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By S. R. B. Cooke, H. S. Choi, I. Iwasaki

Oleic acid is the chief ingredient of fatty acids used as collectors in nonsulfide flotation. With a few notable exceptions, the various quantities of saturated and other unsaturated acids comprising the remainder are usually unspecified. There have been occasional investigations to determine the collecting ability of these other acids and their effect on collection with oleic acid, but much remains to be done in this field. Hukki and Vartiainen, on the basis of tests using palmitic, oleic, and linoleic acids and an impure linolenic acid, concluded: "The collecting power of fatty acids used in flotation increases with increasing unsaturation of the hydrocarbon chain." ' Their work was concerned mainly with the response of ilmenite to the foregoing collectors, although tests were also made with magnetite, pyrite, hematite, and rutile. Cooke and Nummela, employing an almost identical technical procedure to evaluate flotation of hematite, magnetite, and goethite with various fatty acids, including oleic, linoleic, and linolenic acids of the highest purity obtainable, found: "The effectiveness of 18-carbon unsaturated fatty acids, as collectors for hematite, decreases with increase in the number of non-conjugated double bonds." 2 Vn the foregoing investigations, collector efficacy was measured on the basis of reagent addition in moles per liter. Sources of fatty acids which may be used as collectors are legion, but provided the oleic acid content is high enough, cost is normally the determining factor. Usually this restricts severely the purity of the collector in terms of its oleic acid content. Within the past year or so users of crude oleic acid have become somewhat more discriminating, apparently realizing that some of the organic acid impurities may exert deleterious effects upon certain separations. Marine fish oils have been used as collecting agents, particularly in the earlier days of froth flotation. Currently their use is restricted in this field to relatively minor applications, although they are cheap sources of fatty acids. In an effort to increase the range of uses for fish oils, the U. S. Fish and Wildlife Service has awarded contracts to study these materials as sources of new products suitable for commercial development. Funds for these investigations were provided by the Saltonstall-Ken-nedy Act of 1954. One such contract was awarded to the University of Minnesota School of Mines and Metallurgy for the purpose of investigating the use of fish oil fatty acids and their derivatives in ore flotation. Besides the esters of various saturated aliphatic acids and of palmitoleic and oleic acids, fish oil also contains esters of monoethenoid and polyethenoid acids with 20, 22, and 2 carbon atoms. The basic purpose of the investigation was to determine whether the longer-chained unsaturated acids possess collective properties superior to those of the C,, monoethenoid oleic acid, the C16 monoethenoid palmitoleic acid, or the saturated C,, stearic acid and its shorter chain homologues; whether highly unsaturated acids have merit as collectors; whether rela-

Jan 1, 1960

By S. R. B. Cooke, H. S. Choi, I. Iwasaki

In a previous article1 the function of various fatty acids as collectors for iron ores was reported for the two alternate processes; (a) the flotation of iron-oxide minerals, and (b) the flotation of calcium-activated siliceous gangue. The selectivity of separation was shown to be markedly dependent not only on such common parameters as pH and the levels of collector and activator addition, but also on the structure and the degree of unsaturation of the acids used. The iron ores employed consisted primarily of hematite, goethite, and quartz and as the effectiveness of any one acid on the separation depends on the individual response of each constituent mineral toward the given collector, a comprehensive knowledge of the floatability of the individual minerals is desirable for the interpretation of the results obtained. The mechanism by which a collector ion becomes attached to a mineral-solution interface has been a subject of much investigation. From quantitative studies of the properties of the electrical double layer on mercury2 and on several solid surfaces3,4,5,6 , the adsorption of some flotation reagents at the mineral-solution interface is beginning to be understood. For example, it has been demonstrated from streaming potential measurements made on quartz5 and corundum6 that the interfacial electrical condition is strongly dependent on the pH. Thisoccurs presumably through the following electrolytic reaction at the interface, and in the presence of a flotation collector, controls the floatability of the solids. A concurrent investigation of the flotation behavior of goethite and of quartz carried out at the School of Mines and Metallurgy7 has shown a positive correlation with the electrokinetic behavior of these minerals. The purpose of the present investigation was to collect general information on the floatability of hematite, and to investigate the function of various 18-carbon aliphatic acids on the floatability of hematite, goethite, and of activated quartz. Electrophoretic mobility measurements, simplified flotation tests using a modified Hallimond tube, and contact angle and frothability measurements were employed. The results are of direct application in the interpretation of the batch flotation results on natural ores as

