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By R. S. Bradley, B. K. Miller

The principal producing areas of fire clay in Missouri are: (I) the east central district, which includes Audrain, Callaway, Montgomery, Warren, and Boone Counties (Fig. I); (2) the St. Louis district, which includes St. Louis and St. Louis County; (3) the north central Ozark district, which includes Franklin, Gasconade, Osage, Maries, Phelps, and Crawford Counties. Most of the semiplastic‡ fire clay is found in Audrain, Callaway, Montgomery and St. Louis Counties, and in St. Louis. Flint fire clay is found in Callaway, Audrain, and Montgomery Counties and in most of the north centra! Ozark district. High-alumina diaspore clay is found only in the north central Ozark district, except a few deposits found in Montgomery County. This paper is concerned with the semi-plastic fire clay that occurs in the east central Missouri district near Mexico, Audrain County, Missouri, which is mined by the open-pit method as practiced by the A. P. Green Fire Brick Co. About one-fourth of the semiplastic fire clay in that district is mined in shaft mines, and three-fourths in open pits.

Jan 1, 1942

By B. K. Miller, R. S. Bradley

The principal producing areas of fire clay in Missouri are: (I) the east central district, which includes Audrain, Callaway, Montgomery, Warren, and Boone Counties (Fig. I); (2) the St. Louis district, which includes St. Louis and St. Louis County; (3) the north central Ozark district, which includes Franklin, Gasconade, Osage, Maries, Phelps, and Crawford Counties. Most of the semiplastic‡ fire clay is found in Audrain, Callaway, Montgomery and St. Louis Counties, and in St. Louis. Flint fire clay is found in Callaway, Audrain, and Montgomery Counties and in most of the north centra! Ozark district. High-alumina diaspore clay is found only in the north central Ozark district, except a few deposits found in Montgomery County. This paper is concerned with the semi-plastic fire clay that occurs in the east central Missouri district near Mexico, Audrain County, Missouri, which is mined by the open-pit method as practiced by the A. P. Green Fire Brick Co. About one-fourth of the semiplastic fire clay in that district is mined in shaft mines, and three-fourths in open pits.

Jan 1, 1942

By E. C. Truesdale, Gerald Edmunds

A few years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.&apos; During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. Table 1.—Typical Analyses Percentnge by Weight Sum of Zinc Fe, Ib1 Fe Cd 1A1 cd Special High Grade*.......... 0.007b 0.005b 0.005b none O.OIOb C.P. (chemically pure)......... < 0.0002 0.0005c 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 637). b Maximum. &apos; Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By E. C. Truesdale, Gerald Edmunds

A few years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.&apos; During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. Table 1.—Typical Analyses Percentnge by Weight Sum of Zinc Fe, Ib1 Fe Cd 1A1 cd Special High Grade*.......... 0.007b 0.005b 0.005b none O.OIOb C.P. (chemically pure)......... < 0.0002 0.0005c 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 637). b Maximum. &apos; Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

The Round Table on Qualities of Pig Iron, under the auspices of the Joint Committee on Qualities of Pig Iron, which is made up of members of the American Institute of Mining and Metallurgical Engineers, the American Foundrymen&apos;s Association, the American Society for Testing Materials, the Gray Iron Institute, and the Malleable Iron Institute, was held at the Palmer House, Chicago, III., on Oct. 1, 1935. Prcoeedings R. H. SwEEtseR,* New York, N. Y.—Seven years ago last June, in Chicago, we had a round table on qualities of pig iron1, and at that time the foundrymen were out with their battle-axes for the blast-furnace men, and the open-hearth men were doing the same thing. After that meeting there was really a determined effort to find out about the qualities of pig iron, and great progress has been made all along the line. This afternoon we want to have a frank discussion of the qualities of pig iron, whether it is the molten pig iron going into the steel plant, or cold pigs going to the different foundries. We ought to hear something from Dr. J. T. MacKenzie, who is chairman of the Joint Committee, and from Mr. R. E. Kennedy, the Technical Secretary of the American Foundrymen&apos;s Association. J. T. MacKEnzie,† Birmingham, A1a.—As a result of that meeting in Chicago, there was considerable agitation in the Foundrymen&apos;s Association to develop a set of tests for pig iron. One of the difficulties was that nobody talked the same language on shrinkage, draws, live iron, dead iron, and so forth, which were the main complaints against pig iron. By request of a committee of the Foundrymen&apos;s Association, the Bureau of Standards ran a comprehensive set of tests that did develop the principles governing the optical pyrometer as applied to cast iron and pig iron. Then the Bureau went on further with the fluidity test, and developed a method for the absolute changes of volume at the freezing point. There is one serious gap in the yardstick, which has never been developed, and that is the tendency to draws from heavy sections to light. Everyone who has worried about the differences of section, and sponginess in changes of section, realizes that the

