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By John Tyssowski

In 1925, Harry Howard Stout, then metallurgist for Phelps Dodge Corporation, while investigating the cleaning of cathode copper by various gases at elevated temperatures below the melting point of the metal, observed in the laboratory that particles of pure copper heated in a closed tube filled with hydrogen seemingly "stuck together." By further investigation he found that there was actual crystal growth across the boundaries of the particles of pure metal; in other words, there was a complete new crystal realignment and growth throughout the newly formed copper mass. It was coalescence, not adhesion; the several particles had become one unit. From this discovery has been developed the coalescence process, whereby copper of cathode purity is squirted out in semifabricated form from an extrusion press, by the application of about 3000 tons pressure on a 10-in. piston. Stout decided that cathode copper produced by electrolytic deposition was the logical source of the pure copper required for the coalescence process, but as there was no way of reducing the ordinary tough commercial cathodes to the small particles required he was confronted by a serious problem at the outset. Under his direction, this problem was solved by William H. Osborn and Harry Howard Stout, Jr. They developed the process and technique for producing cathode copper in brittle, friable form, and to them must be given the greater part of the credit for this phase of the development program as well as for that relating to the gas cleaning of the cathode particles. Concurrently, the three metallurgists worked on the problem of effecting a complete union of the cathode particles. Adequate washing was all that was needed to free the particles from electrolyte solution and slimes. A press was designed to produce briquettes of the proper porosity and density, and a method was devised of removing surface oxidation from the particles of cathode, by treatment in an atmosphere of deoxidizing gas at an elevated temperature. The temperature was determined at which the surface cleansing and preheating could be done in one operation, and for this a charging and preheating furnace in which there is maintained a positive pressure of deoxidizing gas atmosphere was designed. And finally, a method of feeding the heated briquettes of deoxidized cathode copper into an extrusion press without contamination from the air was evolved. For the final stage, a press was required because not only heat but pressure was required to obtain complete growth of the new crystals between the cathode particles as well as the elimination of all voids or non-coalesced areas. All essential stages of the process are protected by patents or patent applications in the United States and principal foreign countries, and the copper is produced on a commercial scale.

Jan 1, 1941

By S. M. Marshall, A. C. Richardson, H. Y. Yancey

A year ago, Marshall and Bird presented a paper in which a new method of measuring the agglutinating power of coal was described.' The procedure used was to determine the strength of a button containing 10 parts sand and one part coal, formed by carbonizing the mixture in a crucible in an electric furnace. The result of the determination was reported as the total weight in grams required to bring about complete destruction of the button. Correlations were shown between the agglutinating value and some of the characteristics of the different coals that were investigated. This agglutinating test has been in use fairly continuously during the past five years for coals of widely differing coking qualities, and it has shown reasonably concordant results accurate enough for commercial use, although there are many features of the test which should have further scientific study. During the past year a study has been made of some coals of low coking strengths, and incidental to the main investigation some data which appear to be of interest and value were obtained on the loss in agglutinating power caused by exposure to the air. Three coals were investigated, all of which were of the Tertiary age; two were from one field in Asia, and one from a field in the United States. The three were similar, as shown by the proximate and ultimate analyses in Table 1 (moisture-free basis). Coals SA and RA generally contain about 5 per cent. moisture and coal P about 3.5 per cent. moisture on the as-received basis. The large difference in the ash contents of the coals, amounting to practically 10 per cent. between SA and RA, and P, makes difficult a direct comparison of their qualities. In the second section of Table 1 the figures have been put upon an ash-free basis., This table shows that these coals are closely alike. The ultimate analyses are almost identical except for the higher nitrogen content of

