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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machine was built according to the design of D. W. McGlashan.* It consists of a drill press in which the bit has been replaced by a stainless-steel impellor surrounding a stainless-steel sta-tor, as in the Fagergren laboratory machine.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 J. H. Frye, C. P. Sun

A PRIMARY substitutional solid solution is a solution that has the same crystalline structure as the solvent metal, and in which solute atoms have replaced solvent atoms at random on the host lattice. This replacement usually results in an increase in hardness as measured by conventional penetration tests. The factors controlling this hardness increase have been investigated in some detail for copper and silver aneys.1-5 It has been shown that at least, four factors are involved: (I) concentration of solute, (2) row of the periodic table from which the solute is taken, (3) increase in lattice parameter of the solvent produced by the solute, and (4) work-hardening produced by penetration of the hardness indenter.2,4 The last factor is of the utmost importance. An investigation of the available data2.4 leads to the conclusion that the solutes that produce large hardness increases in copper or silver do so principally because they increase the rate of work-hardening. Furthermore, it is doubtful whether any solute produces appreciable hardening in the absence of plastic deformation and hence work-hardening. Thus it is clear that an understanding of the effect of solutes on rate of work hardening is essential to an understanding of the hardness of solid solutions. This effect of solutes is also important in forming operations such as rolling or deep drawing. The presence of elements that confer rapid rates of work-hardening will increase power consumption and may well decrease the amount of deformation possible between anneals. This paper is the report of an investigation of the factors that control rates of work-hardening in copper and silver solid solutions. The silver and copper alloys considered are those in which all solutes are from the B subgroups or second short period of the periodic table. Experience with hardness, with structure of alloys, and with electrical conductivity has proved that results of a fundamental nature are most likely to be obtained if alloys are made up on the basis of the positions of the constituent elements in the periodic table. In previous work, Meyer analysis data on high-purity copper and silver solid solutions were obtained through careful measurements with fully calibrated equipment and these data were corrected to correspond to a standard grain size. From these corrected Meyer analysis data rates of work-hardening have now been calculated. CALCULATION OF RATES OF WORK- HARDENING The Meyer analyses, on which this study of rates of work-hardening is based, consisted in determining impression

Jan 1, 1944

By William J. McCaughey, Richard L. Barrett

For sixty years—in fact, ever since the inception of the basic steelmaking process —basic slags have been the subject of study by chemists, metallurgists and petrog-raphers! with the purpose of providing a better understanding of the reactions between the slag and the metal during the refining process. The result of this work and of the researches of mineralogists and physical chemists into the chemistry of oxide systems is a considerable body of literature dealing not only with slags themselves but with equilibrium relationships in systems synthesized from pure components. Since any actual slag is a multicom-ponent system more complex than any yet worked out in the laboratory, a complete solution to the problem is still far away. The writers have recently published a paper1 which they believe sheds light on the role of the slag in the elimination of phosphorus and it is the purpose of the present paper to discuss the metallurgical applications of that work. Since the pioneer investigations on the constitution of basic slags carried on by Stead and Risdale, Carnot and Richards, Hilgenstock and others in the I88o's, a considerable body of literature on this subject has appeared. Many of the more important of these papers were summarized in the previous paper,l therefore they will not be reviewed here. PetRographic Study The present writers have had occasion, over a period of years, to examine petro-graphically a great number of basic steel-making slags having a very wide range of chemical compositions and made under various conditions of operating practice. Although certain of these slags exhibit some unusual features, it is a remarkable fact that the great majority of mature slags show certain typical characteristics, which persist throughout the wide range of chemical compositions. The typical mature slag usually appears under the microscope to consist of two phases. The phase of primary crystallization is light colored and doubly refracting. If separated mechanically and subjected to chemical analysis, it is found to consist essentially of SiO2, CaO, and P2O6. Sometimes, although not usually, two such silicate-phosphate phases are found. The other conspicuous phase is dark in color and optically isotropic, and occurs as the interstitial material between the grains of the light colored phase. This dark colored interstitial phase when analyzed is found to consist essentially of FeO, Fe2O3, MnO, and MgO. In some 'lags high in iron oxide, particularly those from low-carbon heats, dicalcium ferrite is found. This phase is dark reddish brown in color and anisotropic.

