oxidation procedure. In the modified procedure the charge is simply melted and the desired amount of aluminum, crimped to one end of a tungsten wire, is plunged through the film into the palladium and the wire immediately withdrawn. The trace of tungsten which dissolves along with the aluminum can be avoided, if considered objectionable, by using a palladium wire. In view of the persistence of the alumina film under the conditions of induction-melting it also was decided to ascertain the efficiency of this film in protecting palladium against oxidation during repeated remelting and casting. Melting Equipment and Materials The equipment used for melting and casting consisted of an Ecco GC:6, 6 to 8-kva high-frequency converter and an Ecco M34B centrifugal casting machine. This unit is being increasingly used for making jewelry and dental castings and it also has been found useful in making exploratory melts of a variety of nickel alloys, for which purpose it is well suited on account of its speed of melting and economy of material. A description of the machine and its operation will be published elsewhere.' A common palladium jewelry alloy, 95.5 palladi-um-4.5 ruthenium (referred to as "palladium" in the trade), was selected for the deoxidation tests. It was available as melting stock which had been melted in air to free it from oxidizable impurities, and also as clean scrap from previous melts which had been deoxidized with aluminum. The latter was thought to be typical of clean "palladium" scrap to be found in a manufacturing jeweler's establishment and it is also similar to one brand of "casting palladium." By the same token, the oxidized melting stock corresponds to "casting palladium" after the latter has been melted and thoroughly oxidized: Pure aluminum wire (99.9 pet), 0.032 in. diam; 1 in. = 0.036 g. Scrap tungsten wire, 0.014 to 0.020 in. diam. Argon, commercial water-pumped; 99.9 pet pure Experimental Procedure Samples of about 50 to 75 g of the palladium alloy were melted in a crucible lined with a proprietary refractory alumina cement. Some charges were melted in air, others in argon. The oxidized melting stock was melted and solidified a number of times in order to remove as much oxygen as possible before deoxidizing, but this treatment was unnecessary in the case of scrap. In either case the metal was deoxidized with aluminum (0.01 to 0.05 pet) by the

Jan 1, 1959

By R. A. Wood, R. I. Jaffee, H. R. Ogden, D. N. Williams

Strain-induced porosity has been found to occur in titanium and other materials at tensile strains greater than the uniform elongation of the material. Porosity in titanium increases with increasing strain and temperature, being most severe at 300° to 800°F. Strain-induced porosity is believed to be a normal part of the mechanism of deformation in ductile materials. DURING the past few years there have been numerous references to the occurrence of voids in laboratory test specimens of metals subjected to strain.l-7 These voids have been referred to as intercrystalline cracking, strain-induced porosity, intergranular cav-itation, voids, and porosity. They appear to occur at grain boundaries or interfaces, and are generally associated with large amounts of strain and have been found mostly in creep specimens and to a lesser extent in tensile specimens. Because the phenomenon does not occur unless the material has been strained,

Jan 1, 1960

By J. Gordon Parr, D. H. Polonis

IN a previous study of hypereutectoid Ti-Ni alloys' a substructure was observed in quenched powder specimens when the constitution was 100 pet retained ß body-centered-cubic phase. The alloy powders were quenched from 1000°C by a blast of helium gas and precautions already described were observed throughout the work, to minimize contamination. Ogden et al.2 have previously observed subboundaries in the ß phase of a Ti-Mn-N alloy; but this structure was attributed to nitrogen-rich a precipitation. The nitrogen content of the Ti-Ni alloys does not exceed 0.02 pet and the quenching rate was sufficiently rapid to suppress precipitation reactions. Since X-ray diffraction results have confirmed the absence of any second phase which might account for this phenomenon, it seems unlikely that this substructure is explicable in terms of nitrogen content. Fig. 1 shows the substructure in adjacent grains of 100 pet ß phase in a quenched 6 atomic pet Ni alloy. Fig. 2 shows adjacent ß grains in a similarly treated alloy; one grain contains marked intracrys-talline boundaries and the other is completely free from any substructure. The suberystals appear to have fairly regular shapes, suggesting a regular orientation relationship among them. Tempering the retained ß structure at temperatures below the eutectoid eliminates the substructure at an early stage of ß decomposition. At the present time it is possible only to guess at an explanation for this subboundary phenomenon, since very little work has been reported on substructures resulting from phase changes. It is believed that the present phenomenon is due to poly-gonization resulting from unrelieved stresses set up

