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By R. C. Good

Slag control for any kind of steel, rimming, straight carbon or alloy, should start with the charge and be developed well in advance of the tap because its composition, viscosity and temperature will unquestionably govern the physical and chemical properties of the steel when tapped. In the majority of plants producing alloy steels, primary consideration is given to the chemical specifications; physical characteristics usually occupy secondary place in the melter's mind. Recently, however, buyers have indicated limits of machinability, hardenability, grain size and, of course, always wanted steel free from foreign nonmetallic inclusions. It is these latter specifications that require the attention of the operator to the slag and its control. The slag must act as a vehicle for oxidized elements originating from the metallic portion of the charge; it should hold the oxides of phosphorus, silicon, manganese, iron and chromium that come into contact with it either before or after the refining and finishing stage of the heat. It must be used as a transferring medium of oxygen from the atmosphere or oxide additions to the metal and should permit a free escape of gas generated within the charge. Finally, the slag is the principal controlling factor in regulating the rate of oxidation which in turn eventually determines the quality of the steel as measured for the various characteristics mentioned above. With pig iron of uniform composition, the iron oxide in the slag increases as the limestone is increased but with the same addition of stone in every heat, the iron oxide decreases as the silicon is increased in the charge, and vice versa.

Jan 1, 1935

By Andrew S. McCreath

THE manufacture of pig iron for conversion into steel by the Bessemer and open-hearth processes, is now one of the most important industries of the United States. It is necessary that iron intended for this purpose should be very pure, and especially must it be comparatively free from phosphorus. Great care must therefore he exercised in the selection of proper ores, flux, and fuel. Only such ores as are practically free from phosphorus can be used, and pure fuel is as much a necessity as pure ores; though hitherto iron men have paid comparatively little attention to this point. During the course of my work as chemist for the Second Geological Survey of Pennsylvania, I had occasion to examine some of the bituminous coals of the State for phosphorus, and the results obtained are so interesting that I venture to present them to the notice of the members of the Institute. The coals are arranged in geological order according to the different beds, and the table shows the percentage of phosphorus in the coal and also in the coke. The greatest number of specimens have been selected from the Pittsburgh bed, because it is the principal coal-bed of Southwestern Pennsylvania, and most of the mineral fuel which is mined along the Youghiogheny and Monongahela rivers, to be used in the coke ovens of the Connellsville region and in the blast furnaces and mills of Pittsburgh and its vicinity, and to be shipped to Western and Southern markets, comes from this bed. It will be noticed that many of the specimens examined contain

Jan 1, 1880

By R. C. Good

Slag control for any kind of steel, rimming, straight carbon or alloy, should start with the charge and be developed well in advance of the tap because its composition, viscosity and temperature will unquestionably govern the physical and chemical properties of the steel when tapped. In the majority of plants producing alloy steels, primary consideration is given to the chemical specifications; physical characteristics usually occupy secondary place in the melter's mind. Recently, however, buyers have indicated limits of machinability, hardenability, grain size and, of course, always wanted steel free from foreign nonmetallic inclusions. It is these latter specifications that require the attention of the operator to the slag and its control. The slag must act as a vehicle for oxidized elements originating from the metallic portion of the charge; it should hold the oxides of phosphorus, silicon, manganese, iron and chromium that come into contact with it either before or after the refining and finishing stage of the heat. It must be used as a transferring medium of oxygen from the atmosphere or oxide additions to the metal and should permit a free escape of gas generated within the charge. Finally, the slag is the principal controlling factor in regulating the rate of oxidation which in turn eventually determines the quality of the steel as measured for the various characteristics mentioned above. With pig iron of uniform composition, the iron oxide in the slag increases as the limestone is increased but with the same addition of stone in every heat, the iron oxide decreases as the silicon is increased in the charge, and vice versa.

