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By T. C. Campbell

Copper is extracted from the Chuquicamata oxide ore by a hydro-metallurgical process. The ore is crushed to 3/8-in. sizing, and leached with a sulfuric acid electrolyte. Chlorine is precipitated. and the ferric iron reduced in the enriched electrolyte, after which the copper is recovered by electrolysis with insoluble Chilex and lead-antimony anodes, the spent electrolyte being returned to leaching. Cathodes are melted and refined in market furnaces and cast into commercial wire-bar and cake shapes. Sulfuric acid for the process is supplied by the brochantite in the ore. Water for washing the ore is advanced through the solution system and finally after cutting by electrolysis to from 6 to 16.0 grams per liter is completely stripped by the cuprous chloride method and run to waste. The cuprous chloride so obtained plus that resulting from precipitation of chlorine from strong solution is dissolved in ferrous chloride brine and the copper cemented on scrap iron. The cement so obtained is in part used to reduce ferric iron in electrolyte, and as it is of exceptional purity is also furnace refined and cast into an exceptional quality of fire-refined copper. Fig. 1 is flow sheet of the operation. The reduction plant is composed of seven divisions as follows: (1) crushing, (2) leaching, (3) tailings disposal, (4) dechloridizing, (5) sulfur dioxide treatment, (6) electrolytic tank house, (7) smelting and melting. A brief description of each of these divisions will be given. Crushing Ore that is frequently blocky and up to 5 ft. in section is crushed in four stages to 3/8-in. mesh. The first stage of crushing is called primary and the next three stages are known as secondary crushing. The first stage is accomplished with two 60-in. Superior McCully gyratory breakers by which the ore is broken to 9 in. The second coarse gyratory breakers crush the ore to 3-in. sizing. There are seven No. 10 McCully gyratories in this service, for one of which recently has been substituted a No. 7 cone crusher. The third and fourth stages of crushing are accomplished by fifty 48-in. disk crushers. In the third stage 14 disk crushers break the ore to 1 in., and in the last stage 36 disk crushers turn out the final product of 0.371-in. sizing. Reference to the flow sheets of Figs. 2 and 3

Jan 1, 1934

By Edgar Dunn

PART I.-DETERMINATION OF GASES IN SMELTER FLUES. IN 1907, upon arriving in Anaconda to take up work in the testing department of the Washoe Reduction Works, the. following problem was met at the car step, so to speak: complete and. exact analysis of gases, not only at the stack, but also in all departmental flues. Taken up to employ time not otherwise needed for regular testing department work, instructions were extremely liberal for a commercial plant, to the effect that accuracy should not be sacrificed to speed. In December, 1907, the work was temporarily transferred to the Great Falls Smelter, and some of the methods here given were there worked out. Differences in smelting operations at Great Falls and Anaconda, however, necessitated further investigations and the development of a new method for S03 determinations at the latter plant, where work was resumed in July, 1908, and completed about a year later. At the time of inception of the work, data (not only on percentages, but even on methods) were found to be meager in the extreme, for one or the other of two reasons: either entire lack of experiment at a large proportion of smelters, or disinclination on the part of the managements to divulge data of any description pertaining to either results or methods. In making determinations of gaseous constituents of flues, two methods are open to consideration: 1, the drawing out of a sample, and collection of the same as a whole, to be removed to the laboratory for later analysis; and 2, the absorption in situ on the flue of one certain constituent, disregarding others for the time being, or perhaps combining two or three in one determination. The first is generally the more rapid, but it is also the more inaccurate, method of analysis, even with special type absorption apparatus, being the more largely subject to error, both of reading, and also because of leakage during complicated manipulation in the laboratory. The amount used for analysis must also, because of limit of container, be small for the first method, and an average gas is very seldom obtained, necessitating for a fair average result a large number of determinations. Consequently, when we balance the time spent in a dozen determinations of short-time samples as against the time employed in making two or three long-time determinations of various constituents in situ, we are not so certain in our statement as to the relative speed of the two methods. Moreover, the method of analysis in the laboratory of 100 cc. of flue gas is satisfactory only when constituents thus determined are present in considerable quantity, results being simply approximate when determining such compounds as sulphur dioxide, sulphur trioxide, carbon monoxide and dioxide, and arsenic trioxide and water vapor, none of which are carried in all smelter flues in amounts in excess of (or even approaching) 1 per cent by volume. Special condi-