Jan 1, 1930

By N. A. MacLeod

Ball wear in wet grinding mills has been the subject of considerable discussion in the last few years. Its importance to millmen is obvious in view of the fact that ball wear may cost from 2 to 4 per ton of ore for the more fortunate operators and many times this cost when a refractory ore must be reduced to a fine state of comminution. Consequently, any factual information that may be obtained on the nature of ball wear may be applied to introduce changes leading to lower ball consumption and therefore also to lower costs. In 1940, while employed with the Britannia Mining and Smelting Co., Britannia Beach, B.C., I had occasion to investigate factors that might affect ball consumption. We performed a number of tests, which will be briefly described. These tests originated as a result of changing from a 3½-in. ball to a 2-in. ball of different type of manufacture and were motivated by the desire to obtain the best possible type of 2-in. ball. Our testing was helped by the fact that the company operated a one-ton electric furnace, so that it was quite easy to make steel changes. It should be emphasized at the beginning that these tests produced results that in their general application to milling should be interpreted qualitatively rather than quantitatively. As will be evident in the description of the method used in testing, the balls were subjected to an intermittent batch grinding treatment, which may have produced results in rate of steel wear that may not have an accurate correlation with steel consumption in full scale mill operation. However, with this bed and rather arbitrary method of testing, results were obtained that may be of some interest and may stimulate further work on this subject. Unfortunately, owing to pressure of war work, our tests, which we had intended to repeat on a continuous grinding operation, had to be discontinued. Method of Testing Tests Were made in a Small cylindrical mill, rotating at 72 r.P.m. Internal dimensions of the mill were 10½-in. dia. by 9 in. The cylindrical inner surface was lined with rubber and the two ends were formed by steel plates. A charge of 2000 grams dry feed and 2000 C.C. of water was added evev 2 hr., the mill being drained of pulp before the addition of each charge, by tilting and sluicing with water. The mill was run On afternoon and night shift for daily periods of about 15 hr. total grinding time, and each test lasted from 60 to 150 hr. This batch method of testing involved a higher average pulp temperature in the mill, which undoubtedly affected comparative results in Some of the tests. Hardness oF Ball vs. Wear In these tests, special "eutectoid" steel balls were used, some of which were chill-Cut and quenched, some sand-cast and quenched, and some sand-cast and annealed to a dead soft condition. The results obtained, using as mill feed an ore containing considerable free quartz and

Jan 1, 1947

By N. A. MacLeod

Ball wear in wet grinding mills has been the subject of considerable discussion in the last few years. Its importance to millmen is obvious in view of the fact that ball wear may cost from 2 to 4 per ton of ore for the more fortunate operators and many times this cost when a refractory ore must be reduced to a fine state of comminution. Consequently, any factual information that may be obtained on the nature of ball wear may be applied to introduce changes leading to lower ball consumption and therefore also to lower costs. In 1940, while employed with the Britannia Mining and Smelting Co., Britannia Beach, B.C., I had occasion to investigate factors that might affect ball consumption. We performed a number of tests, which will be briefly described. These tests originated as a result of changing from a 3½-in. ball to a 2-in. ball of different type of manufacture and were motivated by the desire to obtain the best possible type of 2-in. ball. Our testing was helped by the fact that the company operated a one-ton electric furnace, so that it was quite easy to make steel changes. It should be emphasized at the beginning that these tests produced results that in their general application to milling should be interpreted qualitatively rather than quantitatively. As will be evident in the description of the method used in testing, the balls were subjected to an intermittent batch grinding treatment, which may have produced results in rate of steel wear that may not have an accurate correlation with steel consumption in full scale mill operation. However, with this bed and rather arbitrary method of testing, results were obtained that may be of some interest and may stimulate further work on this subject. Unfortunately, owing to pressure of war work, our tests, which we had intended to repeat on a continuous grinding operation, had to be discontinued. Method of Testing Tests Were made in a Small cylindrical mill, rotating at 72 r.P.m. Internal dimensions of the mill were 10½-in. dia. by 9 in. The cylindrical inner surface was lined with rubber and the two ends were formed by steel plates. A charge of 2000 grams dry feed and 2000 C.C. of water was added evev 2 hr., the mill being drained of pulp before the addition of each charge, by tilting and sluicing with water. The mill was run On afternoon and night shift for daily periods of about 15 hr. total grinding time, and each test lasted from 60 to 150 hr. This batch method of testing involved a higher average pulp temperature in the mill, which undoubtedly affected comparative results in Some of the tests. Hardness oF Ball vs. Wear In these tests, special "eutectoid" steel balls were used, some of which were chill-Cut and quenched, some sand-cast and quenched, and some sand-cast and annealed to a dead soft condition. The results obtained, using as mill feed an ore containing considerable free quartz and