Jan 1, 1957

By R. M. Waterstrat

X-ray diffraction and metallographic examination of binary Mn-rich alloys with Ti revealed the presence of intermediate phases in this system. A binary R phase has been identified and also a phase having an a-Mn type structure. The X-ray pattern of the phase TiMn3 is presented and a tentative phase diagram for the Mn-rich portion of this binary system has been constndcted. MANGANESE-rich alloys with titanium have been subjected to thermal analysis at temperatures down to 1100°C by Hellawell and Hume-Rothery.1 Their results indicate the existence of an intermediate phase TiMn3 in this binary system. This phase appears to coexist with the Laves phase TiMn2, and with terminal solid solutions based on the allotropes of manganese, at least down to 1100°C. The above investigators did not attempt to determine the crystal structure of this phase, however. Since, by analogy to the binary systems Mn-V and Mn-Cr3 one might expect to find a phase in this region of the diagram, it seemed desirable to obtain X-ray diffraction patterns of alloys in the concentration range in question, in order to ascertain whether the sigma phase or related structures occur. EXPERIMENTAL PROCEDURES Alloys were prepared by arc-melting electrolytic manganese and iodide titanium in a water-cooled copper crucible under a helium atmosphere. Excess manganese was added to each melt in order to allow for losses incurred during melting. The alloys were then wrapped in molybdenum foil and sealed in evacuated quartz tubes for annealing at various temperatures, as shown in Table I, followed by quenching in cold water. Although the inside of the tubes showed evidence for some loss of manganese from the specimen during annealing, there was no evidence of any reaction between the specimen and either the molybdenum foil or the quartz tube at these temperatures. It was later found that the manganese loss was considerably reduced by annealing these alloys in sealed quartz tubes containing one atmosphere of purified argon. As an added precaution the surface of each specimen was ground off before crushing the alloys to -270 mesh powder, using a hardened steel mortar and pestle. X-ray powder patterns were obtained using either FeKa or CrKa radiation in an asymmetrical focusing camera, which gave excellent dispersion of the closely spaced lines. Pictures were also obtained using a Debye camera of 5-cm radius which provided data in the angular region not covered by the focusing camera. The alloy specimens were polished and examined metallographically, using an etchant consisting of 60 pct glycerine, 20 pct nitric acid, and 20 pct hydrofluoric acid. The 10-g buttons were in each case broken in half and found to be well-melted and free of any gross segregation. One half of certain alloy buttons was submitted to chemical analysis in the "as-cast" condition. No appreciable change in composition seemed to occur during annealing . RESULTS The X-ray pattern of alloy Ti1.17Mn0.83 was found to agree well with that of the ternary R phase which was first found in the Mo-Cr-Co system,' and re-

Jan 1, 1962

By C. E. LAWAL

WITH the object of adapting high-school vocational courses to the industrial needs of the community, a few high-school officials in West -Virginia working with the School of Mines of the State university decided to try an innovation this year. The purpose of this experiment was to teach coal mining in two high schools situated in mining communities. We thought that if a course in coal mining would be included in the list of optional courses offered in the high school, it might interest some of the boys, and if the course were properly taught it would undoubtedly be of inestimable value to those boys who later decided to take up mining work as their vocation. This coal-mining course was started last September in the Berwind and Gary high schools in West Virginia. The high-school officials in their conferences with' us decided that we should work up the outline of this course and they would assign the science teachers of the schools as instructors, with ,the understanding that we would help 'these instructors with this work. We consented to all this and submitted -an outline to the school officials which they are following this year.