Jan 8, 1913

By C. Ernest Birchenall, Robert F. Mehl

APPLICATION of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion coefficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner1 derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smiths on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 ACTIVITIES IN BRASS9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by azn = Pza/Pzn° [I]

Jan 1, 1947

By R. J. P. Lyon, A. E. Prelat, H. Lawrence

Introduction In 1977, the US Bureau of Mines awarded a grant to the state of South Carolina to explore the possibility of using Landsat multispectral scanner (MSS) data as an aid in monitoring surface mining activities in selected counties of the state. Work had been done in Aiken County prior to the grant by USBM and state personnel at the EROS Data Center using both the GE Image 100 and ESL IDIMS systems. The initial work on the 1:100 consisted of locating and measuring the areas of various kaolin mines. The results were excellent on location, identification, and accurate area measurements of several mines as compared with aerial photos of each mine. The effort also included locating and measuring the size of all mines (including sand and gravel) within two US Geological Survey (USGS) 7 % - min quadrangle maps. Line printer overlays using the IDIMS equipment and software resulted in the location of all known mines within an estimated error less than zt 91.4 m. Mine acreage was calculated by counting each symbol (which represented one pixel) and multiplying by 1.1 (the number of acres per pixel). [Fig. 1] shows a portion of one quadrangle overlay. [Table 1] gives a comparison of acreage measured for several mines from the 1-100 and IDIMS system vs. aerial photo measurements. The success of the preliminary work resulted in the South Carolina Land Resources Conservation Commission submitting a proposal to USBM for funding to expand the scope of work to other mineral mining operations within the state and determine if Landsat Imagery could be used to accurately locate and measure mining and reclamation activity on a continuing basis. Three separate tasks were proposed for selected kaolin mines in Aiken County: Task 1, to measure changes in active mine developments over the period 1974-77; Task 2, to measure reclamation activity, and, if time permitted, seasonal changes in mine signatures over the same period of time; and Task 3, to classify one complete mining operation (i.e., differentiate between active, spoil, overburden, water, reclaimed portions and surrounding terrain. The major effort was centered around J.M. Hubeis Richardson mine. Mining operations were progressing in a northerly direction and included three areas of reclamation: one prior to 1974; one started during early 1974; and one reclaimed during 1976. A discussion of all work done under the grant is available in the March 1979 Final Report listed under References. Computer compatible tapes (CCTs) containing MSS data from Landsat Path 18, Row 37, were purchased from the National Aeronautics and Space Administration (NASA) covering the period February 1974 through January 1977. The MSS data were processed on the General Electric Image 100 using parallelepiped classification at the EROS Data Center's Data Analysis Laboratory, Sioux Falls, SD, and at the Stanford Remote Sensing Laboratory, Stanford University, Palo Alto, CA, utilizing both an unsupervised classification (ISOMIX) and a supervised classification (sequential discriminant analysis). Studies at Stanford University Remote Sensing Lab (SRSL). In Feburary 1977, initial work was begun at Stanford using the STANSORT computer program running on a DEC PDP-10 (Honey, Prelat, and Lyon, 1974). This software is fully interactive and designed to study Landsat CCT data at high resolution (small areas) on a pixel-by-pixel basis (Lyon, 1977). Unsupervised Classification. The initial step was to locate the Richardson mine on the positive print of the full Landsat scene from CCT 1644-15252, dated 6/17/74. This was relatively easy due to a large abandoned kaolin mine and a long narrow pond clearly visible in the scene. Two unsupervised classifications of the Richardson mine were run using ISOMIX clustering (Honey, Prelat and Lyon, 1974). (ISOMIX essentially follows the interactive clustering procedures of ISOCLS Kan, Holley, and Parker. 1973). Although the classifications were successfully accomplished, it was apparent from the TV display that the results did not clearly define the mine areas. A supervised classification would have to be made in order to clearly separate each portion of the mine. Supervised Classification. This classification was done using the Stepwise Discriminant Program (BMDO7M) which is part of the BIOMED package (Dixon, 1970) and involved the following steps: Training group populations were selected and the digital

