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By C. H. Wayman, D. W. Fuerstenau

The effect of bubble size and concentration of certain reagents on the terminal velocity, shape, path, and drag coefficients of single air bubbles in distilled water has been investigated. Bubbles of a certain size range rise considerably faster than Reynolds number-drag coefficient relationships predict, whereas a small amount of frothing agent reduces their terminal velocity. The rapid velocity at which bubbles rise in distilled water appears to result from slip at the boundary and from circulation within the bubbles. Surface-active agents retard bubble motion through prevention of both circulation and slip at the boundary. A surface tension concentration gradient helps maintain bubble sphericity. HE gas phase is one of the indispensible in-gredients in flotation operations. Flotation depends on the collision of an air bubble and a mineral particle in a pulp and their ability to remain in contact long enough for adherence to take place. Before it is possible to understand the mechanics of air bubble-mineral particle encounter, it is necessary to learn more about the nature of bubbles themselves before collision with a mineral particle has taken place. To date, little work has been done on air bubbles in flotation systems. In 1945 Fahren-wald' presented a study of the role of frothers on air bubbles and on aeration in flotation, and recently Wark and Sutherland' discussed the work of Rosenberg- in relation to flotation. The research reported in this present article was undertaken to investigate systematically the effect of bubble size and the concentration of certain reagents on the terminal velocity, shape, path, and drag coefficient of single bubbles in distilled water. Most of the work is concerned with the effect of a-terpineol on bubble motion in water, but studies were made with potassium chloride, potassium hydroxide, potassium ethyl xanthate, and potassium amyl xanthate. Experimental Method and Materials: To obtain free bubble rise and reduce wall and surface effects, the investigators used a tank of 5½x5½x30-in. internal dimensions, filled with water to within 4 % in. of the top.' The tank was made of acrylic plastic so that the walls would have good optical properties. Distilled water, which was re-distilled in a block tin still and saturated with air before each test, was used in all the experiments. All solutions were made with reagent-grade chemicals. During each experiment the water was at room temperature, and during the course of an experiment the temperature did not fluctuate more than 0.5°C. Since the experiments were performed over a period of six months, the temperature varied between 25° and 27°C. The temperature at which each series of experiments was conducted is recorded with the data. The experimental apparatus is presented dia-grammatically in Fig. l. Individual air bubbles were generated from purified compressed air through a capillary of 0.003-cm internal diameter at a rate

Jan 1, 1959

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By F. A. Forward, A. H. Ross, J. Halpern

IN treating carnotite ores by carbonate leaching it is often necessary to subject the ore to a prior roast. Among the advantages that may result from roasting are: 1) improvement in settling and filtering characteristics of the ore; 2) destruction of carbonaceous impurities that would otherwise contaminate the leach solution and consume carbonate reagent; and 3) substantial increase in extraction of vanadium, which is usually low when the un-roasted ore is leached. Recovery of vanadium may be an important factor in processing carnotite ores, and the fact that vanadium is usually recovered in good yield by acid leaching has often been an economic advantage over results obtained with carbonate leaching. It has been found that response of an ore to carbonate leaching, following roasting, depends primarily on its composition and on the conditions of the prior roast treatment, particularly with regard to the roasting temperature, the atmosphere maintained above the charge during roasting and cooling, and the presence of certain reagents. These factors, especially the last, virtually determine the extractions of uranium and vanadium attainable by carbonate leaching, as well as the reagent consumption on leaching, whereas adjustment of the leaching conditions has only a limited influence. These variables were examined systematically to elucidate roasting and carbonate leaching of carnotite ores and to establish a treatment yielding high recoveries of both uranium and vanadium. Tests were conducted on samples of four different Colorado Plateau ores, described in Table I. Roasting Procedure: The roasting tests were conducted in an electrically heated furnace in which the temperature was controlled to +15oC. The ore (usually a 500-g charge) was ground to —100 mesh, mixed with the desired reagent, and spread in a silica tray to a bed depth of about 1/2 in. During the roast the charge was rabbled at intervals of 15 min. To provide free access of air the furnace was usually ventilated; however, in a few experiments a controlled atmosphere such as carbon dioxide or hydrogen was maintained above the charge. Leaching Procedure: The pulp, generally comprising 500 g of ore and a 2000-cc solution containing 80 g per liter of Na2CO3 and 20 g per liter of NaHCO3, was agitated in an autoclave at 120°C, under 30 psi O2. Samples were withdrawn periodically, and the solution and ore residue were analyzed. Under the conditions employed, maximum attainable extractions were generally achieved in 4

Jan 1, 1958

By P. L. De Bruyn, R. J. Charles

THE transfer of kinetic energy of translation into other forms of energy by impact is a fundamental process in most crushing and grinding operations. During and after the impact process the original source energy may be accounted for in any of the following possible forms: 1) Kinetic energy of translation of both the impacted and impacting objects. 2) Kinetic energy of vibration of the components of the impact system. 3) Potential energy as strain energy of the components of the system or in the form of residual stresses. 4) Heat generated by internal friction during plastic deformation or during damping of elastic waves. 5) New surface energy of fractured materials. At any instant during the impact process only the strain energy of the components of the system can contribute directly to the brittle fracture process. If fracture is the desired result, as in comminution, it would seem advantageous to choose or arrange the conditions of impact so that a maximum amount of the original kinetic energy could be converted to strain energy at some moment during a single impact. The present work deals with determination of these desirable conditions for a simple case of impact and application of the principles involved to general cases of impact. Experimental Method: Longitudinal impact of a rod with a fixed end was chosen as the impact system for investigation. The rod was mounted horizontally and the fixed end was formed by butting one end of the rod against a rigidly mounted steel anvil. The rod, of pyrex glass, was 10 in. long by 1 in. diam with both ends rounded to a 6 in. radius. The rounded ends permitted reproducible impacts on the free end of the rod and assured a symmetrical fixed end. Pyrex was selected as the rod material because of the marked elastic properties of such glass and the similarity of fracture between pyrex and many materials encountered in crushing and grinding operations. The frequency of natural longitudinal oscillation of the rod was 10 kc, and thus simple electronic equipment could be used for observation of strain changes occurring in the rod at this frequency. As shown in Fig. 1, impacts on the free end of the rod were obtained either by a pendulum device or by a spring-loaded gun. Relatively heavy hammers (100 to 600 g) of mild steel were used in the pendu- lum impacts, while fairly light projectiles (20 to 80 g) were fired from the spring-loaded gun. One of the main objects of the experimental work was to obtain the strain-time history of the rod as a function of the mass and kinetic energy of the impacting hammers. For this purpose a technique involving wire resistance strain gages and a recording oscilloscope was employed. Five gages were applied at equidistant sections along the rod, and by means of a switching arrangement the strain-time history at any section, and for any impact, could be obtained in the form of an oscillograph with a time base. The equation relating strain and voltage change across a strain gage through which a constant current is flowing is as follows: e = ?v/iRF [1] ? = strain, ?v = voltage change, i = gage current, R = gage resistance, and F = gage factor (from manufacturer's data — SRA type, Baldwin Lima Corp.). With the above equation an oscillograph depicting voltage change vs time on a single trace can be converted directly to a strain-time diagram if a calibration of the vertical response on the oscilloscope screen for specific voltage inputs is available. In the present case the calibration was obtained by photographing precisely known audio frequency voltages on the same oscillograph as that on which a voltage-time trace from a strain gage had been made. Synchronization of the beginning of the single trace with the beginning of the impact was accomplished by permitting contact of the impacting objects to close an electrical circuit from which a voltage pulse, sufficient to initiate the trace, was obtained. The struck end of the rod was lightly silvered for purposes of electrical conduction so that it would form one of the electrical contacts. Markers every 100 micro-seconds on the traces served for a time base calibration. Determinations of the kinetic energies of translation prior to impact were made in the case of the pendulum hammers by measuring the height of fall of the hammer and in the case of the projectiles by measuring the exit velocity from the gun barrel by means of an electrical circuit employing light sources, slits, and phototubes.' During the experimental work it became evident that the time of contact between the impacting object and the rod was an important variable in the impact process. Measurements of the times of contact were made, therefore, for every impact for which a strain-time record was obtained. The time of contact was determined by permitting the impacting components, when in contact, to act as a closed switch and discharge a condenser at relatively constant voltage. The discharge was observed and photographed with a time base on the oscilloscope screen.