Jan 1, 1929

By CLYDE M. EYE

THE Sub-province of Benguet is in the North Central part of the Island of Luzon. Baguio, the capital, is situated on a piateau 5000 ft. above sea level, and is the main health resort of the Philippines. It is rapidly becoming the favorite resort for the China Coast as well, and has many miles of beautiful, curving drives with nearly every pine-covered knoll surmounted by a summer home. The United States Army has a recreation post here, known as Camp John Hay, with a well-equipped hospital, and there is a Country Club with a good golf course adjacent. The weather during the winter months and until late spring is ideal. The business center consists mainly of Chinese and Japanese stores, several hotels, and a large public market, in which are displayed all of the vegetables of the temperate zone, which are flown near Baguio, and many tropical and other products brought up from below. This district is reached from the Coastal Plain either by the old Benguet road built in 1904 by the United States Government, or by the Naguilian road, built some years later. The former is now a toll road, with a line of stages operating over it to and from Des Mortes in connection with the government-owned rail- road. Auto travel from Manila is also along this road, the trip from Manila to Baguio requiring about seven hours, following up the great valley north of Manila for nearly 150 miles to the lower end of the Benguet road, and thence to Baguio, 25 miles. This is an interesting, scenic trip; the road is especially famous for the zig zags where it climbs out of the canyon of the Bued River to the plateau. In the September number of the National Geographic Magazine, a fine aerial picture of this road, as well as of other interesting points in various parts of the Philippines, appears. Freight for the district is taken in mainly over the Naguilian road connecting with the railroad at Bauang. This route follows the ridges of the mountain slope with broad vistas and views of the coast.

Jan 1, 1930

By G. W. LAAiIBOURNE

FEW mines possess a history of more fascinating interest than the Ontario at Park City, Utah. The famous Bonanza's production record of over $50,000,000; the great extent of its workings; the remarkable character of its mineralization; the fact that recent discoveries have shattered preconceived theories of the geology of the camp practically assuring the half-century old property a future as active and as prosperous as the past make the Ontario one of the unique mines of the world. A mere accounting of the wealth created by this historic property not only exemplifies the great profits

Jan 1, 1925

By J. D. Allen

In the coal preparation plant at U.S. Steel Corp.'s Concord mine in Alabama, the product moisture was reduced from about 20% to 9% through the development of a workable flowsheet for dying the clean coal. Some of the high points of the conversion of the Concord washer from vibrating screen dewatering to centrifuge drying are presented in this article. The coal preparation plant at the United States Steel Corp.'s Concord mine near Bessemer, Ala., began operations in June, 1950. The basic cleaning circuit consisted of a Chance cone for cleaning the 2-in. x 3/8-in. fraction and concentrating tables for cleaning the -3/8-in. coal fraction. Dewatering of the final product was accomplished with 35-mesh vibrating screens. However, because Concord coal is very friable with 85% passing 3 mesh and 25% passing 28 mesh (Fig. I), a considerable quantity of fines passed through the dewatering screens. To recover these fines, the dewatering screen effluent was sent to two 70-ft-diam hyd rose para tors from which the underflow returned to the dewatering screens and the overflow went to a 175-ft-diam thickener for water clarification, as illustrated in Fig. 2. As might be expected, there was considerable recirculation of the -35-mesh coal in this system. This degraded the coal and led to higher moistures. It also resulted in a fines bleed-off of plant water and thickener underflow to a fine-coal settling pond. In 1961, vacuum filters were installed to supplement the screens and to recover the fine coal lost in the bleed-off. The above system resulted in a product moisture of about 20%. Further reduction to approximately 11% was accomplished by drainage from railroad cars during transit to the coke plant. Control of the moisture at unloading was poor because of variations in operating levels and railroad car availability, but since the Concord coal constituted a relatively small percentage of the over-all coal mix at the coke plant, its high moisture and fluctuations did not seriously hamper coking operations. Early in 1964, however, the proportion of Concord coal was increased with a resulting increase in the moisture of the total coal mix, and this caused difficulties in the coke plant. The increased participation of Concord coal also brought about a shortage of railroad cars which raised the moisture content to a point where the coal became almost impossible to handle. In an effort to alleviate this problem, U.S. Steel initiated a research program to develop a flowsheet for reducing the moisture to approximately 10% and to determine whether the resulting product would be satisfactory for the coke plant. Under this program, an experimental flowsheet for evaluating both a vibratory centrifuge system and a solid bowl centrifuge system was drawn up as shown in Fig. 3. A horizontal vibratory centrifuge was installed to reduce the moisture in the dewatered coarse coal, and a four-cell, flotation machine was installed to clean the -65-mesh portion of the 3/8-in. x 0 table raw coal feed. Several shortcomings in the above circuits were apparent. For one thing, large quantities of repulping water were required. Furthermore, since about half of the flotation feed was of a size consist that could have been cleaned on the tables, these circuits would result in an unnecessary increase in reagent costs and facilities. Maintenance of the hydro separators and pumps for pumping the underflow to the filters,

