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By Alexander Knoll, Dwight L. Baker

The work herein reported shows that galena in certain organic solutions of fatty acids becomes coated with lead soaps, and that this coating is not only highly water-repellent but is also repellent to certain organic liquids, particularly those of high surface tension; i.e., nitrobenzene, diphenylmethane. Wetting Properties of Galena in Nonaqueous Fatty Acid Solutions When a "captive bubble"I is withdrawn from a polished, plane galena surface under a nitrobenzene solution of stearic acid, the air bubble shows a decided tendency to "cling" to the mineral surface. The contact angle, therefore, was greater than zero, although it was not large enough to be measured quantitatively by the captive-bubble method." When pure nitrobenzene was substituted for the nitrobenzene-stearic acid solution, no clinging of the bubble was observed; viz., contact angle = zero. Although the contact angle developed in air-galena-nitrobenzene-fatty acid solution was small, the organic solvent repellency of the galena surface was great enough to enable good recovery in a laboratory flotation cell2 In Table I are given the results of flotation experiments using several different fatty acids dissolved in nitrobenzene.

Jan 1, 1943

By S. F. Ravitz

In his excellent book on the Principles of Flotation, Warkl makes the following significant statement concerning the theory of flotation: Two questions of first-rate importance must be considered . . . First, it must be decided whether the sulfide minerals require a collector in order that they may float, or whether as has been claimed, they possess an inherent float-ability and need no collector. Second, it must be decided whether the xanthate type of collector can react with or be adsorbed by the unchanged sulfide minerals themselves, or whether, as many claim, reaction with the collector is dependent upon initial oxidation of the mineral surface. In the theory of flotation there are no two questions of greater importance than these. Ravitz and Porter2 presented evidence that galena can be floated without a collector, and even without any reagent, provided oxidation products are thoroughly removed from its surface. They found also that thoroughly cleaned galena floated faster when xanthate was used than when a frother alone or no reagent was used, and that, without a collector, the recovery decreased gradually upon exposure of the mineral to air. Their work, however, has met with considerable criticism.l(127).3-6 This paper is presented to answer the objections that have been raised, and to present additional data that confirin their results. The apparatus used to provide oxygen-free conditions for flotation has been described in detail by Ravitz and Porter. An atmosphere of purified nitrogen was maintained within the apparatus; all water and solutions used were freed of dissolved air, and could be transferred where desired by the use of nitrogen Pressure; nitrogen was used as the gaseous medium for flotation. The flotation cell was essentially a glass cylinder 15 cm. long and 4.6 cm. in diameter. Near the bottom was sealed a fritted glass filter, which broke up the gas into small bubbles, and 6 cm. above this filter was a side arm through which the froth overflowed. The pulp was agitated by a glass impeller, which entered the cell through a mercury seal. For each test 17 grams of galena and 75 ml. of water were placed in the cell, after which the speed of the impeller and the rate of gas flow were adjusted. Water was added gradually during the test to keep the froth level at the proper height. The mineral was prepared and cleaned in the following manner. Exceptionally Pure galena was crushed by hand on a clean bucking board, screened to —I50+ 200 mesh, and deslimed on a 200-mesh sieve with a fine spray of water. It was then boiled on a hot plate for a number of hours with several changes of the desired cleaning solution, after which both the solution and the mineral were placed in the "mineral flask" of the apparatus. The cleaning solution was drained off, and the mineral was boiled with oxygen-free water