Jan 1, 1936

The Round Table on Qualities of Pig Iron, under the auspices of the Joint Committee on Qualities of Pig Iron, which is made up of members of the American Institute of Mining and Metallurgical Engineers, the American Foundrymen&apos;s Association, the American Society for Testing Materials, the Gray Iron Institute, and the Malleable Iron Institute, was held at the Palmer House, Chicago, III., on Oct. 1, 1935. Prcoeedings R. H. SwEEtseR,* New York, N. Y.—Seven years ago last June, in Chicago, we had a round table on qualities of pig iron1, and at that time the foundrymen were out with their battle-axes for the blast-furnace men, and the open-hearth men were doing the same thing. After that meeting there was really a determined effort to find out about the qualities of pig iron, and great progress has been made all along the line. This afternoon we want to have a frank discussion of the qualities of pig iron, whether it is the molten pig iron going into the steel plant, or cold pigs going to the different foundries. We ought to hear something from Dr. J. T. MacKenzie, who is chairman of the Joint Committee, and from Mr. R. E. Kennedy, the Technical Secretary of the American Foundrymen&apos;s Association. J. T. MacKEnzie,† Birmingham, A1a.—As a result of that meeting in Chicago, there was considerable agitation in the Foundrymen&apos;s Association to develop a set of tests for pig iron. One of the difficulties was that nobody talked the same language on shrinkage, draws, live iron, dead iron, and so forth, which were the main complaints against pig iron. By request of a committee of the Foundrymen&apos;s Association, the Bureau of Standards ran a comprehensive set of tests that did develop the principles governing the optical pyrometer as applied to cast iron and pig iron. Then the Bureau went on further with the fluidity test, and developed a method for the absolute changes of volume at the freezing point. There is one serious gap in the yardstick, which has never been developed, and that is the tendency to draws from heavy sections to light. Everyone who has worried about the differences of section, and sponginess in changes of section, realizes that the

Jan 1, 1936

By Arthur Phillips, R. M. Brick, A. J. Smith

A previous publication1§ has described the effect of quenching stresses on the lattice parameter values of high-purity aluminum-copper alloys particularly with reference to the solution and precipitation of CuAl². A similar study has been made of the aluminum-rich aluminum-magnesium alloys. Attention has been directed in the present investigation to the magnitude of the quenching stresses as affected by the specimen size and shape, the number of solute atoms and the quenching rate. The effect of cooling stresses in causing plastic defomation or cracking has been considered in relation to the physical properties of the alloy On reheating alloys in the two-phase field, the time required for precipitation to occur has been observed in connection with the degrec of supersaturation, the rate of diffusion of the solute atoms as a function of the comparative atomic radii, degree of strain, temperature of reheating and grain size. A few qualitative comparisons on the relative effect of these factors have been drawn between the aluminum-copper alloys and the aluminum-magnesium alloys. Strain in Solid-solution Alloys A 10 per cent magnesium alloy ill the form of chill-cast bars was furnished by the Aluminum Company of America through the courtesy of L. W. Kempf. Additional alloys were prepared using alllminum (99.95 per cent Al) and high-grade magnesium. The alloys listed in Table 1 were melted in an Acheson graphite crucible under a flux of fused MgCl², CaC12, NaCI. Chill-cast rods were sealed under vacuum in Pyrex glass, homogenized several days at 450&apos; C., air-cooled and machined to rods of from 1/8 to ¾-in. dia. Metal powders taken from these rods with a fine-toothed saw were again sealed under vacuum in

Jan 1, 1935

By R. M. Brick, Arthur Phillips, A. J. Smith

A previous publication1§ has described the effect of quenching stresses on the lattice parameter values of high-purity aluminum-copper alloys particularly with reference to the solution and precipitation of CuAl². A similar study has been made of the aluminum-rich aluminum-magnesium alloys. Attention has been directed in the present investigation to the magnitude of the quenching stresses as affected by the specimen size and shape, the number of solute atoms and the quenching rate. The effect of cooling stresses in causing plastic defomation or cracking has been considered in relation to the physical properties of the alloy On reheating alloys in the two-phase field, the time required for precipitation to occur has been observed in connection with the degrec of supersaturation, the rate of diffusion of the solute atoms as a function of the comparative atomic radii, degree of strain, temperature of reheating and grain size. A few qualitative comparisons on the relative effect of these factors have been drawn between the aluminum-copper alloys and the aluminum-magnesium alloys. Strain in Solid-solution Alloys A 10 per cent magnesium alloy ill the form of chill-cast bars was furnished by the Aluminum Company of America through the courtesy of L. W. Kempf. Additional alloys were prepared using alllminum (99.95 per cent Al) and high-grade magnesium. The alloys listed in Table 1 were melted in an Acheson graphite crucible under a flux of fused MgCl², CaC12, NaCI. Chill-cast rods were sealed under vacuum in Pyrex glass, homogenized several days at 450&apos; C., air-cooled and machined to rods of from 1/8 to ¾-in. dia. Metal powders taken from these rods with a fine-toothed saw were again sealed under vacuum in