Jan 1, 1957

By R. T. Hukki

John F. Myers (Consulting Engineer, Greenwich, Corm.)—Since the art of comminution has lain practically dormant for many years, it is very interesting that R. T. Hukki approaches the subject with a new concept. One is reminded of the research carried on by A. W. Fahrenwald of Moscow, Idaho, a few years ago. Fahrenwald mounted a steel bowl on a vertical shaft. The balls and ore placed in the bowl were rotated at fast speeds, thus simulating the supercritical speeds used by Hukki. The rolling action of the balls against the smooth shell liner has pretty much the same effect. The action is horizontal in one case and vertical in the other. Both researchers report good grinding activity. It is also constructive that such able investigators give to the students of comminution their interpretation of their laboratory results in terms of large-scale operation. History shows that it takes a lot of time for such radically new ideas to be absorbed by the industry. Typical of this is the present-day activity of cyclone classification in primary grinding circuits. The idea of cyclone classification has been kicking around for 30 or 40 years. Certainly we all suspect that the ponderous grinding mills of today, and their accessory apparatus, large buildings, etc., will ultimately give way to small fast units, just as this has occurred in other industries over the past 50 years. At the moment there is no evidence that ball and liner wear is prohibitively high. In fact, at the time Fahrenwald was demonstrating his high-speed horizontal machine at the meeting of the American Mining Congress, several years ago, he assured this writer that the balls retained their shape much longer than they do in conventional tumbling mills. Rods and balls that slide (as some operators in uranium plants are experiencing) get flat. Apparently the balls have a rolling action. Mr. Hukki's references to the processing capacity of the Tennessee Copper Co. mills is adequate. Those studying this subject will be greatly interested in the paper presented by Richard Smith of the Cleveland-Cliffs Iron Co. at the annual meeting of the Canadian Institute of Mining and Metallurgy in Vancouver April 24, 1958. This paper will be published during the latter part of 1958 in the Canadian Institute of Mining and Metallurgy Bulletin. Hukki's pioneering spirit is to be commended. R. T. Hukki (author's reply)—It has been heartening to read the objective discussion by J. F. Myers. The sincerity of his opinions is further strengthened by the fact that the article he has discussed contradicts in a major way the parallel achievements of his life work. Myers is right in his opinion that in general it takes a long time before new ideas are accepted by the industry. On the other hand, revolutions usually take place at supercritical speeds. There are many indications at present that both the unit operation of grinding and the related subject of size control are now just about ripe for a revolution. In grinding, brute force must ultimately give way to science. Rapid progress can be anticipated in the following fields: 1) Autogenous fine grinding at supercritical speeds will be the first advance and the one that will gain recognition most easily on industrial scale. At this moment, little Finland appears to be leading the world. Crocker recently made a statement that in nine cases out of ten, your own ore can be used as grinding medium more effectively and far more economically than steel balls. This is true. The present author would like to introduce a supplementary idea: In eight cases out of the nine cited above, it can be done at the highest overall efficiency in the supercritical speed range. Fine grinding must be based on attrition, not impact. The path of attrition may be vertical, horizontal, even inclined. 2) In coarse grinding, the conventional use of rods is sound practice. However, even the rods can be replaced by autogenous chunks large enough to offer the same impact momentum as the rods. To obtain the momentum, the chunks must be provided with a free fall through a sufficient height in horizontal mills operated at supercritical speeds. Coarse grinding must be based on impact. Detailed analysis of the subject may be found in a paper entitled "All-autogenous Grinding at Supercritical Speeds" in Mine and Quarry Engineering, July 1958. 3) All conventional methods of classification, including wet and dry cyclones, are inefficient in sharpness of separation. Continuous return of huge tonnages of finished material to the grinding unit with the circulating load is senseless practice. In the near future the present methods will be either replaced or supplemented by precision sizing. These three fields are also the ones to which J. F. Myers has so admirably contributed in the past. Fine Grinding at Supercritical Speeds. By R. T. Hukki (Mining EnGineERInG, May 1958). Eq. 9, page 588, should be as follows: T , c, (a — 6') n D Ltph On page 584 of the article the captions for Figs. 4 and 5 have been placed under the wrong illustrations and should be interchanged.