Jan 1, 1969

By G. W. Phelps

The field of industrial minerals is concerned with both sieve size and distribution of sub-sieve particles. A great deal of work has been reported on the techniques designed to provide information of this work. The term sub-sieve is here considered to include particular material that will pass a 325-mesh testing sieve. Plant men require rapid, precise and simple testing techniques that are, if possible, inexpensive with respect to equipment and manpower. A number of particle-size procedures have been developed, based on the Stokes equation for streamline movement of a particle of diam D, moving at velocity V through a liquid of viscosity n. 1 Particles are considered to be rigid, smooth spheres, completely dispersed at low concentration and moving at low velocity through the suspending medium with no slippage between particle and liquid. In particle size determinations the particle moves either from natural gravitational forces or those provided by centrifugal means. The diagram of Fig. 1 shows a spherical particle of density S and diam D moving downward at velocity L/T (or V) through a liquid of density So and viscosity n. The forces of gravity G (natural) or Gc (centrifugal) cause the particle to move through the liquid, thereby creating a viscous drag F or Fc. Within the streamline flow

Jan 1, 1967

By Cyril Wells, Paul E. Busby, Donald P. Hart

EARLY workers in the field have established that the diffusion of nitrogen follows normal diffusion laws. Concentration-penetration data from layer analyses of reasonably pure iron specimens nitrided in an atmosphere of CO-NH, are given in the literature,' and were utilized to calculate diffusion constants for nitrogen. The diffusion of nitrogen in y-iron may be represented approximately by the equation D - 1.07x10-' e-:".'m'"'r The diflusion coefficients, D, given by this relation represent mean values, since carburization occurred simultaneously with nitriding. The rate of diffusion in a-iron has been determined from calculations based on data obtained by measuring the internal friction of samples at each of several frequencies and temperatures.' The expression for the diffusion of nitrogen in a-iron derived from these experiments is D= 1.4x10-1 e-it tudent Increasing carbon content decreases the diffusion of nitrogen in a-iron.3 Oxygen, either dissolved or combined, has been shown' to exert a marked influence on the diffusion of nitrogen from a nitriding atmosphere. D values increase rapidly with increasing amount of dissolved oxide in the metal, but diffusion is completely inhibited if preliminary oxidation has produced the slightest trace of iron oxide on the surface. Diffusion coefficients have also been calculated from permeability and solubility data,' but these values are of questionable accuracy since the boundary conditions assumed may not actually exist. Experimental Method The method selected for determining the diffusion coefficient of nitrogen in a-iron in the present investigation was the so-called fractional saturation method. This method consists of heating the specimen in an atmosphere of H2-NH8 mixtures of known composition for a predetermined time. Following this treatment, the specimen is analyzed for nitrogen; and the diffusion coefficient is calculated from a known relationship of the fractional saturation, time of diffusion, and dimensions of the specimen. This relation is based on a solution of Fick's second law and assumes that the surface of the specimen immediately reaches a given concentration which remains constant during the diffusion anneal. Tabular solutions are available4-5 and provide the relationship between fractional saturation and the quantity \/Dt /a, where D is the diffusion coefficient in cm2 per sec, t is the time of the diffusion anneal in seconds, and a, in the present experiments, is the half-thickness of the slab specimen in cm. The method is adequately discussed elsewhere.9-10 Material The material for this study consisted of 3/32 in. thick (0.24 cm) carbonyl iron plate. The major impurities in this iron are oxygen and carbon, which are readily removed by long time high temperature treatment in an atmosphere of purified hydrogen. In order to reduce the diffusion anneal time for saturation runs, some of this material was rolled to a thickness of 0.015 in. (0.038 cm) prior to the hydrogen treatment. Hydrogen treatments were carried out in a hydrogen-purified Armco iron tube heated in a global

Jan 1, 1957

Organization Place Date 1917 American Electro-Chemical Society Detroit; Mich. May 2-5 American Waterworks Association Richmond, Va. May 7-11 American Institute of Electrical Engineers New York City May 18 America' Society of, Mechanical Engineers Cincinnati, Ohio May 22-25 American Iron and Steel Institute New York City May 25-26 ' Interstate Oil Mill Superintendents Association. Augusta, Ga. May (last wk.) Electric Power Club Hot Springs, Va. June 11-14 Society for the Promotion of Engineering Education .... Evansville, Ind. June 19-22. American Institute of Electrical Engineers Hot Springs, Va. June 25 American Society for Testing Materials Atlantic City, N. J. June 26-30