Jan 1, 1961

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

Flotation data indicate that sulfonate and amine adsorb physically on manganese oxide; oleate also adsorbs physically if the zero point of charge is sufficiently high. Chemisorption of oleate occurs on pyrolusite between pH 8 and 9, and possible mechan- isms of collector adsorption involving metal ion hydrolysis are discussed. The flotation characteristics of most metal oxides1-15 have been examined with standard collectors such as fatty acids and sulfonates. From these studies it would appear as though electrical phenomena are important when shorte r-chained collectors are involved. For example, Iwasaki, Cooke, and Choi9 have shown that dodecyl amine and dodecyl sulfate float iron oxide above and below the zero point of charge, respectively. In another system, D.W. Fuerstenau and Modi10 have shown that dodecyl sulfate, dodecyl

Jan 1, 1969

By J. Leja, J. H. Schulman

FROTH flotation is usually effected by the addition of a collector agent and a frothing agent to an aqueous suspension of suitably comminuted mineral ores. The action of collectors is to adsorb onto the surfaces of minerals to be separated, sensitizing them to bubble adherence. The action of frothers has, in the past, been accepted as that of froth formation only, brought about by a lowering of the air/water interfacial tension. Substances capable of producing froth are classed1a,b according to their relative capacities for production of froth-volume and froth stability in the simple frother-water system. The purpose of this paper is to show that the surface active agents acting as frothers become effective only when there is a suitable degree of molecular interaction taking place between collector molecules and frother molecules at the air/water and solid/ water interfaces. Further, the discussion will demonstrate that the actual mechanism of adherence of an air bubble to a suitably collector-coated particle is due to the molecular interaction collector-frother. This leads to the formation of a continuous interfacial film of associated molecules, anchored to the mineral by polar groups of the collector, and enveloping the whole bubble. The tenacity of adhesion mineral-to-bubble results from the strength and the visco-elasticity of this mixed film. Some 20 years ago Christman2 postulated mutual dependence of collector and frother in effecting flotation. This view was, however, strongly opposed by Wark,3 who pointed out that an addition of frother had no effect on the value of contact angle once this was established in the solution of collector. More recent work by Taggart and Hassialis' indicated that the presence of frother, namely, cresol, leads to the immediate establishment of a contact angle on sphalerite, partially coated with xanthate, whereas an air bubble fails to make contact in potassium ethyl xanthate solution alone, even after 60 min induction time. Wrobel5 raws attention to the selectivity of frothers in flotation. Many instances of antagonistic effects of certain mixtures of frothers (or collectors and frothers) on flotation froth have been known to flotation operators and have been reported in literature. Taggart6 and Cooke7 give several examples of incompatibility of certain ratios of frothers and collectors, e.g., oleate and long-chain sulphates, pine oil and soaps. Monolayer Penetration. Properties of insoluble films produced by molecules of surface active agents orientated at the air/liquid interface are conveniently studied by the Langmuir trough technique, described fully by Adam.' Using the trough technique Schulman and Hughes" and Schulman et al.10a. b, c, d,e established the existence of molecular interactions occur- ring between certain types of surface active agents. Their experiments revealed the phenomenon of penetration of an insoluble monolayer (e.g., a film of a long-chain alcohol) by a soluble agent (e.g., sodium alkyl sulphate) injected into the substrate (water or salt solution). The degree of molecular interaction taking place on penetration is determined by changes in the surface pressure of the resulting film, changes of its surface potential and its mechanical properties (viscosity and rigidity). When the interaction takes place between both polar groups and both hydrophobic groups of the two participating amphipathic molecules a molecular complex is formed. Complexes formed on penetration of the monolayer at interfaces are not necessarily true chemical compounds: they are labile in solution, the activity and reactivity of individual components are greatly different from those of the molecularly associated complex, and on crystallization they usually separate out into components. However, when formed in the orientated state at interfaces they are found to be very stable, although some mixed films spread as monolayers of stoichiometric complexes can show further penetration by subsequent additions of the soluble component injected into the substrate.'" The degree of association between two or more types of surface active agents is very sensitive even to small changes in electric (dipole) moment of the polar groups of the amphipathic molecules as influenced by magnitude and position of neighboring ions or dipoles, their size, concentration, and stereochemistry. In addition, the molecular association is greatly influenced by concentration and type of inorganic salts in the substrate, by its pH, and by temperature. The nonpolar groups of interacting molecules greatly affect the stability of molecular complexes. Progressive shortening of the aliphatic chain of one of the reacting molecules weakens (at an increasing rate) its tendency to form stable complexes. Similarly, introduction of a double bond of cis-form into one of the reacting chains, which changes the straight hydrocarbon chain into a kinked one, or introduction of a branched chain, reduces the stability of the associated complex. Monolayer Adsorption. Using the trough technique and injecting metal ions into the substrate (water or salt solution) underlying insoluble films of fatty acids, alkyl amines, and sulphates, Wolsten-holme and Schulman11a,b,e. ' and Thomas and Schulman" have established conditions, namely, pH, concentration. and steric factors, under which molecular interactions take place between the polar groups of the surface active agents and the metal ions. These interactions are marked by great changes in the solubility and mechanical properties of the monolayer of the agent; no surface pressure increases are observed as in monolayer penetration experiments. The results of these adsorption studies, correlated with flotation experiments, indicated that in the case of fatty acids and alkyl sulphates their adsorption onto minerals of base-metals takes place by a similar