Jan 1, 1943

By S. F. Ravitz

In his excellent book on the Principles of Flotation, Warkl makes the following significant statement concerning the theory of flotation: Two questions of first-rate importance must be considered . . . First, it must be decided whether the sulfide minerals require a collector in order that they may float, or whether as has been claimed, they possess an inherent float-ability and need no collector. Second, it must be decided whether the xanthate type of collector can react with or be adsorbed by the unchanged sulfide minerals themselves, or whether, as many claim, reaction with the collector is dependent upon initial oxidation of the mineral surface. In the theory of flotation there are no two questions of greater importance than these. Ravitz and Porter2 presented evidence that galena can be floated without a collector, and even without any reagent, provided oxidation products are thoroughly removed from its surface. They found also that thoroughly cleaned galena floated faster when xanthate was used than when a frother alone or no reagent was used, and that, without a collector, the recovery decreased gradually upon exposure of the mineral to air. Their work, however, has met with considerable criticism.l(127).3-6 This paper is presented to answer the objections that have been raised, and to present additional data that confirin their results. The apparatus used to provide oxygen-free conditions for flotation has been described in detail by Ravitz and Porter. An atmosphere of purified nitrogen was maintained within the apparatus; all water and solutions used were freed of dissolved air, and could be transferred where desired by the use of nitrogen Pressure; nitrogen was used as the gaseous medium for flotation. The flotation cell was essentially a glass cylinder 15 cm. long and 4.6 cm. in diameter. Near the bottom was sealed a fritted glass filter, which broke up the gas into small bubbles, and 6 cm. above this filter was a side arm through which the froth overflowed. The pulp was agitated by a glass impeller, which entered the cell through a mercury seal. For each test 17 grams of galena and 75 ml. of water were placed in the cell, after which the speed of the impeller and the rate of gas flow were adjusted. Water was added gradually during the test to keep the froth level at the proper height. The mineral was prepared and cleaned in the following manner. Exceptionally Pure galena was crushed by hand on a clean bucking board, screened to —I50+ 200 mesh, and deslimed on a 200-mesh sieve with a fine spray of water. It was then boiled on a hot plate for a number of hours with several changes of the desired cleaning solution, after which both the solution and the mineral were placed in the "mineral flask" of the apparatus. The cleaning solution was drained off, and the mineral was boiled with oxygen-free water

Jan 1, 1943

By Keith Leonard Sutherland

This paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate-free.14 Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. Purity of Reagents The xanthates were purified in the usual manner.' Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes, This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystalline powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. Results The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the "absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1943

By Keith Leonard Sutherland

This paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate-free.14 Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. Purity of Reagents The xanthates were purified in the usual manner.' Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes, This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystalline powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. Results The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the "absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1943

By G. B. Walker, S. A. Falconer, S. J. Swainson, H. H. Vogel

During the past few years much interest and attention has been focused on a relatively new method of ore concentration, which utilizes the principles of sink and float and employs as the heavy medium a suspension in water of a finely ground solid, such as galena or ferrosilicon. Although a relatively recent development, much progress has already been made in applying heavy-media separation processes to a considerable number of ores. Eight plants in this country and abroad are now treating approximately 10 million tons of ore annually by heavy-media separation (sink-float) processes, including lead-zinc, lead, iron, garnet, tin and tungsten. At the annual meeting of the A.I.M.E. in 1941, three interesting papers (unpublished) dealing with heavy-media separation (sink-float) processes of ore concentration as practiced in four commercial units in the United States were presented by Victor Rakowsky, Grover Holt, Elmer Isern and Robert Ammon. These papers gave an excellent exposition of the principles of sink and float, as well as the operating practice in two iron-ore-beneficiation plants, the Harrison and the Merritt, of Butler Brothers, in Minnesota; the Central mill of the Eagle Picher Mining and Smelting Co.; and the Mascot mill, of the American Zinc, Lead and Smelting Co. Augmented by pictorial descriptions and a working model demonstrating the processes, these papers evoked a great deal of interest and discussion. In fact, in reporting the high lights of the meeting in the April 1941 issue of Mining and Metallurgy, Professor Taggart made the statement that " preconcentration by heavy suspension was Miss A.1.M.E 1941 so far as milling is concerned." Although to date the greatest application of heavy-media separation from the tonnage point of view has been for the treatment of lead, zinc and iron ores, these processes have a much wider field of usefulness. In this regard, it is to be noted that recently new heavy-media separation plants for treating cassiterite ore and garnet ore have been placed in successful operation. Moreover, numerous other types of ores have been found to respond well to these processes when tested on a semi-commercial scale, and it is expected that in the near future a considerable number of new plants will be erected. In view of the fact that heavy-media separation processes offer such attractive possibilities, particularly now, when the mining industry is being called on for an even larger production than ever before has been attempted, despite shortages of labor and supplies, it was felt that a description of some of the successful separations that have been worked out during the past year in the Ore Dressing Laboratory of the American Cyanamid Co. on a variety of ores of strategic importance would be of interest. The purpose of this paper, therefore, is to present the essential data relating to investigations of heavy-

