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By H. I. Aaronson, C. Laird

Although the past results of X-ray experiments indicate that the broad faces of 0' plates are coherent with their matrix, dislocations lying in arrays have frequently been observed at these boundaries by transmission electron microscopy. Critical experiments employing the latter technique have been carried out in order to determine the origin of these dislocations. It is concluded that 8' plates are essentially coherent with the matrix at their broad faces throughout the aging temperature/time envelope studied. Virtually all of the dislocation arrays observed are deduced to have been formed by plastic deformation accompanying transformation. The proportion of dislocations arising from convexity of the plates is shown to be negligible by comparison with that from plastic deformation. At the higher aging temperatures, a[001] dislocations appeared in moderate numbers. These dislocations were traced directly, however, to the ledgewise dissolution of 0' occasioned by the formation nearby of 0 crystals. On the other hand, since there is a parametric difference normal to the broad faces of the ?' plates, mismatch dislocations do form at their edges. A previous conclusion that these dislocations have Burgers vectors of type a[001] was confirmed directly. The edges of 0' plates were observed to develop octagonal shapes when growing, but circular shapes during dissolution. 1 HIS paper presents the results of an investigation of the interfacial structures of plates of the transitional phase, 8', formed in an A1-4 pct Cu alloy. In a companion paper, Part 11, the effects of these structures upon the migration kinetics of a:?f boundaries are reported. This work is pa.rt of a general program designed to establish the basis of precipitate morphology. The present authors in Al-Ag,1 and whitton2 previously in U-C alloys, have used transmission electron microscopy to examine directly the vander Merwe3-6 networks of dislocations anticipated7 to compensate the small amount of lattice misfit normally founda at the broad faces of Widmanstatten plates. Since the broad faces of 0' plates are considered to be perfectly coherent with the corresponding habit planes in the a matrix,' no dislocations should be present at these faces. Many reports have been published, however, giving evidence to the contrary.10-18 The primary objective of this investigation was therefore to ascertain the nature of these dislocation structures. An attempt to do this is described in the first three sections of this paper. Inspection of the matching of the a and 8 ' lattices at the orientations of the 0:0' boundary corresponding to the edges of 0' plates raises the possibility that these edges may be made up of rather closely spaced edge- type misfit dislocations oriented so as to be sessile with respect to the lengthening or shortening of the plates. Since this structure should severely inhibit migration of the plate edges (Ref. 7, Part II), a situation not originally anticipated,' an experimental determination of the interfacial structure of the edges of 8' plates was clearly in order, and is reported in Section III. Those aspects of the experimental procedure applicable to both Parts I and I1 are presented in the next section. Specific procedures applicable to individual aspects of each investigation, and also the relevant surveys of the literature, are then individually reported in the appropriate sections. I) GENERAL EXPERIMENTAL PROCEDURE The material used in both parts of these studies was the same as that of a previous investigation:" strips of A1-3.93 pct Cu, 0.009 in. thick, prepared as before, solution-annealed at 548°C for 6 hr, and quenched. Details of subsequent aging, and in some cases deformation treatments, are given in the Experimental Procedure sections of the individual parts of both papers. Specimens of the heat-treated strips were electro-thinned as beforeLg and examined in a Philips EM 200 microscope equipped with a goniometer stage. A commercial hot stage, of the grid-heater type and capable of * 30-deg tilt about one axis in the plane of the specimen, was also used for kinetic studies. The usual precaution of calibrating for the additional heat supplied by the electron beam was taken.19 A 16-mm cine cam-I era mounted outside the viewing window was frequently used to record the transformations. Conventional selected-area diffraction and dark-field viewing techniques were used to identify the precipitates in the foils. Normal bright-field images corresponding to two-beam diffracting conditions or dark-field images were employed to characterize the dislocations observed at the interfaces of the precipitates. The application of these techniques to the study of an interphase boundary, and the interpretation of the images,20'21 has been fully described in a previous paper.'

