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By F. M. Lewis, J. F. Meyers

In the mining and handling of sulphide ores, some degree of oxidation takes place on the sulphide surfaces, which are exposed to the atmosphere. It is, moreover, well known that the oxidation compounds formed are a factor when such ores are subsequently treated by flotation. Modern operating technique and reagents are capable of contending with this condition to a major degree, provided that the proportions of the reagents used are varied correctly. This is particularly true at the Tennessee Copper Co., where the ore treated contains pyrrhotite in addition to other sulphides. A number of soluble salts, some of which are unstable, can be formed during the oxidation of the sulphide ores. Those unstable salts, whose oxygen requirements are unsatisfied, are constantly changing to more stable forms because oxygen reacts with them during the crushing, grinding and other operations of ore preparation. We add no chemicals of any kid to the ore pulp in its preparation for flotation feed. Consequently the only compounds that are present in the flotation feed are those produced by the natural oxidation of the ore in the presence of air and water. The Tennessee Copper Co. ore is composed of from 60 to 70 per cent sulphides and from 40 to 30 per cent non-sulphide material. It is not the purpose of this paper to discuss the nature of these various oxygen-sulphur compounds nor their effect on flotation, but to describe a method for correcting the effect. Suffice it to say that we have found that the reducing sulphur and oxygen salts have a depressing action on our bulk flotation process.' From long experience we find that the best means of correcting for this variation in our work is to increase or decrease the quantity of xanthate, the promoting agent, as the quantity of the reducing salts increases or decreases. It was, therefore, very desirable to provide the operators with some quick and

Jan 1, 1947

By James Norman, Benjamin S. Lindsey

BaritE (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the 'more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some kinds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to 100 per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaSO4, II.II per cent SiO², and 2.85 per cent R²O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of non-metallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is scparated. Laboratory Flotation Work Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coe1 for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1942

By Benjamin S. Lindsey, James Norman

BaritE (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the 'more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some kinds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to 100 per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaSO4, II.II per cent SiO², and 2.85 per cent R²O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of non-metallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is scparated. Laboratory Flotation Work Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coe1 for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1942

By H. S. Martin

The Phosphate Recovery Corporation operates three flotation plants, Nos. 1 and 2 concentrators about three miles northeast of Mulberry, Florida, and No. 3 plant at Wales, Tennessee. These plants represent the first commercial phosphate flotation operation and are also believed to be the largest nonmetallic flotation operation in the world at the present time. The details of this paper will be confined to plant No. 2, this being the newest and largest concentrator in Florida, and the flow sheet being practically the same as at plant No. 1. The No. 3 plant has been operated but a short time and has been shut down since December, 1932, on account of the decrease in phosphate rock production. The phosphate washers usually are located centrally on a known deposit so that about two hundred acres of ground can be mined economically to each washer location. The washers are moved to new areas when the distance becomes too great for economical pumping. The flotation plants are built either adjacent to a washer, so that current debris may be utilized, or on the site of a former washer where there is sufficient accumulated debris available for mining, and the flotation plants must also be moved from time to time. Most of the water used in the Florida flotation plants is recovered after passing through a circulating system where most of the fine suspended matter is settled out, but some make-up water is obtained from deep wells near the plant. Power is obtained from the Tampa Electric Co. through the distribution facilities of the International Agricultural Corporation. Flotation concentrate is hauled from the plant by trolley over the International Agricultural Corporation's trolley system, to the drying plant at Prairie, one mile northwest of Mulberry. Ore Treated In the pebble phosphate district of Florida, the phosphate mineral, or collophane, is usually found in horizontal beds of varying thickness