Jan 1, 1943

By G. B. Walker, S. J. Swainson, S. A. Falconer, H. H. Vogel

During the past few years much interest and attention has been focused on a relatively new method of ore concentration, which utilizes the principles of sink and float and employs as the heavy medium a suspension in water of a finely ground solid, such as galena or ferrosilicon. Although a relatively recent development, much progress has already been made in applying heavy-media separation processes to a considerable number of ores. Eight plants in this country and abroad are now treating approximately 10 million tons of ore annually by heavy-media separation (sink-float) processes, including lead-zinc, lead, iron, garnet, tin and tungsten. At the annual meeting of the A.I.M.E. in 1941, three interesting papers (unpublished) dealing with heavy-media separation (sink-float) processes of ore concentration as practiced in four commercial units in the United States were presented by Victor Rakowsky, Grover Holt, Elmer Isern and Robert Ammon. These papers gave an excellent exposition of the principles of sink and float, as well as the operating practice in two iron-ore-beneficiation plants, the Harrison and the Merritt, of Butler Brothers, in Minnesota; the Central mill of the Eagle Picher Mining and Smelting Co.; and the Mascot mill, of the American Zinc, Lead and Smelting Co. Augmented by pictorial descriptions and a working model demonstrating the processes, these papers evoked a great deal of interest and discussion. In fact, in reporting the high lights of the meeting in the April 1941 issue of Mining and Metallurgy, Professor Taggart made the statement that " preconcentration by heavy suspension was Miss A.1.M.E 1941 so far as milling is concerned." Although to date the greatest application of heavy-media separation from the tonnage point of view has been for the treatment of lead, zinc and iron ores, these processes have a much wider field of usefulness. In this regard, it is to be noted that recently new heavy-media separation plants for treating cassiterite ore and garnet ore have been placed in successful operation. Moreover, numerous other types of ores have been found to respond well to these processes when tested on a semi-commercial scale, and it is expected that in the near future a considerable number of new plants will be erected. In view of the fact that heavy-media separation processes offer such attractive possibilities, particularly now, when the mining industry is being called on for an even larger production than ever before has been attempted, despite shortages of labor and supplies, it was felt that a description of some of the successful separations that have been worked out during the past year in the Ore Dressing Laboratory of the American Cyanamid Co. on a variety of ores of strategic importance would be of interest. The purpose of this paper, therefore, is to present the essential data relating to investigations of heavy-

Jan 1, 1943

By Foster Fraas

Most commercial electrostatic separators utilize the electrical property of conductivity, but although based on the same principles, they are constructed in a variety of forms, a common one being the simple roll type. Some information obtained during an investigation of that type of separator, and which indirectly is applicable to other types, is presented here. In Fig. I material discharged from hopper 6 is fed onto grounded rotating roll 2. Electrode 3 is at a high electrical potential with respect to roll 2, and any conductive particle in contact with roll 2 therefore acquires an electrical charge of such polarity that, when present in the electrical field, the force on it is in the direction of electrode 3. A detailed description of the charging by conductance as utilized in electrostatic separators may be found in a previous publication.' As a result of this force, the path of the projected particle is changed in increasing amounts in the direction toward region C as the magnitude of the charge is increased. With the dividing edge 4 the projected particles may be divided into two fractions —those in region C designated as "deflected" or"deflectant"and those in region B designated as "residue." When material is passed over the roll only once, a complete separation is seldom obtained, therefore most commercial separators contain several roll-separator units in series, and some practical machines use as many as I2. In this paper a "pass" means the passage of material over a single-roll unit. The procedure is to repass either residue B with a low potential on electrode 3 or deflectant C with a high potential on 3. Most electrostatic separations follow a flowsheet of roughing and cleaning either the concentrate or the tailing, or both. In a specific instance, a dry, heated mixture of wet cleaned chromite and garnet from an