Jan 1, 1969

By Paul Girard

"The copper property of Madeleine Mines Ltd. is in Lapotardiere and Boisbuisson townships, Gaspe North. The initial find was made in 1964, and subsequently a copper deposit of 5.3 million tons of ore was outlined. The property lies in Ordovician sedimentary and volcanic rocks near the major granite intrusive of the McGerrigle Range. The host-rock is a 300-foot-thick metamorphosed silty shale unit, close to the contact of the intrusive. The structure itself coµsists of a southerly-dipping monocline or the south limb of an anticline, on which a large dragfold has been imposed.Chalcopyrite, bornite and chalcocite are the principal sulphides present in the ore. Of particular interest is the zoning arrangement of these sulphides. The orebody is chimney-like in shape and appears to be a fracture-filling deposit that is genetically related to the granite intrusive and is confined within a highly fractured zone of very brittle rock. The deposit presents features uncommon to any of the other known copper deposits in the Gaspe Peninsula."

Jan 1, 1969

By Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.' This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

By T. M. Storer

Much has been written and many discussions held on the virtues (and evils?) of a Company-owned motor fleet. Almost invariably these dialogues take a generalized form and thereby lose something since the individual circumstances, geography and philosophy - particularly in diverse industries, is never quite the same. In considering the nature of my remarks today, I felt a departure from the general approach might be in order, and in lieu of that, will attempt to present a concise picture of how we in the Lehigh Portland Cement Company view this problem and the steps we have taken in our efforts to solve it. At the outset a word may be in order about the Lehigh Company itself, what we do, and the problems that confront us specifically as well as the cement industry at large. We are primarily a manufacturer of portland cement operating 10 plants with a total annual capacity of about 23,000,000 barrels. We market this material in 30 states, shipping both from the plants directly as well as through a system of 18 distribution terminals. About 150,000 truckloads of cement are shipped to customers each year.

Jan 1, 1969

By J. G. Davis

Continental Oil Company has spent over four years of research on the fundamentals of potash solution mining. This work included laboratory investigations of salt solution, brine flow, selective extraction of KC1 from sylvinite, and control of cavity geometry. Laboratory results were expanded by means of a series of field tests, and subjects such as well completion and hydraulic fracturing were added to the investigation. Both single-well and multi-well mining systems were studied in the field work. The current paper discusses one field test in which potash was solution mined from a thin sylvinite ore zone in the Carlsbad Potash Basin. A two-well mining system was used for this test. The potential economic value of solution mining has been recognized for many years, and applicable United States patents date back into the past century. Principal advantages of the process over conventional mining include (1) the use of drilled holes and solution techniques in- stead of excavated shafts and caverns and (2) the ability to mine both land and marine deposits through any type of overburden geology and below conventional mining depths.

Jan 1, 1969

By V. A. Danielson

The Bureau of Mines studied waste disposal methods a1 a coal mine in Kentucky and another in Alabama to develop cost estimates, to provide better knowledge of current practices, and to guide consideration of alternate disposal methods. Costs of the existing waste disposal systems at each mine were estimated using present-day costs of equipment and labor. Costs of waste disposal systems using alternate equipment were also estimated. Although total disposal costs were essentially the same for both operations, reclamation costs will differ because of different reclamation practices.

Jan 1, 1969

By F. T. M. White, W. A. Bardswick

"The parameters of airborne minerallic particulates which create industrial dustiness, together with the physiological hazards caused by their inhalation, are reviewed. Various techniques of dust sampling are discussed and analysed, and the parameters referred to above are classified as the basis for methods of assessing the physical, chemical and mineralogical characteristics of dust-particle suspensions. The paper surveys those methods of assessment currently accepted by various statutory authorities, and reviews other methods that warrant attention and newer techniques that are being developed."

Jan 1, 1969

By G. L. Alston

The mine disaster last November in northern West Virginia has compelled the coal mining industry to take a closer look at the methods of transporting and applying rockdust. The USBM has indicated they would like to see a minimum of 80% incombustble in the back entries and want rockdust to be maintained to within 40 feet of the face at all times. With today's high rate of advance of mining machines it will be necessary to apply dust in the immediate returns continuously and the working places mutt have dust applied during the operating shift. The inspectors have become more demanding in requiring clean-up of coal and coal dust in the working place before rockdust is applied and are insisting on better clean-up and better rockdust applications along belt conveyors. Maintaining a constant application of rockdust in the back entries can be done with a Trickle-Duster. The machine is designed with hopper capacities of either 400 or 1,000 pounds of dust. The discharge rate of dust being fed through 1-1/2 inch diameter hose can be adjusted from 1/2 to 5 pounds per minute. The hose is extended into the return through the last open breakthrough and the return air carries the rockdust along w th the coal dust, depositing them uniformly on rib, roof and bottom.

