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By E. O. Karenna, A. D. Smigelskas

This is the third paper in a series on the diffusion of zinc in alpha brass.' At the time of the first paper it was accepted that diffusion in a substitutional type of solid solution depended upon an equal interchange of solute and solvent atoms across the diffusion interface (or past a given lattice reference point). Discrepancies in the size of the areas under the diffusion curves on each side of the interface, if observed, were explained on some other basis than the fact that the solute atoms might cross the diffusion interface without an equal number of solvent atoms diffusing across the interface in the opposite direction. The second paper presented evidence indicating that zinc atoms in alpha brass diffuse across the interface more rapidly in one direction than the copper atoms diffuse across the interface in the opposite direction. This phenomenon forced the interface to move in the opposite direction of the diffusion of zinc atoms to provide space for the additional zinc atoms dissolved in the alpha brass. That the interface and columnar grain structure on one side would remain intact during this mass movement was not expected; how ever, it is gratifying that they did. While the evidence was sufficiently satisfying to the author, it was decided that additional experiments were in order to prove that zinc diffuses more rapidly than copper in alpha brass. It is the purpose of this paper to present the results of these experiments. Procedure A bar of 70-30 wrought brass was selected, to avoid the relatively large volume change in going from beta to alpha brass as in the previous investigation. A bar 7 in. (18-cm.)* long and about 3/4 in. (1.9 cm.) wide was surface ground and polished with abrasive paper on plate glass to 0.4184 0.0002 in. (1.062j + 0.0005 cm.) thick. Six0.00j-in. (0.013-cm.) diameter molybdenum wires, chosen because of their very low solubility in coppcr and alpha brass, were strctched lengthwise along each of the two plane surfaces. Glass tubes placed at right angles to the wires every 1/2 in. held the wires tightly against the brass. The sample was then emersed in an acid copper sulphate plating bath and electroplated to a depth of about 0.020 in. (0.050 cm.) copper on all sides. The glass tubes were no longer necessary to hold the molybdenum wires in place and were removed. The sample was then electroplated to a depth of

Jan 1, 1947

By Leonard D. Jaffe, Donald C. Buffum

THE importance of temper brittleness in alloy steels has long been realized in Europe, In the United States recognition of its importance has developed within the last several years. Many brittle failures encountered in parts made of alloy steel are undoubtedly attributable, wholly or in part, to temper brittleness. These failures have occurred particularly at low temperatures, under shock loading, and in the presence of notches, restraints and combined stresses. It has been almost universally accepted that plain carbon steels are not susceptible to temper brittleness. As a result, considerable effort has been expended in attempts to discover the manner in which alloying elements introduce temper brittleness. It is desired to raise the possibility that plain carbon steels are not only susceptible to temper brittleness, but are much more susceptible than alloy steels, in the sense that they embrittle much more rapidly. It is suggested that previous views, (that plain carbon steels are not susceptible), are based upon an erroneous interpretation of the experimental results. INTERPRETATION OF PREVIOUS DATA For many years the standard criterion for susceptibility of a steel to temper brittleness consisted of comparison of the energy absorption, in a notched-bar impact test at room temperature, of specimens that had received two heat treatments.1 One specimen (or group of specimens) was quenched, tempered, and quenched from the temper. The other specimen (or group) differed only in having received an embrittlement treatment, which might consist of a slow cool from the tempering temperature, or of an isothermal hold in the range 450-550°C subsequent to quenching from the temper. If the energy absorption of the specimen receiving the embrittlement treatment was lower than that of the specimen not given this treatment, it was said that the steel was susceptible to temper brittleness, If the energy absorptions were the same, it was said that the steel was not susceptible. Several investigators2,3 found that plain carbon steels showed negligible difference in energy absorption in such tests (at least when their manganese content was below 0.60 pct), and concluded that plain carbon steels are not susceptible to temper brittleness. Recently the deficiencies of the criterion mentioned above have been pointed out.4-6 The criterion now generally used for susceptibility to temper brittleness retains the heat treatments used in the earlier scheme, but instead of the notched-bar impact tests being made only at room temperature, they are made over a range of temperatures, covering the transition from ductile to brittle fracture, If the transition temperature of the specimens receiving the embrittlement treatment is higher than those

Jan 1, 1948

By Arthur L. Christenson, Clarence E. Jackson

In the establishment of the relationship between weldability and hardenability, two methods have been employed in correcting for the grain growth produced in the heat-affected zone: first, the hardenability calculated from chemical composition* may be corrected to the grain size observed in an actual weld? or, second, a hardenability test may be made on the steel quenched from a temperature high enough to produce a grain size comparable to that found in the heat-affected zone.8 In order to obtain grain sizes in the end-quench hardenability bar comparable to those resulting in the base metal from the welding cycle, a quenching temperature of 2Ioo°F. has been used. In studies of the end-quench hardenability specimen quenched from 2Ioo°F. instead of from a lower temperature of I7OO°F., it is impor-TaiiT to ascertain The relative cooling rates for various distances along the bar. It is a question as to whether the cooling occurs at the same rate or whether there is any significant difference from the standard cooling-rate curve published by Jominy and confirmed by others.4,5 This paper reports experimental evidence concerning the effect of quenching temperature on the cooling rates in the end-quench hardenability test. The effect of quenching temperatures on cooling rates has been studied by a number of investigators.6'7 French has considered this effect from both theoretical and experimental aspects. In French's studies on complete quenching of spheres and rounds, an increase in the quenching temperature caused an increase in the cooling rate at 720°C. at the center of the specimen. The center cooling velocity also has been shown to be dependent upon the surface per unit volume for the type of specimens studied; the velocity of cooling increases with an increase in the surface per unit volume. Three methods of indicating the rapidity of cooling of a body of metal during a quenching operation have been propped: I. The time it takes for the metal to cool from the quenching temperature to a temperature halfway between the quenching temperature and the temperature of the quenching medium (half-temperature time): Grossmann, Asimow and Urban7 justify the use of this criterion by the fact that the half-temperature time includes the temperature and time of incubation as well as the zone of formation of pearlite and, further, the data so derived accord very closely with experimental values. 2. The time interval the metal remains in a given temperature range; for example,