Jan 1, 1982

By JAMES J. DOUGHERTY

THIS paper is a general discussion of developments in our reverberatory smelting practice during the past five years. It deals briefly kith changes in furnace types ; changes in furnace feed ; de- crease in the amount of slag produced; relation of slag assays to copper loss in the slag; increase in the grade of matte and furnace capacities. The reverberatory is but one unit in the copper plant ancl 'any discussion of it must be considered with reference to the other units and to the plant as a whole. A change in the grade of concentrates at the concentrator puts an entirely new aspect on reverberatory smelting and, likewise, a change in the grade of matte at the reverberatory affects the rate and cost of converting. The introduction of differential flotation in 1927 had a very marked influence on all smelting operations and its effect will be noted

Jan 1, 1930

By Neils Hansen

The microstructure of dispersion-strengthened aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum oxide has been examined by optical and transmission electron microscopy, and the flow stress has been determined at room temperature and at 400C by tensile testing. Products were examined as recrystallized and as high-temperature extruded, and the microstructures consisted of a fine dispersion of oxide particles in a matrix divided by respectively recrystallized grain boundaries and subgrain boundaries. The flow stress (0.2 pct offset) at room temperature of recrystallized dispersion strengthened aluminum aluminum-oxide products is the superposition of dispersion strengthening and grain boundary strengthening. This superposition has been found to be linear. The flow stress (a) can be related to the grain size (t) by the Petch equation: ing content of oxide and k is a constant independent of the oxide content. For extruded products a similar relation has been found by replacing the grain size by the subgrain size. The k-value is of the same order for the two types of structure, which shows that the subgrain boundaries are as effective slip barriers as grain boundaries. Tensile testing at 400C of re-crystallized and extruded products shows that oxide dispersion strengthening is very effective, whereas the strengthening effect of grain boundaries and subgrain boundaries is small. THE microstructure of dispersion-strengthened products consists of hard particles finely distributed in a metal matrix. The strengthening effect of the dispersed phase has been fairly well established,1 and it has been found that the size and volume fractions of the dispersed particles are important structural parameters. However, in many dispersion-strengthened products which have been worked and heat-treated during manufacture the matrix is divided into well-defined grains or sub-grains, which may also have a strengthening effect. A model of the matrix strengthening in dispersed products worked during manufacture has been proposed,2 introducing the energy of the structure as a strengthening factor, especially at low temperatures. A difficulty in this model is, however, to relate this (stored) energy to the structural parameters directly observable as for instance grain size. The strengthening effect of the matrix grain size after recrystallization has been in- vestigated for nickel-thoria (TD-Nickel) products3 and for copper aluminum-oxide products. Conclusive results were, however, not obtained as the grain size of TD-nickel was constant. 5 to II , after recrystallization at temperatures from 700 to 1200°C and as the copper products containing 5 to 1 wt pct of aluminum oxide could not be recrystallized even after severe cold reduction and heat treatment at 1050C. For aluminum aluminum-oxide products containing from 1 to 5 wt pct of aluminum oxide it has been shown that the tensile strength at room temperature decreases when an extruded product is cold-worked and recrystallized. The matrix in the extruded products is divided into well-defined subgrains of micron size, and as the grain size of the recrystallized products is about two orders of magnitude higher, it is obvious that grain boundary strengthening occurs. Preliminary results8 have indicated that the flow stress containing no grain boundaries, A is a constant and t is the subgrain size. At elevated temperatures the effect of boundaries is more complex; it has been shown11 that recrystallized products having an oxide content of about 3 wt pct are more creep resistant than extruded material in the temperature range 400° to 600°C, whereas on application of a higher strain rate the tensile flow stress (0.2 pct offset) is higher in extruded than in recrystallized aluminum—5 wt pct aluminum oxide products at temperatures from room temperature to 427°C (800), Finally it has been shown12 that the Brinell hardness at 350°C of extruded products having about the same content of aluminum oxide increases with decreasing grain size, determined by X-ray line-width measurements. The present study was undertaken to obtain a quantitative relationship between the tensile strength and the grain size of aluminum aluminum-oxide products in the recrystallized as well as in the extruded state. The tensile testing was performed at room temperature and at 400uC. The grain size of the recrystallized products was varied by changing the degree of cold-work preceding the recrystallization heat treatment. In extruded products grain (or subgrain) size variations were obtained by high-temperature heat treatment after extrusion. EXPERIMENTAL a) Materials. Aluminum aluminum-oxide products have been manufactured by consolidation of aluminum powder covered with a layer of aluminum oxide formed during powder manufacturing. The products examined were manufactured from atomized powder containing