Jan 1, 1935

By John Mark Patek

Knowledge of the relative floatability of silicate minerals is increasing in importance as flotation is being applied to the concentration of nonsulfides. Many silicates are in themselves commercial products amenable to concentration by flotation. Moreover, the selective flotation of other nonsulfide minerals, such as cassiterite, depends largely upon the floatability of associated gangue silicates. Differences in floatability existing between the various silicates have not- been sufficiently appreciated; for example, the feldspars that differ greatly in floatability have generally been merely treated as "feldspar." It was the purpose of the work described in this paper to determine by experiment the differences in floatability between silicates; to investigate the causes for such differences, and to discover a means of predetermining approximate floatability without the necessity of experimentation. Determining Floatability The relative floatability of 20 silicates so selected as to represent all of the more common silicate types1 was obtained by flotation tests enumerated in Table 1. The mineral to be floated was crushed dry on a steel plate, and screened repeatedly during crushing through an 80-mesh screen in order to produce a sand with all grains as close to 80 mesh as possible. The sand was placed in dilute (6N) hydrochloric acid until free of soluble foreign material, and then washed with tap water about ten times in order to remove both acid and fines. The resultant product, which averaged 82 per cent plus 200 mesh, was floated in 50-gram charges in a 50-gram Denver celluloid flotation machine with 0.008 gram of terpineol, and from 0.01 to 0.05 gram of oleic acid in a solution acidified with sulfuric acid. The degree of separation of one mineral from another was determined by counting under a nlicroscope the grains of each mineral, both in the concentrate and in the tailings, and comparing their relative abundance in each. Unless the comparison showed a decided difference in amount,

Jan 1, 1935

By Will H. Coghill, J. Bruce Clemer

Flotation has been so closely allied with the sulfide minerals and their early and associated oily reagents that the term "oil flotation" has erroneously been applied to the entire flotation process. Today, the term "chemical flotation" might be used to advantage. Flotation literature has dealt primarily with the removal of sulfides from non-sulfide gangues, and the separation of one sulfide from another. Now, the application of the process to the separation of nonsulfide minerals is coming to the fore; and from the standpoint of the number of commercial minerals involved, the flotation of nonsulfides offers the larger field. Here, soap or soap-forming substances, such as the fatty acids and their derivatives, are used; hence there may well be a subdivision of the chemical flotation process called "soap flotation." Early experimenters learned that it was easy to form a froth or foam that would carry a part or all of the ore charge over the lip of the flotation machine; but this could not be regarded as flotation because of the lack of selectivity. Doubtless soap was one of the first reagents tried, and doubtless it was rejected on account of its gangue-carrying properties. Now this same gangue-carrying ability makes soap an acceptable reagent, for we are dealing with that which, among sulfides, is considered "gan-gue." As in the flotation of sulfides, so in the flotation of nonsulfides, the selective flocculation of the mineral and the dispersion of the gangue are the first objectives. In fact, these two phenomena epitomize flotation. They depend upon the unlike surface properties of the respective minerals; and as long as the components of an ore have unlike surface properties, a separation is possible, at least in theory. Often in nonsulfide flotation it makes little difference which mineral floats and which is depressed; generally only a separation is sought.

Jan 1, 1935

By A. F. Knoll, T. Clinton Taylor

Qualitatively, galena (native lead sulfide) reacts with aqueous solutions of the xanthates,1 and has its surface sufficiently altered so that there is a tendency for air bubbles to attach themselves to the mineral crystals where there was no such effect before the treatment. This property is utilized in froth flotation operations where the mineral sulfide particles are raised into the froth and the gangue whose surface is not altered remains behind. The results of a study of this reaction were reported2 recently and certain tentative suggestions about the interaction of galena and the alkali xanthates were offered. In this paper, there is set down the results of a detailed quantitative investigation of the ions involved in this interaction with a view to finding out more about the condition existing immediately at the surface of a crystal like a heavy metal sulfide after treatment with an organic reagent. Past experimental experience showed that finely ground galena shaken with aqueous potassium xanthate abstracts xanthate ion and at the same time sulfate ion, reducing ions of the type (SmOn)= where the ratio of m to n is less than 4:l (as in sulfate), sometimes hydroxyl ion, are thrown into solution.3 Ions Involved in Xanthate-galena Interaction The present quantitative study of the galena-aqueous potassium xanthate system shows that at the lower concentrations of potassium xanthate (less than about 25 mg. per liter) the amount of xanthate ion abstracted by the galena can be accounted for by the amount of reducing ions of the (SmOn)= type and sulfate ion thrown into solution. At these