Jan 1, 1959

By R. Schuhmann, J. Th. Overbeek, P. L. De Bruyn

THE technique of concentrating valuable minerals from lean ores by flotation depends upon the creation of a finite contact angle at the three-phase contact, mineral-water-air. If the mineral is completely wetted by the water phase, contact angle zero, there is no tendency for air bubbles to attach themselves to the mineral. However, when the contact angle is finite, the surface free energy of the system, water-air bubble-mineral particle, can be diminished by contact between the bubble and the particle, and if not too heavy the mineral will be levitated in the froth. With a few exceptions, all clean minerals are completely wetted by pure water. Thus the art of flotation consists in adding substances to the water to make a finite contact angle with the mineral to be floated, but to leave the other minerals with a zero contact angle. The contact angle concept and experimental measurements of contact angles have played important roles in flotation research for several decades.'-" Nevertheless, there remain unanswered some basic questions as to the scientific significance of the contact angle and the nature of the processes by which flotation reagents affect contact angles. The contact angle is a complex quantity because the properties of three different phases, or rather of three different interfaces, control its magnitude. Considering the interfaces close to the region of ternary contact to be plane, the relation among the contact angle and the three binary interfacial tensions is easily derived. The condition for equilibrium among the three surface tensions, Fig. 1, or the requirement of minimum total surface free energy leads to Young's equation, Eq. I: ysa — ysl = yLA cos 0 [1] According to this equation, the contact angle has one well-defined value. Actually it is found in many experiments that the value of the contact angle depends on whether the air is replacing liquid over the solid (receding angle) or the liquid is replacing air (advancing angle). The receding angle is always the smaller of the two.4 Two explanations have been offered for this experimental fact. According to some investigators,5-8 roughness of the surface causes apparent contact angles that are different for the receding and the advancing cases although the actual local contact angle may be completely determined by Eq. 1. The other explanation involves the hypothesis that the solid-air interface after the liquid has just receded is different from the same interface when no liquid has previously covered it.1,4 Adsorption of constituents of the air or liquid might play a role here. In this discussion the difference between advancing and receding contact angle will be neglected and plane surfaces where Eq. 1 describes the situation will be considered. But there is still a fundamental obstacle to the application of Young's equation. The surface tension of the liquid (rla) can easily be determined, but the two surface tensions of the solid (rsa and ySL) cannot be measured directly. Eq. 1, however, is not without value. By contact angle measurements it is possible to establish how ysl — ysl varies with the addition of solutes to the liquid phase. Also, Eq. 1 affords a convenient starting point for calculating net forces and energy changes involved in the process of bubble-particle attachment.1,2 . If for the moment surface tension of the liquid (yLa) is considered a constant, an increase in ysa — ysL, will tend to decrease the contact angle. A decrease in ySA — ysl, corresponds to an increase of the contact angle. In cases where ySA — ySL > yLa the contact angle is zero; it will only reach finite values when ysa — ysa has been decreased below YLA. Thus on the basis of Young's equation and contact angle measurements alone, it can be learned how flotation reagents affect the difference Ysa — ysl, but no conclusions can be drawn as to the effects of reagents on the individual surface tensions ysa, and ysL, not even as to signs or directions of the surface tension changes resulting from reagent additions. A quantitative relationship between the surface tension or interfacial tension and the adsorption occurring at a surface or an interface is given by the Gibbs equation, which for constant temperature and pressure reads dy = — 2 T, du, [2] where dy is the infinitesimal change in surface tension accompanying a change in chemical potential

Jan 1, 1955

By R. Schuhmann, J. Th. Overbeek, P. L. De Bruyn

W. E. Ewers (Commonwealth Scientific and Industrial Research organization, Melbourne, Australia)— Any attempt to elucidate further the meaning of the contact angle, particularly if it deals with the magnitudes of those mysterious quantities rsa and YRL, is certain to receive attention from those interested in the fundamentals of flotation. It is imperative, therefore, that attention should be drawn to a serious defect in the treatment by de Bruyn, Overbeek, and Schuhmann. Their Eq. 5 dy = — ld/u — Th2odiH2n states correctly the relationship between the change in surface free energy dy, the surface excesses Tx and Th2o of the components x and H2O and the changes du, and dph2o in the chemical potentials of these components. This equation applies for constant pressure and con- stant temperature and for the interface of the solid in contact with the solution of X. The relation remains valid when 1.1 is defined so that TH2O becomes zero and the equation becomes dr = — r:dur [17] From this equation de Bruyn et al. correctly concluded that increased adsorption of the collector at the liquid solid interface would reduce the interfacial energy ysl. Their second conclusion, however, that an increase in the contact angle, corresponding to a greater decrease in rsa than in rsL can be attributed to greater adsorption of X at the solid-air interface than at the solid-liquid interface is quite unjustified. The portion of the solid surface from which the collector solution has been displaced by air must be considered in terms of the equilibria between the gaseous phase and the surface. If the pressure and temperature

Jan 1, 1955

By Strathmore R. B. Cooke, Iwao Iwasaki, C. S. Chang

The effects of aeration on an aqueous suspension of pyrrhotite were studied and their results correlated with flotation tests using xanthates as collectors. The effects of copper activation and of pH variation were determined and possible mechanisms postulated. PYRRHOTITE has long been considered a gangue mineral to be eliminated as tailing in the treatment of various sulphide ores. However, in recent years the world-wide lack of sulphur resources has called attention to this mineral as a potential source of both sulphur and iron. Its importance as an economic mineral, however, has not been particularly emphasized. For this reason very little is known about its response to flotation, except that it can be depressed easily in alkaline circuit, by long aeration,1,2 addition of oxidizing agents,3 or by starch.' The object of this work was to study the floatabil-ity of pyrrhotite. This includes the effect of oxidation by aeration, of copper activation, and of change in pH. Preparation of the Pyrrhotite Sample: It was desirable that the highest grade of pyrrhotite obtainable be used for this experiment, since the presence of other minerals could affect the surface properties.5 However, no pyrrhotite was available as crystals, and massive deposits of hydrothermal origin commonly contain considerable amounts of chalcopyrite. Pyrrhotite concentrate was, therefore, prepared from a sulphide deposit occurring near Aitkin, Minn. The deposit is of pyrometamorphic nature consistirlg mainly of pyrrhotite and pyrite with graphite, silicates, and carbonates as gangue. The ore, already crushed through 3 mesh when received, was screened at 65 mesh and the undersize discarded. The oversize was crushed through rolls, and then stage-ground dry in an Abbe porcelain mill, the —65 mesh portion being screened out after every 15 min of grinding until all the material passed through this size. The ground product was then concentrated with a drum-type dry magnetic separator. The rougher concentrate was cleaned twice and then demagnetized. The final product was split in a Jones splitter and stored in air-tight bottles. Microscopic examination of the concentrate showed that it was relatively clean and free of pyrite, locked particles, and gangue. By means of the krypton gas adsorption method," the specific surface was determined to be 3000 cm2 per g. The chemical and screen analyses of the final concentrate are given in Tables I and II respectively. It is a well-recognized fact that the oxidation of some sulphide ores during stockpiling, grinding, and conditioning affects their flotation behavior. The problem of oxidation may become serious in the case of pyrrhotite, since this is known to be more easily oxidized than many other sulphides. To ascertain the extent of oxidation, an experiment was carried out by aerating an aqueous suspension of pyrrhotite with air, oxygen, and nitrogen as follows. A 300-g sample of pyrrhotite in 2700 ml of water was agitated and simultaneously aerated in a Fager-gren-type laboratory flotation machine. A Precision wet test meter was connected to the air inlet valve, the flow rate of the gas being kept constant at 0.3 cu ft per min throughout the experiment. Samples of approximately 30 ml each were taken from the cell at 0, 4, 10, 20, 35, 60, and 90 min. After the pH was taken, each sample was filtered and the filtrate was analyzed for total iron and sulphur. The iron was determined colorimetrically by the thioglycolate method using a green filter.' The filtrate was oxidized with bromine to convert all of the soluble sulphur compounds into sulphate and this was determined with a Parr turbidimeter." When aeration tests were made in alkaline circuit, calcium hydroxide or sodium hydroxide was added at regular intervals to maintain a constant pH. A similar procedure was followed in an experiment to determine the abstraction of copper. ion by pyrrhotite. In this case various quantities of cupric chloride were added. The filtrate from each sample taken was analyzed for copper, total iron, and sulphur. The carbamate method with a green filter was used for the copper analysis,' since this method could tolerate a considerable amount of iron in the solution. A pneumatic cell, made from a 350-ml fritted glass Buechner funnel, was used for this experiment. The detail of the assemblage has been described elsewhere." In the present work a stainless steel baffle was inserted in the cell. This baffle overcame the tendency for the coarse pyrrhotite particles to be swirled around the wall of the cell and thus fail to collect in the froth. A 50-g sample of pyrrhotite was added to the cell which contained 260 ml of water. When pretreat-ment of the sample was desired, reagents, such as activator and pH regulator, were then added and the pulp was conditioned for a specified conditioning time. Prior to the addition of the collector approximately 15 ml of the solution were removed for pH measurement and for iron and sulphur analyses. Copper when used as activator was also determined. Collector and frother were then added and the pulp was conditioned for an additional 2 min. Air was admitted to the cell and the froth removed. The separation required from 4 to 6 min, depending on the characteristics of the froth. The float and non-float products were filtered, dried, weighed, and assayed for iron.