Jan 1, 1969

By Robert E. Charles

Much has been said about digital computer control of metal and mineral ore dressing processes, but little has been done. This pa- per discusses what practical use can be made today of a digital computer in an ore concentrator and how such application can be made successfully. A hypothetical, but commercially common, grinding and flotation circuit is presented in terms of analog measurements which can and are being made in existing plants and a centralized computer control system which is reasonable in terms of today's technology. Dangers and possible disadvantages of such an approach are discussed as well as estimated benefits. Possible future benefits are presented in terms of improved control technology. Development of new measuring devices is not considered as a criterion for computer benefits. The control systems described have been utilized successfully in existing ore dressing operations. However, the degree of success or failure of analog systems is generally left to the interpretation of management rather than absolute analysis. Many factors affect the economic operation of a mineral recovery circuit such as size of facility, flow sheet design, number of operating personnel, percent of recoverable mineral in the ore body, loss to tails, and haulage rates. In existing mills where little or no instrumentation has been used, it is extremely difficult to prove or disprove the advantage of analog control systems on one mill line versus its sisters due to the lack of standards and the lack of ability to separate final products by ton.

Jan 1, 1969

By James S. Browning

Mica mining in the United States is confined largely to pegmatites and schists in a few well-defined areas. The largest region extends from central Virginia southward through western North and South Carolina, northern Georgia, and east-central Alabama. 1, 2, 3 Whereas in western North Carolina these pegmatite dikes are weathered to only a shallow depth, they are deeply weathered in the Carolina Piedmont and in Georgia and Alabama. Particularly in Georgia and Alabama, mica is found in the decomposed slates and schists adjacent to the pegmatites, and in deeply weathered granites. Most flake mica is obtained as the major marketable product by crushing and milling pegmatites.4 To a lesser extent, mica is produced as a byproduct of feldspars and spodumene.6 Past research by the Bureau of Mines has developed two methods for mica flotation. One method utilizes acid-cationic flotation for recovery of mica." This method requires thorough desliming of the ore with consequent fine mica losses. The other method utilizes an alkaline-anionic-cationic process for recovering fine size mica from pegmatite ores after desliming sufficiently to remove clay materials but not so drastically as to remove the fine mica. 8, 9, 10, 11, 12, 13 The latter process has also been successfully applied to a micaceous schist ore from California.14 This report summarizes the results of these research studies. Both of the flotation processes developed by the Bureau of Mines have been adopted by the mica industry and are being commercially utilized separately and in combination for flotation of mica from weathered pegmatite ores.