Jan 1, 1944

By William J. McCaughey, Richard L. Barrett

For sixty years—in fact, ever since the inception of the basic steelmaking process —basic slags have been the subject of study by chemists, metallurgists and petrog-raphers! with the purpose of providing a better understanding of the reactions between the slag and the metal during the refining process. The result of this work and of the researches of mineralogists and physical chemists into the chemistry of oxide systems is a considerable body of literature dealing not only with slags themselves but with equilibrium relationships in systems synthesized from pure components. Since any actual slag is a multicom-ponent system more complex than any yet worked out in the laboratory, a complete solution to the problem is still far away. The writers have recently published a paper1 which they believe sheds light on the role of the slag in the elimination of phosphorus and it is the purpose of the present paper to discuss the metallurgical applications of that work. Since the pioneer investigations on the constitution of basic slags carried on by Stead and Risdale, Carnot and Richards, Hilgenstock and others in the I88o's, a considerable body of literature on this subject has appeared. Many of the more important of these papers were summarized in the previous paper,l therefore they will not be reviewed here. PetRographic Study The present writers have had occasion, over a period of years, to examine petro-graphically a great number of basic steel-making slags having a very wide range of chemical compositions and made under various conditions of operating practice. Although certain of these slags exhibit some unusual features, it is a remarkable fact that the great majority of mature slags show certain typical characteristics, which persist throughout the wide range of chemical compositions. The typical mature slag usually appears under the microscope to consist of two phases. The phase of primary crystallization is light colored and doubly refracting. If separated mechanically and subjected to chemical analysis, it is found to consist essentially of SiO2, CaO, and P2O6. Sometimes, although not usually, two such silicate-phosphate phases are found. The other conspicuous phase is dark in color and optically isotropic, and occurs as the interstitial material between the grains of the light colored phase. This dark colored interstitial phase when analyzed is found to consist essentially of FeO, Fe2O3, MnO, and MgO. In some 'lags high in iron oxide, particularly those from low-carbon heats, dicalcium ferrite is found. This phase is dark reddish brown in color and anisotropic.

Jan 1, 1944

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:I 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 stator, 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, 1942

By B. M. Larsen, T. E. Brower

INTRODUCTION THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slagmetal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is .partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the continual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process, In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium, On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. PROBABLE CHEMISTRY OF DESULPHURIZATION Since there is little evidence that sulphur atoms in the iron solution are associated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* [(FeS) -, [FeS],[I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) = (CaS) + (FeO), [2] and, (FeS) + (MnO) ;:2 (MnS) + (FeO). [31]

Jan 1, 1948

By D. Van Winkle, C. Zener, H. Nielsen

THe internal friction of metals has been studied frequently at elevated temperatures.1-4 In most cases it rises rapidly with increasing temperature. The notable exceptions are ferromagnetic materials, and lead.2 This paper describes an investigation of the general features of the high-temperature internal friction of 70-30 alpha brass. Experimental Method The internal friction of a metal is a measure of the rate at which it dissipates energy of vibration. The measure adopted here, I/Q, is (I/2p) times the specific damping capacity, a measure commonly used by engineers. In the measurements of this investigation, the stress level was kept so low that the observations were independent of the stress, The general method of making such measurements, and of observing temperature of a specimen during a measurement, has been described.5.6 The driver and detector coils were wound with wire insulated with glass thread, in order to withstand the high temperatures used. In previous work electrical eddy currents in the specimen served as the coupling between the mechanical vibration of the specimen and the electrical circuits of the driver and detector. The high values of the internal friction in the present investigation rendered this coupling insufficient. In order to increase this coupling, pole pieces cut from ordinary telephone diaphragms were attached to the specimen. A mixture of French chalk and water glass proved a satisfactory cement. All measurements were made at the fundamental frequency for transverse vibration, which lay between 600 and goo cycles per second. Specimens The measurements described herein were made upon a single cylindrical rod of brass, kindly furnished by Dr. Cyril Stanley Smith, of the American Brass Co. This rod was the specimen E of the set of alpha-brass rods described in an earlier paper.6 Successively larger grain sizes were obtained by annealing at .successively higher temperatures. A slice was cut off one end after each set of measurements. Grain counts were made on each slice by W. E. Lindlief, of the American Brass Co. Nine fields were viewed on each piece, located as shown in Fig. I. Results are given in Table I. The grain size is defined in the usual way; namely, Grain size = I/n1/2 where n is the mean number of grains per square millimeter. Experimental Results This paper is concerned exclusively with the part of the internal friction that be. comes dominant at high temperatures. It is thus desirable to separate this part of the internal friction from the part that is