Jan 1, 1935

By Plato Malozemoff, A. M. Gaudin

IN modern practice the major portion of an ore is reduced to flotation size by fine grinding. As the result of grinding fine enough to liberate most of the minerals, a substantial portion (generally 5 to 15 per cent) of the ore is inadvertently reduced to a size much finer than that necessary for liberation. This portion of most flotation pulps is very refractory to recovery by flotation. A reduction of one-quarter or more in recovery in this range of extremely fine particles can be observed. The loss in metals caused by overgrinding is appreciable. That this loss is characteristic of very fine particles has been suspected for some time;(l)† however, it was definitely quantified only recently.(2) Definite reduction in float-ability with reduction in particle size beyond a critical size of maximum floatability can be accepted now as an established fact. Formulating the Hypothesis In looking for the cause of the ill behavior of the finest particles it may be well to consider the essential differences between fine and coarse particles. A difference that immediately comes to mind is their intrinsic difference in size and consequently in relative extent of surface. If one agrees that attachment of mineral particles to bubbles must follow direct encounter of particles with bubbles one is forced to conclude(3) that the probability of encounter between a mineral particle and a bubble varies directly as the size of the particle, provided the particle is small compared to the bubble. In other words, the finer the particle the poorer its chance of being recovered in a given time of flotation. There is an effect, implicit in this theory, which should overcome the effect of excessive fineness of the particles; namely, flocculation of the particles. The floccules can be conceived as being simply larger particles and therefore capable of becoming attached to bubbles. And, indeed, in all the cases in which a sulfide mineral of near-colloidal size was successfully floated the mineral (but not necessarily the gangue) was flocculated. Moreover, it was shown experimentally(4) that galena previously flocculated by inorganic flocculators and then added to gangue

Jan 1, 1935

By G. R. M. Del Giudice

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

Jan 1, 1935

By A. B. Cox, L. W. Wark

In the paper on the development of the flotation process at Broken Hill (Australia) prepared by the Broken Hill Branch of the Australasian Institute of Mining and Metallurgy and published in its Proceedings for 1930 (N. S. 80), it is stated that the concentration of ores by flotation has been established on a commercial basis in Australia since 1904 and that differential flotation was practised at Broken Hill in 1912. Since then, progress in flotation practice throughout the world has been rapid, and during recent years the knowledge of the reactions between comparatively modern so-called chemical promoters or collecting agents and the mineral surfaces has been broadened by the published accounts of many investigators, particularly those working in American universities. Because of the benefits the Australian mining industry has derived from the flotation process, it was felt that the industry should take some part in the efforts that are being made to extend the knowledge of the principles on which the flotation process is based. Accordingly, early in 1930, three Broken Hill mining companies—the Broken Hill South, the North Broken Hill, and the Zinc Corporation—together with the Electrolytic Zinc Co. of Australasia, Ltd., and the Mount Lyell Mining & Railway Co., established a laboratory in the chemistry department of the University of Melbourne for the purpose of investigating the principles underlying flotation. Subsequently, the Burma Corporation, Ltd., expressed a desire to cooperate. The two authors are directly employed and controlled by these six organizations, and the cost of the investigation is divided equally among them. The research has been carried out under the general direction and in close cooperation with Harry Hey, chief metallurgist for the Electrolytic Zinc Co. of Australasia, Ltd., and the authors desire to place on record their indebtedness to him for his ever willing help and constructive criticism. After an extensive search of the literature, it was decided to determine in a preliminary investigation whether the effect of chemical collectors could be evaluated quantitatively by the "contact-angle" method. This preliminary investigation showed that with the bubble machine of