Jan 1, 1970

By J. H. Pratt

In a recent paper* on the origin of corundum associated with the peridotites of North Carolina, attention was called to the constant occurrence of the mineral, chromite, in these rocks. The field-data obtained during the preparation of that paper have been used largely in the present paper. During the past summer the general occurrences of chromite have been carefully studied, and those in North Carolina have been especially examined in the field. It is purposed to give, in this paper, the reasons why the chromite should be regarded as having been formed at the same time with the peridotites, having been held in solution by the molten mass of the peridotite, and crystallizing out among the first minerals as the mass began to cool. This theory is essentially the same as that advanced by me for the origin of the corundum associated with the peridotite rocks, and a similar line of reasoning has been used to substantiate the theory proposed. Investigations concerning the igneous origin of some of the ores have been materially aided, during recent years, by the skillful experiments of Morozewicz and Lagorio,§ and by researches that show us, more clearly, why we should regard a fused mass of rock as a liquid, having similar properties to an ordinary solution. These experiments have shown that a molten basic glass, similar in composition to the basic magnesian rocks, dissolves alumina readily, and that upon cooling, the first minerals to separate out are corundum and spinel.

Jan 1, 1900

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

Jan 4, 1920

By G. R. M. Del Giudice

A survey of the flotation literature of the past 10 years indicates an increasing use of the microscope as a tool for investigation. Thus, the metallurgical microscope has been used by Tucker and Head;' Taggart, Taylor and Ince;2 Ince,3 and del Giudice4 to examine mineral surfaces that had been subjected to the action of various flotation reagents and to the action of slime pulps. It has also been used by Gaudin, Groh and Henderson;5 Martin;6 Morrow and Griswold;7 and others to examine bakelite briquets of mill products. The microscope with transmitted light, both with bright-field and dark-field illuminations, has been used by Taggart, Taylor and Knoll8 and by Ince9 to observe Brownian motrement and flocculation in flotation pulps. The use of the microscope at low-power magnifications with incident illumination for the examination of mill products has been known for years.10 Finally, del Giudice11 has used a relatively new type of illumination, the Ultropak, for the examinntion of slime-coatings.

Jan 1, 1935

By Isobel Clark

The increasing complexity of modern mining technology makes it ever more difficult to decide on the 'best* way to solve problems in mine planning. Yet with escalating costs it becomes increasingly more important for the mining engineer to be able to evaluate quantitatively the implications of the 'what happens if' postulation on the efficiency and economics of exploitation. The use of a model of the orebody can yield an estimate, not just of overall expected results, but also of the sensitivity of these results to possible variations in the orebody. Estimation techniques, such as Kriging, will produce the expected value for the grade of ore at any given point, or over any given volume within a deposit. However, the actual grades mined during production will - of necessity - differ from the predicted values. These possible variations, and the sensitivity of the management decisions to them, can be investigated in detail by the use of simulation. An orebody can be simulated which follows the known characteristics of the deposit at any given stage in development. These properties might be the histogram of grade values, the semivariogram from the samples, the actual borehole assays, geological constraints and/or interpretation, topography, lease boundaries etc. This would be one possible 'realisation' of the deposit as dictated by the currently known data. If several of these simulations are carried out, each conditioned to the current knowledge of the orebody, then it is possible to gain an idea of the range of possible outcomes of any mining procedure or decision taken - all of which are equally likely. Not only can the best decision then be taken, but its sensitivity to the inherent variation within the orebody, and to the ever present estimation errors may be thoroughly studied.