Jan 1, 1935

By J. C. Reed, J. M. Hansell

Cinnabar was discovered in southwestern Arkansas on Little Missouri River in sec. 1, T.7S., R.26W., in April, 1930, and near Antoine Creek in sec. 28, T.6S., R.23W., some 15 miles farther east in May of the same year. It was not, however, until June, 1931, that cinnabar was identified as such in a specimen from the original discovery area sent to W. M. Weigell by Walter F. Hintze of Murfreesboro. Almost simultaneously2, in July, 1931, Moritz Norden of Hot Springs identified specimens from the Antoine Creek area as cinnabar. Immediate interest in the district followed the identification of cinnabar and by January, 1932, the district was known to extend as a mineralized belt about one mile wide trending east-northeast from sec. 13, T.7S., R.27W., in Howard County across central Pike County and into Clark County to sec. 19, T.6S., R.23W., thence extending southeast into sections 33 and 34 of the same township. Since then, cinnabar has been found in sec. 6, T.7S., R.22W., thus giving a total east-west length to the district of approximately 30 miles. Interest focused mainly on the two discovery areas, with the result that mining development has progressed most rapidly in those localities. In the Antoine Creek area the Arkansas Quicksilver Co. has done considerable exploration work and has retorted the high-grade ore so obtained. In the Little Missouri area the Southwestern Quicksilver Co. has had a 12-ton rotary furnace in more or less continuous operation since April, 1932, and has been the largest producer in the district. In March, 1934, the United States Geological Survey began a study of the Arkansas quicksilver district, which was made possible by an allotment of funds from the Public Works Administration. Until

Jan 1, 1935

By J. C. Reed, J. M. Hansell

Cinnabar was discovered in southwestern Arkansas on Little Missouri River in sec. 1, T.7S., R.26W., in April, 1930, and near Antoine Creek in sec. 28, T.6S., R.23W., some 15 miles farther east in May of the same year. It was not, however, until June, 1931, that cinnabar was identified as such in a specimen from the original discovery area sent to W. M. Weigell by Walter F. Hintze of Murfreesboro. Almost simultaneously2, in July, 1931, Moritz Norden of Hot Springs identified specimens from the Antoine Creek area as cinnabar. Immediate interest in the district followed the identification of cinnabar and by January, 1932, the district was known to extend as a mineralized belt about one mile wide trending east-northeast from sec. 13, T.7S., R.27W., in Howard County across central Pike County and into Clark County to sec. 19, T.6S., R.23W., thence extending southeast into sections 33 and 34 of the same township. Since then, cinnabar has been found in sec. 6, T.7S., R.22W., thus giving a total east-west length to the district of approximately 30 miles. Interest focused mainly on the two discovery areas, with the result that mining development has progressed most rapidly in those localities. In the Antoine Creek area the Arkansas Quicksilver Co. has done considerable exploration work and has retorted the high-grade ore so obtained. In the Little Missouri area the Southwestern Quicksilver Co. has had a 12-ton rotary furnace in more or less continuous operation since April, 1932, and has been the largest producer in the district. In March, 1934, the United States Geological Survey began a study of the Arkansas quicksilver district, which was made possible by an allotment of funds from the Public Works Administration. Until