Jan 1, 1955

By Adrian C. Dorenfeld, Theodore Balberyszski, Strathmore R. B. Cooke

This paper reports results of studies of sulfidiza-tion of base-metal oxides and silicates with gaseous sulfur, hydrogen sulfide gas and pyrite and of their subsequent flotation with xanthate collectors. It has been established that a 100% conversion of the oxides of lead, zinc, copper and manganese into their respective sulfides is possible and is a function of reaction time and temperature. Sulfidization of chrysocolla (with malachite and azurite inclusions) resulted in a product containing covellite, chalcocite and digenite in proportions depending on conditions of sulfidization. Reacting cassiterite with gaseous sulfur, H2S or pyrite at various reaction temperatures resulted in its partial conversion to a tin sulfide. Flotation of the products of sulfidization indicated that their behavior is similar to that of natural sulfide minerals, the recovery being a function of the con-version of the oxides to their respective sulfides. The gradual depletion of high-grade sulfide mineral deposits has turned the attention of the mineral industry to the recovery of metals from the oxides and silicates. Anionic (fatty acid) and cationic collectors have in some cases made flotation of nonsulfides possible, although, in general, flotation of oxide ores is not as yet an economic process. Consequently, many attempts have been made to sulfidize the surface of the relevant oxide mineral and thus make it amenable to to In recent years, Bautista and sollenberger4 have investigated the conversion of a number of oxides to sulfides by reacting them with molten sulfur. This paper presents the results of .investigations carried out at the School of Mineral and Metallurgical Engineering at the University of Minnesota to study the flotation characteristics of some sulfidized minerals. It is divided into two parts: The first describes the sulfidization of a number of oxides and a silicate, and the second presents the flotation behavior of the products of sulfidization. SULFIDIZATION OF METAL OXIDES AND SILICATES Experimental Procedure: SULFIDIZATION WITH HYDROGEN SULFIDE GAS — Sulfidization with H2S gas was carried out in a horizontal tube furnace (Fig. 1). The temperature of the furnace was regulated by means of a Variac and determined with a chromel-alumel thermocouple. The constant temperature zone in the furnace was about 6 in. in length, and it was within this zone that the experiments were carried out. The gases employed were supplied from standard compressed gas cylinders, and passed through a glass-wool filtering tower before entering the Pyrex reaction tube. Gaseous products were bubbled through a water tower (used as a flow indicator) and excess H2S was burned off at the end of the outlet tube. Samples of reagents or minerals were placed in a 3-in. Alundum boat and inserted within the constant temperature zone of the furnace. Nitrogen gas (6 ppm O2 content) was passed through the tubes at room temperature to remove air in the tube, and continued to pass while the furnace was heating up. When the required temperature was reached, H2S was allowed to enter the tube and the supply of nitrogen was shut off. At the end of the reaction period, the reverse procedure was carried out, the samples being cooled to room temperature in a nitrogen atmosphere. The flow rate of H2S gas was maintained fairly constant in all experiments, although the rate was not determined. SULFIDIZATION WITH SULFUR POWDER - To study the sulfidization of minerals with sulfur (liquid or gaseous), samples of the mineral, together with a measured quantity of sulfur powder, were placed in a stainless steel (SS316) reaction vessel (Fig. 2). The reaction vessel was heated in a vertical resistance coil furnace, the temperature being regulated through a Variac. At the end of the experiment the vessel was cooled to room temperature before the sample was removed. Cooled products were leached with CS2 to remove any free sulfur. SULFIDIZATION OF TIN CONCENTRATES - Fifty gram samples of sulfidized tin ore were prepared by mixing -48 mesh Bolivian tin concentrate with -48 mesh Ottawa sand in various proportions and sulfi-dizing these samples with H2S in the horizontal tube

Jan 1, 1969

By C. R. Ramachandra, C. C. Patel

Flotation of chalcopyrite from a low grade ore was studied by using different xanthates and dixanthogens as collectors and by conditioning the flotation pulp with oxidizing gaseous systems. The improvement in the recovery of chalcopyrite with the oxidizing systems was mainly due to the auto-activation of chalcopyrite, leading to the enhanced adsorption of xanthates and dixanthogens even when the latter were formed by oxidation of the xanthates. With air or oxygen as oxidizing system, the amount of ethyl xanthate required at pH 8.5 was much less than normally employed in the industry, the recovery being 97-99% of chalcopyrite with a concentrate of 24% copper. With isopropyl and isoamyl xanthates, the recovery was improved but the grade was lowered. By conditioning the pulp with air-CO2 or oxygen-CO2 mixture, the recovery was lowered with ethyl xanthate only, mainly due to the depressant action of bicarbonate formed. Flotation with dixanthogens gave cleaner concentrates of chalcopyrite. because iron pyrite did not float with these collectors. Of the dixanthogens tried, diisopropyl dixanthogen gave the highest recovery, 99% chalcopyrite with a concentrate containing 28.5 to 30% copper, when the pulp at pH 8.5 was condi-tioned with air. Isopropyl dixanthogen was found to be the best collector of all the xanthates and dixanthogens studied. It was found that the adsorbed ethyl, isopropyl and isoamyl xanthates at chalcopyrite surface, activated by cupric sulfate, and at iron pyrite surface were oxidized to the corresponding dixanthogens to different degrees in presence of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture.' The dixanthogen formed at chalcopyrite surface was, however, firmly adsorbed while that at iron pyrite surface was easily desorbed. Since dixanthogens formed have greater hydrophobicity than the corresponding xanthates, as revealed by contact angles,1,2 the former were expected to improve the flotation results. It was, therefore, thought desirable to find out the effect of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture on the selective flotation of chalcopyrite when individual xanthates were used as collectors. The effect of direct use of dixanthogens as collectors on the selective flotation of chalcopyrite was also investigated. For these studies, low grade chalcopyrite ore, received from the Indian Copper Corp., Ltd. (I.C.C.), Ghatsila, Bihar, was employed. At the milling plant of the I.C.C., chalcopyrite is floated at a pH of 8.5, employing ethyl xanthate as collector. EXPERIMENTAL Materials Employed: XANTHATES - Ethyl, isopropyl and isoamyl xanthates of potassium were prepared in a pure state by the methods described earlier.4 A 0.03% aqueous solution of a xanthate was freshly prepared in air-free distilled water for flotation studies. DIXANTHOGENS - Diethyl, diisopropyl and diisoamyl dixanthogens were prepared by the oxidation of xanthates by iodine and purified by extraction with petroleum ether. A 0.03% alcoholic solution of dixanthogen was used as a collector. FROTHER - A 0.2% solution of pine oil in ethyl alcohol was employed. SODIUM CARBONATE - A 0.4 N solution was used. ORE - The composition of the -100 +200-mesh size (Tyler standard) powdered ore, as determined by standard methods of analysis, was: copper 1.57%, iron 10.29%, sulfur 3.15% and acid insolubles 66.10%. Iron present as chalcopyrite (CuFeS2) was 1.38%, while that present as iron pyrite (FeS,) was 1.37%. Both chalcopyrite and iron pyrite were found to be liberated from the gangue minerals and from each other, as observed under a microscope. Flotation of Chalcopyrite with Xanthates in Presence of Different Gaseous Systems: Fifteen grams of -100 + 200-mesh size ore were shaken well with 100 ml of distilled water. The pH of the pulp was adjusted to 8.5 by the addition of sodium carbonate solution. Then 0.1 ml of xanthate solution (0.005 lb xanthate per ton of the ore) was mixed with the pulp, and the latter together with washings transferred to a