Jan 1, 1944

By Arthur L. Christenson, Clarence E. Jackson

In the establishment of the relationship between weldability and hardenability, two methods have been employed in correcting for the grain growth produced in the heat-affected zone: first, the hardenability calculated from chemical composition* may be corrected to the grain size observed in an actual weld? or, second, a hardenability test may be made on the steel quenched from a temperature high enough to produce a grain size comparable to that found in the heat-affected zone.8 In order to obtain grain sizes in the end-quench hardenability bar comparable to those resulting in the base metal from the welding cycle, a quenching temperature of 2Ioo°F. has been used. In studies of the end-quench hardenability specimen quenched from 2Ioo°F. instead of from a lower temperature of I7OO°F., it is impor-TaiiT to ascertain The relative cooling rates for various distances along the bar. It is a question as to whether the cooling occurs at the same rate or whether there is any significant difference from the standard cooling-rate curve published by Jominy and confirmed by others.4,5 This paper reports experimental evidence concerning the effect of quenching temperature on the cooling rates in the end-quench hardenability test. The effect of quenching temperatures on cooling rates has been studied by a number of investigators.6'7 French has considered this effect from both theoretical and experimental aspects. In French's studies on complete quenching of spheres and rounds, an increase in the quenching temperature caused an increase in the cooling rate at 720°C. at the center of the specimen. The center cooling velocity also has been shown to be dependent upon the surface per unit volume for the type of specimens studied; the velocity of cooling increases with an increase in the surface per unit volume. Three methods of indicating the rapidity of cooling of a body of metal during a quenching operation have been propped: I. The time it takes for the metal to cool from the quenching temperature to a temperature halfway between the quenching temperature and the temperature of the quenching medium (half-temperature time): Grossmann, Asimow and Urban7 justify the use of this criterion by the fact that the half-temperature time includes the temperature and time of incubation as well as the zone of formation of pearlite and, further, the data so derived accord very closely with experimental values. 2. The time interval the metal remains in a given temperature range; for example,

Jan 1, 1944

By Michael B. Bever, Carl F. Floe

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By Carl F. Floe, Michael B. Bever

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By Horace Pops

Isothermal sections in the copper -rich region of the Cu-Si-Zn a1by system have been determined at 8473 760; 6003 and 482°C by means of microscopic examination with confirmatory X-ray diffraction work. The stability of the bee 0 phase decreases both with decreasing temperature and with increasing copper content. The silicon-n&apos;ch 0 phase decomposes upon quenching from high temperatures either by a martensitic or by a "massive" transformation, depending upon the solute content. A two-phase equilibrium is found to exist in the Cu-Si-Zn system between the hep < phase of the Cu-Si system and the bee ß phase of the Cu-Zn system. It is shown that the isothermal limits of the primary solid solution at 760; 6003 and 482°C are in part affected by the intermediate phases which follow them in the ternary system Possible electron-concentration and size effects upon phase boundaries are discussed. ALTHOUGH the mechanical and physical properties of silicon brasses have been measured in great detail, the factors which influence these properties are not well-understood, partly because the knowledge of the phase relationships in the Cu-Si-Zn system is limited. Gould and Ray1 studied the effects of silicon upon the hardness and structure of Cu-15 pet Zn and Cu-40 pet Zn alloys. They proposed an isothermal section at 800°C which was not based upon experimental data, since the binary phase diagrams had not been completely determined. Using Cu-Si-Zn alloys containing approximately 5 wt pet Si, vaders2 determined the boundary, at 750°C, between the copper-rich solid solution and an unidentified second phase. Masing and wallbaum3 examined a vertical section through the ternary diagram in the region between Cu-20 pet Zn and Cu-10 pet Si alloys, but they emphasized uncertainty about their data. Mima and Hasegawa4 studied the liquidus surface of Cu-Si-Zn alloys, phase transformations in high silicon-bearing (20 to 25 at. pet) alloys,5 and the phase relations in low silicon-bearing Cu-Si-Zn alloys.6 Their experiments were based upon thermal analyses and metallographic observations. The compositions of the phase boundaries were not determined with high precision, and the crystal structures of the phases were not reported. Because of uncertainties in the existing literature, it became of interest to determine more accurately the phase relations in copper-rich Cu-Si-Zn alloys. The crystal structures, stability, and phase boundaries of the primary solid solutions and several intermediate phases were determined, and the data are reported as partial isothermal sections.