Jan 1, 1969

By R. S. Rickard, M. C. Fuerstenau

Anodic polarization curves for iron dissolution and cathodic polarization curves for copper deposition and ferric and hydrogen ion reduction were studied. These results were used to predict the relative rates of the reactions: The rates of the first two reactions were found to be first order with respect to the reacting ion, and the rale-controlling step was diffusion of the ions to the callzode surface. The rate of hydrogen ion reduction in an oxygen-free solution is dependent on the reciprocal of the square root of the hydrogen ion activity. In solutions containing oxygen, the rate of hydrogen reduction becomes dependent on the square root of the partial pressure of oxygen. At equal concentrations copper precipitation occurs about twice as fast as ferric ion reduction. In an air-saturated solution containing 0.01 M cupric ion at pH 2, the rate of hydrogen ion reduction zs about 10 times slower than that of copper precipitation. At pH values below 3, the rate of hydrogen reduction in oxygen-free solutions is very slozu. COPPER cementation has been utilized industrially for many years as a means of recovering copper from aqueous solutions. There are many different types of cementation plants, but all simply provide a means of contacting iron with relatively dilute copper solutions. In the past little or no attention has been paid to rates or mechanisms of the reactions involved. As a result, this and other studies'-3 have been undertaken recently to establish the important parameters in this system. The reactions involved in copper cementation by iron are: Since transfer of charge is involved in every case, these reactions should be considered from an electrochemical point of view. In any electrochemical system involving electrolytic conduction, passage of electrons necessitates ion transfer to the respective electrodes according to Faraday's law. The current in the system will be proportional to the rate of ion transfer, and, therefore, when the current in the galvanic cell is known, the rates of the reactions involved can be determined. Galvanostatic electrode measurements5" are applicable for these electrochemical studies, in that with this technique polarization curves (current density vs electrode potential) are established by impressing a constant current through an electrode and measuring the electrode potential. Once the current density, electrode potential, and reacting area are known for each reaction in this cementation system, the rates of the iron-consuming reactions can be determined. EXPERIMENTAL MATERIALS Several metal electrodes were used in this investigation; they are shown in Table I. Solutions were made with reagent-grade salts and conductivity water. Air, nitrogen, and oxygen were employed. All of these gases were saturated with water and degreased prior to use. EXPERIMENTAL PROCEDURE The experimental work was divided into two general areas. The first area involved galvanostatic measurements, which were used to determine the rates of reactions as a function of various parameters. The second area comprised actual cementation experiments to check the rates predicted from the electrode measurements. Galvanostatic Electrode Experiments. Polarization curves were obtained using a standard galvanostatic technique5'= with the apparatus shown in Fig. 1. The various electrode polarization experiments were run the same way except for changes in solution composition, polarity, and type of measured electrode. The general procedure involved the following steps: 1) a solution was made 0.5 M in sulfate ion and to the desired cation concentrations; this solution was placed in a constant-temperature bath and saturated with the desired gas; 2) the electrodes were cleaned and placed in the electrode holder; 3) the previously cleaned apparatus was assembled and immersed in a constant-temperature water bath (temperature controlled to ± 0.05"C); 4) the electrode was then positioned; the solutions were introduced, and the polarization meas-

Jan 1, 1969

By Gonzalo Barrientos

Instrumentation and observation of real mine structures helped define the pressure arch at White Pine, a large copper mine in sedimentary rocks. The pressure arch, which is attributed to inherent horizontal stresses, is used in the design of mine openings.

Jan 1, 1969

By J. M. Toye

The Canadian nuclear fuel business relates primarily to supplying fuel for Candu reactors. The product development, manufacturing and marketing activities of our nuclear fuel industry will therefore be determined by the rate of growth of the Candu nuclear reactor business. The nature of this relationship between the Canadian nuclear fuel industry and the Canadian Heavy Water Reactor program will be considered, with particular reference to the factors influencing future economic growth.

Jan 1, 1969

By K. Torssell, U. Lindborg

The kinetics of precipitation deoxidation is considered from a theoretical point of view. The size distribution and the total content of deoxidation products are estimated statistically as a function of time, taking into account Stokes and gradient collisions between the particles and separation at the top surface of the bath. The assumption is made that two particles coalesce into one larger particle as a result of a collision. General expressions are derived and calculations are carried out numerically for the case of silica particles in liquid iron. The analysis predicts a three-stage behavior for the removal of oxygen, an incubation stage, a stage of rapid separation, and a slow final stage where the content approaches the equilibrium value. The agreement with experimentally determined size distributions and deoxidation times is considered to be good. A quantitative estimation of such growth mechanisms as diffusion from the melt and redistribution of oxygen from small particles to large ones shows that these latter mechanisms cannot explain the experimentally observed gvowth of inclusions. This also indicates that collisions provide the important growth mechanism. OXIDE inclusions precipitate when a deoxidizer like silicon or aluminum is added to a steel bath. The inclusions grow and the large particles tend to separate from the bath. For each type of oxide the growth determines the sizes of the final inclusions as well as the total inclusion content of the steel. The mechanism of growth is controversial, however. It has been suggested that an inclusion grows principally by diffusion of atoms through the melt to the inclusion particle or principally by collisions and coalescence with other inclusions. Diffusion growth is always present to some extent but recent experiments and calculations by Torssell,' Kniippel et 'a1.,2 Sano et al. and Miya-shita4 indicate that collisions may be more important than previously realized. A detailed analysis has so far been lacking. The present paper is a quantitative, statistical analysis of the growth and separation of inclusions and is based on a collision theory. Nuclea-tion is not considered. The numerical estimates are based on the experimental conditions of Torssell's' investigation and comparisons are made with his observations. Torssell' studied the growth and separation of silica particles in liquid iron. Samples were taken from a 0.6 kg iron bath at various times after the addition of silicon. By a particle-counting technique developed by Bergh and Lindber~the size distribution of the inclu- sions was determined. The number of particles at the first sampling, 10 sec after silicon addition, was of the order of 3 x lo7 to 10' per cu cm, the largest particles having a radius of 2 to 4 pm. The volume fraction was 0.001 to 0.004; i.e., the dispersion was very dilute. During subsequent holding the largest particles increased their radius by a factor of 10 after about a minute, and the whole size distribution was displaced toward larger values. These results were obtained with allowance for precipitation of the equilibrium concentration of oxygen during solidification. The bath contained less than 0.01 pct of C. Figs. 1 and 2 show the typical appearance of the inclusions. Most particles are very closely spherical and appear to have been liquid or semiliquid in the melt. The observed number of inclusions, about 5x 10' per cu cm, is of the same order of magnitude as found by ~er~h.' This is a large value. It follows that the diffusion distances are very short and that the precipitation