Jan 1, 1935

By Andrew S. McCreath

The manufacture of pig iron for conversion into steel by the Bessemer and open-hearth processes, is now one of the most important industries of the United States. It is necessary that iron intended for this purpose should be very pure, and especially must it be comparatively free from phosphorus. Great care must therefore he exercised in the selection of proper ores, flux, and fuel. Only such ores as are practically free from phosphorus can be used, and pure fuel is as much a necessity as pure ores; though hitherto iron men have paid comparatively little attention to this point. During the course of my work as chemist for the Second Geological Survey of Pennsylvania, I' had occasion to examine some of the bituminous coals of the State fix phosphorus, and the results obtained are so interesting that I venture to present them to the notice of the members of the Institute. The coals are arranged in geological order according to the different beds, and the table shows the percentage of phosphorus in the coal and also in the coke. The greatest number of specimens have been selected from the Pittsburgh bed, because it is the principal coal-bed of Southwestern Pennsylvania, and most of the mineral fuel which is mined along the Youghiogheny and Monongahela rivers, to be used in the coke ovens of the Connellsville region and in the blast furnaces and mills of Pittsburgh and its vicinity, and to be shipped to Western and Southern markets, comes from this bed. It will be noticed that many of the specimens examined contain

Jan 1, 1880

By H. C. Kenny

THE annealing or softening temperature of cold-worked copper is appreciably increased by almost unbelievably small amounts of silver. As indicated by some data in this paper, the softening temperature of high-conductivity, tough-pitch copper may be increased from 200° to 350° C. by the addition of only 15 oz. per ton (0.052 per cent) of that element. Because it has this higher annealing temperature as compared with the silver-free metal, silver-bearing copper finds considerable use in industry. For example, when hard-rolled copper is used in operations that involve soldering or tinning, silver-bearing copper insures against loss of strength, whereas silver-free copper becomes "dead soft." Yet-though several investigators, beginning with Caesar and Gerner1 in 1916, have shown that small amounts of silver do definitely raise the softening temperature of copper-data are lacking on the problem: What is the specific influence of different amounts of silver on this tem-perature? It was to help in filling this gap in the knowledge of what might be termed "alloy coppers" that the data given herein were obtained. The softening of cold-worked copper depends, of course, on a number of factors, of which the composition of the material is only one. Other highly important factors are the degree to which the material is cold-worked and the time it-is held at the annealing temperature. The method of cold working and the grain size of the metal produced are also signifi-cant. All these variables were taken into account in the investigation reported here, and the influence of silver on the electrical conductivity and on the working was also considered.

Jan 1, 1934

By Claude H. P. Lupis, John F. Elliott

QUITE generally an increase in the temperature tends to bring a system closer to ideality. It is reasonable as a first approximation to consider that the excess free energy will vary linearly with the temperature, or: where t may be defined as the "characteristic temperature" of the solution, or the temperature at which the system would become ideal if the results at T were linearly extrapolated. It must be emphasized that consideration of this hypothetical property is an appeal to intuition rather than an established physical concept. The order of magnitude of 7 for dilute solutions will depend on the nature of the solvent; a value of 3000° + 1000°K may be suggested for ordinary metallic solutions. In terms of free energy, entropy, and enthalpy first-order interaction coefficients, differentiation of the above equations with respect to composition leads to The concept of t offers a simple and plausible interpretation of Chipman and corrigan's3 recent empirical correlation between and a for a number of groups of ternary systems 1-24. The authors found that in each group the ratio was approximately constant. The corresponding calculated from their data by Eq. [4] are listed in Table I. The expected order of magnitude is obtained for 7. As noted by Darken,4 if a regular solution is not assumed, thus if utj) # 0, Chipman and Crrigan's results imply that, as T is increased, ultimately changes in sign, Fig. 1. Clearly Eq. [4] is valid only in a limited range of temperatures since at the temperature 7 at which the system becomes ideal not only should become null but also and . Thus, both and are functions of

Jan 1, 1967

By U. C. Tainton

FOR the last 15 years lead has been the standard material for anodes in electrolytic zinc production and it has been generally accepted that this lead should be as free as possible from impurities. Laist1 says, "Next in importance to the purity of solution is the purity of the electrodes and tank lining material. The purest lead obtainable should be used for anodes." The same conclusion is expressed by Ingalls2 and by two German investigators who say that experiments have demonstrated that the purer the lead, the greater is its resistance to corrosion during electrolysis.3 Pure lead, however, while the best material hitherto available for anodes, is not entirely free from objection. The plain lead anode gradually disintegrates under electrolysis, so that the life of an anode, say ¼ in. thick, is frequently not more than two years. Part of the lead from the anode finds its way to the cathode, lowering the purity of the deposited zinc and decreasing the hydrogen overvoltage. The rest of the lead that comes from the disintegration of the anode goes into the manganese dioxide which is precipitated in the cells, rendering unsaleable what might otherwise be a valuable by-product. Yet a further disadvantage of plain lead anodes comes from their tendency to bend or buckle during electrolysis, as a result of intercrystalline oxidation. This makes it necessary to use a fairly wide spacing between anode and cathode to avoid short circuits, and thus leads to a higher power consumption than would otherwise be necessary. The power consumption is also affected by the high decomposition voltage at a lead peroxide surface.