Jan 1, 1964

By A. Mitchell, T. Bagshaw

A recent paper by Thomas1 has presented new data on the solubility of hydrogen in solid silver at 1 atm pressure in the temperature range 600° to 963°C. However, no data is reported in the literature on hydrogen solubility in liquid silver. The Sieverts technique which has been described previously2,3 was used in the present work. Charges of approximately 160 g were melted in Morgan "purox" recrystallized alumina crucibles and purified helium was used for the determination of the "hot volume" during each experiment. A chemical analysis of the silver indicates that the impurity content (Cu + Al) is less than 0.02 wt pct. Hydrogen solubility in the temperature range 963° to 1200°C was investigated. The results of three experiments are shown in Table I. Fig. 1 shows an Arrhenius plot of the present work together with the solid-state data of Thomas, Steacie, and johnson,4 Eichenauer et al.,5 and Siegelin et al.6 The following expression has been derived from the Arrhenius plot of the present data: log (solubility of hydrogen, cm3 per 100 g) = 2.154-3512.0/ToK The heat of solution derived from Fig. 1 is 31,150 cal per g mole H2 compared with the value of 33,020 cal per g mole H2 obtained by Thomas and 12,000 cal per g mole H2 obtained from the data of Steacie. It was observed that hydrogen evolution took place when the silver melts were solidified under 1 atm of hydrogen, which would not be expected from an extrapolation of the results of Steacie. Schenck and Lange7 have observed that, for several transition metals at their melting points, the ratio of the hydrogen solubility in the liquid to that in the solid lies in the range 2.1 to 3.1. The present results and those of Thomas are in accord in this respect having a ratio of 2.8. &apos;C. L. Thomas: Trans. TMS-AIME, 1967 vol. 239, pp. 485-96. 2T. Bagshaw and A. Mitchell: I. Iron Steel Inst., 1966, vol. 204, p. 87. &apos;M. Weinstein and J. F. Elliott: Trans. TWS-AIME, 1963, vol. 227, p. 382. &apos;E. W. R. Steacie and F. M. G. Johnson: Proc. Roy. Soc. (London), Ser. A, 1928, vol. 117, pp. 662-79. &apos;W. Eichenauer et al.: Z. Metallk., 1958, vol. 49, pp. 220-25. 6W. Siegelin et al.: Z. Elektrochem., 1957, vol. 61, pp. 359-66. &apos;H. Schenck and K. W. Lange: Arch Eisenhuettenw., 1966, vol. 37, no. 9, pp. 739-48.

Jan 1, 1969

By G. Thodos, E. M. Phillips

A reduced density correlation for the gaseous and liquid regions of ethane has been developed from all the experimental PVT data available in the literature for this substance. Saturated vapor and liquid densities reported for methane, propane and n-butane were utilized to establish the rectilinear-diameter line for ethane. This line was then used with the saturated-vapor data for ethane to produce the saturated envelope for this substance. Most of the saturated liquid data reported for ethane were found to be inconsistent with the saturated-liquid curve resulting from this study. The correlation covers the regions 0.65 < TR <6.0 and 0 < PR < 15. For regions for which no experimental data have been reported, the isobars of the correlation were extended by the use of the theorem of corresponding states. This correlation is presented both on rectilinear and log-log coordinates. INTRODUCTION At the present time, there is considerable interest in the exact PVT behavior of pure hydrocarbons. Matschke and Thodos12 recently have developed a comprehensive compilation of experimental vapor and liquid density data for methane. Similar studies have been conducted for other pure substances.4, 7 In the present study the density data available in the literature for gaseous and liquid ethane have been critically reviewed and utilized to develop a reduced density correlation for this substance. SATURATED LIQUID AND VAPOR DENSITIES The rectilinear-diameter rule proposed by Cailletet and Mathias5 states that the sum of the saturated liquid and vapor densities of a pure substance is a linear function of temperature which passes through the critical point. This law, although empirical, has been well established by continued verification since its conception in 1886. This rule has been applied to the saturated density data of methane,6 propane 17 and n-butane8 to produce the straight lines presented in Fig. 1 which pass through the critical point TR = 1.00, Pr = 2.00. The rectilinear-diameter relationship for ethane was established from the lines for the other substances in Fig. 1 by plotting the quantity p~, + PR against zc for different reduced temperatures. A critical analysis of the saturated vapor and liquid densities reported for ethane by Kuenen,10 Maass and McIntosh,11 and Sage, Webster and Lacey18 revealed that the values of PR1 + pr resulting from these studies were inconsistent with the rectilinear-diameter line obtained from the reliable density data of the other substances, as shown in Fig. 1. In the analysis of these data, reduced quantities were calculated using the critical con-

By W. A. Bates, R. J. Miller

Although cresylic acids have been standard frothers in flotation for many years, there has been little discussion of their nature in the metallurgical literature. Aside from references in the patent literature, the paper by Landolt, Hill, and Lowyl in 1930, which resented a study of the frothing and collecting properties of some of the constituents of crude cresylic acids, represents the only contribution of this type. The close froth control required in the delicate selective separations of present-day flotation operations have required the flotation metallurgist to choose his frothers with care, and have caused him to require of the manufacturer a closely controlled, uniform product. A background of knowledge of the chemical composition and physical and chemical properties of the frothers, by which their action may be correlated, should aid in selecting frothers for particular flotation requirements. Further, the recent almost complete replacement in flotation of coal-tar cresylic acids by those derived from petroleum makes it especially desirable to review the flotation behavior of the acids from the old and the new sources. In view of these facts the Milling Methods Committee of the A.I.M.E. suggested to the Oronite Chemical Co. of San Francisco the preparation of a paper on the subject, and this paper has accordingly been prepared as a contribution by the California Research Corporation, the research affiliate of the Oronite Chemical Co. The discussion is from the following aspects: (I) constitution and properties; (2) sources; (3) comparison of coal-tar and petroleum cresylic acids; (4) characteristics as frothers, with particular reference to the effect of the substitution of petroleum acids for coal-tar acids. Constitution and Properties Cresylic acids are commonly regarded as mixtures of orthocresol, metacresol and paracresol. This was, indeed, the former meaning of the term, but in recent years it has been loosely applied to any mixture of alkyl phenols boiling above 190°C.; that is, excluding only phenol itself. This means that cresylic acids, as they are known today, may consist of mixtures, not only of the three isomeric cresols, but of six xylenols and of a variety of higher boiling homologues. Generically the constituents of cresylic acids are alkyl phenols, and they are often so designated in the literature to avoid the more indefinite term, "cresylic acids." They form an homologous series starting with phenol, which has the familiar benzene ring, with an hydroxyl group in place of one of the hydrogen atoms. The series of alkyl phenols is formed by the substitution of alkyl side chains, such as methyl, ethyl, propyl, butyl, etc., for hydrogen atoms of the benzene ring of phenol. Some