Jan 1, 1977

By Charles T. Holland

In connection with the problems of bumps in coal mines, much has been written concerning the manner in which roof action and methods of mining enter into the pressure effects observed but little has been written upon the relationship between the physical properties of coal and associated rocks and the cause of bumps. The question of the strength of bituminous coal, of its elasticity, and the energy it can absorb and store has been neglected to a considerable extent in connection with this problem. It is generally agreed that one of the necessary conditions for bumps is a strong coal.' Therefore, since the strength of coal is an important factor, a study of this property should be made. several investigators have conducted laboratory experiments upon the strength of coal, using small cubical or rectangular test pieces. An attempt will not be made to go into all of these investigations, but they are briefly summarized in Table I. Experiments of the U. S. Bureau of Mines and of Lawall and Holland (pp. 27 and 34 of ref. 9), however, indicate that regardless of whether the coal is a soft and weak semihituminous (Pocahontas No 3) or a hard and strong bituminous (Stockton) coal, the maximum ultimate unit stress developed in laboratory tests is higher in small cubes than in larger cubes of the Same coal.

Jan 1, 1942

By Charles T. Holland

In connection with the problems of bumps in coal mines, much has been written concerning the manner in which roof action and methods of mining enter into the pressure effects observed but little has been written upon the relationship between the physical properties of coal and associated rocks and the cause of bumps. The question of the strength of bituminous coal, of its elasticity, and the energy it can absorb and store has been neglected to a considerable extent in connection with this problem. It is generally agreed that one of the necessary conditions for bumps is a strong coal.' Therefore, since the strength of coal is an important factor, a study of this property should be made. several investigators have conducted laboratory experiments upon the strength of coal, using small cubical or rectangular test pieces. An attempt will not be made to go into all of these investigations, but they are briefly summarized in Table I. Experiments of the U. S. Bureau of Mines and of Lawall and Holland (pp. 27 and 34 of ref. 9), however, indicate that regardless of whether the coal is a soft and weak semihituminous (Pocahontas No 3) or a hard and strong bituminous (Stockton) coal, the maximum ultimate unit stress developed in laboratory tests is higher in small cubes than in larger cubes of the Same coal.