Jan 1, 1929

By A. G. Taylor, H. P. Ehrlinger, U. C. Tainton

FOR the last 15 years lead has been the standard material for anodes in electrolytic zinc production and it has been generally accepted that this lead should be as free as possible from impurities. Laistl says, "Next in importance to the purity of solution is the purity of the electrodes and tank lining material. The purest lead obtainable should be used for anodes." The same conclusion is expressed by Ingalls2 and by two German investigators who say that experiments have demonstrated that the purer the lead, the greater is its resistance to corrosion during electrolysis.3 Pure lead, however, while the best material hitherto available for anodes, is not entirely free from objection. The plain lead anode gradually disintegrates under electrolysis, so that the life of an anode, say 1/4 in. thick, is frequently not more than two years. Part of the lead from the anode finds its way to the cathode, lowering the purity of the deposited zinc and decreasing the hydrogen overvoltage. The rest of the lead that comes from the disintegration of the anode goes into the manganese dioxide which is precipitated in the cells, rendering unsaleable what might otherwise be a valuable by-product. Yet a further disadvantage of plain lead anodes comes from their tendency to bend or buckle during electrolysis, as a result of intercrystalline oxidation. This makes it necessary to use a fairly aide spacing between anode and cathode to avoid short circuits, and thus leads to a higher power consurnption than would otherwise be necessary. The power consumption is also affected by the high decomposition voltage at a lead peroxide surface.

Jan 1, 1929

By Earl Bardwell

IN his paper entitled, Development of Hindered-Settling Apparatus, Dr. Richards has related the history of the development of the hindered-settling classifier and given illustrations of the several types of this apparatus which lie has designed.1 An earlier paper,2 Close Sizing Before Jigging, shows the nature of the hindered-settling phenomenon and the results which it produces. In the first-mentioned paper Dr. Richards describes the method of getting hindered settling and shows the relation that the constriction bears to the classifier. The question of proper ratios between the area of the sorting column and the area of the constriction opening Dr. Richards leaves open, aside from certain statements as to the ratios which have been found to give good results in practice. While working with a hindered-settling classifier of the type now in use at the Boston & Montana Reduction Plant of the Anaconda Copper Mining Co. a number of interesting facts were brought out which have thrown considerable light on the question of proper ratio between the area of the sorting column and the area of the constriction and which will be made the subject of this paper. Free and Hindered Settling. -If a, mineral particle be dropped into a vessel containing still water, the particle will sink in accordance with the laws of free settling in water, which are as follows: 1. Of two grains having the same specific gravity but differing in size, the larger will settle in still water at the greater velocity. 2. Of two grains having the same size but differing in specific gravity, the heavier grain will settle at the greater velocity.

Jan 8, 1913

By W. F. Wheeler

In the study of the coals of Illinois now being carried on by the State Geological Survey, an attempt is being made to determine the most satisfactory basis of comparison between different coals. The following discussion is based upon work done for the Survey in the laboratories of the State University and under the general direction of Prof. S. W. Parr. "Pure coal" has been defined by Mr. A. Bementl as ash- and moisture-free coal, and the use of this pure coal" as a basis for comparing different bituminous coals has lately been much discussed among engineers in the middle West. By some the B.t.u. of the pure coal is being used to check calorimetric results, and to calculate the calorific value of different coal-samples from the same seam, for which purposes it is necessary to assume—first, that the composition and calorific value of pure coal from different parts of the same coal-seam are uniform, and, second, that these values remain constant after the coal is mined, both of which assumptions there are reasons to believe are inconsistent with the facts. Certain variables are included in pure coal, as ordinarily defined, and disregard of them may lead to serious error. In any event, where delicate shades of difference are involved, no sure interpretation of results car] be made, unless these variables be eliminated. As a basis of comparison between coals, ash- and moisture-free coal is much to be preferred to " dry coal," and still more is it to be preferred to moist coal," as ordinarily reported in analyses. There are, however, two constituents other than ash