Jan 1, 1963

By Jonas Svensson

A new method is described for the production of cold-bonded pellets using a hydraulic binder, such as portland cement. Large-scale pilot-plant tests have proved that self-fluxing pellets of high reducibility and good handling strength can be made by the method. Blast-furnace trials have shown that the pellets are an acceptable burden material, comparable with self-fluxing sinter or heat-hardened pellets. Economic factors of commercial-scale production are discussed. The Grangcold Pellet Process—for which patents have been applied or already granted in a number of coun-tries—uses a hydraulic adhesive such as portland cement, slag cements, pozzolanic cements, etc., for the production of cold-bonded pellets. The idea of using a hydraulic binder for the agglomeration of iron-ore fines is not new. Portland cement was proposed as an adhesive for cold-bonded iron-ore briquettes in patents granted more than 50 years ago.' In a report on the briquetting of iron-ore fines, published in Stahl und Eisen in 1959; it is stated that briquettes bonded with portland cement are used on a small scale at an ironwork in Germany. According to the report, the briquettes showed excellent strength in the blast furnace although their general use was made impossible because they required a long hardening time, during which they are sticky, soft, and difficult to store and handle. The Grangcold Pellet Process has overcome this particular disadvantage by mixing the balls with a suitable amount of the balling concentrate before storing them. The pellets are embedded in the concentrated during storing in such a way that they are isolated from each other and thus prevented from sticking together to form clusters. Thanks to the embedding concentrate, the pellets are subjected to a more or less uniform pressure from all sides which does not deform them. Thus, the mixture can be stored in a stockpile or in a bin until the pellets have hardened sufficiently. The concentrate is separated from the pellets by means of screening. The concentrate is returned to the balling operation and the pellets are either shipped to the blast furnace or stored for final hardening. The binder preferred for the Grangcold Pellett Process is portland-cement clinker, ground without the admixture of gypsum in order to avoid sulfur in the pellets as far as possible. Usually a 10% binder content is used. Two-thirds of the portland-cement clinker consist of lime and the rest is silica, alumina, and ferric oxide. Thus, self-fluxing or overbasic pellets are produced with this binder if the amount of silica in the concentrate used does not exceed 4%. The Grangcold Pellet Process was developed by the mineral Processing Laboratory of the Granges Co. Work started in 1963 with batch-scale tests. In 1966, a small pilot plant was put into operation in which 1800 tons of pellets were produced using 10% of rapid-hardening portland cement as a binder. Favorable results from a blast-furnace test with this batch led to the decision to erect a larger pilot plant which went into production in the summer of 1967. Since then, approximately 100,000 tons of cold-bonded pellets have been produced, mostly with 10% gypsum-free portland cement as a binder. Several full-scale blast-furnace trials have been performed with the pellets. The results of the trials indicate that the Grangcold pellets constitute a satisfactory blast-furnace feed. An industrial plant for the production of Grangcold pellets with a rated capacity of 1.5 million tpy is now under construction at the Granges Co.'s mine at Grangesberg. The plant will come into operation in the summer of 1970. Results from Laboratory Work Pellets made from iron-ore concentrate bonded with portland cement harden slowly and their handling is very critical until they have hardened enough to loose their stickiness. It is therefore especially important to study the progress of the hardening action and the factors influencing it. This is best achieved by investigating the relationship between the compressive strength of the cement-bonded pellets and the curing time under varied conditions. The general course of this relation-

Jan 1, 1971

By M. E. Wadsworth, T. D. Chatwin

The kinetics of sulfidization of hematite (Fe203) by H2S gas at various partial pressures have been determined over the temperature range of 170° to 500°C. The process was controlled by thin films of pyrite (FeS2) and troilite (FeS) which were protective and formed diffusional layers. At higher temperatures the thermodynamic drive to form FeS2 decreased, and consequently the rate of formation of FeS, decreased. Conditions for the development of thin layers of FeSz consisting of 10 to 100 atomic diameters are presented. Laboratory flotation results on synethetic ores indicate floatability identical to that of pyrite of normal xanthate flotation. The prospect of high-temperature sulfidization of metal oxides using H2S, S, or other sulfur bearing compounds is intriguing as a potential activation process for flotation since the thermodynamics are very favorable for a large number of systems. If the kinetic parameters are sufficiently well understood it may be possible to provide surface sulfide layers a few angstroms thick, thus imparting normal sulfide floatability characteristics to the oxide. For thin layers the total sulfur pick-up would be small except for very high surface area materials but in most cases this sulfur could be readily removed by roasting if necessary. The general reactions for the sul-fidization of metal oxide MxO, to a metal sulfide MpSq using H2S may be written for the three conditions py > xq; py < xq; and py = xq: A large thermodynamic advantage is obtained in many systems because of the relatively large negative free energy of formation of H,O compared to H,S. For the temperature range 2S° to 1500°C &apos; where AFOis the standard free energy and T is absolute temperature. As is evident from Eqs. 4 and 5, the free energy of formation of H ,0 is approximately 35 to 37 kilocalories per mole greater than that for H,S over broad variations of temperature. For oxide-sulfide systems as outlined above, sulfidization may be expected to occur for the conditions: Groups I and 111: that is, if the terms on the right are more negative than those on the left the reaction is expected to occur thermodynamically. The value hFg,(,) is included in Eq. 6 since hFLzs is based upon gaseous S2 rather than the normal reference state, orthorhombic sulfur. The