Jan 1, 1942

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By N. F. Schulz, H. A. Lex

Representative samples of typical manganiferous iron ores from the Cuyuna Range, Minn., were reduced to the metallic iron state at temperatures just short of fusion with an excess of coke in the manner prescribed by the R-N Direct Reduction Process. The magnetic separation characteristics of the reduced ores were determined at several grinds by means of the Davis magnetic tube concentrator. The efficiency of metallic iron concentration by magnetic separation was a direct function of the degree of metallization of the ore sample and of the degree of liberation at-tained in grinding. Some improvement of liberation characteristics was observed if a small amount of sodium chloride was present in the ore during reduction. Despite the extremely fine-grained structure of the crude ores, iron concentrates containing more than 90% Fe at iron unit recoveries of 90% or more were obtained from well-metallized samples of three of the four ores tested. The rejection of manganese to the tailings corresponding to such separations varied from 80% to 95%. The manganiferous iron ores of the Cuyuna Range in Minnesota constitute a major potential source of manganese in the United States provided that a technically and economically feasible process can be devised for its recovery. The iron and manganese of these ores occur chiefly as oxides or carbonates in the form of very small, irregular, discrete grains embedded in a matrix of quartz or other siliceous gangue. The present investigation was undertaken as a sequel to an earlier one conducted jointly by the U.S. Bureau of Mines and the R-N Corp. Those results indicated that the R-N Direct Reduction Process might be a means for recovering both a metallic iron concentrate and a marketable manganese by-product from Cuyuna manganiferous iron ores.' The R-N Process is one of many proposed schemes for the treatment of crude iron ores involving the di- rect reduction of the iron content to metallic iron followed by physical extraction of the iron. In general, it consists of the following stepsz2 1) Iron oxide in crushed natural ores or iron concentrates is about 95% reduced to metallic iron at elevated temperatures but without fusion in a rotary kiln in the presence of a solid carbonaceous fuel (usually coke), limestone, and combustible gases. 2) The kiln product, consisting of metallized ore, excess coke, lime, and coke ash is cooled. The excess coke is recovered and recycled to the kiln feed. 3) The metallized ore is ground for liberation and magnetically separated to yield a metallic iron concentrate. 4) The metallic iron concentrate is agglomerated by a briquetting process. The reduction kiln temperatures must be high enough for the desirable chemical reactions to proceed at practical rates without causing fusion of any of the ore constituents. The time of exposure of the ore to the reducing conditions must be ample for 90% to 95% metallization of the iron oxides present. If more than 95% of the iron is metallized, however, difficulties may arise in the briquetting step, presumably because of accompanying higher carbon content of the metallic iron. Although not always necessary, powdered limestone or dolomite may be added at some time during reduction to aid in eliminating sulfur and phosphorus from the final product.3,4 Other additives, notably sodium chloride, when present during reduction, result in improved liberation characteristics of the metallic iron from certain reduced ores.'v6 Under the reducing conditions normally employed, P(co + H2)= 1 atmosphere, and 1830' to 2150°F (1000° to 1170°C), the R-N Process is claimed to be adaptable to a wide variety of low, medium, and high grade iron and manganiferous iron ores. The manganese oxides and carbonates are reduced mostly to nonmagnetic MnO which is rejected to the nonmagnetic tailings. Manganese-bearing pyroxenes of the original ore, however, may be rejected poorly, if at all, apparently because these minerals occur within the iron lattice or are entrapped in the metal particles.7 The investigation was limited to studies of the Cuyuna ores listed in Table I, which were reduced to the metallic iron state under various conditions

Jan 1, 1969

By J. D. Embury, R. M. Fisher, A. S. Keh

An investigation of the defect structure and properties following large strain deformation has been carried out using transmission electron microscopy and mechanical testing for a range of ferrous materials and for copper. It is shown that, for a variety of ferrous materials, a cellular substructure is developed during the initial stages of working and on further deformation the dimensions of this substructure are reduced. Quantitative measurements of the flow stress and the scale of the substructure indicate that the strength of heavily worked materials is largely determined by the spacing of cell walls. These cell walls act as dislocation barriers in a manner analogous to grain boundaries. FCC materials do not harden as extensively as bcc after cold working and the present observations on copper indicate that the dimensions of the substructure in fcc materials are not markedly reduced on deformation. The differences between the fcc and bcc structures produced by large plastic strains are ascribed to differences in the extent of dynamic recovery. It is tentatively proposed that the greater stability of substructural barriers in bcc structures results from strong interstitial Pinning effects. It is proposed that for large plastic strains the work-hardening process may be considered in terms of the reduction of substructural-barrier spacing during the working process. This pvovides a simplified hut useful analysis of the strain hardening occurring during mechanical processes. THE mechanisms of strain-hardening processes have occupied the attention of numerous investigators over the past three decades and a multitude of theories have emerged in this field. The majority of previous work has been concerned with the development of a description of the plastic behavior of single crystals in terms of dislocation theory.'" In contrast, scant attention has been given to the strengthening mechanisms operative during mechanical working processes such as rolling and drawing. The large plastic strains involved in these processes make it difficult to correlate the observations with any elementary dislocation theory. Further, as Bullen and coworkers3 have opined, for large plastic strains both hardening and recovery occur simultaneously and thus it is extremely difficult to estimate the effect of plastic strain on the ambient internal stress field. It is probable that for large plas- tic strains any theoretical estimate of the internal stress field must be made in terms of complex dislocation groups. Although some valuable theoretical work has been done toward calculating the elastic properties of dislocation groups4 any detailed self-consistent model for large plastic strain is as yet impossible. With these limitations in view it is still of value to examine the mechanical properties of highly strained materials as a function of their substructure. This relationship is explored in the present communication for a variety of materials subjected to rolling, drawing, or swaging. The primary object of this investigation has been to establish the validity and the limitations of the substructural strengthening mechanism proposed by Embury and eisher' for drawn pearlitic wire and by Meieran and Thomas for drawn tungsten wire. No attempt has been made to delineate the basic interaction mechanism which occurs between a slip dislocation and the substructure and the authors believe that a great deal more experimental evidence must be compiled before these fundamental aspects can be explored. Also, no specific attention has been given to the detailed formation of substructure during working. Experimental Details. A variety of materials were used in this investigation, the compositions and heat treatment of which are tabulated in Table I. The commercially pure iron is referred to throughout this report as Ferrovac E. The mechanical working processes were all performed at room temperature. The wire drawing was performed on a manual drawing bench. Reductions of between 10 and 20 pct in area per pass were used in both swaging and drawing. The experimental parameter used to evaluate the mechanical properties of the materials was the 0.2 pct proof stress. This was determined for wire samples using an Instron tensile machine at a crosshead speed of 0.02 in. per min. The techniques for preparation of samples for transmission electron microscopy have been described previo~sl~.~ Specimens from wire samples were prepared from longitudinal sections and in some cases from transverse sections. To evaluate the substructural characteristics of rolled materials, thin foil samples were prepared of both the face and edge sections. Results. One of the more familiar ways of expressing work hardening in mechanical working is by the flow stress as a function of reduction in cross-sectional area. Fig. 1 shows such a plot for Ferrovac E eutectoid carbon steel and for copper. The curve for Ferrovac E is characterized by an initial stage of rapid work hardening and a final stage of rapid work hardening separated by an intermediate stage with a low rate of work hardening. This behavior is typical of many ferrous materials and the drawn pearlite wire previously investigated by Embury and Fisher is a more pronounced example. Copper shows an initial