Jan 5, 1917

By V. J. Parks, Leonard Obert, A. J. Durelli

The state of stress in the region where core discing initiates has been investigated through the use of three-dimensional photoelastic models and the results of this study have been compared with those of a previous investigation of rock models. This comparison showed that discing initiates at a point of maximum shear stress, but that the magnitude of the shear stress, as determined photoelastically, is much larger than the shear strength of the rock as deter-mined from conventional triaxial testing. Moreover the shear stress required to produce discing is not constant, but depends on the applied stress field. Possible explanations for these effects are included in this article. In both exploration core drilling and overcore drilling to determine the stress in rock, occasional sections of the core obtained are broken into a series of discs.I* This discing phenomenon has been investigated in the laboratory to ascertain the state of stress required to produce it. The objective of the study was to obtain information that would make it possible to approximate the state of stress in subsurface rock from which disced cores are obtained. Referred to as the discing test, this laboratory study was conducted to determine the applied axial and radial loads required to produce discing in cylinders of rock from several sources. The dimensions of these cylinders are given in Fig. 1. Discing was produced by first applying an axial load to the cylinder and then diamond drilling the core along its axis. The radial load was then incrementally increased until discing initiated. The discs fractured or ruptured* on surfaces approximately normal to the axis of the core (planes A, B, C, D, E, Fig. 2). In many instances, the bottommost disc fractured before the drill had advanced past the points F and F', cre- ating a mush room-shaped fracture surface FEF'. Alternatively, it was also found that the same shaped fracture surface could be created by first drilling in an unloaded core to some point, say F and F', and then triaxially loading the core until fracture occurred on the plane FEF'. Jaeger and cook4 produced similar fracture surfaces in specimens subjected only to a radial biaxial load. From these laboratory studies and observations made in the field, it can be inferred that fracture or rupture initiates in the proximity of the lowest point in the kerf area, (at F and F', Fig. 2) and that the fracture or rupture surface progresses inward from this point. The experiments described above, however, do not provide any information as to the state of stress at the point at which fracture or rupture initiates. In the investigation discussed in the following sections, a three-dimensional photoelastic analysis was conducted to determine the stress distribution in the proximity of the kerf area of a triaxially loaded plastic (epoxy) cylinder containing a short section of core.

Jan 1, 1969

By J. E. House, J. L. Drobnick, R. R. Swanson, D. W. Agers

The paper describes an improved process for the recovery, purification, and concentration of copper values from acidic dump leach liquors. The process employs a new liquid ion exchange material (LIX® 64 reagent) capable of separating copper values from iron and other impurities common to dump leach liquors in the typical pH range of 1.4-3.0. Properties and performance of the reagent are discussed. Design scale-up information for both pilot plants and commercial installations, including preliminary economics, are presented. Economic considerations include the production of electrolytic copper from the purified copper aqueous concentrate. INTRODUCTION Since the commercial acceptance of the liquid ion exchange process in the mineral processing industry, it has been predicted that a wide selection of chemical reagents to efficiently and economically separate many metals in solution under a wide range of conditions would be commercially available. Several years ago, General Mills began a basic research and development program to determine if it were possible to develop a reagent to extract economically metallic ion from existing process streams. Progress toward reaching this objective was reported in late 1963, when development of quantities of LIX -63 reagent, a highly selective reagent for the extraction of copper, was introduced. The properties of this reagent are described in a previous paper.' The development work with this reagent indicated that perhaps the largest potential application for a copper extractant, the treatment of acidic dump leach liquors, would not be economically possible with LIX-63 because of limitations of the reagent to extract copper below a pH of 3.0. The relatively small pH adjustment required with LIX-63 would result in a significant processing cost and the undesirable precipitation of ferric hydroxide from the liquor. This pointed to the need for another copper extractant which would extract copper from dump leach liquors without pH adjustment. General Mills was successful in synthesizing a molecule which does not have the pH limitation of the LIX-63, yet possesses the selectivity-solubility properties required of a metallic extractant. The resulting LIX-64 reagent broadens the pH range from which copper can be effectively extracted and separated from other metallic impurities. Of special significance is the fact that the reagent, LIX-64 was developed by combining the technical requirements of a specific problem in hydro-metallurgy with theoretical organic and physical chemical principles.