Jan 1, 1943

By Foster Fraas

Most commercial electrostatic separators utilize the electrical property of conductivity, but although based on the same principles, they are constructed in a variety of forms, a common one being the simple roll type. Some information obtained during an investigation of that type of separator, and which indirectly is applicable to other types, is presented here. In Fig. I material discharged from hopper 6 is fed onto grounded rotating roll 2. Electrode 3 is at a high electrical potential with respect to roll 2, and any conductive particle in contact with roll 2 therefore acquires an electrical charge of such polarity that, when present in the electrical field, the force on it is in the direction of electrode 3. A detailed description of the charging by conductance as utilized in electrostatic separators may be found in a previous publication.' As a result of this force, the path of the projected particle is changed in increasing amounts in the direction toward region C as the magnitude of the charge is increased. With the dividing edge 4 the projected particles may be divided into two fractions —those in region C designated as "deflected" or"deflectant"and those in region B designated as "residue." When material is passed over the roll only once, a complete separation is seldom obtained, therefore most commercial separators contain several roll-separator units in series, and some practical machines use as many as I2. In this paper a "pass" means the passage of material over a single-roll unit. The procedure is to repass either residue B with a low potential on electrode 3 or deflectant C with a high potential on 3. Most electrostatic separations follow a flowsheet of roughing and cleaning either the concentrate or the tailing, or both. In a specific instance, a dry, heated mixture of wet cleaned chromite and garnet from an

Jan 1, 1943

By Arthur Taggart

Recent jig practice has shown such marked departures from the pronouncements of the textbooks, particularly as to particle size recovered and size range of feed, as to make it desirable to reexamine the mechanism of jig action. This paper presents the results of such a study. The general conclusions of the Paper are: I. A jig bed is a bi-functioned as well as bi-parted body. The upper layer comprises a plastic stream moving slowly in a substantially horizontal direction from feed lip to tail board. It serves to rough out tailing and light middling and to pick up heavy middling and lift it out 01 the jig box. The lower layer acts as the ultimate separating means by absorbing concentrate and rejecting heavy middling. 2. The separating function of the lower layer is performed in three definitely diflerent ways, depending upon the relative sizes of the grains presented to it and those composing it. Experimental The experimental work consisted of close and long-continued visual observations of operating beds in a plunger jig, eccentric driven, and in determinations of the settling rates of various metal spheres through a quartz bed under various conditions of operation. Falling velocities were measured by an ingenious method devised by A. 6. Dorenfeld, a student in the Mining Department at Colum- bia. Spheres of different metallic alloys, 3/8-in. diameter, were cast with a short piece of fine copper wire frozen in to Serve for suspension-A short piece of black cotton thread was looped to the top of the wire to serve as an indicator. The set-up for a test is shown in Fig. I. The thread should be boiled, if necessary, to make it freely water absorbent. The piece of clean plate glass D is supported rigidly at the proper height in a vertical position. The white scale E is similarly supported behind the glass. At the beginning of a test, D is filmed with water by holding it (best with clean rubber finger cots) under running tap water. It is then clamped in approximate position and C, already wet, is laid across it and drawn straight and vertical with the upper end at or near the top of D, and the ball A slightly above the top of the expanded bed. The water film holds the string to the glass. For a test the string is released, its upper end position noted just after the top of the ball becomes submerged, when the corresponding time is read, and thereafter simultaneous readings of position and time are taken as desired. Results of the visual studies of the bed are given at the pertinent places in the following discussion. Results of the settling tests are summarized in Figs- 2 and 3. Definitions The name bed as used herein refers to the entire mixture of solids and water filling the jig box. A layer is a stratum of a bed composed of particles of substantially the same specific gravities. A granular product is long-range when it approximates a crushed or ground product limited as to upper size only; a short-rafzge product is one closely sized. A bed is loaded when operating with continuous feed and discharge of products; it is unloaded when pulsating norma11y but neither being fed nor