Jan 1, 1908

By C. A. Stetefeldt

In May and June, 1885, I was engaged in examining the goldores of Las Minas, in the State of Vera Cruz, Mexico, with a view of finding a cheap and efficient method for extracting the gold. The following minerals could be plainly seen in the ore : magnetite, pyrites of iron, pyrites of' copper, quartz, and garnet. Neither galena nor zinc-hlende mere visible, but the ore contained a trace of lead, and in some samples of ore from the Muertos mine, 1.19 per cent. of zinc mas found. Antimony and arsenic were not present. Native gold could scarcely be seen in specimens of' the ore, and it only appeared—mainly in extremely fine particles—after pulverizing and washing. Magnetite was in every instance the most prominent mineral, its quantity varying between 43 and 67 per cent. Determinations of copper and sulphur showed that from 3.5 to 7 per cent. pyrites of copper, and from 3 to 22 per cent. pyrites of iron were present. The gold-value of the ore varied between 0.3 oz. and 0.8 oz. per ton. I do not speak of specimens, but of average samples of large quantities of ore put through the battery. In ore that had been crushed through a No. 40 screen, the gold appeared, in part, as free gold, the rest being thoroughly mixed with the magnetite and pyrites, both minerals containing about the same percentage of gold. If this free gold was brought in contact with pure quicksilver it (lid not amalgamate readily, even if the quicksilver was charged with sodium amalgam.

Jan 1, 1886

By P. E. Doherty, R. S. Davis

Sub boundaries and micropores, as well as certain other imperfections, may be revealed in aluminum by the formation of pits on the surface during cooling from elevated temperatures. The pits are attributed to the condensation of vacancies from supersaturated solution. This "vacancy pit" phenomenon has been used as an etching technique for studying the structure of aluminum specimens grown from the melt. Three fundamental structures were studied: stria-tions, cells, and dendrites. Two types of striations, as well as a crosswise structure are reported. Mic-roporosity is observed to occur in the cell walls on freezing. Subboundaries between primary, secondary, and tertiary branches are observed in dendritic growth. A special case is cited in which cellular growth suppresses the formation of striations. SMALL, well-defined pits have been observed to form on the surfaces of electropolished aluminum specimens during cooling from elevated temperatures.' This phenomenon was attributed to the condensation, from supersaturated solution, of vacancies at particular points on the surface. It was shown that the amount of cooling required for the formation of pits increased exponentially with decreasing holding temperatures in a way that was consistent with the thesis that a critical supersaturation of vacancies was required for the pits to form. Pits do not form in the vicinity of certain imperfections, namely, subgrain or normal graind boundaries, phase boundaries, certain surface irregularities, and pores. The width of the pit-free region increases with decreasing cooling rate. This observation suggests that the imperfections in question are effective sinks for vacancies and that the pit-free region around them is material that is not sufficiently supersaturated with respect to vacancies to nucleate the surface pits during cooling.

Jan 1, 1962

By Charles R. Fettke

In the present day manufacture of glass nearly pure quartz sands are used almost exclusively as the source of the silica, which is the major constituent of all common varieties of glass. Ordinary soda-lime, such as bottle, common tableware, plate, and window glasses, contains from 65 to 75 per cent. of silica. Occurrence Glass sands occur in nature either in the form of loose, unconsolidated sediments or in deposits in which the individual grains have been more or less thoroughly bound together by some cementing agent so as to form sandstones. While deposits of sand and sandstones occur both widely and abundantly distributed, deposits that are sufficiently free from other constituents than quartz grains, so that they can be employed in the manufacture of the better grades of glass, are, comparatively speaking, of rare occurrence. The major portion of the glass sand produced in the United States comes from sandstones. In order to be suitable for glass sand, they should be rather friable. The rock should break down readily along the cementing material between the grains and should not break across the grains rather than along the bond. Some of the sandstones used are so friable that only light shots of slow-burning dynamite are necessary to disintegrate them sufficiently for hydraulic mining, while others have to be passed through crushers in order to disintegrate the rock into its individual grains. MINERALOGICAL COMPOSITION An ideal glass sand is made up entirely of grains of the mineral quartz free from inclusions of foreign substances. Sands containing 100 per cent. silica, however, are not found in nature, although some very nearly approach this composition.