Jan 1, 1967

By R. M. Goldhoff, J. W. Spretnak, R. Speiser

IT has been observed by Grange and Garvey' that the homogenization of boron-treated steels could lead to complete elimination of the hardenability effect caused by boron. The experimental conditions leading to this conclusion involved the heating of steel specimens with and without boron at 2350°F for 24 hr. To prevent oxidation and decarburization, the specimens were encapsulated under vacuum in silica tubes. This observation of permanent deterioration of boron effect was noted in both a 0.63 pct plain carbon steel and a 0.25 pct C low alloy steel, both of which had been treated with ferroboron and homogenized at 2350°F for 24 hr. In another series of boron-treated steels which had been homogenized for shorter times, the effect was to reduce, but not completely eliminate, the boron effect. Under these circumstances, it was presumed that longer heating times would cause permanent deterioration of the boron effect in this series of steels also. Since the characteristic grain boundary constituent could not be formed in any of these steels after homogenization, it was concluded that possibly boron was being converted into an ineffective form through chemical combination resulting from prolonged heating at high temperatures. Assuming the validity of this observation, a series of experiments to establish the relationship between temperature of homogenization and kinetics of deterioration was contemplated. Initially an attempt was made to reproduce the results just described. For this purpose commercial lots of AISI 8640 and AISI 86B40 steels were used. The analyses of these steels appear in Table I. Hardenability evaluation was on the basis of the hardness of normalized sections. Grange and Garvey' pointed out that these steels are air hardening to some extent and such a technique can be used. For these tests the specimens were held for 20 min in a salt bath at 1600°F and then cooled in still air. Several evacuated silica capsules containing pairs of the test steels were made up and heated for 24 hr at 2350°F. A number of failures occurred among these capsules, but evaluation of the specimens successfully treated indicated a complete deterioration of the boron effect. However, examination of the surface of the treated specimens showed that some reaction, probably with the silica tube, had taken place, since none of the specimens was bright. One further test was made at 2350°F for 12 hr, using a pair of specimens wrapped in tantalum foil prior to encapsulation. These specimens appeared bright after treatment, and their hardenability evaluation showed that no deterioration had taken place. Since these steels are extremely sensitive to de-boronization at high temperatures and particularly at long times of holding, the experimental observations raised some doubt as to the real occurrence of the permanent deterioration effect. To resolve this question an experiment was undertaken in which the high temperature portion of the treatment was completed in vacuum. For this purpose a molybdenum wound resistance furnace capable of maintaining good vacuum was used. All the pertinent accessories to this furnace were machined from molybdenum stock in order to withstand the high temperature involved in the experiment. With this equipment a temperature of 2400 °F was obtained and held under a pressure of 5x10-" mm Hg for 24 hr. A specimen of each of the two test steels was suspended in the furnace and both were heated simultaneously. Temperature was measured with a standardized Pt—Pt-13 pct Rh thermocouple, whose millivoltage at 2400°F was extrapolated from the standardization equation, good up to 2200°F. The complete evaluation of these specimens is shown in Table 11. The hardness values attained by each steel after normalizing, both before and after the prolonged high temperature treatment, remain the same. A microscopic study of the decomposition products present in the microstructures of specimens at various points in the heat treatment correlated with the hardness values observed. It seems that no permanent loss of boron hardenability effect occurs, at least in these Grainal-treated steels, when deboronization is circumvented. Acknowledgments This work was conducted under the sponsorship of the Aeronautical Research Laboratory, Wright Air Development Center, under Contract No. AF 18(600)-94, and their support and permission to publish is gratefully acknowledged. A note of thanks is also extended to the Republic Steel Corp. for supplying the materials used in the work. References ' R. A. Grange and T. M. Garvey: Factors Affecting the Harden-ability of Boron Treated Steels. Tro.ns. ASM, 1946, vol. 37, p. 136.