Jan 1, 1969

By Harold F. Yde

Hydraulic tailings fill in the Butte deep level mines was based upon studies made in 1958 by the Anaconda Company Mining Research Department, which published Bulletin No. 35, entitled "Hydraulic Stope Filling". Since then, many things have changed. At the time of the Research Departments study, dry mine tailings were hauled by rail cars from the Anaconda tailings ponds, twenty-five miles distant, to the underground mines' tailings fill plants at the Leonard Anselmo, and Mt. Con Mines. Now, with the installation of the new Weed Concentrator in Butte, tailings is delivered by pipeline to a cyclone at the Kelley Shaft, and stope filling has become more highly automated and streamlined. Presently, mill tailings at approximately thirty percent solids by weight, is pumped from the concentrator, eight thousand feet horizontally and upward, to the Kelley Fill Plant, where they are dewatered and deslimed by three Krebs Model D20B Cyclones, which discharge the material into the cased and grouted mine delivery bore holes at desired densities up to seventy percent solids. The vertical boreholes and four-inch rubber lined Victaulic pipe carry the material downward to horizontal distribution lines, which in turn tap into the stops-filling, three inch, unlined steel Victaulic pipelines. The slurry may travel several thousand feet before it finally discharges into the stope, where it lends support to the mined-out area.

Jan 1, 1969

By B. W. Firth

Increasing depth in vertical mine shafts penalises conventional hoists in at least four distinct ways: rope weight becomes limiting; travel time increases; the obstruction of ventilation becomes more serious; and with friction drives, rope wear due to torque is aggravated. Travel speed is limited by instability of poorly sprung conveyances on inaccurately aligned flexible rails, and also by the cost of installed power to meet an inherently peaky demand. These problems call for a review of existing designs, firstly in respect of the furniture (Buntons and guides) obstructing the air flow, and secondly in regard to the hoist running in the shaft.

Jan 1, 1969

By Melvin W. Kraschnewski

In 1966 Central Ohio Coal Company and Bucyrus-Erie signed a contract authorizing Bucyrus-Erie Company to design and build a 220 cubic yard dragline. This dragline would be used for stripping overburden from their coal reserves located near Cumberland, Ohio. The size of the machine was arrived at after a thorough application study of their annual coal output requirement, depth of overburden and type of terrain. The design and construction of this machine which has been designated by BECO as model number 4250-W is the title of this paper. Size wise based on machine weight the 4250-W represents an increase factor of three over our largest current dragline. Probably the easiest way of presenting a machine of this size is to build it from the bottom up.

Jan 1, 1969

By Carl L. Morris

This short dissertation concerning "what the client expects from the engineer" is directed mainly at the design and construction of metallic ore concentration or beneficiation plants. However, practically the same conditions apply to the design and construction of cement and lime manufacturing facilities, with the exception that the latter facilities reflect the client's and engineer's concepts of customer service and in some cases reflect promotional considerations for the product manufactured and distributed. The client expects his engineering contractor to contribute in an efficient, cooperative, and economical manner current industry-wide know-how and experience to the specific project under consideration through the client's organization

Jan 1, 1969

By S. E. Piper, E. M. Buchalter, R. P. King, E. T. Woodburn

The problems involved in an optimum decision making model for flotation circuit are, first of all, to characterize the feed material in terms of parameters which can quantitatively describe the network flotation action in terms of a feasible set of control actions. Once the characterization has been postulated, it is then necessary to devise tests relating to parameter sensitivity, in order that credibility of the model predictions can be assessed. Once a credible model is available, the optimum control set is determined by a hill climbing technique. Details will be reported as to the credibility of model predictions using the stochastic flotation model on a network and further, computational problems associated with hill climbing for a complex objective function are reviewed. Discussion is presented on use of the Rosenbrock technique with constraints and use of a modified objective function with constrained derivatives when employing Fletcher and Powell technique.