Jan 1, 1955

By Strathmore R. B. Cooke, Eugene L. Talbot

THE perfluoro acids and derivatives show unusual surface-active properties that qualify them as possible flotation reagents. They lower the surface tension of water from 15 to 20 dynes below that obtainable with the corresponding hydrocarbon compounds.1, 2 Fluorochemicals adsorb very strongly on solid surfaces to give films that exhibit larger contact angles than films of the corresponding hydrocarbons."' * The large contact angles probably result from the terminal —CF3 group. The perfluoro acids are made by electrolysis of the corresponding carboxylic acid in anhydrous hydrogen fluoride.5 From the perfluoro acids many derivatives may be obtained, such as amides, amines, alcohols, xanthates, ethers and esters and others. Since the fluorinated analogues of the conventional hydrocarbon flotation collectors possess enhanced surface properties, a few were selected for testing. Because a survey of all possible minerals and reagent combinations would be out of the question, hematite was chosen to represent a nonsulphide system and pyrite to represent a sulphide system. The fluorinated reagents used in these experiments were prepared in the research laboratories of Minnesota Mining & Mfg. Co. Some were synthesized especially for this research. They are not available cokmercially. Separation of Nonsulphide Ores: The separation of oxides from silica has always been a challenge to the flotation industry because differences in surface properties of the minerals are normally insufficient to produce clean concentrates. Oleic acid," rosin acids,' and amine salts% ave been used to considerable extent to effect separation of metal oxides and silica. The system hematite-silica was chosen to represent the nonsulphides both because of its difficulty of separation and because large tonnages of easily obtainable material are available, such as gravity concentration tailings and nonmagnetic taconites on the Mesabi Range. The wash-ore tailings used here contained approximately 35 pct iron after desliming. Samples of the material used in this work were part of the same lot used by Chang, Cooke, and Huch9 and were prepared in an identical manner. Reagents for Nonsulphide Ores: Since one of the purposes of this investigation was to compare hydrocarbons with fluorocarbons, reagents of known behavior such as oleic acid, and the alkali metal salts of certain resin acids (Dresinates), were established as standards. Hydrocarbons and fluorocarbons of comparable chain length and other experimental fluorocarbons were tried as collectors for hematite. A list of the materials used and the concentrations of their stock solutions are given in Table I. Since silica can be selectively floated from hematite by conventional reagents," a few fluorocarbon reagents were also tried for this purpose. Their composition and concentrations are given in Table 11. Most of these reagents served the dual function of collector and frother. In the case of F-11 flotation did not occur but it served as a frother when F-6 was employed as a collector. Reagent grade sulphuric acid and sodium hydroxide were used to regulate the pH. Deionized water containing less than 0.1 ppm of salts expressed as NaCl was used for all solutions and flotation tests. The pneumatic flotation cell consisted of a 350-ml fritted glass Buechner funnel with a source of filtered air which could be controlled by a needle valve." A 50-g sample of ore and 250 ml of deionized water were added to the flotation cell and stirred slowly. The reagents were added and the pulp was conditioned before air was admitted to the cell. Approximately 15 ml of the pulp were removed for pH determination before flotation was started and were then returned to the system. The pH was again measured after flotation. Air was admitted to the cell until no further flotation occurred or until the character of the float changed markedly. Both the float and the nonfloat products were filtered, dried, weighed. and assayed for iron. The cell was washed in hot water and rinsed with deionized water after each test. Occasionally the cell was cleaned with concentrated hydrochloric acid to remove iron oxide particles from the glass frit. Experimental Results: Above a pH of 8, sodium oleate was an effective collector for hematite. The emulsification of equal parts of heavy fuel oil (20"

Jan 1, 1956

By M. A. Cook

Sutherland used an ion-pair adsorption model to derive the author'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'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', X-, or R', 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,' 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.' 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 L. J. Erck, T. E. Ban