Jan 1, 1969

By M. A. Cook

Sutherland used an ion-pair adsorption model to derive the author&apos;s hy-drolytic pee-acid) adsorption equation for the contact bubble curves of Wark and Cox. To do so it was necessary to postulate that the sum of coverages of surface anion sites by the collector and depressant anions is practically unity. It is here shown that the free energy of Sutherland&apos;s postulated collector ion (x-)-depressant ion (OH-) exchange reaction (for no other than the OH- to compete with X-), namely EX + (OH-) Z SOH- + X-, is in some cases positive and X- should not even adsorb. Also, in many cases the (OH-) adsorption must be quite negligible even though the collector covers only about a sixth of the mineral surface at the threshold of air bubble contact. This, however, contradicts the postulate that permits one to derive the correct bubble contact eqwztion for the ion-pair model. Furthermore, the requirement for charge neutrality leads in the ion-pair model to the (impossible) constancy of the ratio @+)/(OH-) along a contact bubble curve in which pH may change by more than seven units. HYDROLYTIC ADSORPTION EQUATION Hydrolytic (free-acid or free-base) and ion-pair (H&apos;, X-, or R&apos;, OH-) adsorption models of the collector in metal sulfide and similar flotation systems are superficially alike and somewhat difficult to differentiate. This is because they yield, under seemingly valid assumptions, equivalent forms of the equations describing the distribution of the collector between the aqueous solution and the mineral surface. This has been discussed by the author and associates1-4 and more recently by Sutherland,&apos; both for simple collector-mineral and for more complicated collector-depressant-mineral systems. In the hydrolytic adsorption model the equations describing the contact bubble curves of Wark and coxeJ7 are as follows :2 Here X is the collector anion, D- the depressant anion, 9, and On are the fractions of the free-acid sites S on the surface of the mineral covered by collector and depressant free acids, respectively, and @ is the fraction of uncovered sites. Kx is the free-acid collector dissociation equilibrium con- stant, K1 that for the free-acid collector adsorption, KD that for the free-acid depressant dissociation, and K2 the equilibrium constant for the free-acid depressant adsorption. Eqs. 1 to 5 yield upon simultaneous solution the result is the critical free-acid concentration for bubble contact in the absence of depressant-free acid. Eq. 8 expresses the conditions along a simple collector-mineral contact bubble curve for the case HD = 0, or V = 0. Last and Cook showed that Eq. 6 applies generally and with good accuracy in the collector-depressant-metal sulfide mineral systems. Inci-dentally, it has been shown by infrared absorption studies that in some cases the free-acid adsorption process splits out water.&apos; In this case, Eq. 2 might be written SHOH + HX Z SHX + H20, with a similar equation replacing Eq. 4 for depressant-free acid-water exchange. This possibility does not change, however, the basic equations or considerations of the hydrolytic adsorption model. Indeed, this type of free acid-water exchange reaction was predicted for fluorite and iron ore flotation by oleic acid in the dry grinding and boiling processes.410

Jan 1, 1961

By A. F. Witt, A. M. Gaudin, A. K. Biswas

Finite contact angles in the rutile-water-organic liquid system are traceable to contamination or are due to addition of a surface-active agent. Finite contact angles are invariably accompanied by hysteresis.1-7 Besides surfactant concentration and pH, the nature of the organic liquid is found to be a factor influencing the magnitude of contact angle hysteresis. In a recent paper the authors have reviewed principles and applications of measurement methods for contact angles and their hysteresis.22 In this paper, these methods are applied to a system consisting of rutile, an organic liquid (benzene, decane, or dode-cane) and water. Surfactant (dodecylamine hydro-chloride) was used at various concentrations and various pH values. MATERIALS A synthetic rutile crystal supplied by the Linde Co. was used. It is a cylinder 1/2 in. diam, with faces cut perpendicular to the c-axis. The crystal is stated to be alumina-free and to be 99.9% pure. Rutile is a high surface energy solid, its calculated average field strength being 2.7 x 105 e.s.u.,9 its dielectric constant10 is 114. The zero point of charge of rutile was measured11 and found to be at pH 6.0. The atomic distances and bond angles of the tetragonal crystal of rutile have been precisely determined.l2 The organic liquids were specially purified. Reagent grade benzene was repeatedly shaken with concentrated sulfuric acid to remove thiophene, then neutralized with sodium hydroxide solution, rinsed with distilled water, dried overnight over anhydrous calcium chloride and filtered. The refractive index of this chemically purified benzene was 1.4977 (at 25°C) - very close to that of pure benzene (n25 1.4979).13 Both n-decane and n-dodecane were washed with aqueous sodium hydroxide, concentrated sulfuric acid (repeatedly, until the acid layer was colorless) and again with alkali, to free the organic hydrocarbon from fatty acids and unsaturated hydrocarbons. The organic phases were subsequently washed with distilled water and dried over anhydrous sodium sulfate. The filtered hydrocarbons were then distilled under vacuum (9-10 mm pressure). Decane, thus purified, showed traces of unsaturated and of carboxylic compounds. On gas chromatographic analysis the purified n-dodecane showed the presence of two impurities. However, the relative retention times of these components did not change substantially when measured on a polar or a nonpolar column. This indicates that the compounds were probably in the same polarity class, i.e. the components were nonpolar like dodecane. Conductivity water has always been one of the liquids. Conductivity of the water used was 10-6 ohm-&apos; cm". Dodecyl ammonium chloride was prepared from pure amine (supplied by Armour and Co., Chicago), by Li in the MIT Mineral Engineering Laboratory.14 The critical micelle concentration at 25°C is known, 0.0138 mol per liter15 or 3.06 gpl. All our experiments have been done at concentrations lower than the critical micelle concentration. The glass vessels, glass drop holder and the rutile crystal were all cleaned with hot chromic acid followed by distilled water, concentrated hydrochloric acid, and again distilled water, and conductivity water. During the experiments, a nitrogen atmosphere was maintained. For this purpose, commercially purified nitrogen was further purified by passing it over hot copper wire at 450°C, then through columns of acidic chromous chloride solution, concentrated alkali solution and distilled water. APPARATUS AND METHODS Hysteresis was produced by the "captive drop" or constant volume drop method as well as by the "expanding-contracting drop" or variable volume drop method. The image of the drop while it is expanding, contracting or moving is projected on a screen and photographed. The developed film is projected through an enlarger and the contact angles measured with a protractor.