Jan 1, 1926

By F. D. Rosenthal, F. J. Dunkerley, G. J. Mills

Activities, free energies, and heats and entropies of mixing of liquid Pb-Zn alloys have been obtained by the electrode-potential method between 400° and 650°C. The large positive deviations observed from Raoult's law are in agreement with the phase diagram, which indicates a wide immiscibility field. A vapor-pressure method was used to extend the activity measurements to 900°C, allowing the maximum of the immiscibility gap to be estimated by thermodynamic calculation. Data on the mono-tectic and eutectic points compare favorably with previously existing work. SEVERAL long-standing methods have been in use for the study of phase diagrams from measurement of the activities of the component metals.' The use of thermodynamic analysis for interpreting equilibria data is comparatively recent, however. Such analysis is usually undertaken by first evaluating the principal thermodynamic functions as, for example, the enthalpy, entropy, and free energy of the alloy constituents. These, in turn, quite often can be correlated with the interatomic potential energies and atomistics of the system, from which a clearer understanding of the causes leading to deviations from ideal behavior is gained. The present study of liquid Pb-Zn alloys is concerned with a determination of these quantities by electrode-potential and vapor-pressure measurements, using these values in calculations involving phase equilibria and to obtain a theoretical insight into an alloy system exhibiting strong positive deviations from ideal metallic solution. A considerable portion of the previously reported work is based on thermal analysis. Supplemented by optical studies of solid alloys, these techniques have revealed the essential nature of the immiscible mixtures that are formed. It is difficult, however, using the phase-

Jan 1, 1959

By John Griffen

THEORY HYDRAULIC classification as explained by Rittinger and others was largely restricted to conditions wherein the free-falling velocities of the particles were conceived as governing the separations effected (see chapter 9). The laws governing classification under free-falling conditions have been summarized by Chapman and Mott as fo1lows:l Nomenclature r represents, in a particle of irregular shape, the round-hole screen through which the particle would pass, or some other linear dimension of the particle equivalent to d, the diameter of a sphere. s, the specific gravity of the particle. 1, the specific gravity of the water used as a medium. K, a constant. W, the velocity of the water. In an Upward Current of water 1. A particle will move upward if [V > K dr(s - 1)] and, by suit- ably regulating the speed of the water current, the larger and heavier particles may be made to fall downward against the current, leaving the smaller, lighter particles in suspension in the current. 2. Particles such that [- = -] cannot be separated in an upward- current classifier with any one velocity of current. Coal particles having a specific gravity of 1.35 cannot be separated from refuse particles of [2.5 - 1 2.5 sp. gr.] unless the ratio of diameters is less than [ 4.3 to 1, 1.35 – 1] and the raw coal must be screened to size limits within this ratio if they are to be separated. Cone-shaped vessels or vessels of other shapes that allow the use of different velocities of current at different points in the flow are used to modify this limitation.

Jan 1, 1943

By P. Chiotti, G. R. Kilp

IN the study of zinc-zirconium1 and zinc-uranium2 systems, vapor-pressure measurements were made in order to establish the equilibrium phase diagrams for a pressure of 1 atm. In each of these systems, only zinc has an appreciable vapor pressure over the temperature range investigated. The zinc pressure was measured over a sufficiently wide temperature and composition range to permit calculation of the standard free energy, enthalpy, and entropy of formation for the compounds ZrZn, ZrZn2, ZrZn3, ZrZn6, ZrZn14 , and U2Zn17. In these calculations the compounds were treated as line compounds. Although the exact composition range was not determined, metallographic and thermal data indicate that the solubility range for these compounds is small. It is to be noted that the compound initially reported to correspond to the formula UZn9, 2 has been shown by the crystal structure work of Makarov and vinogradov3 to correspond to the formula U2Zn17,. The crystal structure is similar to that for the compounds Th2M17, investigated by Florio,4 et al; here M represents iron, cobalt, or nickel. Therefore, thermodynamic calculations are based on the formpla U2Zn17 EXPERIMENTAL The dew-point method employed to measure the vapor pressure of zinc over uranium-zinc alloys has been described previously.2 The same procedure and apparatus were used in measuring the zinc pressure over zinc-zirconium alloys. In the case of alloys in the two-phase region consisting of a zirconium and the compound ZrZn, the Knudsen effusion method was employed to obtain a few values in the temperature range 600" to 560°C. In most cases, tantalum crucibles were used to contain the zirconium alloys. THERMODYNAMIC PROPERTIES OFU2Zn17 A least-squares treatment of the vapor-pressure data obtained for 35 and 65 wt pct U alloys in the temperature range 650° to 940°C gave lOg10PAtm = 7,713/T + 6.33 Here, as in following equations, T represents degrees kelvin and P represents the zinc vapor pressure in atmospheres. The probable errors for the two constants were calculated to be 60.68 and 0.0563, respectively. This relation represents the equilibrium dissociation pressure for the reaction U2Zn17 (s) - 2U(s) + 17Zn(v) The solubility of zinc in solid uranium is negligible and the only additional information required to calculate the free energy of formation of U2Zn17 is the free energy of vaporization of pure zinc. K. K. Kelley5 gives the relations, AF°= 30,902 + 6.03Tlog T + 0.275 X 10-3T2 - 45.03T