Jan 1, 1947

By Eugene F. Poncelet

Glass squares compressed on edge by steel jaws in poor contact with them developed jagged "partial-contact" cracks caused by the formation of local tensile stresses. Compressed by steel jaws in perfect contact, they developed smooth "release cracks" during release of the pressure, caused by the formation of local tensile stresses during the release of the pressure. All these cracks were parallel to the pressure. A Microflash photograph of a disintegrating specimen under sufficient pressure reveals a network of fractures roughly normal to each other, also "release cracks" and a disintegration cloud. The Griffith theory is amended to account for the formation of a first crack. A new theory, based on the theory of thermal agitation and wave propagation, is proposed to account for the progress, velocity and forking of cracks. The network of fractures is shown to have been caused by reflection at a free boundary of pressure pulses emanating from a first crack. Postulating equal distribution of energy in the pulses emitted on either side by a crack in particles, the smaller fragments are shown to continue fracturing preferentially while some of the coarser fragments remain as residual pieces. As comminution of the smaller fragments proceeds, the solid is reduced to a collection of residual particles of smaller and smaller sizes, accounting for the disintegration cloud. Experimental Procedure Apparatus A crushing device was built, consisting of a steel frame and two polished, hardened steel jaws to crush plate-glass samples. This device was placed between the plates of a hydraulic press (Fig. I). For centering the pressure, the upper jaw was guided vertically and provided with a rounded top. Later it was replaced by a steel jaw ground out of a 2½-in. steel ball, the lower surface being ground to an optical flat (Fig. 2). Four rollers were used to eliminate side thrust. Screws and centering blocks served to center the specimen in the crushing device. Hard steel shims placed under the shoulder of the upper jaw limited the "follow through'' of the jaw after failure of the specimen. Stress distribution was first examined with a polariscope mounted on an optical bench, using monochromatic light. It was found convenient to mount polaroid, quarter wave and monochromatic plates directly on the device itself. A Microflash unit* was used as light source for the photographs. A gold-paint pattern was fused on the plate-glass specimens and connected into the spark-

Jan 1, 1947

By Eugene F. Poncelet

Glass squares compressed on edge by steel jaws in poor contact with them developed jagged "partial-contact" cracks caused by the formation of local tensile stresses. Compressed by steel jaws in perfect contact, they developed smooth "release cracks" during release of the pressure, caused by the formation of local tensile stresses during the release of the pressure. All these cracks were parallel to the pressure. A Microflash photograph of a disintegrating specimen under sufficient pressure reveals a network of fractures roughly normal to each other, also "release cracks" and a disintegration cloud. The Griffith theory is amended to account for the formation of a first crack. A new theory, based on the theory of thermal agitation and wave propagation, is proposed to account for the progress, velocity and forking of cracks. The network of fractures is shown to have been caused by reflection at a free boundary of pressure pulses emanating from a first crack. Postulating equal distribution of energy in the pulses emitted on either side by a crack in particles, the smaller fragments are shown to continue fracturing preferentially while some of the coarser fragments remain as residual pieces. As comminution of the smaller fragments proceeds, the solid is reduced to a collection of residual particles of smaller and smaller sizes, accounting for the disintegration cloud. Experimental Procedure Apparatus A crushing device was built, consisting of a steel frame and two polished, hardened steel jaws to crush plate-glass samples. This device was placed between the plates of a hydraulic press (Fig. I). For centering the pressure, the upper jaw was guided vertically and provided with a rounded top. Later it was replaced by a steel jaw ground out of a 2½-in. steel ball, the lower surface being ground to an optical flat (Fig. 2). Four rollers were used to eliminate side thrust. Screws and centering blocks served to center the specimen in the crushing device. Hard steel shims placed under the shoulder of the upper jaw limited the "follow through'' of the jaw after failure of the specimen. Stress distribution was first examined with a polariscope mounted on an optical bench, using monochromatic light. It was found convenient to mount polaroid, quarter wave and monochromatic plates directly on the device itself. A Microflash unit* was used as light source for the photographs. A gold-paint pattern was fused on the plate-glass specimens and connected into the spark-

Jan 1, 1947

By Neil O. Johnson

In the cyanidation of gold, silver and mixed ores, the solids, suspended in the pulp after fine grinding, primary settling and scries agitation arc subjected to a washing step known, generally, as countercurrent decanta-tion, abbreviated C.C.D The conventional C.C.D. plant consists of a series of separate thickeners—three to five in number—arranged in series on slightly different elevations. Solids settled in the first thickener are pumped at maximum density into the second thickener, where they arc diluted with weak solution overflowing the third. After settling in the second thickener they are pumped to the third, where the process of repulping with still weaker solution is repeated, and so on throughout the system, until they reach the last thickener and are repulped with barren solution or water. Recently there has been developed a new type of thickener, known as the Dorr Washing Tray Thickener, consisting of up to five individual thickeners, which performs in a single unit all the functions of a conven-tional C.C.D plant. Fig. 1 illustrates the essential features. It is a multicompartment tray thickener, in which the trays operate in scries instead of in parallel for countercurrent washing. Feed enters the top compartment via a central, semisubmerged feed well. Strong solution overflows into a peripheral launder. Solids settle to the bottom, are raked to the center and flow into the top of the second compartment, directly below, via an inverted cup and scal. Solids pass downward, compartment by compartment, against a counter flow of wash solution and finally of fresh water. Thus, in accord-:trice with the basic C.C.D. principle, the solids transfer the dissolved metal content to the wash solution and finally are removed by a diaphragm pump from the bottom compartment virtually free of valuable material. Similarly, the wash water, as it flows through the system, becomes increasingly enriched in dissolved metal until it overflows from compartment two and returns to the process.