Jan 1, 1935

By A. B. Cox, L. W. Wark

In an earlier paper1 measurements of contact angles due to the effect of xanthates on mineral surfaces were reported. The solutions in which these measurements were made differed widely from those of modern flotation circuits. It is intended, however, by introducing, one at a time, the other principal reagents of flotation, to approach gradually the solution composition of flotation liquors. The work now described is an attempt to determine the effect of one of the most important of these reagents—namely, sodium cyanide—on the establishment of air-mineral contact. The work has been carried out for the following companies: Broken Hill South, North Broken Hill, Zinc Corporation, Electrolytic Zinc of Australasia, Mount Lyell Mining and Railway, and Burma Corporation. Since the effect of cyanide is inseparably connected with the alkalinity, the results cited below deal with the mutual effects of alkalis and cyanide. Alkalis alone exert a significant effect on the air-mineral contact but comparatively large amounts are required. Since the addition of a small amount of cyanide greatly decreases the degree of alkalinity necessary for the suppression of contact at surfaces of any of the minerals experimented with (except galena) and since alkalis are rarely used alone in practice, little attention has been paid to cyanide-free solutions. It was shown in the previous paper that, excluding the dixanthogen effect, whenever contact was practicable at all in an ethyl xanthate solution the angle of contact was 60". There is, therefore, less necessity to measure equilibrium contact angles; in fact, the experiments herein described have generally been conducted with a view to determining whether contact is possible and not to measuring the actual value of the contact angle. The separations which have generally to be effected in dealing with complex sulfide ores are: (1) galena from sphalerite, pyrite, etc.; (2) sphalerite from pyrite and/or gangue minerals; (3) copper minerals from pyrite and gangue minerals; (4) pyrite from gangue minerals; (5) chal-

Jan 1, 1935

By A. B. Cox, L. W. Wark

An attempt has been made to compare the influences of the two most widely used depressants—alkalis and sodium cyanide—and the most widely used activator—copper sulfate—on the air-mineral contact induced by five sulfur-bearing compounds: (1) sodium di-ethyl dithio-phosphate (sodium Aerofloat); (2) potassium ethyl xanthate; (3) sodium di-ethyl dithiocarbamate; (4) potassium iso-amyl xanthate; (5) potassium di-n-amyl dithiocarbamate. Three different organic types are included in lhis group and for two of these types a higher and a lower homologue have been tested. The study of potassium ethyl xanthate, the preliminary results of which have been described,' was continued until there had been obtained a comprehensive account of the influence of variations in pH value and in the concentrations of xanthate, sodium cyanide and copper sulfate on the adsorption of this xanthate by galena, sphalerite, pyrite and chalcopyrite. With concentrations of copper sulfate and collector that the work with ethyl xanthate indicated would give the most illuminating. results, the other four collectors were tested, in a less exhaustive way. The same general principles determine the influence of alkalis, cyanide and copper sulfate, no matter to which type the collector belongs, but there is a gradation in the quantitative measure of such influence. In the list above, the five collectors are cited in the order of their capacity to withstand the depressants, sodium Aerofloat being the least resistant, potassium di-n-amyl dithiocarbamate the most resistant. This order coincides substantially with that of the solubilities of the heavy metal salts formed by double decomposition with the collectors, those formed from sodium Aerofloat being most soluble. There is little difference between the third and fourth members of the series, and under certain conditions their positions are reversed. In general, then, of the three types of collectors investigated, the dithiophosphate type is most easily influenced by depressants, and the

Jan 1, 1935

By G. G. Griswold, B. S. Morrow

The copper-bearing ores concentrated at the Anaconda plant of the Anaconda Copper Mining Go. are principally a mixture of copper and iron sulfides associated in a gangue consisting of quartz, lightly altered granite and feldspars, with sphalerite and galena and more rarely barite and hubnerite as accessory minerals. The predominant sulfide is pyrite. The copper minerals present are: chalcocite, bornite (erubescite), enargite, chalcopyrite, covellite, tetrahedrite and some tennantite. Normal concentrator practice removes a slime prior to ball-mill grinding. The deslimed ore is ground to approximately 10 per cent plus 65 mesh for flotation. Two selective flotation circuits are used, one for deslimed ore and one for slime. Microscopic studies of concentrator products disclose such an interlocking of copper minerals with pyrite that any material increase in concentrate grade entails additional grinding unless recovery is sacrificed to a considerable extent. During the latter part of 1931 and the early part of 1932 the problem of producing a high-grade concentrate (40 per cent Cu) with at least no