Jan 1, 1967

G. K. BURGESS, ? Washington, D. C.-At the Bureau of Standards it was decided, in order to study the high-aluminum end of these curves, that efforts should be made to prepare pure aluminum, and the promise of getting aluminum, practically free from the two elements that have such great effect in very small quantities, namely, silicon and iron, and which

Jan 12, 1919

By K. Mukherjee

A quasi-thermodynamic calculation is presented for estirt~ating vacancy Parameters in fcc metals. For fcc metals the equilibrium vacancy concentration at the melting point can be approximated by a constant mole fraction. The Gibbs free energy of formation of the vacancies can then be expressed as a simple function of the absolute melting temperature alone. From this description the formation energy Ef, the vibrational entropy Sv, and the formation volume of a vacancy can be calculated in terms of known thermodynamic parameters. The calculated values are in good agree-rnent with available experimental results. IT appears that many of the physical parameters associated with lattice defects can be empirically related to thermodynamic melting parameters.'-7 Besides the implicit correlations between melting phenomenon and point defects, the melting temperature itself at atmospheric pressure can be used as a reference temperature for the purpose of comparison of vacancy concentrations in a given crystal class. The concentration at the melting point then corresponds to the maximum vacancy super saturation in the crystalline state at a fixed pressure. For pure fcc metals such as Au, Cu, Al, Ag, Pb, and Pt the mole fraction of vacancies at the melting point8 is of the order of 10*"3 to 10"1. The equation expressing the equilibrium vacancy concentration at the melting point contains three parameters: the formation energy, the vibrational entropy, and the absolute melting temperature, see Eq. [2]. Since these three parameters cover a wide range of values8 in the above-mentioned metals, it can be assumed that in other fcc metals, for which no reliable data are available, the mole fraction of vacancies at the melting point most likely lies in the range 10~3 to lO"4. This is then the basis of the calculations described in this article. Within this range the mixing entropy can be linearized and the vibrational entropy, the formation energy, and the vacancy formation volume can be calculated in terms of known thermodynamic constants. 1} LINEARIZATION OF MIXING ENTROPY The Helmholtz free energy of a crystal containing n vacancies at the melting point can be writteng as where Ef, T,, k, and S, are the formation energy of a vacancy, the absolute melting temperature, Boltz-mann's constant, and the vacancy formation entropy, respectively. After applying Stirling's approximation in Eq. [l] and minimizing with respect to n where (n/N), is the equilibrium vacancy concentration in mole fraction at the melting temperature at 1 atm pressure. If instead of setting (6~/6n) = 0 immediately after Stirling's approximation in Eq. [I], the configurational partition function is simplified, then some useful and significant results can be obtained by utilizing the experimental inforrnation After applying Stirling's approximation and rearranging is plotted as a function of (n/N) in Fig. 1. The points, not all of which are shown, are fitted by a straight line substituting from Eq. [5] into Eq. [I] and minimizing with respect to n combining Eqs. [6] and [2] It must be emphasized that Eq. [7] is only a crude approximation based on an oversimplified model of