Jan 1, 1939

By Neil O. Johnson

In the cyanidation of gold, silver and mixed ores, the solids, suspended in the pulp after fine grinding, primary settling and scries agitation arc subjected to a washing step known, generally, as countercurrent decanta-tion, abbreviated C.C.D The conventional C.C.D. plant consists of a series of separate thickeners—three to five in number—arranged in series on slightly different elevations. Solids settled in the first thickener are pumped at maximum density into the second thickener, where they arc diluted with weak solution overflowing the third. After settling in the second thickener they are pumped to the third, where the process of repulping with still weaker solution is repeated, and so on throughout the system, until they reach the last thickener and are repulped with barren solution or water. Recently there has been developed a new type of thickener, known as the Dorr Washing Tray Thickener, consisting of up to five individual thickeners, which performs in a single unit all the functions of a conven-tional C.C.D plant. Fig. 1 illustrates the essential features. It is a multicompartment tray thickener, in which the trays operate in scries instead of in parallel for countercurrent washing. Feed enters the top compartment via a central, semisubmerged feed well. Strong solution overflows into a peripheral launder. Solids settle to the bottom, are raked to the center and flow into the top of the second compartment, directly below, via an inverted cup and scal. Solids pass downward, compartment by compartment, against a counter flow of wash solution and finally of fresh water. Thus, in accord-:trice with the basic C.C.D. principle, the solids transfer the dissolved metal content to the wash solution and finally are removed by a diaphragm pump from the bottom compartment virtually free of valuable material. Similarly, the wash water, as it flows through the system, becomes increasingly enriched in dissolved metal until it overflows from compartment two and returns to the process.

Jan 1, 1939

By H. Brevers, Maurice Rey

Through circumstances connected with the war, the senior author lost his records, therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH of about 8. Flotation of Realgar Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arseno-pyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed non-polar and the other polar, a distinction that has been stressed in a previous paper.' Depression of Realgar and Flotation of Cinnabar Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1943

By Maurice Rey, H. Brevers

Through circumstances connected with the war, the senior author lost his records, therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH of about 8. Flotation of Realgar Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arseno-pyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed non-polar and the other polar, a distinction that has been stressed in a previous paper.' Depression of Realgar and Flotation of Cinnabar Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

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 Alfonso Rizo-Patrón, A.M. Gaudin

Previous studies of activation in flotation have directed attention to the action of the activator on the mineral to be floated rather than to the relationship of the activator to the collector. The latter phase of the problem, however, seems to have definite scientific, if not also practical, interest. In the investigation reported in this paper, experiments were carried out, largely with quartz as subject, barium as activator, and oleate as collector. The results obtained indicate that a I: I ratio of collector ion to activator ion gives optimum results, and that a 2:1 ratio almost fails to achieve activation and flotation. Yet, a 2:I ratio would have been expected on stoichiometric grounds, had the coating been a normal salt of the activator ion with the collector ion, since barium is a divalent cation and oleate a monovalent anion. To interpret and rationalize the observations, considerations of the crystal chemistry of quartz are helpful. The point of view to which these considerations lead may be of general applicability to systems involving suspensions of solids in liquids; they confirm that an adsorbed coating is inescapable. Apparatus and Supplies The experimental work consisted in barium-ion abstraction tests, hydrogen-ion and hydroxyl-ion abstraction tests, flotation tests, and determinations of the surface of the crushed quartz. The flotation machine was built according to the design of D. W. McGlashan.* It consists of a drill press in which the bit has been replaced by a stainless-steel impellor surrounding a stainless-steel sta-tor, as in the Fagergren laboratory machine. The air intake is controlled by a valve, and the cell consists of a beaker. The quartz was obtained from vein quartz stored in large chunks. It was first crushed to 20 mesh, then sized on a 28-mesh screen. The 20 to 28-mesh size alone was retained for use. This size was freed of coarse iron by passage through a Ball-Norton magnetic separator, bleached with boiling hydrochloric acid to remove residual abraded iron, washed with distilled water until the washings were thoroughly free of ferrous, ferric, and excess hydrogen ion, and stored in covered Pyrex beakers under water until used. The barium was used as barium chloride, Baker's analyzed C. P. The oleate was used as sodium oleate. It was prepared from sodium hydroxide, Baker's analyzed C. P., and oleic acid purified by R. R. de Arellano3 in the laboratories at the Massachusetts Institute of Technology. The purification procedure was elaborated from the recent $researches of Brown and Shinowara.2 It consisted in: (I) saponification of olive oil with potassium