Jan 1, 1935

By Walter E. Duncan, Oscar F. Tangel, A. M. Gaudin, Franklin Dewey, R. A. Johnson

Xanthates have been used as collectors of sulfide minerals in the concentration of ores by flotation for over a decade, yet much remains to be done to elucidate the underlying reasons for the remarkable effectiveness of these compounds in this connection. Briefly stated, the known facts concerning the effect of these reagents on the floatability of minerals are as follows: 1. Xanthates are without effect on silicates, silica, and generally on minerals currently regarded as "gangues." 2. Xanthates in very small amount increase enormously the floatability of sulfides of copper, lead, silver, iron and mercury. 3. If zinc sulfides are first '(activated," as by treatment with a copper salt, they are readily floated by xanthates; otherwise not. 4. Elemental copper, silver and gold have their floatabilities increased by xanthates. 5. Sulfides of elements that are not typically metallic—e.g., stibnite, realgar, molybdenit—are not made to float markedly better by treatment with xanthates. 6. Oxidized minerals of lead and copper are floated if treated with large amounts of xanthates, but not so if treated with amounts of the same order of magnitude as required for sulfide flotation. Oxidized zinc minerals are not floated unless xanthates having unusually long hydrocarbon chains (e.g., eight carbon atoms or more) are used. Iron oxides and carbonate are not floated by xanthates. From a flotation standpoint the most striking feature about xanthates is the very small amount required to accomplish startling changes in the behavior of some minerals. The amounts used in practice to effect excellent concentration are frequently of the order of 0.05 lb, of agent per ton of ore; that is, of the order of one part of agent per forty thousand parts of ore. Changes in amount of agent of the order of 0.01 lb. per ton of ore (or 0.002 lb. per ton of pulp, on a 4:l basis) have marked effects on the metallurgical results obtained. Yet these changes represent a variation of but one part per million parts of pulp.

Jan 1, 1935

By G. R. M. Del Giudice

The term "slime-coating" is not new in the art of flotation; the phenomenon has been observed and described by Taggart;(l)† Taggart, Taylor, and Ince;(2) and by Ince.(3) Notwithstanding that flotation was introduced for the treatment of finely crushed ore, the adverse effects of slimes have been recognized since the earliest days of the process, and the Elmore, Delprat, Potter, and other processes actually specified desliming of the ore prior to treatment. The cause of this trouble has been studied and described by Taggart;(1) Taggart, Taylor, and Ince;(2) Ince;(3) Morrow and Griswold;(4) and by Gaudin and Malozemoff.(5) Old Theory of Slime-coatings At present, so far as published work shows, there seems to be but one theory for the mechanism of slime-coatings. Ince(3) states that they are due to attraction between electrostatic charges of opposite sign on the sulfide and on the slime particles, supporting this theory by migration experiments in the Burton tube. He also used the microscope in conjunction with a glass cell employed by Beans and Eastlack(6) in studying migration, but met with interference from endosmosis. Several attempts have been made in the Department of Mineral Dressing at Columbia University to duplicate Ince's experiments with the Burton tube, but the results have never been convincing. Formation of precipitates which settled through the pulp levels, and evolution of gas at the electrodes, which disturbed the interface between the pulp and the distilled water above it, seriously interfered with observations. However, by use of the migration cell shown in Fig. 1, endosmosis effects and the disturbances due to precipitation and gas evolution were avoided, and distinct and reproducible migrations or absence of migration were observed. The cell was made of bakelite and had platinum electrodes. Objectives were employed which had a working distance of at least three millimeters,1 and the parts of the mounting which came in contact with