Jan 1, 1942

By J. H. Frye, C. P. Sun

A Frimary substitutional solid solution is a solution that has the same crystalline structure as the solvent metal, and in which solute atoms have replaced, solvent atoms at random on the host lattice. This replacement usually results in an increase in hardness as measured by conventional penetration tests. The factors controlling this hardness increase have been investigated in some detail for copper and silver alloys.1-5 It has been shown that at least four factors are involved: (1) concentration of solute, (2) row of the periodic table from which the solute is taken, (3) increase in lattice parameter of the solvent produced by the solute, and (4) work-hardening produced by penetration of the hardness indenter.2,4 The last factor is of the utmost importance. An investigation of the available data2,4 leads to the conclusion that the solutes that produce large hardness increases in copper or silver do so principally because they increase the rate of work-hardening. Furthermore, it is doubtful whether any solute produces appreciable hardening in the absence of plastic deformation and hence work-hardening. Thus it is clear that an understanding of the effect of solutes on rate of work-hardening is essential to an understanding of the hardness of solid solutions. This effect of solutes is also important in forming operations such as rolling or deep drawing. The presence of elements that confer rapid rates of work-hardening will increase power consumption and may well decrease the amount of deformation possible between anneals. This paper is the report of an investigation of the factors that control rates of work-hardening in copper and silver solid solutions. The silver and copper alloys considered are those in which all solutes are from the B subgroups or second short period of the periodic table. Experience with hardness, with structure of alloys, and with electrical conductivity has proved that results of a fundamental nature are most likely to be obtained if alloys are made up on the basis of the positions of the constituent elements in the periodic table. In previous work, Meyer analysis data on high-purity copper and silver solid solutions were obtained through careful measurements with fully calibrated equipment and these data were corrected to correspond to a standard grain size. From these corrected Meyer analysis data rates of work-hardening have now been calculated. Calculation of Rates as Work- HARDENING The Meyer analyses, on which this study of rates of work-hardening is based, consisted in determining impression

Jan 1, 1944

By C. Zener, H. Nielsen, D. Van Winkle

THe internal friction of metals has been studied frequently at elevated temperatures.1-4 In most cases it rises rapidly with increasing temperature. The notable exceptions are ferromagnetic materials, and lead.2 This paper describes an investigation of the general features of the high-temperature internal friction of 70-30 alpha brass. Experimental Method The internal friction of a metal is a measure of the rate at which it dissipates energy of vibration. The measure adopted here, I/Q, is (I/2p) times the specific damping capacity, a measure commonly used by engineers. In the measurements of this investigation, the stress level was kept so low that the observations were independent of the stress, The general method of making such measurements, and of observing temperature of a specimen during a measurement, has been described.5.6 The driver and detector coils were wound with wire insulated with glass thread, in order to withstand the high temperatures used. In previous work electrical eddy currents in the specimen served as the coupling between the mechanical vibration of the specimen and the electrical circuits of the driver and detector. The high values of the internal friction in the present investigation rendered this coupling insufficient. In order to increase this coupling, pole pieces cut from ordinary telephone diaphragms were attached to the specimen. A mixture of French chalk and water glass proved a satisfactory cement. All measurements were made at the fundamental frequency for transverse vibration, which lay between 600 and goo cycles per second. Specimens The measurements described herein were made upon a single cylindrical rod of brass, kindly furnished by Dr. Cyril Stanley Smith, of the American Brass Co. This rod was the specimen E of the set of alpha-brass rods described in an earlier paper.6 Successively larger grain sizes were obtained by annealing at .successively higher temperatures. A slice was cut off one end after each set of measurements. Grain counts were made on each slice by W. E. Lindlief, of the American Brass Co. Nine fields were viewed on each piece, located as shown in Fig. I. Results are given in Table I. The grain size is defined in the usual way; namely, Grain size = I/n1/2 where n is the mean number of grains per square millimeter. Experimental Results This paper is concerned exclusively with the part of the internal friction that be. comes dominant at high temperatures. It is thus desirable to separate this part of the internal friction from the part that is