Jan 1, 1957

By Edwin B. Eckel

This paper, based on brief field examination and on data supplied by the operators, records the condition of the Italian mercury industry as of March 1945, not long after Italy's collapse. Except for the once-Italian but now Yugoslavian Idria mine near Trieste, virtually all the known mercury deposits are in the Monte Amiata district in Siena and Grosseto Provinces, 75 miles north of Rome. This district contains the Abbadia San Salvatore. the Siele. the Argus, and the Cerreto Piano mines besides numerous prospects and unproductive mines. Under pressure from Germany the principal mines were highly productive during the early part of the war, but production fell off long before its end. All of the mines were damaged in some way at the German withdrawal but by September 1944 the Abbadia had resumed production and several others were only lacking power by the early spring of 1945. The Monte Amiata district is characterized geologically by a thick series of sedimentary rocks that range from Triassic to Eocene in age . and are surmounted on Monte Amiata itself by a thick cap of extrusive trachyte. Bodies of travertine and of landslide detritus, younger than the trachyte, are rather widespread. The structure is complex and little known but most of the ore deposits seem to lie along or near a major, north-trending fault or on associated cross-fractures. Cinnabar is the only important ore mineral and clay minerals are by far the most abundant products of hydrothermal alteration. A southward increase in the amount of stibnite, relative to cinnabar, suggests horizontal zoning. The grade of ore ranges from 0.60 to 3.0 Pet and the reserves, as compared with those in American mines, are enormous. Even in the face of war-time scarcities, the mines are remarkably self-sufficient and labor is plentiful, but the costs of production are estimated to be not greatly below those of the better American mines. Notes on the principal mines, on the mining and metallurgical methods, and on the manufacture of synthetic cinnabar are included in the paper. Introduction With but few brief interludes, Spain and Italy, including the Idria mine near Trieste, which has passed from Austrian to Italian to Yugoslavian hands in the Past 3 decades, have led the world in the production of mercury, or quicksilver, for many centuries. Despite their enviable position with respect to the supplies of a metal so essential in both war and peace, there is a notable lack of up-to-date information in America on the mercury industry of either country. Duschak and Schuette' and Schuettez,3 give by far the best summaries in English known to the writer, but the latest firsthand report cited by them on the Italian mines was published in 1915.' Having been deeply interested in the geology and economics of mercury for several years, the writer naturally felt most fortunate in being the to obtain enough firsthand information on the Italian industry to fill at least a few of the gaps in our knowledge. The opportunity came during the war, soon after this industry, together with the rest of Italy, had capitulated to the Allies. Many of the facts presented here are thus definitely "dated," but others are of less transitory nature, and even the dated facts should be of interest in showing the strength and

Jan 1, 1949

By Edwin B. Eckel

This paper, based on brief field examination and on data supplied by the operators, records the condition of the Italian mercury industry as of March 1945, not long after Italy's collapse. Except for the once-Italian but now Yugoslavian Idria mine near Trieste, virtually all the known mercury deposits are in the Monte Amiata district in Siena and Grosseto Provinces, 75 miles north of Rome. This district contains the Abbadia San Salvatore. the Siele. the Argus, and the Cerreto Piano mines besides numerous prospects and unproductive mines. Under pressure from Germany the principal mines were highly productive during the early part of the war, but production fell off long before its end. All of the mines were damaged in some way at the German withdrawal but by September 1944 the Abbadia had resumed production and several others were only lacking power by the early spring of 1945. The Monte Amiata district is characterized geologically by a thick series of sedimentary rocks that range from Triassic to Eocene in age . and are surmounted on Monte Amiata itself by a thick cap of extrusive trachyte. Bodies of travertine and of landslide detritus, younger than the trachyte, are rather widespread. The structure is complex and little known but most of the ore deposits seem to lie along or near a major, north-trending fault or on associated cross-fractures. Cinnabar is the only important ore mineral and clay minerals are by far the most abundant products of hydrothermal alteration. A southward increase in the amount of stibnite, relative to cinnabar, suggests horizontal zoning. The grade of ore ranges from 0.60 to 3.0 Pet and the reserves, as compared with those in American mines, are enormous. Even in the face of war-time scarcities, the mines are remarkably self-sufficient and labor is plentiful, but the costs of production are estimated to be not greatly below those of the better American mines. Notes on the principal mines, on the mining and metallurgical methods, and on the manufacture of synthetic cinnabar are included in the paper. Introduction With but few brief interludes, Spain and Italy, including the Idria mine near Trieste, which has passed from Austrian to Italian to Yugoslavian hands in the Past 3 decades, have led the world in the production of mercury, or quicksilver, for many centuries. Despite their enviable position with respect to the supplies of a metal so essential in both war and peace, there is a notable lack of up-to-date information in America on the mercury industry of either country. Duschak and Schuette' and Schuettez,3 give by far the best summaries in English known to the writer, but the latest firsthand report cited by them on the Italian mines was published in 1915.' Having been deeply interested in the geology and economics of mercury for several years, the writer naturally felt most fortunate in being the to obtain enough firsthand information on the Italian industry to fill at least a few of the gaps in our knowledge. The opportunity came during the war, soon after this industry, together with the rest of Italy, had capitulated to the Allies. Many of the facts presented here are thus definitely "dated," but others are of less transitory nature, and even the dated facts should be of interest in showing the strength and