A discussion of laboratory procedures used to determine pellet quality and to simulate handling and firing conditions. Strength-temperature relationships in pelletizing; effect of chemical additives on agglomeration; and crushing, abrasion, and impact resistance of the pelletized products are discussed with respect to five different iron ore concentrates. IN most routine experimental work on products and processes, method:; of operation and product evaluation are established from accurately controlled laboratory tests. With particular emphasis on the pelletization of fine iron ore concentrates, standardized procedures of laboratory production and product testing have been established at Cleveland-Cliffs Iron Co. Research Laboratory at Ishpeming, Mich. A program of this nature was used for investigating the agglomeration characteristics of various iron ore concentrates. The factors which control the process were studied and subsequently controlled for these investigations. Pelletizing as applied to iron ore agglomeration involves the preparation of spheroidal masses from a fine moist concentrate, followed by high-tempera-ture firing to produce a final product. The preparation of moist spherorids is generally designated as balling. This produces the so-called green pellets or balls. After, these have been fired they are called pellets. Balling is accomplished by rolling moist concentrates in a revolving drum until small spheroids form by a snow-balling action. These balls are then heated in a shaft furnace, or a modification of this device, to a temperature high enough to cause agglomeration within the individual balls while they descend countercurrent to hot oxidizing gases. By this process the lour strength balls are converted through various chemical and physical-chemical processes into hard pellets. With correct balling and firing, the pellets are strong, resist abrasive action and handling treatments, and provide a suitable blast furnace and open hearth feed. In 1950 Tigerschiold and Ilmoni developed a working hypothesis to explain the formation and stability of green pellets.' Their work was presented on the basis of geologists' discoveries concerning the soil-water system and C. V. Firth's early postulates of green pellet formation.' Fundamental reactions oc-curing within fired pellets have been described by Cooke and Ban, who showed the microstructure changes caused by different firing temperatures." All these investigators have provided scientific clarifications of agglomeration by the pelletizing process and have opened avenues for greater development. Mineral grain growth and ceramic bond formation are the two basic phenomena imparting coherency to particles within a fired pellet of iron ore. Each of these is established by the transfer of thermal energy to the mineral particles. Grain growth mechanisms are chiefly physical reactions wherein smaller particles consolidate into larger ones, with resulting decrease in surface energy conforming with the second law of thermodynamics. Ceramic bond formation is a chemical reaction usually between basic and acid metallic oxides of the gangue and ore minerals. CaO, MgO, A1203, and FeO of Fe3O4, react in varying proportions with SiO, or Fe2O3, to form a great series of compounds or amorphous solid solutions. These product bond iron mineral particles together by a bridging action or by direct reaction with the surfaces of the particles. The result of the grain growth-ceramic bond formations is a consolidated, coherent compact of gangue and iron minerals formerly held together by much weaker bonds of interstitial water and forces common to dry, unconsolidated particles.4 With respect to iron ore agglomeration, these high temperature bonding reactions have been described by Schwartz, who referred to the bonds in sinters," and by Cooke and Ban, who referred to the bonds in fired pellets." The extent of the bonding phenomena and the consequent strength of fired pellets is governed by

Jan 1, 1954

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

By B. J. Yamada, D. W. Fuerstenau

Long-chained neutral molecules (decyl alcohol) increase the flotation of corundum with sodium dodecylsulfate and trimethyldodecylammonium chloride as collectors. This phenomenon is postulated to result from coadsorption of the neutral molecules with the collector ions. Flotation and streaming potential experiments have shown that sodium laurate is an effective collector for corundum at more dilute concentrations than sodium dodecylsulfate or sulfonate.1>2 It has been postulated that this phenomenon results from the adsorption of both laurate ions and lauric acid molecules, whereas sodium dodecylsulfate can be adsorbed only as dodecylsulfate ions, since this collector does not hydrolyze under flotation conditions. Similar effects have been observed in alkaline solutions with dodecylammonium chloride and trimethyldodecylammonium chloride as collectors.' If in- creased flotation occurs with the collectors which hydrolyze because of adsorption of the neutral molecules, purposeful addition of long-chained molecules should increase the flotation rate of minerals with such collectors as sodium dodecylsulfate or trimethyldodecylammonium chloride because these long-chained molecules should coadsorb with the collector ions. The effect of neutral molecules on flotation in these cases must depend on an adsorption mechanism which differs from that proposed by Cook for the adsorption of xanthic acid molecules by galena. For neutral molecules to function as collectors in the flotation of insoluble oxide minerals, adsorption of organic ions must first occur to provide a means of anchoring the fatty acid or amine molecules. Without adsorption of collector ions, flotation does not occur even in the presence of large quantities of neutral molecules, as is indicated by the cessation of flotation at low pH values with soaps as collectors or at high pH values with primary amine salts as collectors.' Neutral molecules, such as fatty acids, must be adsorbed through van der Waals attraction between the hydrocarbon chains of the adsorbed soap ions and the hydrocarbon chains of the fatty acid molecules. The mutual association of hydrocarbon chains results