Jan 1, 1943

By Arthur Taggart

Recent jig practice has shown such marked departures from the pronouncements of the textbooks, particularly as to particle size recovered and size range of feed, as to make it desirable to reexamine the mechanism of jig action. This paper presents the results of such a study. The general conclusions of the Paper are: I. A jig bed is a bi-functioned as well as bi-parted body. The upper layer comprises a plastic stream moving slowly in a substantially horizontal direction from feed lip to tail board. It serves to rough out tailing and light middling and to pick up heavy middling and lift it out 01 the jig box. The lower layer acts as the ultimate separating means by absorbing concentrate and rejecting heavy middling. 2. The separating function of the lower layer is performed in three definitely diflerent ways, depending upon the relative sizes of the grains presented to it and those composing it. Experimental The experimental work consisted of close and long-continued visual observations of operating beds in a plunger jig, eccentric driven, and in determinations of the settling rates of various metal spheres through a quartz bed under various conditions of operation. Falling velocities were measured by an ingenious method devised by A. 6. Dorenfeld, a student in the Mining Department at Colum- bia. Spheres of different metallic alloys, 3/8-in. diameter, were cast with a short piece of fine copper wire frozen in to Serve for suspension-A short piece of black cotton thread was looped to the top of the wire to serve as an indicator. The set-up for a test is shown in Fig. I. The thread should be boiled, if necessary, to make it freely water absorbent. The piece of clean plate glass D is supported rigidly at the proper height in a vertical position. The white scale E is similarly supported behind the glass. At the beginning of a test, D is filmed with water by holding it (best with clean rubber finger cots) under running tap water. It is then clamped in approximate position and C, already wet, is laid across it and drawn straight and vertical with the upper end at or near the top of D, and the ball A slightly above the top of the expanded bed. The water film holds the string to the glass. For a test the string is released, its upper end position noted just after the top of the ball becomes submerged, when the corresponding time is read, and thereafter simultaneous readings of position and time are taken as desired. Results of the visual studies of the bed are given at the pertinent places in the following discussion. Results of the settling tests are summarized in Figs- 2 and 3. Definitions The name bed as used herein refers to the entire mixture of solids and water filling the jig box. A layer is a stratum of a bed composed of particles of substantially the same specific gravities. A granular product is long-range when it approximates a crushed or ground product limited as to upper size only; a short-rafzge product is one closely sized. A bed is loaded when operating with continuous feed and discharge of products; it is unloaded when pulsating norma11y but neither being fed nor