Jan 1, 1964

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957

By M. E. Wadsworth, J. S. Cho

Colloidal silica dissolved in aqueous suspensions of high surface area thoria was permitted to adsorb on the thoria surface. Silica in three forms was identified by means of infrared spectroscopy and characterized by Si-O vibrational modes in the 9.0 to 10.5 region. A band at 9. 1 was attributed to free unad-sorbed silica, while adsorbed silica resulted in bands of greatest absorbency at 9.4 or 10.3p, depending upon the character of the surface bonding. Size considerations, the amount of silica adsorbed, and the character of the infrared spectrum for strongly adsorbed silica has been interpreted as evidence of formation of chain or layer silica linkages on the thoria surface. Infrared spectroscopy has been used successfully in recent years for the identification of minerals and synthetic inorganic substances. Unfortunately, infrared studies of silicate minerals have not proceeded to the point that unambiguous assignments may be made for Si-O vibrational modes as affected by lattice substitutions and structures. Several investigators have presented infrared spectra of silicate minerals, 1,7 and their work has pointed to the potential value of infrared to identify minerals as well as to note the sensitivity of various Si-O modes to structural and substitutional environments. The strong infrared absorption of various Si-O vibrational modes makes the infrared method a very useful tool for the study of silica adsorbed on the surface of solids of high surface area. Spaepen et a18 studied the adsorption of silica on thoria surfaces from aqueous solutions of silicic acid up to 300°C. A general review of the application of the infrared method to the study of surface adsorption has been presented by Pliskin and Eischens.9 EXPERIMENTAL Du Pont colloidal silica, Ludox SM (16.36% SiO2) and Ludox HS (30.25% SiO2) in aqueous suspensions were used as the sources of silica for the adsorption studies. The thoria used for this study was supplied by Union Carbide Nuclear Co.* under the preparation *Chemical Technology Div., Union Carbide Nuclear Co., Oak Ridge, Tenn. . number D-16-650. It was fired from the oxalate at 650°C and had a surface area of 32.4 ± 0.6 m2 per g measured by nitrogen adsorption. The chemical analysis of the D-16 thoria in ppm was: CO3= (5500), NO3- (< 4), so4±PO4 (100), and Si (20). The Ludox silica was placed in contact with the thoria in a two-liter autoclave10 between room temperature and 250°C. Slurries were made by placing 1 g of thoria in one liter of distilled water containing various additions of the silica sol. Samples were removed from the autoclave by opening a small stainless steel valve. Extracted samples were centrifuged for 10 min and excess solution was decanted. The sample was then dried for several hours at 80°C. Infrared samples were prepared by thoroughly mixing 10 mg of the thoria with 400 mg KBr in polystyrene vials on a "Wig-L-Bug" amalgamator. Pellets were pressed under vacuum and had final dimensions of 1.2 cm diam and 1.2 mm thick. Infrared spectra were

Jan 1, 1963

By J. M. W. Mackenzie

The interactions between oil drops and mineral surfaces have been examined for the cetyltrimethylammonium bromide (CTAB)-quartz and sodium dodecyl sulfate (SDS)-hematite systems. The results have been interpreted using a electrical double layer interaction model, a "sweeping-penetration" model based on steric interactions and a free energy of adhesion model. The adsorption of long-chain ions at the mineral interface was also studied and found to follow a Fuerstenau-Modi model of combined Coulombic and chain-chain interaction forces. The basis of the emulsion flotation process and the feature which makes it differ from conventional flotation is: encounter, followed by adhesion, between oil drops and mineral particles which are suspended in an aqueous environment. The manner in which the adhesion between these two phases contributes to the flotation process may be through the formation of min-eral-oil drop-mineral linkages, mineral-oil drop-air bubble linkages, or a combination of both. Possible flotation mechanisms derived from these adhesion processes are shown schematically in Fig. 2 while Fig. 1 shows an example of the first mechanism for quartz particles which have been floated using a cetyltrimethyl-ammonium bromide (CTAB)-Nujol emulsion as collector. In Fig. 2 the three phases, mineral, oil, and air, for convenience have been shown as having approximately equal size. This would not always be the case in an actual emulsion flotation operation. For the flotation of sand-sized particles of approximately 0.5 mm diam, the mineral particles would be at least ten times the size of the largest emulsion drops present in the system, while in the flotation of —10u slime particles, the mineral phase may be of the same order of size as the oil phase. The air bubbles in a flotation cell are normally about 1 to 2 mm in diam and therefore, in general, would be larger than the oil drops. Although the relative size of the three phases does not alter the basic adhesion processes between oil drops, mineral particles, and air bubbles, which depend on the physical and chemical properties of the interfaces involved rather than on the extent of these interfaces, it does alter the degree of deformation of the oil drops and air bubbles which will occur on adhesion. For mechanisms 1 and 2 to take place, the oil-water and mineral-water interfaces must be partially replaced by a mineral-oil interface while in mechanism 2 there is the additional requirement that the oil-water and air-water interfaces must be replaced by an oil-air interface. In view of the importance of the oil drop-mineral particle encounter and subsequent adhesion stages to both of the emulsion flotation mechanisms discussed, a study has been made of some physicochemical factors which control these processes for Nujol-cetytri-methylammonium bromide (CTAB)-quartz and Nujol-sodium dodecyl sulfate (SDS) -hematite systems. Experimental Electrokinetic Measurements.—The zeta potential of mineral particles was measured using a streaming potential technique similar to that described by Fuerste-nau.1 The streaming potential was measured using a multirange electrometer while the plug conductivity was measured using a 50 cycle sec1 bridge. Measurements were made on 28 x 65 mesh particles. Contact Angle Measurements.—A captive bubble technique was used to measure the contact angles for air bubbles and oil drops. The angles were measured on fracture faces of unmounted minerals which proved easier to clean than polished mounted specimens and should more closely represent a flotation system. Reagents: These have been described in a previous publication.0 Minerals: Rock crystal quartz from the New England district, N.S.W., was used for contact angle and streaming potential measurements. The quartz was hand