Jan 1, 1962

By R. W. Smith, R. W. M. Lai

Although several recent papers have shown that equilibrium contact angle in dodecylamine solution-quartz systems can often be directly correlated with flotation behavior, it appears that under conditions of relatively high amine strength and pH such a correlation can't be made. Under these conditions, when there are precipitated amine dipoles present, it appears that a dynamic contact angle formed immediately after introduction of fresh gas bubbles into the system is also of importance. The dynamic angle decreases in magnitude as a function of time. Apparently the decrease is the result of changes in interfacial tensions (liquid-gas and solid-gas) as a function of time. Dynamic angles of the type described can't be observed in trimethyldodecylammonium chloride solution-quartz systems. Several recent papers1-3 have shown quite conclusively that contact angle data can often be correlated directly with flotation behavior in cationic surfactant solution-quartz systems. At the same time, Iwasaki, Cooke, and Colombo4 have shown data for a dodecylammonium chloride solution-goethite system where, in the vicinity of pH 12 and a collector concentration of 10" M, 100% flotation occurs when equilibrium contact angle appears to be zero. A clue to this discrepancy can be found in the work by smith2 who reported the occurrence of dynamic, time dependent, contact angles in a quartz-dodecyl-amine solution system at relatively high pH values and at surfactant concentrations greater than or equal to 10-4 M. It was found that under these conditions, if a fresh bubble was brought into contact with a properly conditioned and polished quartz surface, a large angle was obtained. The large angle, however, instantly started to diminish in magnitude, sometimes to a smaller stable angle and sometimes to its complete disappearance. Also, if the bubble was preconditioned for some minutes (or sometimes even seconds) in the same amine solution, the smaller or sometimes zero stable angle was obtained when the bubble was brought in contact with the quartz surface. One is immediately led to the thought that perhaps it is these dynamic angles when they exist, not stable angles, that are of primary importance in flotation. The present investigation attempts to further study the relationship between contact angle and flotation

Jan 1, 1967

By A. M. Gaudin, D. W. Fuerstenau

IN concentration of certain ores by soap flotation, prevention of quartz flotation is desired; the contrary is true in treatment of some oxide iron ores. Experimental study of the flotation of quartz goes back at least a quarter of a century.' Clean quartz does not float with fatty acids or soaps but does float when activated by one of many metallic salts. Control of pH is important. Broadly speaking the problem of quartz flotation has been approached from the empirical side, as was the related topic of flocculation or dispersion of quartz suspensions? Empirical studies indicated the existence of critical relationships between the additions of collector and activator. These additions were not stoichiometric for the formation of soaps of the activator cation. For example, Gaudin and Rizo-Patrona found optimum quartz flotation at pH 10.6 using barium activation and oleate collection when the molar ratio of oleate to barium was 1 to 1 instead of 2 to 1, as would be called for formation of Ba(OL),. Cooke and Digre" ' found that if calcium is the activator, a minimum quantity of that agent is required for effective flotation when the pH is 11.5. In other words, if the concentration of Na' exceeds 10 -2.5 mols per liter or if the concentration of H exceeds 10-11 mols per liter, the concentration of Ca++ in solution required for quartz activation is increased. This suggests that H+ is much more effective than Na+ on 10-2.5 quartz, perhaps in the ratio ofp or 108. Schuh- mann and Prakash6 studied anew the activation of quartz by barium, calcium, aluminum, and ferric iron. Salts of these metals are activators provided they are in stoichiometric excess over the collector used with them. Alkaline-earth salts are effective only in alkaline circuits. Important as they are in giving data on the effect of various agents on quartz, all these studies fail to give information on the detailed structure of the quartz-solution interface. A beginning in this direction was made by Gaudin and Chang,? who measured the adsorption of radioactively marked barium and laurate ions at quartz surfaces, and by Gaudin. Spedden, and Laxen,8 ho measured the adsorption of radioactively marked sodium at quartz surfaces. Work has also been done by Bell0 n measurement of the adsorption of sodium ion and chloride ion at quartz-solution interfaces. In all these experimental measurements of adsorption, the solid was centrifuged or filtered from the bulk of the liquor with which it had been associated; and the composition of the solid surface was ascertained by analysis, after allowance was made for the ionic composition of the liquor included with the centrifuged solids on the assumption that it is identical to the bulk liquid. Adsorption measurements give only the total amount of collector adsorbed at the quartz-solution interface; they give no indication of the distribution of these adsorbed ions at the interfacial layer. It is the ionic structure of the solid-solution interface and its importance to flotation that is the subject of this paper. The structure of this interfacial layer can be investigated by means of electrokinetic methods so that by combining electrokinetic studies with adsorption measurements, a more complete picture of the quartz surface may be obtained. The following studies were made to ascertain how electrolytes used in the soap flotation