Jan 1, 1967

By William E. Ford, Edward Salisbury Dana

The aluminate, ferrates, etc., allied chemically to the borates, have been already intro- duced among the oxides. They include the species of the Spinel Group, pp. 418-423, also Chrysoberyl, p. 423, etc. SUSSEXITE. In fibrous seams or veins. H. = 3. G. = 3.42. Luster silky to pearly. Color white with a tinge of pink or yellow. Translucent. Index, 1.59.

Jan 1, 1922

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.'-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc's were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

By A. H. Larson, T. P. McNulty

RECENTLY, an investigation of the absorption of sulfur dioxide gas in molten binary copper alloys was conducted. A Sieverts-type apparatus, consisting of a mercury-filled gas dispensing buret and a mercury manometer, was used initially for determining the volume of gas absorbed as a function of pressure. The equilibration behavior of the alloys studied indicated that the mercury in the gas measuring system was absorbing sulfur dioxide. Owing to the widespread use of mercury as a displacement medium in absorption studies, an investigation was made to determine the nature and magnitude of the mercury - sulfur dioxide absorption effect. The gas measuring system was modified by substituting a Worden Quartz Products Type PDHV fused-quartz-spiral pressure gage for the mercury-filled dispenser and manometer. The dispensed gas volume at known temperature and atmospheric pressure was measured by evacuating a Pyrex vessel of known volume and by admitting sulfur dioxide into the vessel until the attached quartz pressure gage registered atmospheric pressure. Atmospheric pressure was measured concurrently with a separate mercury barometer. The volume of the empty sample chamber and its attendant apparatus was determined by measuring the equilibrium pressure accompanying the addition of a measured volume of sulfur dioxide into the initially evacuated system. The volume of the mercury sample was calculated from the density of mercury at the temperature of the study (25°C). Measured volumes of sulfur dioxide were then dispensed into the system and the equilibrium pressure accompanying each gas addition was determined. From the difference between the system volume and the mercury volume, the number of moles of gaseous sulfur dioxide remaining in the system at each pressure was calculated. The difference between the number of moles of gas dispensed into the system, denoted Enso2: and the number of moles of gas remaining in the system after absorption equilibrium had been attained, denoted nso2(g), was equal to the number of moles of absorbed gas, denoted nSO2. The number of moles of absorbed gas was then converted to absorbed volume, denoted VSo2, in cu cm at stp conditions of (PC and 760 mm Hg. Table I contains calculated values of Snso2, nSo2(g), and VSo2 for different sulfur dioxide pressures. In the original system, denoted Run I, volume limitations of the gas dispensing system prevented absorption studies at equilibrium pressures near atmospheric pressure, so a different gas dispensing system, denoted Run 11, was used for determining the last pressure reading in Table I. The data in Table I are expressed in terms of the absorption of sulfur dioxide in 49.68 cu cm of mercury. In Fig. 1, these data are expressed in terms of the absorption of sulfur dioxide in 100 cu cm of mercury. Since the absorption data plotted in Fig. 1 show a linear relationship, the volume of sulfur dioxide absorbed in mercury is a function of the first power of pressure. The absorption reaction is So2(gas) = SO2 (in Hg) The first-power pressure dependence, coupled with the fact that the sulfur dioxide could be removed from the mercury by applying vacuum, indicated reversible

Jan 1, 1967