Jan 1, 1947

By R. J. Miller, W. A. Bates

ALTHOUGH cresylic acids have been standard frothers in flotation for many years, there has been little discussion of their nature in the metallurgical literature. Aside from references in the patent literature, the paper by Landolt, Hill, and Lowy1 in 1930, which presented a study of the frothing and collecting properties of some of the constituents of crude cresylic acids, represents the only contribution of this type. The close froth control required in the delicate selective separations of present-day flotation operations have required the flotation metallurgist to choose his frothers with care, and have caused him to require of the manufacturer a closely controlled, uniform product. A background of knowledge of the chemical composition and physical and chemical properties of the frothers, by which their action may be correlated, should aid in selecting frothers for particular flotation requirements. Further, the recent almost complete replacement in flotation of coal-tar cresylic acids by those derived from petroleum makes it especially desirable to review the flotation behavior of the acids from the old and the new sources. In view of these facts the Milling Methods Committee of the A.I.M.E. suggested to the Oronite Chemical Co. of San Francisco the preparation of a paper on the subject, and this paper has accordingly been prepared as a contribution by the California Research Corporation, the research affiliate of the Oronite Chemical Co. The discussion is from the following aspects: (I) constitution and properties; (2) sources; (3) comparison of coal-tar and petroleum cresylic acids ; (4) characteristics as frothers, with particular reference to the effect of the substitution of petroleum acids for coal-tar acids. CONSTITUTION AND PROPERTIES Cresylic acids are commonly regarded as mixtures of orthocresol, metacresol and paracresol. This was, indeed, the former meaning of the term, but in recent years it has been loosely applied to any mixture of alkyl phenols boiling above 190°C.; that is, excluding only phenol itself. This means that cresylic acids, as they are known today, may consist of mixtures, not only of the three isomeric cresols, but of six xylenols and of a variety of higher boiling homologues. Generically the constituents of cresylic acids are alkyl phenols, and they are often so designated in the literature to avoid the more indefinite term, "cresylic acids." They form an homologous series starting with phenol, which has the familiar benzene ring, with an hydroxyl group in place of one of the hydrogen atoms. The series of alkyl phenols is formed by the substitution of alkyl side chains, such as methyl, ethyl, propyl, butyl, etc., for hydrogen

Jan 1, 1946

By R. J. Miller, W. A. Bates

Although cresylic acids have been standard frothers in flotation for many years, there has been little discussion of their nature in the metallurgical literature. Aside from references in the patent literature, the paper by Landolt, Hill, and Lowyl in 1930, which resented a study of the frothing and collecting properties of some of the constituents of crude cresylic acids, represents the only contribution of this type. The close froth control required in the delicate selective separations of present-day flotation operations have required the flotation metallurgist to choose his frothers with care, and have caused him to require of the manufacturer a closely controlled, uniform product. A background of knowledge of the chemical composition and physical and chemical properties of the frothers, by which their action may be correlated, should aid in selecting frothers for particular flotation requirements. Further, the recent almost complete replacement in flotation of coal-tar cresylic acids by those derived from petroleum makes it especially desirable to review the flotation behavior of the acids from the old and the new sources. In view of these facts the Milling Methods Committee of the A.I.M.E. suggested to the Oronite Chemical Co. of San Francisco the preparation of a paper on the subject, and this paper has accordingly been prepared as a contribution by the California Research Corporation, the research affiliate of the Oronite Chemical Co. The discussion is from the following aspects: (I) constitution and properties; (2) sources; (3) comparison of coal-tar and petroleum cresylic acids; (4) characteristics as frothers, with particular reference to the effect of the substitution of petroleum acids for coal-tar acids. Constitution and Properties Cresylic acids are commonly regarded as mixtures of orthocresol, metacresol and paracresol. This was, indeed, the former meaning of the term, but in recent years it has been loosely applied to any mixture of alkyl phenols boiling above 190°C.; that is, excluding only phenol itself. This means that cresylic acids, as they are known today, may consist of mixtures, not only of the three isomeric cresols, but of six xylenols and of a variety of higher boiling homologues. Generically the constituents of cresylic acids are alkyl phenols, and they are often so designated in the literature to avoid the more indefinite term, "cresylic acids." They form an homologous series starting with phenol, which has the familiar benzene ring, with an hydroxyl group in place of one of the hydrogen atoms. The series of alkyl phenols is formed by the substitution of alkyl side chains, such as methyl, ethyl, propyl, butyl, etc., for hydrogen atoms of the benzene ring of phenol. Some

Jan 1, 1947

The Institute is custodian of funds for support of numerous gold medals and prizes and has representatives on boards awarding still others. Details regarding the Institute Awards are given below. The Institute is represented on the boards of the John Fritz Medal, the Hoover Medal and the Washington Award, in connection with the three national societies of Civil, Mechanical and Electrical engineering; and, also, in the case of the Washington Award, with the Western Society of Engineers. Robert W. Hunt Medal and Prize THE partners of Robert W. Hunt established a fund which was presented to the Institute at a fitting ceremony on May 27, 1920, to establish an annual medal and a sum of money to be awarded under the following rules: 1. The award shall consist of two prizes: first of a gold medal, second of a sum of money; a certificate to accompany each prize. The money prize shall not be awarded to a member over 40 years of age, but under unusual circumstances, both prizes may be allotted to one person provided that he is not over 40 years of age. In general it will be understood that the Committee shall award the money prize to the younger men, rather than the medal. 2. The awards shall be made not oftener than once a year to that person or persons contributing to the Institute the best original paper or papers on iron and steel. The scope of the term "iron and steel" shall be determined by the subcommittee considering the awards. In general, papers dealing with the practical side of the subject have preference over those dealing with the theoretical side in recognition of the fact that Captain Hunt&apos;s main contributions to the industry have been in the improvement of production and quality of material. 3. A subcommittee of three to five, including the Chairman of the Iron and Steel Division, shall be appointed by the Iron and Steel Division annually to adjudge the award subject to approval. 4. The awarding committee shall submit its report to the Iron and Steel Committee at its October meeting, and the award shall be certified to the Secretary of the Institute in time to permit the presentation to be made at the Annual Meeting of .the Institute. 5. The recipient of the award shall be designated "The Hunt Medalist." Awards of the medal have been made as follows: 1920—-Robert Woolston Hunt. 192G—John A. Mathews. 1926—Charles Lewis Kinney, Jr. 1929—Edgar Collins Bain. 193G—James Aston. Awards of the prize have been made as follows: 1928—C. H. Herty, Jr. 1929—William E. Griffiths.