Jan 1, 1935

Cinnabar was discovered in southwestern Arkansas on Little Missouri River in sec. 1, T.7S., R.26W., in April, 1930, and near Antoine Creek in sec. 28, T.6S., R.23W., some 15 miles farther east in May of the same year. It was not, however, until June, 1931, that cinnabar was identified as such in a specimen from the original discovery area sent to W. M. Weigell by Walter F. Hintze of Murfreesboro. Almost simultaneously2, in July, 1931, Moritz Norden of Hot Springs identified specimens from the Antoine Creek area as cinnabar. Immediate interest in the district followed the identification of cinnabar and by January, 1932, the district was known to extend as a mineralized belt about one mile wide trending east-northeast from sec. 13, T.7S., R.27W., in Howard County across central Pike County and into Clark County to sec. 19, T.6S., R.23W., thence extending southeast into sections 33 and 34 of the same township. Since then, cinnabar has been found in sec. 6, T.7S., R.22W., thus giving a total east-west length to the district of approximately 30 miles. Interest focused mainly on the two discovery areas, with the result that mining development has progressed most rapidly in those localities. In the Antoine Creek area the Arkansas Quicksilver Co. has done considerable exploration work and has retorted the high-grade ore so obtained. In the Little Missouri area the Southwestern Quicksilver Co. has had a 12-ton rotary furnace in more or less continuous operation since April, 1932, and has been the largest producer in the district. In March, 1934, the United States Geological Survey began a study of the Arkansas quicksilver district, which was made possible by an allotment of funds from the Public Works Administration. Until

Jan 1, 1935

By J. C. Reed, J. M. Hansell

Cinnabar was discovered in southwestern Arkansas on Little Missouri River in sec. 1, T.7S., R.26W., in April, 1930, and near Antoine Creek in sec. 28, T.6S., R.23W., some 15 miles farther east in May of the same year. It was not, however, until June, 1931, that cinnabar was identified as such in a specimen from the original discovery area sent to W. M. Weigell by Walter F. Hintze of Murfreesboro. Almost simultaneously2, in July, 1931, Moritz Norden of Hot Springs identified specimens from the Antoine Creek area as cinnabar. Immediate interest in the district followed the identification of cinnabar and by January, 1932, the district was known to extend as a mineralized belt about one mile wide trending east-northeast from sec. 13, T.7S., R.27W., in Howard County across central Pike County and into Clark County to sec. 19, T.6S., R.23W., thence extending southeast into sections 33 and 34 of the same township. Since then, cinnabar has been found in sec. 6, T.7S., R.22W., thus giving a total east-west length to the district of approximately 30 miles. Interest focused mainly on the two discovery areas, with the result that mining development has progressed most rapidly in those localities. In the Antoine Creek area the Arkansas Quicksilver Co. has done considerable exploration work and has retorted the high-grade ore so obtained. In the Little Missouri area the Southwestern Quicksilver Co. has had a 12-ton rotary furnace in more or less continuous operation since April, 1932, and has been the largest producer in the district. In March, 1934, the United States Geological Survey began a study of the Arkansas quicksilver district, which was made possible by an allotment of funds from the Public Works Administration. Until

Jan 1, 1935

By Alexander L. Field

In the light of the experimental data on equilibrium for the reaction C + FeO = Fe + CO in molten steel recently obtained by Kinzel and Egan,l it is necessary to revise current theories regarding the nature of equilibrium between carbon and FeO in the basic open-hearth furnace. According to the measurements of these investigators the equilibrium constant m for the above reaction for a pressure of dissolved CO equal to 1 atm. is equal to 0.0005 at 1550" C., when concentrations of carbon and FeO are expressed in percentages by weight. Their work also shows that, with the pressure of CO fixed at 1 atm., not only is the product of carbon and FeO constant, but carbon and FeO are each independently constant—a circumstance which might have been predicted from theoretical considerations. At 1550" C., carbon is constant at about 0.025 per cent. and FeO at about 0.020 per cent., with the pressure of dissolved CO equal to 1 atm., the product of these two constants being equal to the originally mentioned constant of 0.0005. Available data on the dissolved FeO content of samples taken from the metal bath at practical slag-metal equilibrium prove that this FeO content is determined solely by temperature and the effective FeO content of the slag. The distribution constant r at 1550" C., as determined by Herty, Gaines, Larsen, Simkins, Geruso and Watkins2 is equal to 0.0086. A slag would have to contain 0.020 = 2.3 per cent. effective 0.0086 FeO or less in order to prevent the metal from containing more dissolved FeO than that required for equilibrium with CO at 1 atm. pressure. Such low percentages of FeO are never found in basic open-hearth slags at the completion of a heat when rate of carbon drop has become practi-