Jan 1, 1956

By David R. Mitchell, Ernest M. Spokes

MINING ENGINEERING, page 373, March 1958, vol. 211) S. C. Sun: This article by Spokes and Mitchell deserves high commendation. For many years mineral dressers have been at a loss to explain the variation in magnetic susceptibility of the same mineral species obtained from different localities. In fact, they do not even have a list of accurately measured data on the specific magnetic susceptibility of weakly magnetic minerals to consult. Experience as a university teacher has firmly convinced me that the average student has more difficulty in acquiring a satisfactory knowledge of magnetism than of any other branch of mineral dressing. This is almost entirely because the subject has been treated far too much from a strict practical standpoint and far too little from a fundamental one. It is no exaggeration to state that almost all the published theoretical discussions are based on the experimental results of manufactured chemicals and alloys, but not of naturally occurring minerals. In an attempt to remedy this state of affairs, the author of this article not only set up a new magnetic balance in the Department of Mineral Preparation of The Pennsylvania State University, but also performed work of fundamental value, thus pointing the way to further research. This is evidenced by the fact that an investigation of the magnetic susceptibilities of manganese minerals was recently completed by S. G. Watt under the direction of David R. Mitchell, now acting dean of the College of Mineral Industries of the Pennsylvania State University. D. J. Cook is studying the magnetic susceptibility of titanium minerals under my supervision. It is hoped that our research program can be continued for several years and that similar investigations will be initiated at other universities and research institutions. Ernest M. Spokes (author's reply): The discusser has touched the heart of a pedagogical problem in the field of minerals beneficiation—students do not understand magnetism and, as a result, neither do the graduate engineers. Only recently has the average course in engineering physics started teaching the fundamentals of magnetism, as they are understood in modern physics, in addition to the classical treatment of the mathematical aspects of magnetic phenomena. It is to be hoped that this increasing instruction in fundamentals will improve our understanding and inspire research to determine more of the basic magnetic data that are essential if we are to see improved methods of separation by magnetism.

Jan 1, 1959

By L. W. Pommier, F. B. Brien, A. K. Bhasin

In the field of mineral processing, although many operations are applied to suspensions of ore particles in fluids, there is a lack of fundamental knowledge relative to the flow resistance encountered by immersed bodies moving through solid-liquid suspensions. Previously proposed equations, based on the Ostwald-de Waele (power-law) model for non-Newtonian fluids, are exam ined in the turbulent flow region relative to a number of pertinent variables and their effects on the movement of immersed bodies. As more knowledge is acquired in regard to the effects of suspension variables on the rheological properties, useful relationships may be proposed to allow predictions of conditions to achieve optimum results for engineering purposes. In the field of minerals processing, many operations are applied to suspensions of ore particles in fluids. The differential movement of solids of various sizes and densities in suspensions is of utmost importance to gravity concentration, wet classification, flotation, hydrometallurgy, and pipeline transport of solids. The subject is also of importance to other branches of engineering; for example, those involved with soil mechanics, ceramic slips, and oil-well drilling fluids. There is a lack of fundamental knowledge relative to the flow resistance encountered by immersed bodies moving through solid-liquid suspensions. The problems encountered in the direct application of the well-known Stokes and Newton's Laws to non-Newtonian systems have been examined in a previous paper.' Equations were proposed based on the Ostwald-de Waele (power-law) model for non-Newtonian fluids. This present paper examines these equations in the turbulent flow region relative to a number of pertinent variables and their effects on the movement of immersed bodies. It is thought that, as more knowledge is acquired as to the effects of suspension variables on the rheological properties, useful relationships may be proposed to allow prediction of conditions to achieve optimum results for engineering purposes. The purpose of this paper is to make an initial assessment of the nature and magnitude of pertinent suspension variables. In order to avoid too voluminous a document, the examination of kinetics and mechanisms will be omitted at this time. THEORY A Newtonian fluid is defined as a fluid in which the stress is proportional to the rate of strain, 2 i.e.: H = viscosity; see Table I. for list of symbols The following equations are conventionally used to assess the motion of spherical particles moving under laminar and turbulent flow conditions through Newtonian fluids: When these relationships are applied in practice to suspensions, the liquid density is substituted by a composite suspension density, and viscosity is usually taken as that of the suspending liquid or an approximated "apparent viscosity." However, suspensions are non-Newtonian in character3 and thus, more than one viscosity parameter is required to describe their behavior. A number of models have been proposed for non-Newtonian fluids;2,4 among these the simplest is the Ostwaldde Waele or power-law model for incompressible fluids which for one dimensional flow may be reduced to:

Jan 1, 1970

By M. H. Childs, K. E. Merklin

Blast furnace feed specifications are being revolutionized because of the large increase in iron pellet production from low-grade ores of the Lake Superior region. Recent laboratory findings aimed at a better understanding of factors influencing the physical quality of pellets produced from taconite concentrates are reviewed. Tests for determining better product quality, the effects of additives, and production factors are discussed. The current revolution in specifications for blast furnace feed is typified to a great extent by the recent tremendous growth in iron ore pellet production from low grade ores of the Lake Superior region. Indeed, pellets are responsible, at least in part, for many of the stringent new requirements that are being placed on the suppliers of furnace raw materials. As the tonnage of pellets going to the steel mills increases, more and more attention is being turned to the detailed characteristics that make this product an ideal blast furnace feed. Control of quality in pellets is similar to that of any other product. A basic understanding of the factors that are encountered in their production, from the crude ore through to the finished product, is required, along with careful process supervision and frequent quality checks. Normally, chemical grade is not a problem. This usually can be controlled within the desired specifications by minor operating variations in the con- centrator. While future changes in requirements may result in the need for self-fluxing pellets1 or other chemical changes, today's quality demands center primarily around the physical characteristics of the pellets. It is in this area that many of the recent laboratory studies have proven helpful to the operating plants. A better understanding of the physical factors involved in pelletizing has provided the basis for a continuing program of quality improvement. Tigerschiold and Ilmoni2 and Cooke with various associates are responsible for the development of much of the basic understanding of the pelletiz-ing process. These earlier findings have served as a most useful background for this work. LABORATORY PROCEDURES Magnetite concentrates produced from eastern Mesabi Range magnetic taconites were used for all of the work reported herein. The sizing and chemical analysis of a random sample are shown in Table t Additives usually are mixed with the concentrates in taconite plants before pelletizing to improve the strength characteristics of the unfired balls. Ben-tonite, soda ash, and coal are in common use. The bentonite used in these studies was of the Wyoming sodium type; the soda ash was a standard commercia1 brand. Anthrafines were used where coal was called for. The procedure for making batches of balls at the Hibbing Laboratory is as follows: In an especially designed mulling equipment 2800 g of dry ore are mixed for 10 min with the desired additives. Water is added and mixing continued for 1 1/2 min. The charge is removed from the muller and put through a mechanical shredder to break down any lumps that may have formed. sixty previously formed seed balls are placed in the balling drum, which is in fact a 6 x 16-in. diam airplane tire turning at 53 Wm. Two thousand grams of the shredded concentrate and additive mix are fed by hand into the tire at a con-

Jan 1, 1961

By R. W. Lai, I. Iwasaki

Some physical as well as chemical aspects of the methods of dispersion of various corn starches and their derivatives are investigated and their effects as depressants in anionic silica flotation of iron ores ascertained. The adsorption behavior of starches on hematite and quartz is strongly affected by their molecular sizes as inferred from viscosity measurements. The implication of this behavior on flotation and flocculation is discussed. Mechanical treatment of causticized starch solutions is shown to reduce the starch requirements in flotation appreciably. Starches and starch products have been used as depressants for iron oxides both in amine flotation of siliceous gangue and in soap flotation of activated silica from iron ores. Cooke and his associates1,2,3,4 extensively studied the effects of certain starches and their derivatives in the amine flotation of iron ores at near-neutral pH and found that although most starches were good flocculants for hematite and de- pressed that mineral more or less selectively1,3 they did not flocculate quartz suspensions. Further, that replacement of active groups in corn starch modified its behavior as a flocculant for hematite or quartz suspensions1 and as an iron oxide depressant. Schulz and cooke2 showed that many starches and their derivatives, except aminoethyl starch, were abstracted more effectively by Brazilian hematite than by quartz and that the adsorption of a starch product was strongly dependent on pH and on the presence of calcium ion. In soap flotation of calcium-activated quartz, certain starches and their products have been used to depress iron oxides.5'6 The behavior of these substances in flotation appears at times to be at variance with those previously reported and especially with results obtained in the Mines Experiment Station laboratories. This is attributed, at least in part, to differences in flotation procedure and flowsheets and in the method of preparing the depressant. Most of the investigators referred to above, solubilized the starch products by autoclaving at 120°C. Others have used acid,7 alkali8 or oxidizing agents.9 In view of the limited knowledge of the depressing action of starches and their derivatives in iron ore flotation, particularly in soap flotation of calcium-activated silica at high alkalinity, an extensive study