Jan 1, 1930

By A. U. Seybolt

RECENTLY, cases of coexisting ordered and disordered phase equilibria have been reported among face-centered cubic metals,1"3 but not on body-centered cubic systems.4 McQueen and Kuczynski5 showed a single line as the boundary between ordered solid solution of Fe3Al type and corresponding disordered solution in the Fe-A1 phase diagram based mainly on dilatometric and magnetic measurements. Such a single line would indicate a second or higher order transition. or an absence of coexisting order and disorder. The writer found previously a two-phase equilibrium region at 800°C consisting of ordered and disordered solid solutions of Fe3Si in a matrix of approximately 1-6 wt pct Si (Fe3Si is of 14.3 wt pct Si). A similar two-phase region of ordered and disordered Fe3Al solid solutions might be expected if the similarity between Fe3Si and Fe3Si structures hold true. In the present investigation, a wire of 22 at. pct Al, balance Fe and 0.0513 cm in diameter was subjected to electrical resistivity measurement in vacuum as a function of temperature between 300 and 800°C, see Fig. 1. There was excellent agreement between data taken on heating and on cooling: no hysteresis was observed. The Curie temperature was determined to be 640 °C which agrees with the finding by McQueen and Kuczynski.5 But in addition, there were two transitional points in the resistance-temperature plot at 510oC and 400 "C. The former is thought to be a connection with the transition from disordered state to a coexisting order and disordered equilibrium state; while the latter, from such coexisting state to ordered state. Fig. 2 shows a phase diagram where the suggested two-phase region lies between dotted lines. The solid lines are those of McQueen and Kuczynski.5 Since these authors found only a single-phase boundary between ordered and disordered Fe3 Al, it would seem likely that the dilatometric method used by these authors was not sufficiently sensitive to resolve the ordering reaction into the two-phase boundaries. In addition, their phase diagram conflicts with the statement they make on P. 1 of their paper: "The sharpness of the peaks indicates that ordering to Fe3A1 is a first order reaction." The suggestion of coexisting order plus disorder in Fe3A1 must be considered tentative until confirmed by high-temperature X-ray examination. If

Jan 1, 1961

By R. H. Dourson, B. H. Sage, W. N. Lacey

The compositions of coexisting phases in the methane-propane-n-pentane system were determined at 160° and -2 20°F. throughout the two-phase region, at pressures above 500 lb. per sq. in. The experimental results permitted the calculation of gas-liquid equilibrium constants as well as the establishment of the critical behavior of this ternary system. Although many binary paraffin hydrocarbon systems have been investigated, the experimental work relating to the phase behavior of ternary paraffin hydrocarbon mixtures at elevated pressures is relatively scarce, being limited to a study of the meth-ane-propane-PL-pentane system at 100°F.l,2 However, Guter and co-workers have studied the phase behavior of the methane-ethane-ethylene system at relatively low temperatures. Information concerning the phase behavior of ternary systems is of value in predicting the behavior of the components in multicomponent systems, since the influence of pressure, temperature, and concentration may be individually ascertained. In the light of the importance of such information, the study of this ternary system was extended to higher temperatures in order to increase the field of temperature in which the data could be applied. Since all states encountered in this investigation are above the critical temperature of methane, the details of its phase behavior are not of direct significance. The properties of propane in the heterogeneous region were taken from a correlation3 based upon recently published data. The corresponding information for n-pentane was taken from experimentally measured vapor pressures and volumetric data.4 The rnethane-propane system has been studied throughout the two-phase region at temperatures above 70°F.,5 while the phase behavior of the propane-n-pentane system has been established for temperatures above 160°F.6 The volumetric and phase behavior of the methane-72-pentane system has been studied in detai1.7,8 The experimental measurements serve to establish with adequate accuracy the phase behavior of the components and of the constituent binary systems for this ternary system. It is believed that, with the exception of the measurements for the methane-propane system, the uncertainties in the earlier data relating to the pure substances and the binary mixtures are probably less than those associated with the values reported here. Method The methods and apparatus employed in this investigation have been described.137 In principle, the method involved the withdrawal of samples of the coexisting gas and liquid phases from a vessel containing a heterogeneous mixture of methane, propane and n-pentane. Provision was made so that

Jan 1, 1943

By W. N. Lacey, R. H. Dourson, B. H. Sage

The compositions of coexisting phases in the methane-propane-n-pentane system were determined at 160° and -2 20°F. throughout the two-phase region, at pressures above 500 lb. per sq. in. The experimental results permitted the calculation of gas-liquid equilibrium constants as well as the establishment of the critical behavior of this ternary system. Although many binary paraffin hydrocarbon systems have been investigated, the experimental work relating to the phase behavior of ternary paraffin hydrocarbon mixtures at elevated pressures is relatively scarce, being limited to a study of the meth-ane-propane-PL-pentane system at 100°F.l,2 However, Guter and co-workers have studied the phase behavior of the methane-ethane-ethylene system at relatively low temperatures. Information concerning the phase behavior of ternary systems is of value in predicting the behavior of the components in multicomponent systems, since the influence of pressure, temperature, and concentration may be individually ascertained. In the light of the importance of such information, the study of this ternary system was extended to higher temperatures in order to increase the field of temperature in which the data could be applied. Since all states encountered in this investigation are above the critical temperature of methane, the details of its phase behavior are not of direct significance. The properties of propane in the heterogeneous region were taken from a correlation3 based upon recently published data. The corresponding information for n-pentane was taken from experimentally measured vapor pressures and volumetric data.4 The rnethane-propane system has been studied throughout the two-phase region at temperatures above 70°F.,5 while the phase behavior of the propane-n-pentane system has been established for temperatures above 160°F.6 The volumetric and phase behavior of the methane-72-pentane system has been studied in detai1.7,8 The experimental measurements serve to establish with adequate accuracy the phase behavior of the components and of the constituent binary systems for this ternary system. It is believed that, with the exception of the measurements for the methane-propane system, the uncertainties in the earlier data relating to the pure substances and the binary mixtures are probably less than those associated with the values reported here. Method The methods and apparatus employed in this investigation have been described.137 In principle, the method involved the withdrawal of samples of the coexisting gas and liquid phases from a vessel containing a heterogeneous mixture of methane, propane and n-pentane. Provision was made so that