Jan 1, 1930

By Cyril Wells, Robert F. Mehl

The diffusion of carbon in gamma iron plays an essential role in many metallurgical processes. In carburizing, in graphitizing, in homogenizing, in the formation of pearlite from austenite, and in other processes, migration of carbon in gamma iron occurs.1&apos;2 A full understanding of the rate at which these processes occur obviously requires a knowledge of the rate of diffusion of carbon. In carburizing, for example, the depth of carbon pentration is determined by the carbon concentration in solid solution at the surface, and by the rate of diffusion inward of the carbon. Until reliable data on the rates of diffusion of carbon are available it is unlikely that a full quantitative description of this process will be obtained. In the formation of pearlite from austenite, the segregation of carbon and alpha iron from the austenite obviously requires the diffusion of carbon; the rate at which pearlite nodules grow is evidently controlled at least in part by the rate of diffusion of carbon; it is unlikely that we shall understand the factors that determine the rate of growth unless data on rates of diffusion of carbon, and the variation of these with composition, grain size, and temperature are available. Accordingly it was decided: (1) to determine, more accurately than hitherto, the diffusion coefficients of carbon in austenite over a wide temperature and a wide concentration range, (2) to study the influence of grain size and impurities on this diffusion coefficient, and (3) to study the effect of manganese and nickel on the rate of diffusion of carbon in the austenite of manganese and nickel steels, respectively; the influence of carbon on the rate of diffusion of manganese and of nickel will be made the subject of later papers. The rate of diffusion of carbon in gamma iron has been studied by Runge3 by Tammann and Schonert4, by Bramley and co-authors,5-14 and

Jan 1, 1940

By Cyril Wells, Robert F. Mehl

The diffusion of carbon in gamma iron plays an essential role in many metallurgical processes. In carburizing, in graphitizing, in homogenizing, in the formation of pearlite from austenite, and in other processes, migration of carbon in gamma iron occurs.1&apos;2 A full understanding of the rate at which these processes occur obviously requires a knowledge of the rate of diffusion of carbon. In carburizing, for example, the depth of carbon pentration is determined by the carbon concentration in solid solution at the surface, and by the rate of diffusion inward of the carbon. Until reliable data on the rates of diffusion of carbon are available it is unlikely that a full quantitative description of this process will be obtained. In the formation of pearlite from austenite, the segregation of carbon and alpha iron from the austenite obviously requires the diffusion of carbon; the rate at which pearlite nodules grow is evidently controlled at least in part by the rate of diffusion of carbon; it is unlikely that we shall understand the factors that determine the rate of growth unless data on rates of diffusion of carbon, and the variation of these with composition, grain size, and temperature are available. Accordingly it was decided: (1) to determine, more accurately than hitherto, the diffusion coefficients of carbon in austenite over a wide temperature and a wide concentration range, (2) to study the influence of grain size and impurities on this diffusion coefficient, and (3) to study the effect of manganese and nickel on the rate of diffusion of carbon in the austenite of manganese and nickel steels, respectively; the influence of carbon on the rate of diffusion of manganese and of nickel will be made the subject of later papers. The rate of diffusion of carbon in gamma iron has been studied by Runge3 by Tammann and Schonert4, by Bramley and co-authors,5-14 and

Jan 1, 1940

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The two earlier papers in this series1,2 presented data on the rate of diffusion of carbon and of manganese in gamma iron. Apart from their scientific interest, these data are needed chiefly in order to treat data on carburization, on rate of formation of pearlite, and on rate of austenit-izing in a quantitative way.1&apos;2&apos;9&apos;10 In the present investigation rates of diffusion of nickel in ?-Fe over wide temperature and concentration ranges have been determined, and the effects of carbon, of im- purities, and of grain size on these rates have been studied. Claussen,3 using the data of Fry,4 has calculated the diffusion coefficient of nickel in y-Fe as 9.2 X 10-11 sq. cm. per sec. at 1200ºC., but had no data from which to calculate the variation of D with concentration, temperature, and percentage of carbon. Method and Materials Method.—Nickel was diffused along the axis of a cylindrical specimen across a concentration gradient, concentration-penetration curves were determined and D values calculated from Grube or Matano solutions.5 Details of the method are given

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The two earlier papers in this series1,2 presented data on the rate of diffusion of carbon and of manganese in gamma iron. Apart from their scientific interest, these data are needed chiefly in order to treat data on carburization, on rate of formation of pearlite, and on rate of austenit-izing in a quantitative way.1&apos;2&apos;9&apos;10 In the present investigation rates of diffusion of nickel in ?-Fe over wide temperature and concentration ranges have been determined, and the effects of carbon, of im- purities, and of grain size on these rates have been studied. Claussen,3 using the data of Fry,4 has calculated the diffusion coefficient of nickel in y-Fe as 9.2 X 10-11 sq. cm. per sec. at 1200ºC., but had no data from which to calculate the variation of D with concentration, temperature, and percentage of carbon. Method and Materials Method.—Nickel was diffused along the axis of a cylindrical specimen across a concentration gradient, concentration-penetration curves were determined and D values calculated from Grube or Matano solutions.5 Details of the method are given

Jan 1, 1941

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.&apos; It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942