Jan 1, 1965

By W. V. Long, D. H. Reynolds, R. B. Bhappu

Equilibrium distribution coefficients were determined for some monovalent and polyvalent ions for several absorbing and exchanging media as functions of pH and initial ion concentration. Among ions studied were NH4 (I), K(I), Ni(II), Ce(III), Th(IV), and Mo(VI). Absorbents used were: ion exchange resins; a tertiary, and a quaternary amine in an inert solvent; and some activated carbons. The ions studied were in aqueous HCI, HNO3, H2SO4, or HC104 solutions. The classical mass action expression proved of little value in describing the variations observed. The data indicate that the determining factors in absorption and ion exchange may be the ionic species in the aqueous solution, which in turn depend upon pH, dilution, and perhaps other conditions. Three sorption processes have become prominent in recovering values from leach solutions. These are: 1) ion exchange, 2) solvent extraction (liquid ion exchange), and 3) physical adsorption by materials of high specific surface. In the first two of these processes the exchange reaction is considered chemical in nature, and is discussed in terms of the mass action principle. The third is considered a surface phenomenon and is discussed in terms of surface areas and various forms (Gouy, Stern, Grahame, etc.) of the Helmholtz double-layer theory. Generally speaking, we have found in chemical analysis and hydrometallurgical studies that there are close similarities between the three sorption processes, and also differences which are difficult to reconcile with any of the usual theoretical treatments. That others have experienced the same troubles is shown by the fact that usable processes, in chemical analysis as well as in hydrometallurgy, generally are discovered by empirical procedures. EXPERIMENTAL CONSlDERATlONS The gaps between theory and practice have allowed many conflicting statements to appear in the litera- ture. To learn, in particular, the behavior of some metallic ions on a cation exchange resin at a constant pH, equilibration studies were made over a wide range of concentrations.' Results are shown in Fig. 1 for four metals in hydrochloric acid solution on a strongly acidic cation exchange resin, AG 50W-X8 (Bio-Rad). The distribution coefficient, defined as D = amount of metal extracted per g of resin/amount of metal unextracted per ml of solution is seen to vary in a way to support all manner of reports about its behavior with changes in solution concentration. The metals used were chosen from those least likely to form stable chloro-complexes. The changes of slope in the various isotherms may reflect formation of unsuspected chloro-complexes of low stability (ion-pairing for example) whose concen-

Jan 1, 1967

By R A. Medower

This paper provides a glimpse into the future of minerals processing with emphasis on æAutomation InnovationsÆ for the new millennium, particularly those involving advanced process control and innovative new applications of process control technology in 2007.

Jan 1, 2000

By Horace Freeman

Introduction In the aggregate, directly and ?indirectly, the pulp and paper industry ? consumes very large quantities of a variety of minerals, or compounds prepared from minerals. This is especially true in the manufacture of news-print, but fine papers, also, account for some of this consumption, in the processes of loading, coating, and otherwise improving the finish. The more important of the minerals used in the industry in Canada are briefly dealt with in the following pages. The list is by no means exhaustive, however. Thus, barite, lithopone, zinc oxide, zinc sulphide, and titanium oxide are used in small quantities in Canada in filling and coating paper. Up to the present time, however, the quantities of these materials used in the paper industry have not sufficed to encourage their manufacture in Canada. In the case of barite (barium sulphate)-or of witherite (barium carbonate)-it may be said that, should deposits of commercial size be discovered in Canada, the ore would have considerable export value, for use in the paper and other industries. China-Clay (Kaolin) Considerable quantities of china-clay are used for brightening and improving the finish of paper, and there is a growing tendency to use larger amounts of this material in newsprint manufacture. No china-clay suitable for paper manufacture is at present produced in Canada, but samples have been forthcoming recently from a deposit near St. Remi d'Amherst, Labelle county, Que., about thirty miles north of the Ottawa river and approximately midway between Montreal and Ottawa, and plans are under way to conduct large-scale tests with this material. Present sources of supply are the United States, England, and Russia.

Jan 1, 1934

By C. E. T. White

Although trace amounts of Indium are found in many ores, commercial production of the metal has come almost exclusively from residues, flue dusts and slags generated by Zinc recovery operations. Our paper attempts to summarize the various approaches used to recover Indium from these by-products. Some comments on production and price trends are included as well as our views on future availability.

Jan 1, 1982

By Russell G. Shomperlen

Grinding mills in excess of 5 meter diameter and 3500 kilowatts per mesh are putting new demands on big gears. This paper returns to the basics of ring gear design beginning with the fundamental power formulas specified by AGMA. Specific emphasis is given to those elements in the rating equations which require closer attention as gear diameters and transmitted power increase. Strict process control in the manufacture of the gear blank is also stressed. Finally, the writer offers a guide to proper installation, lubrication and maintenance.

Jan 1, 1981