Jan 1, 1935

By G. R. M. Del Giudice, A. F. Taggart, Othon A. Ziehl

In a previous paper1 in which one of the authors collaborated, it was postulated that All dissolved reagents which, in flotation pulps, either by action on the to-be-floated or on the not-to-be-floated particles affect their floatability, junction by reason of chemical reactions of well recognized types between the reagent and the particle affected. This generalization, apparently, like many pioneer structures, had for certain observers a flimsy appearance, and these, judging its stability rather by the number than by the character of its foundation posts, have attempted variously to overthrow it, either by the frontal attack of general denial, or by the flanking movement involved in assuming that those cases in which the facts were unknown or unproved were, therefore, discordant. But as time has passed and further evidence on the question has accumulated, it has become apparent that the results of verifiable experiments add stone by stone to the substructure of the hypothesis, and that the super-tructure has lost nothing in weathering. The present paper constitutes an examination of the opposing positions in the light of the more recent evidence developed. It will clarify the discussion if, at this point, we state more fully the implications of the disputed hypothesis. In the first place, it is explicitly limited to reagents that are dissolved in the water of the flotation pulp. Next, it refers only to such of these dissolved reagents as act on the solid particles in the pulp to affect their floatability. This includes the collectors, activators, and certain depressors and gangue-control reagrnts, but not the pure frothers, and not, necessarily, conditioners whose function seems to be merely that of pH control, although in certain cases it has been demonstrated that such control has the effect of regulating the primary reaction of the collector, depressor, or the like. Finally, there is no limitation as to the nature of the chemical reaction postulated.

Jan 1, 1935

By Walter Kauzmann

EyRing'S general theory of shear rates as a function of the properties of molecular units of flow is outlined and applied to the creep of metals. This theory regards the unit molecular processes involved in the flow of matter as typical chemical reactions requiring an energy of activation in order to proceed. The externally applied stresses are assumed to influence the rate of flow solely by lowering the activation energy for flow in one direction and raising that for flow in the other, owing to the work that is done by or against the external forces in going from the normal to the activated state. The rates of flow in the two directions are then no longer equal arid there is a net, macroscopically observable flow in one direction. This is understood to be the physical basis for the well-known exponential dependence of the creep rate on the stress. The amount by which the activation energy is raised and lowered by a given external stress is directly related to the molecular dimensions of the unit of flow, so that some insight into these call be found from the behavior of the strain rate with changing stress. When Eyring's equation is applied to the flow of ordinary liquids, such as water or benzene, it has been found from the values of the constants required to fit the observed data that the unit molecular process here involves the passage of single molecules by one another. In metallic creep, on the other hand, the unit molecular process is shown probably to involve the shear of rather large blocks of material (100 to 1000 or more atoms on a side). This agrees with present ideas of crystal flow by means of dislocations such as have been presented by Taylor, Oroaan, and Polanyi, as opposed to flow by a mechanism related to that taking place in atomic diffusion. The dimensions of the dislocations are found to depend markedly on the temperature. The questions of why some metals are so much softer than others, the effects of impurities on hardness, the softness of single crystals, and the role of self-diffusion in creep are considered in the light of the theory and it is shown how answers to these questions (and others similar) might be obtained by use of the theory.

Jan 1, 1941

By Walter Kauzmann

EyRing'S general theory of shear rates as a function of the properties of molecular units of flow is outlined and applied to the creep of metals. This theory regards the unit molecular processes involved in the flow of matter as typical chemical reactions requiring an energy of activation in order to proceed. The externally applied stresses are assumed to influence the rate of flow solely by lowering the activation energy for flow in one direction and raising that for flow in the other, owing to the work that is done by or against the external forces in going from the normal to the activated state. The rates of flow in the two directions are then no longer equal arid there is a net, macroscopically observable flow in one direction. This is understood to be the physical basis for the well-known exponential dependence of the creep rate on the stress. The amount by which the activation energy is raised and lowered by a given external stress is directly related to the molecular dimensions of the unit of flow, so that some insight into these call be found from the behavior of the strain rate with changing stress. When Eyring's equation is applied to the flow of ordinary liquids, such as water or benzene, it has been found from the values of the constants required to fit the observed data that the unit molecular process here involves the passage of single molecules by one another. In metallic creep, on the other hand, the unit molecular process is shown probably to involve the shear of rather large blocks of material (100 to 1000 or more atoms on a side). This agrees with present ideas of crystal flow by means of dislocations such as have been presented by Taylor, Oroaan, and Polanyi, as opposed to flow by a mechanism related to that taking place in atomic diffusion. The dimensions of the dislocations are found to depend markedly on the temperature. The questions of why some metals are so much softer than others, the effects of impurities on hardness, the softness of single crystals, and the role of self-diffusion in creep are considered in the light of the theory and it is shown how answers to these questions (and others similar) might be obtained by use of the theory.