Jan 1, 1943

By Shiou-Chuan Sun

There are several postulations for the mechanism of slime-coating. Incel proposed the electrostatic hypothesis, del Giudice2 suggested the chemical theory; Bankoff3 reported that slime-coating is inhibited whenever the surfaces of the slime particles are ionized sufficiently for Brownian movement to occur, and is facilitated when they are not. These postulations were examined by experiments involving the Burton tube, the cataphoretic cell, and slime-coating. The techniques involved will be described elsewhere in this paper. The electrostatic hypothesis, supported by migration experiments in a Burton tube, was abandoned by del Giudice.2 Experiments of mineral migration in a Burton tube. after the idea of Ince with modification, indicated that this apparatus was inefficient for accurate observation. A cataphoretic cell was constructed. The experimental data, as shown in this paper, enable the correlation and advancing of this hypothesis. Del Giudice's chemical hypothesis considered that slime particles are attached to the galena surfaces by a cement formed as the result of a metathetical reaction between the sulphide and the slime particles. Applying this hypothesis, the calcite slime particles were cemented to the galena surface by the formation of a cementing lead carbonate. In a similar way, lead silicate was considered as the cement of quartz slime coating on galena. Experiments verifying this hypothesis were carried out according to the following procedure: Fresh mineral particles selected from the central part of the broken lumps and examined first under a microscope for ascertaining a clean surface were placed in a small beaker (1.5-in. dia. by 2.5 in. deep) half filled with one kind of slime pulp. The dilution of all slime pulp was 4:I and the particle size of slime was minus 400-mesh. After agitation for 5 min. the specimen was removed by a sharp-end tong and washed gently three times in three separate distilled water baths. It was dried before a small electrical fan and examined immediately under a microscope. A photograph was made of the observation. With reference to the published solubilities,' several of these experiments, which contradict the chemical hypothesis, are listed as following: I. The coating of fluorite slime on the galena surface was light but the coating of galena slime on the fluorite surface was heavy. In a similar way, the coating of quartz slime on the galena was fairly light, but the coating of galena slime on the quartz particle was heavy. According to the chemical hypothesis, using the same constituents and regardless of which is the slime, the density of the coating should be expected to be the same. This, however, as shown above, is not true. Moreover, fluorite (CaF2), having a solubility of 16 mg.4a per liter of water, should not be

Jan 1, 1943

By Shiou-Chuan Sun

There are several postulations for the mechanism of slime-coating. Incel proposed the electrostatic hypothesis, del Giudice2 suggested the chemical theory; Bankoff3 reported that slime-coating is inhibited whenever the surfaces of the slime particles are ionized sufficiently for Brownian movement to occur, and is facilitated when they are not. These postulations were examined by experiments involving the Burton tube, the cataphoretic cell, and slime-coating. The techniques involved will be described elsewhere in this paper. The electrostatic hypothesis, supported by migration experiments in a Burton tube, was abandoned by del Giudice.2 Experiments of mineral migration in a Burton tube. after the idea of Ince with modification, indicated that this apparatus was inefficient for accurate observation. A cataphoretic cell was constructed. The experimental data, as shown in this paper, enable the correlation and advancing of this hypothesis. Del Giudice's chemical hypothesis considered that slime particles are attached to the galena surfaces by a cement formed as the result of a metathetical reaction between the sulphide and the slime particles. Applying this hypothesis, the calcite slime particles were cemented to the galena surface by the formation of a cementing lead carbonate. In a similar way, lead silicate was considered as the cement of quartz slime coating on galena. Experiments verifying this hypothesis were carried out according to the following procedure: Fresh mineral particles selected from the central part of the broken lumps and examined first under a microscope for ascertaining a clean surface were placed in a small beaker (1.5-in. dia. by 2.5 in. deep) half filled with one kind of slime pulp. The dilution of all slime pulp was 4:I and the particle size of slime was minus 400-mesh. After agitation for 5 min. the specimen was removed by a sharp-end tong and washed gently three times in three separate distilled water baths. It was dried before a small electrical fan and examined immediately under a microscope. A photograph was made of the observation. With reference to the published solubilities,' several of these experiments, which contradict the chemical hypothesis, are listed as following: I. The coating of fluorite slime on the galena surface was light but the coating of galena slime on the fluorite surface was heavy. In a similar way, the coating of quartz slime on the galena was fairly light, but the coating of galena slime on the quartz particle was heavy. According to the chemical hypothesis, using the same constituents and regardless of which is the slime, the density of the coating should be expected to be the same. This, however, as shown above, is not true. Moreover, fluorite (CaF2), having a solubility of 16 mg.4a per liter of water, should not be

Jan 1, 1943

By Arthur F. Taggart, A. W. Thomas, T.C. Fitt

It was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a component of the pulp, of a mass solubility of the general order of a fraction of a milligram to I 5 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.= The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends. to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. Experimental Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well be~ond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipitation from hydrochloric acid solution of arsenic-free zinc, and was washed as lot I. Lot 3 was prepared by heating a portion of lot 2 in absence of air at 1200° to r300°C. for one hour."