Jan 1, 1943

By D. R. Packard, J. D. Verhoeven

The resistivity us atom fraction relationships for dilute solutions of cadmium, mercury, and tin in molten sodium have been determined. With these data and the resistivity capillary-reservoir technique, the electro-transport mobilities, effective valences, and the diflusion coefficients of the three solutes have been determined. The mobilities are found to be higher than in other molten alloys by a factor of around 20. The results are compared to the Mmgelsdorf model for electrotrmtsport. The high values found for the mobility to diffusion coefficient ratio indicate that small quantities of the alkali metals should be susceptible to purification from many solutes by means of electrotransport. PASSAGE of a direct electric current through a liquid metal containing a solute will usually cause a relative motion between the solute and solvent atoms of the alloy. This electrotransport phenomenon may be described experimentally in terms of the mobility of the solute atoms, i.e., the drift velocity of the solute relative to the solvent per unit electric field. In dilute solutions of liquid alloys this relative mobility becomes a measure of the velocity of the solute with respect to the observer since the motion of the solvent is negligible. The mobility is a significant parameter in evaluating the potential usefulness of electrotransport for such things as purification or solute control upon solidification. Prior to around 1958, quantitative data for the mobility of solutes in liquid metals were restricted to some solutes in liquid mercury. Since that time ad- ditional data have been reported for the mobility of solutes in liquid mercury, bismuth, tin, and lead, as shown in Table I. In 1963 Drakin et al.11 reported some values of a transport number for mercury and thallium in molten sodium and potassium. When these values were converted to mobilities, it was found that the mobilities were higher than any of the previously reported values by a factor of around 20, as shown in Table I. Drakin&apos;s experimental technique did not eliminate the presence of back-diffusion and consequently his data were expected to be lower than the true values. The purpose of the present investigation was to determine the mobility of a number of solutes in molten sodium with an experimental technique which eliminates back-diffusion errors. EXPERIMENTAL The technique used to determine the mobility was a resistivity capillary-reservoir technique which had previously been used with a high degree of precision on Sn-Bi alloys.4 This technique consists of dipping the vertical Pyrex capillary cell shown in Fig. 1 into a molten bath of alloy while the bath and capillary are under vacuum. The capillary is then filled by intro-

Jan 1, 1969

By Ming-Kao Yen

A considerable amount of work has been reported in the literature in regard to the texture and earing behavior of copper strip. The rolling texture of copper has been confirmed as (110) [112] and (112) [111], which yields ears of a drawn cup at the position 45" from the rolling direction.1-3 The recrystallization texture has been established as the cubic or (100) [001] texture, where the earing positions are at 0" and 90" to the rolling direction.4-8 It has also been reported that in the development of cubically aligned grains of copper strips, the percentage of this cubic texture increased with an increase of final reduction and final annealing temperature.8,9 A comprehensive study on H.C. copper (British commercial copper of high-conductivity quality = Cu 99.95 pct, O2 0.03 pct, Ag 0.003 pct, Fe 0.005 pct and Pb < 0.001 pct) was made by Cook and Richards.6 They concluded that the recrystallization textures could be described as one or more of the following textures: (1) a single texture (100) 10011, (2) a twin texture (110) [112] and (3) a random orientation, depending upon the previous history of the specimen concerned. The effect of various alloying additions in copper was reported by Dahl and Pawlek.10 They found that certain alloying additions, such as 5 pct Zn, 1 pct Sn, 4 pct Al, 0.5 pct Be, 0.5 pct Cd, or 0.05 pct P suppressed the formation of cubic texture. Brick, Martin and Angierll reported that the cold rolled textures due to various additions fitted a rather simple pattern. However, the recrystallization textures were subject to very considerable variations. In the discussion of this paper, Baldwin stated that deoxidized copper containing 0.02 pct P gave a complicated recrystallization texture at lower temperature. When this copper was annealed at high temperature, a single texture appeared which was described as (110) [ill] but. according to a pri- vate communication from Baldwin, this orientation reported was in error and should have been reported as (110)[112]. He also reported that the earing positions of drawn cups were at 60" to the rolling direction.12 Recently, Howald, in his discussion on the paper by Hibbard and Yen,13 reported that the rolling texture of phosphorus deoxidized copper, containing from 0.006 to 0.020 pct phosphorus, was of the pure copper type. When these coppers were annealed at lower temperatures, they exhibited a random orientation, and when they were annealed at higher temperatures they had a mixed (111)[110] and (100)[001] texture, depending on the severity of the final reduction and annealing temperature. However, the specific influence of phosphorus and other impurities on the recrystallization textures and the deep drawing properties of copper strip has not been thoroughly reported. Therefore, an attempt has been made in the present work to determine the rolling and recrystallization textures and also the earing behavior of five types of commercial copper and thereby to evaluate the effect of phosphorus and some other significant impurities on the development of texture for cold reductions of about 87 to 89 pct. Materials Used The five types of copper employed in the present investigation were two phosphorus deoxidized coppers of different phosphorus content (0.007 and 0.013 pct P), an oxygen-free copper (OFHC), an electrolytic tough-pitch copper, and a fire-refined tough-pitch copper. These materials were subjected to a thorough spectroscopic and chemical analysis. The designations and the chemical compositions were as shown in Table 1. The coppers, FA1, FA2 and FA3. were hot-forged from 3-in. billets into a ½ X 6-in. plate and cold rolled to the ready-to-finish gauge indicated below. FA4 and FA5 were hot rolled and scalped to ready-to-finish gauge. The grain size of all the materials in the ready-to-finish condition was about 0.030 to 0.045 mm. Table 2 shows the last stage of the production schedule for each copper strip used. Experimental Procedure ANNEALING, GRAIN SIZE AND HARDNESS DETERMINATIONS Specimens of each type of copper were finally annealed in air for periods of one hour at temperatures ranging from 300 to 1600°F and were subsequently cooled in air. The average grain diameter of the annealed specimen was estimated by comparing with a standard grain size chart. Hardness was determined on the Rockwell 15 T scale. CUPPING TESTS Cups were made in a blanking and drawing set, in which blanks of 2-in. diam were drawn to a cup of 1.25-in. diam with an average depth of about 0.75 in. The clearance between the punch and die was about 0.032 in. The ears of the cup were measured with a special fixture which read the height of ears to one-thousandth of an inch on every ten-degree interval along the circumference of the cup. POLE FIGURES The usual transmission diffraction method with unfiltered copper radiation was employed to determine the pole-figures of the specimens cold-rolled or annealed at 900°F. All the pole-figures were derived from the positions of intensity maxima on 111 diffraction rings of the X ray photo-grams taken at 10 rotation of a