Jan 1, 1942

By J. H. Frye, C. P. Sun

A Frimary substitutional solid solution is a solution that has the same crystalline structure as the solvent metal, and in which solute atoms have replaced, solvent atoms at random on the host lattice. This replacement usually results in an increase in hardness as measured by conventional penetration tests. The factors controlling this hardness increase have been investigated in some detail for copper and silver alloys.1-5 It has been shown that at least four factors are involved: (1) concentration of solute, (2) row of the periodic table from which the solute is taken, (3) increase in lattice parameter of the solvent produced by the solute, and (4) work-hardening produced by penetration of the hardness indenter.2,4 The last factor is of the utmost importance. An investigation of the available data2,4 leads to the conclusion that the solutes that produce large hardness increases in copper or silver do so principally because they increase the rate of work-hardening. Furthermore, it is doubtful whether any solute produces appreciable hardening in the absence of plastic deformation and hence work-hardening. Thus it is clear that an understanding of the effect of solutes on rate of work-hardening is essential to an understanding of the hardness of solid solutions. This effect of solutes is also important in forming operations such as rolling or deep drawing. The presence of elements that confer rapid rates of work-hardening will increase power consumption and may well decrease the amount of deformation possible between anneals. This paper is the report of an investigation of the factors that control rates of work-hardening in copper and silver solid solutions. The silver and copper alloys considered are those in which all solutes are from the B subgroups or second short period of the periodic table. Experience with hardness, with structure of alloys, and with electrical conductivity has proved that results of a fundamental nature are most likely to be obtained if alloys are made up on the basis of the positions of the constituent elements in the periodic table. In previous work, Meyer analysis data on high-purity copper and silver solid solutions were obtained through careful measurements with fully calibrated equipment and these data were corrected to correspond to a standard grain size. From these corrected Meyer analysis data rates of work-hardening have now been calculated. Calculation of Rates as Work- HARDENING The Meyer analyses, on which this study of rates of work-hardening is based, consisted in determining impression

Jan 1, 1944

By Rizo-Pairón Alfonso, 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 I 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 stator, 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, 1942

By William J. McCaughey, Richard L. Barrett

FOR sixty years-in fact, ever since the inception of the basic steelmaking process -basic slags have been the subject of study by chemists, metallurgists and petrographers, with the purpose of providing a better understanding of the reactions between the slag and the metal during the refining process. The result of this work and of the researches of mineralogists and physical chemists into the chemistry of oxide systems is a considerable body of literature dealing not only with slags themselves but with equilibrium relationships in systems synthesized from pure components. Since any actual slag is a multicomponent system more complex than any yet worked out in the laboratory, a complete solution to the problem is still far away. The writers have recently published a paper1 which they believe sheds light on the role of the slag in the elimination of phosphorus and it is the purpose of the present paper to discuss the metallurgical applications of that work. Since the pioneer investigations on the constitution of basic slags carried on by Stead and Risdale, Carnot and Richards, Hilgenstock and others in the 1880's, a considerable body of literature on this subject has appeared. Many of the more important of these papers were summarized in the previous paper,' therefore they will not be reviewed here. PETROGRAPHIC STUDY The present writers have had occasion, over a period of years, to examine petrographically a great number of basic steel- making slags having a very wide range of chemical compositions and made under various conditions of operating practice. Although certain of these slags exhibit some unusual features, it is a remarkable fact that the great majority of mature slags show certain typical characteristics, which persist throughout the wide range of chemical compositions. The typical mature slag usually appears under the microscope to consist of two phases. The phase of primary crystallization is light colored and doubly refracting. If separated mechanically and subjected to chemical analysis, it is found to consist essentially of SiO2, CaO, and P2O5. Sometimes, although not usually, two such silicate-phosphate phases are found. The other conspicuous phase is dark in color and optically isotropic, and occurs as the interstitial material between the grains of the light colored phase. This dark colored interstitial phase when analyzed is found to consist essentially of FeO,Fe2O3, MnO, and MgO. In some slags high in iron oxide, particularly those from low-carbon heats, dicalcium ferrite is found. This phase is dark reddish brown in color and anisotropic.