Jan 1, 1969

By D. A. Elgillani, M. C. Fuerstenau

In this paper, oxidation potentials measured in the presence of various concentrations of cyanide, ferro-cyanide, and ferricyanide and ethyl xanthate at various values of pH are related to flotation response. Eh-pH diagrams are presented to show that the formation of surface ferric ferrocyanide is probably responsible for depression when cyanide is added. The influence of cyanide on the depression of pyrite with xanthates as collector has been the subject of a number of investigations,'-6 and several theories on the mechanism of depression have evolved from these studies. Wark and Cox7 and Gaudin8 have suggested that the depressing effect is due to a competition of cyanide ion with xanthate ion for the surface. Cook and his colleagues9-11 have explained this phenomenon in terms of competition between hydrocyanic acid and xanthic acid. Sutherland 12 has shown that although both of these theories accurately describe the relation between pH value and cyanide addition at constant collector addition, they fail to describe the relation between pH value and the amount of collector required to cause flotation. Taggart 13 suggested that depression in these systems is due to the formation of a reaction product between ferric ion at the pyrite surface and ferrocyanide ion derived from solution. Majumdar4,6 has attempted to prove this hypothesis by measuring the contact angles of pyrite in the presence of 25 mg per liter ethyl xanthate and different concentrations of potassium ferrocyanide and ferricyanide. In all cases the contact angles were quite high up to pH 10. These results indicate that pyrite should not be depressed by either potassium ferrocyanide or ferricyanide. In view of these facts, Majumdar has assumed that the compound Fe(CN)2 forms at the surface. Gründer and Bornl4 have stated that depression may be due to the formation of the compound K2Fe(II)Fe(CN)6 at the pyrite-solution interface. This compound is thought to be an interaction product between the K2Fe(CN)6-2 ion from solution and the Fe++ ion at the pyrite surface and, accordingly, K4Fe(CN)6 should depress pyrite at least as effectively as KCN. This was proven experimentally, but there was no simple relation between the depression of pyrite and the concentration of either KCN or K4Fe(CN)6 in solution. In view of the many mechanisms that have been proposed for pyrite depression by cyanide, it is apparent that a clear understanding of the phenomena occurring in these systems is lacking. One reason for this may be the fact that the species responsible for pyrite flotation in the presence of xanthate is not the xan-thate ion but rather dixanthogen.15 Since the oxidation of xanthate to dixanthogen is dependent on the oxidation potential of the solution, it would seem that knowledge of these potentials would be a requisite to understanding the pyrite-xanthate-cyanide system. It is the object of this paper to measure both the oxidation potential and pH of the pyrite systems in the presence of various concentrations of cyanide, ferrocyanide, and ferricyanide and xanthate and to relate these values to flotation response. EXPERIMENTAL MATERIALS AND 'TECHNIQUES In the experiments discussed here, pure potassium ethyl xanthate was used as collector, and reagent grade potassium cyanide, potassium ferrocyanide, and potassium ferricyanide were used as depressants. Reagent grade HC1 and KOH were added for pH adjustment. Conductivity water, made by passing distilled water through an ion exchange column, was used in all experimental work. Two natural samples of pyrite were used in the investigation. Sample preparation for flotation included dry grinding with a mortar and pestle and sizing the product to 100 x 200 mesh. Prior to flotation, a 0.75-gm sample of pyrite was added to a solution containing a known amount of depressant at the desired pH value, and the system was conditioned for 4 min. Following this, a known amount of collector was added and the system was conditioned for another 4 min. The pH — termed flotation pH - was measured; the pulp was transferred to a Hallimond cell, and flo-

Jan 1, 1969