Jan 1, 1950

By B. C. Allen

Grain boundary grooving has been studied in chromium, molybdenum, and tungsten under a variety of conditions using high vacuum techniques and tantalum -gettered argon. The average surface free energy of solid chromium, and the chromium-liquid silver interface free energy were respectively found to be 2200 ± 250 and 500 i 130 ergs per sq cm from groove formation kinetics and estimates of pertinent volume difffusion coefficients. The results for chromium were unffected by variations in interstitial content ranging from 0.003 to 0.09 pct C, or 0.003 to 0.03 pct O. Surface diffusion is the primary mechanism of groove formation in chromium under 1 atm argon at 1200" to 140O°C, and is essentially unaffected by 0.003 to 0.09 pct C, 0.003 to 0.03 pct O , metastable nitrogen contents up to -0.01 pct, and up to 2 torr Ag vapor. At higher temperatures, the major mechanism is volume diffusion in argon or evaporation-condensation in stutic vacuum. Surface diffusion occurs in molybdenum at 0.5 to 0.96 and in tungsten at 0.5 to 0.9 of the absolute melting tempera -ture by a single mechanism, possibly by the migration of single adatoms or vacancies. Results were slightly affected by up to 23 tory Sn vapor, and in molybdenum were essentially unaffected by 0.5 Ti or carbon in the range 0.002 to 0.02 pct. Volume difffusion through the liquid is the mechanism of groove formation in chromium-liquid silver at 1200" to 1400°C and in molybdenum-, Mo-0.5Ti-, and tungsten-liquid tin at 1200" to 2000°C. The solid-liquid interface free energies involved were estimated from grooving kanetics. WHEN a grain boundary intersects a solid surface, a groove tends to form along the line of intersection at temperatures above about half the absolute melting point (0.5 TM). The groove progressively grows by preferential atomic migration either by diffusion or evaporation. Establishment of a groove angle occurs in accordance with the grain boundary and surface free energies involved. The motivation for groove formation is a reduction in the total surface free energy of the system. This study is a continuation of previous work on thermal grooving of chromium, molybdenum, and tungsten.&apos; The temperature ranges were extended, and the effect of metallic and interstitial impurities was evaluated. The results were such that certain interface free energies and surface self-diffusion coefficients were deduced from the grooving kinetics. EXPERIMENTAL WORK Materials and Preparation. As indicated in Table I, the 0.05-0.08-cm-thick chromium, molybdenum, and tungsten sheet used was nominally 99.99 pct after recrystallization. Two lots of molybdenum with about the same analysis, Mo-0.5Ti,* and tungsten were ob- *Alloy compsitions are expressed in weight percent . tained commercially. Extruded chromium rod,&apos; prepared from iodide process crystals, was warm rolled to sheet at 700°C. Sheet of three Cr-0 impurity alloys containing up to 0.03 pct 0 was prepared by warm rolling arc melted, extruded, and swaged rod. Two Cr-C impurity alloys containing up to 0.09 pct C were made by equilibrating unalloyed chromium with a known amount of CH4 for 24 hr at 1150°C in previously evacuated quartz capsules. Chromium containing nominally 0.015 and 0.06 pct N was similarly prepared by equilibration with NH3. The sheet was recrystallized to give a stable grain size about equal to the sheet thickness. Molybdenum and Mo-O.5Ti were recrystallized in a tantalum resistance furnace 1 hr at 1 x lo-5 torr at 2300" and 220O°C, respectively. Tungsten was similarly annealed for 1 hr at 2500°C. Chromium and its impurity alloys were outgassed at 1100°C and recrystallized 1 hr at 1700°C under 1 atm Ar. Except for nitrogen, the impurity content stayed roughly constant. Nitrogen in both alloys was reduced to <0.001 pct. In fact, over 80 pct of the added nitrogen was lost after outgassing at llOO°C and annealing sheet 1 hr at 1300°C in argon in the presence of tantalum. Such a rapid loss can be rationalized since -2 torr N are required for equilibrium with 0.04 pct N in solution,3 while the equilibrium pressure is ~10-5 torr over tantalum at 1300°C.4 The recrystallized sheet was cut into small coupons which were metallographically ground and polished on one side with a minimum of grain boundary relief. The surface roughness was on the order of 0.01 µ. The tin and silver used were nominally 99.999 spec-trographically pure. After being outgassed at 1100°C and equilibrated in a molybdenum crucible for 0.5 hr at 1800°C in argon, the tin contained 3 ppm 0, <0.3 ppm N, and 0.1 ppm H. Following outgassing at 900°C and equilibration in a chromium crucible 1 hr at 1400°C in argon, the gas content of the silver was 1 ppm O, <0.5 ppm N, and 0.3 ppm H. Grooving Under Argon or Vacuum. All specimens were placed in unsealed containers made from rod or sheet of the same alloy, thereby enabling the polished surface to achieve gas-solid equilibrium. The annealing fixtures are shown in Fig. 1. The specimen was placed in a resistance furnace with a tantalum or Ta-10W heating element plus tantalum fixtures or radiation shields. Chromium was outgassed at 1100°C, and molybdenum and tungsten were outgassed at 1900°C to 1 x l0-5 torr or at the grooving temperature, whichever was lower. In vacuum anneals, the specimen was then heated directly to the intended grooving temperature. In argon anneals, 99.996 Ar was admitted