Jan 1, 1943

By Alfonso Rizo-Patrón, A. M. Gaudin

Previous studies of activation in flotation have directed attention to the action of the activator on the mineral to be floated rather than to the relationship of the activator to the collector. The latter phase of the problem, however, seems to have definite scientific, if not also practical, interest. In the investigation reported in this paper, experiments were carried out, largely with quartz as subject, barium as activator, and oleate as collector. The results obtained indicate that a I: I ratio of collector ion to activator ion gives optimum results, and that a 2:1 ratio almost fails to achieve activation and flotation. Yet, a 2:I ratio would have been expected on stoichiometric grounds, had the coating been a normal salt of the activator ion with the collector ion, since barium is a divalent cation and oleate a monovalent anion. To interpret and rationalize the observations, considerations of the crystal chemistry of quartz are helpful. The point of view to which these considerations lead may be of general applicability to systems involving suspensions of solids in liquids; they confirm that an adsorbed coating is inescapable. Apparatus and Supplies The experimental work consisted in barium-ion abstraction tests, hydrogen-ion and hydroxyl-ion abstraction tests, flotation tests, and determinations of the surface of the crushed quartz. The flotation machine was built according to the design of D. W. McGlashan.* It consists of a drill press in which the bit has been replaced by a stainless-steel impellor surrounding a stainless-steel sta-tor, as in the Fagergren laboratory machine. The air intake is controlled by a valve, and the cell consists of a beaker. The quartz was obtained from vein quartz stored in large chunks. It was first crushed to 20 mesh, then sized on a 28-mesh screen. The 20 to 28-mesh size alone was retained for use. This size was freed of coarse iron by passage through a Ball-Norton magnetic separator, bleached with boiling hydrochloric acid to remove residual abraded iron, washed with distilled water until the washings were thoroughly free of ferrous, ferric, and excess hydrogen ion, and stored in covered Pyrex beakers under water until used. The barium was used as barium chloride, Baker's analyzed C. P. The oleate was used as sodium oleate. It was prepared from sodium hydroxide, Baker's analyzed C. P., and oleic acid purified by R. R. de Arellano3 in the laboratories at the Massachusetts Institute of Technology. The purification procedure was elaborated from the recent $researches of Brown and Shinowara.2 It consisted in: (I) saponification of olive oil with potassium

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 A. W. Gauger

For perhaps one hundred years scientists have been engaged in attempts at devising a satisfactory method of classification of coal. During this time many charts, tables and graphs have been proposed, some of which have had considerable merit, but no one system has been found to be applicable to all ranks of coal, nor has any one system received general acceptance. In many of the proposals, water eliminated between room temperature and 105" C. has been regarded as extraneous matter and calculations have been made to the air-dry or water-free basis. Such methods of calculation do not lend themselves to satisfactory grouping of the high-moisture coals.1, 2 A consideration not only of the properties of the high-moisture coals and their behavior on drying but of the generally accepted ideas of the coalification process and the role of water in this process indicates that water is an essential constituent of all coals and therefore should not be neglected. For example, in such low-rank coals as the lignites of the Northern Great Plains' deposits the inherent moisture of the lignite as mined plays a very important part in the physical properties thereof. Freshly mined lignite contains upwards of 30 per cent water and is extremely tough and resistant to shock. Upon exposure to the atmosphere, the lump loses part of its moisture and checks and splits, leaving a friable and broken up residue. So far as we have been able to determine, water is the only thing lost in this process and we are forced to the conclusion that moisture plays an extremely important part in the structural properties of the original lignite. With reference to the coalification process, Mack and Hulett3 pointed out in 1917 the important part that water played therein. They observed that water cannot be removed from peat or coal by pressure alone, but only as the result of chemical reaction, and suggested that peat in its early stages may be largely a hydrosol. Slow chemical changes occur over a long period of time until finally the mass becomes more largely a hydrogel. These views are substantiated to some extent by the experi-

Jan 1, 1932

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