Jan 1, 1943

By Arthur F. Taggart, T. C. Fitt, A. W. Thomas

It was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a component of the pulp, of a mass solubility of the general order of a fraction of a milligram to I 5 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.= The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends. to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. Experimental Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well be~ond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipitation from hydrochloric acid solution of arsenic-free zinc, and was washed as lot I. Lot 3 was prepared by heating a portion of lot 2 in absence of air at 1200° to r300°C. for one hour."

Jan 1, 1943

By Oliver C. Ralston, James E. Norman

Separation of minerals by froth flotation is rightly called an art. It can truthfully be said that no two ores separate in the same way. The difference in results obtained when natural and synthetic mixtures of minerals are separated is so great that such tests frequently have been worthless in attempting to select conditions in which a natural mixture will separate. With a few rare exceptions, the natural mixture is much more difficult to treat than a synthetic mixture, and a much poorer separation is obtained. Perhaps several experimenters have wondered why 10 or 20 per cent of a mineral being floated from an ore does not float and is different from the 90 or 80 per cent that is recovered. In experimental tests on pure sphalerite, observers' have noted that varying amounts of sphalerite may be froth-floated with pine oil alone, the amount recovered in the froth depending apparently upon the source of the sulphide. The only explanation of results such as these, barring insufficiency of frother or time of flotation, is that the surface of the mineral floated is different from that of the mineral depressed. This difference often has been found to be caused by natural contamination of mineral surfaces, apparently brought about by weathering and exposure to natural solutions. There is virtually no rock that is absolutely unweathered. One of the writers had an exceedingly instructive experience in 1931 while working with United Verde copper-zinc iron sulphide ore in Arizona. Nonselective flotation of chalcopyrite and sphalerite away from some of the pyrite was all that could be accomplished. All known depressants produced only slight effect. Sodium cyanide showed some effect, but so much had to be used that only a small amount of chalcopyrite could be

Jan 1, 1939

By Oliver C. Ralston, James E. Norman

Separation of minerals by froth flotation is rightly called an art. It can truthfully be said that no two ores separate in the same way. The difference in results obtained when natural and synthetic mixtures of minerals are separated is so great that such tests frequently have been worthless in attempting to select conditions in which a natural mixture will separate. With a few rare exceptions, the natural mixture is much more difficult to treat than a synthetic mixture, and a much poorer separation is obtained. Perhaps several experimenters have wondered why 10 or 20 per cent of a mineral being floated from an ore does not float and is different from the 90 or 80 per cent that is recovered. In experimental tests on pure sphalerite, observers' have noted that varying amounts of sphalerite may be froth-floated with pine oil alone, the amount recovered in the froth depending apparently upon the source of the sulphide. The only explanation of results such as these, barring insufficiency of frother or time of flotation, is that the surface of the mineral floated is different from that of the mineral depressed. This difference often has been found to be caused by natural contamination of mineral surfaces, apparently brought about by weathering and exposure to natural solutions. There is virtually no rock that is absolutely unweathered. One of the writers had an exceedingly instructive experience in 1931 while working with United Verde copper-zinc iron sulphide ore in Arizona. Nonselective flotation of chalcopyrite and sphalerite away from some of the pyrite was all that could be accomplished. All known depressants produced only slight effect. Sodium cyanide showed some effect, but so much had to be used that only a small amount of chalcopyrite could be

Jan 1, 1939

By K. O. Stamm, B. A. Rogers

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By B. A. Rogers, K. O. Stamm

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942