Jan 1, 1970

By A. E. Lee

THE Blackwell Zinc Co., Inc., a subsidiary of the American Metal Co., Ltd., operates a horizontal retort zinc smelter at Blackwell, Okla. The plant has 14 furnace blocks of 800 retorts each, fired with natural gas on a 48 hr cycle. Over 13,000 tons of zinc-bearing material, chiefly sulphide flotation concentrates, are treated monthly to produce slab zinc and high lead-cadmium fume. In 1942 a program of rebuilding and modernizing the smelter was started. By 1947 furnace smelting capacity had been increased to a point where roasting and sintering facilities were inadequate, and it was necessary to purchase oxidized materials to supplement sinter production. The seven 210 ft Ropp roasters and three 42 in. x 44 ft Dwight-Lloyd machines then in use had been in service at least 20 years and were in need of major rebuilding. Thus it was entirely practical to consider all new equipment and a change of method rather than rebuilding and repairing obsolete units. A study of the problem indicated that roasting as such could be eliminated and roasting and sintering accomplished in one step by a modification of the Robson process,&apos; which had been used since the early 1930&apos;s by the National Smelting Co., Ltd., at their plants at Avonmouth, England, and Swansea Vale, South Wales. Francis P. Sinn, General Manager, Zinc Smelting Operations, The American Metal Co., Ltd., who was familiar with the practice in England, suggested the use of one large machine for the entire operation from concentrate to sinter. One step sintering appeared to best meet Blackwell&apos;s plant requirements and indicated substantial savings in labor, gas, coal, and repair costs. Choice of Machine Size The sinter machine size was set at 12x168 ft for a rated capacity of 540 tons per day. This tonnage, produced on a five day week, would meet the seven day requirements of the 14 furnace blocks. The one large machine was quoted at a lower cost than two or more 6 ft wide machines of similar total capacity. Further, the larger machine could be housed in a smaller structure and only one set of equipment for charge preparation and delivery and for disposal of sinter cake was needed. One machine on a five day week made possible a concentration of the skilled operating personnel and required less men than a plant including two or more machines and related equipment circuits. Fewer units of equipment meant less maintenance, and the two down days weekly allowed ample time to repair and, if necessary, to make up lost production. Experience had indicated better sintering quality and rates with larger masses of material, not only on wider machines, but also in deeper beds. The ratio of windbox perimeter to area for the 12x168 ft machine is 0.179, compared to 0.353 for a 6x102 ft machine and 0.617 for a 42 in. x 44 ft machine. This meant less air leakage with resulting fan power savings and less spoilage of charge along the pallet sides. Performance Initial operation of the new sinter plant was made in November 1951 and regular production attained late in December. The average product sinter output during 1952 and the first half of 1953 has been 18.2 tons per hr. The average for one month has been as high as 22.4 tons per hr. Considerable experimenting with varied operating conditions accounts in part for the below capacity — 24 tons per hr — average output, and work to further improve production rate continues. A typical sinter analyses is 66.0 pct Zn, 0.3 pct Pb, 0.1 pct Cd, 0.3 pct S, 8.0 pct Fe, 2.0 pct SiO,, 0.8 pct CaO, and 0.2 pct MgO. Use of this material has made possible increases in furnace burden and improved furnace operation over the former practice using sinter made from Ropp roasted concentrates. Better lead and cadmium elimination in sintering has permitted the furnace production of slab zinc lower in lead and cadmium. Anticipated economies of operation have largely been gained. The sinter plant is operated by seven men per 8 hr shift — one head operator, three equipment operators and three sweepers — plus one oiler on day shift only. While it has been necessary at times to operate seven days a week to produce the required sinter tonnage, the five day work week usually has been adequate. Consumption of natural gas for sinter bed ignition is 200,000 to 300,000 cu ft per day. Green Ore Sintering Practice The 30 to 31 pct sulphur content of the —200 mesh zinc concentrates is the fuel used to sinter the charge, no coal addition being required. In the feed to the machine, sufficient concentrates are added to crushed return sinter fines containing 0.3 to 0.5 pct sulphur to produce a charge averaging 5.0 to 6.5 pct sulphur. Since the return sinter used in Blackwell&apos;s practice is varied from — 1/2 to — 1/8 in., the actual sintering mixture of fine sinter and concentrates is somewhat higher in sulphur. The coarser sinter particles are too large to resinter and merely aid porosity in the sinter bed. The ratio of concentrates to return sinter in the charge ranges from about 1:4 to 1:5.5. Variations are based on the appearance of pried up bed sections, bed exit gas temperature trends, windbox suctions, and return sinter size. Sufficient sulphur must be used to obtain fritting of the charge into a soft sinter cake and to aid in the elimination of lead and cadmium. Excessive feed sulphur will result in partial slagging of the cake impairing porosity and prolonging sintering time.

Jan 1, 1954