Jan 1, 1944

By W. H. Blauvelt

W. H. BLAUVELT, Syracuse, N. Y. (communication to the Secretary*).-I have read Mr. Howland's paper on Calculations with Reference to the Use of Carbon in Modern American Blast Furnaces with much interest, and believe that his method of analysis of the subject will be of material assistance in our study of the action of coke in the blast furnace. Mr. Howland quotes Professor Richards' statement that from the standpoint of the generation of the maximum quantity of heat in the furnace, Grüner was right in saying that all the carbon burned in the furnace should be first oxidized at the tuyères to CO and all reduction of oxides above the tuyères should be caused by CO, which thus becomes CO2. It is clear that the maximum quantity of heat is generated in the furnace when the greatest amount of carbon is burned to CO2 irrespective of whether it is burned at the tuyères or further up the furnace. So it would appear that Grüner's theory is sound regarding the maximum production of heat only because if all the carbon is burned to CO at the tuyères the reduction of the ores will have to be effected by the further oxidation to CO2. Whereas, if the reduction of the ores is effected in part by solid carbon, part of this carbon might be oxidized only to CO, resulting in a higher percentage of CO in the escaping gases than from Grüner's "ideal conditions.? But in studying the combustion of coke in the furnace, it is clear that the production of the maximum quantity of heat is not of the first importance in blast-furnace operation, or in the utilization of the fuel charged into the furnace. To my mind the production of a high thermal head at the tuyères is of the first importance, and the best coke is that which reaches the tuyères in proper condition to produce the highest temperature at the tuyères, and in just sufficient quantity to do the amount of work required there under the conditions produced by this maximum temperature. The combustion of a much larger amount of fuel at the tuyères, under conditions that will fall short of producing the highest possible temperature, cannot produce as good results, either in fuel economy or output. If this statement is correct, does it not correspond with Mr. Howland's statement that too much wind is inimical to low coke consumption? Nothing is more fatal to obtaining the highest temperatures than an excess of air for combustion. In the blast furnace an excess of air dilutes and cools the products of combus-

Jan 10, 1916

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By John T. Eash

During the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. Selection or Composition While the final criterion of the suitability of an alloy for a bearing must of course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstruc-ture, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig' 1. I' In the tin bronze contains the hard alpha + delta

Jan 1, 1946

By John T. Eash

During the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. Selection or Composition While the final criterion of the suitability of an alloy for a bearing must of course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstruc-ture, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig' 1. I' In the tin bronze contains the hard alpha + delta

Jan 1, 1946

By John T. Eash

DURING the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin, 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. SELECTION OF COMPOSITION While the final criterion of the suitability of an alloy for a bearing must 0f course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstructure, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig. I. In addition, the tin bronze contains the hard alpha + delta eutectoid constituent distributed through-

Jan 1, 1945

By Blake M. Loring

Recently the S-curves for 30 to 40 alloy steels have been pub1ished.l.2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.29 per cent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr, at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1¼ by ½ by ? in. Wires attached to the samples were used for handling. instead of tongs, to avoid chilling. The specimens were heated at 845°C. for ½ hr. and quenched into constant-temperature salt baths held at various temperatures from 205' to 650°C. The time required to transfer the specimens was found to be about 1½ sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 2I°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1942

By Blake M. Loring

Recently the S-curves for 30 to 40 alloy steels have been pub1ished.l.2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.29 per cent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr, at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1¼ by ½ by ? in. Wires attached to the samples were used for handling. instead of tongs, to avoid chilling. The specimens were heated at 845°C. for ½ hr. and quenched into constant-temperature salt baths held at various temperatures from 205' to 650°C. The time required to transfer the specimens was found to be about 1½ sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 2I°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1942