Jan 1, 1971

By C. M. Loeb, A. M. Gaudin, J. H. Brown

THE object of most size reduction operations in the mineral industry is to liberate the grains of valuable minerals in the ore from those of the gangue. This is usually accomplished by crushing and grinding the entire mass of ore until there is only a small probability that any single particle contains more than one mineral. During this size reduction only limited control exists over size or composition of the particles exposed to the breaking action, and there is no control over the paths followed by cracks generated during the operation. This lack of control usually results in overgrinding and in production of large quantities of very fine material. The first detriment, overgrinding, is costly in itself, but when combined with the second factor it is doubly so. Not only is the fracture of a free particle unnecessary—the fracture of these particles may also make subsequent separation operations difficult, inefficient, and wasteful. It has been pointed out&apos; that if the object of size reduction is to liberate the valuable mineral component of the ore then, ideally, fracture should follow intergranular paths to the exclusion of trans-granular ones. This would result in liberation of the valuable minerals with as little size reduction as possible. This ideal comminution operation is referred to as intergranular comminution, and it was the object of the investigation to determine the extent to which it could be developed by heat treatments. There are many indications in the literature that heating rocks prior to crushing may be favorable. Reports by Holman,2 Yates3 and Myers&apos; are pertinent. These investigators showed that heating certain rocks prior to crushing them did, in fact, improve their crushing characteristics in that fewer fines were produced, although the fact that intergranular comminution was being effected apparently was overlooked. In addition, Sosman noted that if there is appreciable anisotropism in the thermal coefficients of expansion of even a pure mineral, then considerable permanent separation of the grains of the rock can be expected as a result of heating the rock to a high temperature.&apos; By the same token, if there are ap- preciable differences in the thermal expansion coefficients of the various minerals of a multi-component rock, similar results should be obtained by heating this rock. This has been tested, partially, by Brenner," who obtained patents covering the heat treatment of some pegmatitic rocks in order to facilitate comminution of these materials. It has also been demonstrated that this may occur in taconite." Also, the possibility of causing decomposition of one mineral in a rock as a means of promoting intergranular fracture has been considered. Seigle2 and Schiffman et al. have obtained patents on such processes as applied to calcareous iron ores. These reports all indicate that heat treatments prior to crushing may contribute materially to intergranular comminution, but they also indicate that no organized attempt has been made to determine the controlling factors of the method or to determine its applicability in general. The present article is a report on the initial phase of such an investigation. The authors have reviewed the claims of prior investigators and have attempted, also, to establish the factors that might determine the applicability of heat treatments in the mineral industry. In this work 2000-g samples of various rocks were heated in a small laboratory furnace and crushing and sizing operations were carried out in standard laboratory equipment. All samples of each rock were as nearly identical as possible in particle size, grain size, and composition and contained only lumps coarse enough to contain many grains each. Tests on Granite A number of tests were made on a coarse grained Finnish granite obtained in the form of coarse chips from a local monument yard. This rock exhibited little variation from piece to piece in either composition or grain size. The minerals contained were quartz, orthoclase, small amounts of hornblende, and minute quantities of mica. Grain size ranged from about 1 mm to about 3 mm. Temperature of the Heat Treatment: In some cases the granite was heated to a particular temperature and crushed, hot, immediately upon withdrawal from the furnace—in others the rock was allowed to cool before crushing, but without quenching to room temperature after heating. In most tests on granite the heating period was about 2 hr with the furnace at the highest temperature for about 1 hr. Cases in which these periods were varied greatly will be presented separately.

Jan 1, 1959

By B. H. Bergstram, C. L. Sollenberger

When glass spheres are crushed by slow compression loading, the outer lune-shaped fragments resulting from the fracture consistently fly outward at high velocity. About 45 pct of the strain energy fed into the sphere-platen system reappears in the form of the kinetic energy possessed by these fragments. These measurements were obtained from high-speed photographs. This kinetic energy can be utilized for addtional comminution if the fragments are allowed to impact against a suitable structure. Comminution theory has advanced considerably in recent years by the study of this unit operation under laboratory conditions. Some of the parameters have been isolated, but the experimental measurements of the pertinent quantities, such as energy, particle size, etc., are still only made prior to and after the conclusion of a fracture sequence. The catastrophic fracture process itself has not been adequately studied from a comminution point of view. It has recently been suggested by Gilvarry that the fragments which result from the free crushing of a single glass sphere by slow compression contain a considerable amount of kinetic energy after fracture. This kinetic energy, if properly directed, possibly can be partially utilized to cause additional fracture. In this paper a hypothesis will be presented which suggests that this kinetic energy is necessarily present and that its dissipation is the process by which a large part of the thermal energy imparted to the crushed product is generated. Evidence supporting the existence of kinetic energy and its utilization for secondary fracture will also be presented. THEORETICAL A previous paper4 has shown that the load-deformation curve of a system composed of an elastic sphere gripped by a pair of parallel platens, can be predicted by a consideration of the theories of Hertz as summarized by Timoshenko.&apos; The deformation A, of one half of the system is given by which states that the deformation is a function of the mutually applied load, P, the radius of the sphere, R; and the respective physical properties of Poisson&apos;s ratio, v, and Young&apos;s modulus of elasticity, Y. The shape of experimental load-deformation curves conform to this relationship. The energy input to the sphere-platen system, can be predicted from the integral of the load acting through the appropriate distance, dA. Since dA can be evaluated in terms of P from the derivative of Eq. 1, this integral can be integrated between limits of 0 and P. The test sphere, however, is loaded at not one but at two points of contact, i.e., at both ends of a diameter, and hence the total energy input, E, is twice the energy input at each end, or The energy input to the system calculated from this equation corresponds to the energy computed from the measured area under the load-deformation curve. Timoshenko, considering the impact of two perfectly elastic spheres, has shown that the inter-penetration distance A is given by - m f (D (^ * ^t w as modified for the special case where one sphere is of infinite radius, i.e., its surface is a plane; where M is the mass of the finite sphere of radius R, and V is the velocity of approach at the start of an impact and also equals the final velocity of separation for perfectly elastic bodies. Because A is also a function of the load and the elastic properties, as shown in Eq. 1, the velocity, V, can also be calculated in terms of the elastic properties and maximum load, P, or

Jan 1, 1961

By W. J. Carlson, I. lwasaki

Manganese and silica in nonmagnetic tailings from the direct reduction-magnetic separation step were so closely associated that no physical concentration methods were effective. Dilute sulfuric acid dissolved manganese and iron rapidly; manganese in the form of silicates was virtually insoluble in sulfuric acid solutions, thereby governing the maximum extraction attained by leaching. Autoclave leaching at elevated temperatures and at high oxygen pressures reduced the iron extraction to less than one tenth without affecting the manganese extraction. There was an indication that autoclaving solubilized the manganese silicates appreciably. Elimination of iron from leach solutions was carried out by aerating the solution in the pH range of 6.5-7; a platinum-calomel electrode pair provided a reliable indicator for the end point of iron removal. The purified leach solutions were free of interfering impurities for the recovery of manganese as metal, dioxide, or carbonate. Manganiferous iron ores of the Cuyuna Range, Minn., are too low in iron content to be directly useful as iron ores, and too low in manganese content to be termed manganese ores. Common methods of physical beneficiation such as gravity concentration and flotation have not been successful in upgrading this material. The R-N process, when applied to manganiferous iron ores,1&apos;2 produces sponge iron by direct reduction of iron oxides, while leaving manganese as manganous oxide. From fine grinding and magnetic separation of the reduced ore, a tailing is produced which is relatively rich in manganese and low in iron content. The nonmagnetic tailing can readily be leached with acids and then further processed to recover manganese in various forms. In this way, two processes, neither of which would be an economic solution to the Cuyuna ore problem by itself, may be combined to produce two marketable products, thereby rendering the over-all process economically more attractive. This article reports on the results of a leaching study on the nonmagnetic tailings, both in a batch agitation vessel and in an autoclave; on the problems involved in the purification of leach liquors by aeration; and on the recovery techniques used to produce manganese metal by electrolysis, manganese dioxide either by electrolysis or by autoclaving, and

Jan 1, 1968