Jan 1, 1941

By Walter Kauzmann

All viscous or plastic flow of incompressible matter is the result of shear strain; the changing shape of any body that is being plastically deformed can be completely described in terms of the shear strain occurring at each point in the body.† Furthermore, the relative amounts of shear strain occurring in different parts of a body under stress depend upon the relative rates of shear strain at those different points, so that if the dependence of the shear rate of any material on the temperature, shear stress, previous history, etc., were understood, the principles of plastic deformation would be known, and we could calculate how a body made of a given material, having a given shape, and subject to a specified system of forces, would change its shape with time. It may be said, then, that the problem of plasticity resolves itself into, first, the problem of the rates of pure shear processes, and second, the application of what is known about pure shear to actual cases. It is the purpose of this work to investigate the former problem —i.e., the dependence of shear rates on temperature, stress, etc.—from the standpoint of .recent developments in the field of chemical-rate theory and with particular reference to the phenomena occurring in the creep of metals and in the plastic flow of crystalline solids in general. It is left for the mechanical engineer, and perhaps the expert in hydrodynamics, to deal with the problem of app1ications.l Resolution of Macroscopic Shear into Microscopic Movements; Resemblance to Chemical Reactions Just as any large body is made up of many small units, or atoms, so macro-scopically observable shear is the result of many microscopic unit shear processes; just as the understanding of the behavior of large bodies demands the understanding of the atoms of which it is made, so the understanding of macroscopic shear demands the understanding of these fundamental unit processes. The study of shear from this "atomistic" point of view has made considerable progress. There has been fairly complete understanding of shear processes in gases for a long time, at least for non-turbulent flow, as a chapter on gaseous viscosity in any text on the kinetic theory of gases will prove' In recent years Andrade2 and Eyring3 have presented important theories for the flow of liquids and amorphous solids. Becker14 Orowan,5 Taylor,6 Burgers,7 and Kanter8 have considered the plastic flow of crystalline solids from this

Jan 1, 1941

By Walter Kauzmann

All viscous or plastic flow of incompressible matter is the result of shear strain; the changing shape of any body that is being plastically deformed can be completely described in terms of the shear strain occurring at each point in the body.† Furthermore, the relative amounts of shear strain occurring in different parts of a body under stress depend upon the relative rates of shear strain at those different points, so that if the dependence of the shear rate of any material on the temperature, shear stress, previous history, etc., were understood, the principles of plastic deformation would be known, and we could calculate how a body made of a given material, having a given shape, and subject to a specified system of forces, would change its shape with time. It may be said, then, that the problem of plasticity resolves itself into, first, the problem of the rates of pure shear processes, and second, the application of what is known about pure shear to actual cases. It is the purpose of this work to investigate the former problem —i.e., the dependence of shear rates on temperature, stress, etc.—from the standpoint of .recent developments in the field of chemical-rate theory and with particular reference to the phenomena occurring in the creep of metals and in the plastic flow of crystalline solids in general. It is left for the mechanical engineer, and perhaps the expert in hydrodynamics, to deal with the problem of app1ications.l Resolution of Macroscopic Shear into Microscopic Movements; Resemblance to Chemical Reactions Just as any large body is made up of many small units, or atoms, so macro-scopically observable shear is the result of many microscopic unit shear processes; just as the understanding of the behavior of large bodies demands the understanding of the atoms of which it is made, so the understanding of macroscopic shear demands the understanding of these fundamental unit processes. The study of shear from this "atomistic" point of view has made considerable progress. There has been fairly complete understanding of shear processes in gases for a long time, at least for non-turbulent flow, as a chapter on gaseous viscosity in any text on the kinetic theory of gases will prove' In recent years Andrade2 and Eyring3 have presented important theories for the flow of liquids and amorphous solids. Becker14 Orowan,5 Taylor,6 Burgers,7 and Kanter8 have considered the plastic flow of crystalline solids from this

Jan 1, 1941