Jan 1, 1949

By B. A. Kulp, R. R. Reeber

Lattice parameters for the wurtzite form of' CdS mere measured by powder X-ray diffraction techniques over the temperature range 26° to 1000 K'. A negative thermal -expansion coefficient was determined parallel and perpendicular to the c axis below 13.5°K. Near 808°K, the curves of the a, parameter, the differential thermal expansion, and the resistivitv vs absolute temperature exhibited a reversible discontinuity. j\. direct determination of the lattice parameters of CdS over an extended temperature range is of particular use in interpretation of the effects of high pressure on the band structure of semiconductor materials. For example, Langer' has studied the effects of pressure on the absorption edge of CdS from 77°K to room temperature. In order to properly interpret his results it is necessary to know the change in lattice constants as a function of temperature for the wurtzite, zincblende, and rocksalt2 modifications of this material. Thermal-expansion measurements for CdS, wurtzite phase, have previously been determined over a limited temperature range.s74'5 The zincblende phases, of other compounds with similar bonding, have been investigated by Novikova et a! .'' Previous thermal-expansion measurements for metals with hexagonal symmetry have for the most part used bulk sample techniques for low-temperature result. Most X-ray measurements at low temperature have been on materials with cubic symmetry.'jQ The use of X-ray powder-diffraction techniques offers a convenient and accurate method of measurement over a wide temperature range. The X-ray method, besides measuring unit cell size, also provides information about change in structure type and the nature of some of the stacking defects present. I) EXPERIMENTAL PROCEDURE The thermal expansion was measured by X-ray powder-diffraction techniques. Lattice parameters for the range 300" to 1000°K were determined in a 19-cm Unicam camera. From 26" to 300°K a 34-cm back-reflection camera with the Van Arkel" film arrangement was used. The sample was bonded to a copper cold finger below a helium, hydrogen, nitrogen, oxygen, dry ice, or ice brine bath in a metal cryistat. che inner bath was surrounded by another one for radiation shielding. Nitrogen was used in this outer bath for the very low-temperature runs while dry ice and acetone was used for the 195°K point. CuKa X-rays, filtered with a nickel foil, entered the cryostat through a 0.001-in.-thick aluminum window. During a typical 9-hr exposure the sample was continuously rotated through a 30-deg arc. Heat losses from the sample holder limited the minimum temperature attained to 26°K with helium in the inner dewar. Temperature calibration between 25" and 125°K was determined with an Allen Bradley 300-ohm carbon resistor. The resistor was attached to the back of the copper finger with a thin layer of silicone grease. Liquid He, HZ, N2, and O2 baths were used to calibrate the resistor. Temperature variation is estimated to be *2"K with a slightly higher uncertainty at room temperature and 264°K. The thermal expansion of high-purity germanium from 373" to 900°K was measured as a calibration for the Unicam camera. This value was compared with the known value1' for the thermal expansion. A discontinuity in the thermal-expansion coefficient of the CdS a, parameter was observed. Similar discontinuities in the resistivity and differential thermal analysis at the same absolute temperature indicate that the temperature error is *5°K in the temperature range above 500°K. Temperature errors in the Unicam camera below 500°K are appreciably higher due to large gradients in the resistance furnace. II) SAMPLE PREPARATION The CdS was Eagle Picher ultrapure grade. The crystallite size range of the as-received powder

Jan 1, 1965

By J. W. JESSUH

TO certain people the name of Northern Rhodesia brings only a vague recollection of a distant country somewhere in Africa; to others, it means a big game territory and the opportunity for excellent shooting; to some, a land of sunshine and peace; but to mining men the name signifies the land where the latest discoveries of copper ore are astonishing the mining world and bid fair, in a few years, to make Northern Rhodesia one of the largest copper- producing countries. There is a fascination about this part of the globe that is somewhat similar to southern California, and at the same time there is that feeling of mystery peculiar to a tropical climate. Perhaps it is the isolation, the fear of wild animals, or the influence of an undefinable something which cannot be expressed.

Jan 1, 1931