Jan 1, 1961

By A. A. Jr. Smith, J. S. Smart

The controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modern copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range o to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously. Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,'v2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of %-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 8jo°C. from a surface scale. Test wires wcre drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in., and a final cold reduction of 75 per cent to 0.081 in. Oxygen-bearing slugs made by remelting nere hot-rolled to 4ia in.. drawn to 0.162 in., annealed for 30 min. at 6o0°C. and cold-drawn 75 per cent to 0.081 inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 3i6-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700' to 8o0°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals wcre of one hour duration followed by a rapid quench in 10 per cent HZSO*. Effect of Phosphorus The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1946

By C. G. Durdaller, W. H. Robinson, G. M. Pound

The nucleation rate of the a (pay) to 0 (white) tin transformation was measured as a function of temperature and a tin particle size using an X-ray diffraction technique. The powder specimens of a tin were essentially monodisperse and the small dinzension of the particles of these specimens was varied from 13 to 75 p. Several types of nucleation sites of differing potency were fbund to be operative in the nucleation process, but it could not be determined whether these sites were on the free surface of the tin particles or within the volume. Assuming that they were on the free surface, the average density of the most potent sites was calculated to be 2.5 to 5.3 x 10' sites per sq cnz through the application of a Poisson distribztion finction to the isothermal data. Analysis of the temperature dependence' of the rate constmts at a given fraction transformed suggests that the active sites are regions of higher free energy and not catalytic interfaces. Appreciable induction periods were observed at the lower temperatures of transformation. Experimental studies1 of solid-solid phase transformations have led to the belief that the new phase nucleates at structural imperfections. The purpose of the present work was to learn more about the mechanism of nucleation in solids and the nature of the singularities at which nucleation occurs. In this investigation nucleation rates in the isothermal transformation of gray to white tin were measured by an X-ray diffraction technique using essentially monodisperse powders of gray tin. This particular phase transformation was chosen for study because it presented fewer experimental difficulties than most others. The experimental temperature-control problems were minimal because the two phases coexist in equilibrium at 13.3"C, and measurable transformation rates occur at temperatures only slightly above room temperature. The growth rate of the P phase into the a2 is sufficiently fast to make the measured transformation rate equivalent to the nucleation rate, provided that the particle size of the samples is small enough; for the experimental temperatures used in this study, the particle diameter must be less than 100 p. EXPERIMENTAL TECHNIQUE The P tin used in this study was obtained from Capper Pass and Son Ltd., North Ferriby, Yorkshire, England, and was of 99.999 pct purity. It was transformedS to the a phase and ground into a fine powder in an agate mortar. This powder was separated by a Roller air classifier into seven fractions whose dimensions, as determined by microscopic measurement of many thousands of particles, are given in Table I and whose distribution of size within each fraction is given in Figs. 1 and 2. The shape of the particles was roughly that of an oblate spheroid,

Jan 1, 1964

By A. A. Smith, J. S. Smart

THE controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modem copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range 0 to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously.1-2-3 Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,1, 2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of 3/8-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 850°C. from a surface scale. Test wires were drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at o.3125, 0.257, o.204 and o.162 in., and a final cold reduction of 95 per cent t0 0.081 in. Oxygen-bearing slugs made by remelting were hot-rolled to 5/16 in., drawn to 0.162 in., annealed for 30 min. at 600°C. and cold-drawn 95 per cent to 0.081inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 5/16-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700° to 800°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals were of one hour duration followed by a rapid quench in 10 per cent H2SO4. EFFECT OF PHOSPHORUS The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1945

By A. A. Jr. Smith, J. S. Smart

The controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modern copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range o to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously. Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,'v2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of %-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 8jo°C. from a surface scale. Test wires wcre drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in., and a final cold reduction of 75 per cent to 0.081 in. Oxygen-bearing slugs made by remelting nere hot-rolled to 4ia in.. drawn to 0.162 in., annealed for 30 min. at 6o0°C. and cold-drawn 75 per cent to 0.081 inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 3i6-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700' to 8o0°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals wcre of one hour duration followed by a rapid quench in 10 per cent HZSO*. Effect of Phosphorus The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1946