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By T. C. M. Pillay, John Chipman

The Si-0 equilibrium in liquid iron was investigated in some detail by Gokcen and Chipman1 who reported equilibrium constants of the following reactions: In each case the thermodynamic equilibrium constant K was obtained by extrapolating K' to infinite dilution. Their results on reaction [I] were consistent with those of earlier observers, and there seems to be little doubt as to the approximate validity of the equilibrium product determined. On the other hand, the results on reactions [2] and [3] indicated unusual curvilinear relationships between the activity coefficients of silicon and of oxygen and the silicon concentration. Since a linear relation is observed in all other similar instances, it was concluded that some source of error had affected the gas-metal equilibrium relationships. Recently the authors undertook a restudy of these equilibria with the view especially to establishing the equilibrium constant of reaction [2]. Their experiments, however, were discontinued before a tbroughly satisfactory answer had been obtained and consequently have remained unpublished until the present time. Quite recently Matoba, Gunji, and Kuwana2 published the results of a very thorough study of these equilibria. It is the purpose of the present note to Compare these three sets of experimental data, a comparison which leads to Confirmation of the results of Matoba and coworkers. The experimental arrangements described by Dutilloy and Chipman were employed. A controlled mixture of Hz, H,0, and argon was led into the induction furnace over the surface of the Fe-Si melt contained in a silica crucible. On account of the slow approach to equilibrium, runs were continued for at least 8 hr and, in some cases, as much as 12 hr. Samples were taken by means of silica tubes at the start and during the final 4-hr period of each run. Out of twelve runs only seven appeared to have approached equilibrium with sufficient certainty to be reported here. The results of these experiments, all at 1600°c, are shown by the triangles in Fig. 1. Equilibrium was approached from both oxidizing and reducing conditions and the direction of approach is indicated by the shape of the triangle. Attempts to extend the study to higher silicon concentrations were unsuccessful on account of the transfer of silica from the metal bath to the upper portions of the crucible by means of a silicon-monoxide mechanism. Matoba, Gunji, and Kuwana used similar methods and approached equilibrium from both sides. Their results at three temperatures are shown by the solid lines of Fig. 1. A line corresponding to 1600 deg is interpolated from their equations and is shown by the dotted line. The results of Gokcen and Chipman at 1600 deg in the range 0.02 to 2.0 pct Si are also shown. At concentrations up to about 0.6 pct Si, these investigators approached equilibrium from both directions, and their results in this range appear to be trustworthy. Above 1 pct Si, however, all of their experiments involved oxidation only, as shown by a decrease in the silicon content of the bath. It now seems certain that they failed to reach equilibrium at these higher silicon concentrations and that the curvilinear relation shown by their results is incorrect. It is evident that their results in the lower silicon range are in good agreement with those of Matoba and coworkers. In fact, a straight line drawn through their results would parallel the dotted line and would differ from it by only 0.05 in log K. The new data also lie close to that line. It may thus be concluded that the three sets of data are in good agreement and that the equations proposed by Matoba and coworkers for reaction [2] are satisfactory . They take the limiting value of log K', at 0 pct Si as log K ,. The slope of each line gives the value

Jan 1, 1962

By M. T. Simnad, R. F. Mehl, L. Yang

Techniques for studying marker movement in K-Rb interdiffusion have been worked out. The results indicate that Rb diffuses faster than K and that the ring mechanism of diffusion cannot be the dominant one operating in this case or probably in cases involving other alkali metals, despite their low ion core repulsive energies. SEVERAL theoretical attempts have been made in the past decade to elucidate the mechanism of diffusion in body-centered-cubic metals. No general agreement, however, has been reached by different authors. Zener,1 and later LeClaire,2 on the basis of a correlation between the entropy of activation for self-diffusion and the temperature dependence of the elastic constants, predicted that a ring mechanism should operate in the diffusion of body-cen-tered-cubic metals. Paneth3 calculated the activation energies of various ring, vacancy, and interstitial mechanisms for the self-diffusion in alkali metals and concluded that the most likely one was based on the linear motion of "crowdions," which is in fact a different form of interstitial diffusion. Fumi,1 however, showed that the experimental values of the activation energies for self-diffusion in the alkali metals could be better accounted for if the diffusion process in these metals was assumed to follow a vacancy mechanism. The same conclusion was reached by Kojima5 for the self-diffusion in lithium. Experimental evidences published during the past few years seem to exclude the ring mechanism as the predominating one in the diffusion of body-centered-cubic metals. For instance, maker movement has been observed in ß-brass, first in this laboratory" and later by Resnick and Baluffi.5 Shewmon and Bechtoldh also found marker movement in the body-centered-cubic system Ti-Mo and showed that the argument which led Zener and LeClair to favor a ring mechanism was not incompatible with a vacancy mechanism. In spite of this, it seemed to the authors that further experimental tests should be made by studying the Kirkendall effect in body-centered-cubic systems that characteristically have small ion core repulsion, such as the alkali-metal systems. Since the ion core repulsion term constitutes the main part of the activation energy needed for the rotation of a ring, such a test should be the most critical of all. The system K-Rb was chosen for experimental study because these metals form a continuous series of solid solutions. Experimental Investigation Owing to the extremely active nature of these two metals, a brass dry box (18 x 11 x 10 in.) was built for making the diffusion couple. It had a big lucite window on top, two side ports through which neo-prene-rubber gloves were inserted, and another side port covered with an optically flat-glass window for microscopic examination of the sample. Inside the box there were a circulating fan driven with a rotating horse-shoe magnet located outside the box, a heater used to generate potassium vapor for getter-ing the box, and a cold trap for keeping the inside of the box cool. Chemically pure grade K and Rb were triple distilled before they were transferred in vacuum into cylindrical steel molds kept in pyrex-glass ampules, Fig. 1. The latter together with the tools needed for making the diffusion couple were put into the dry box. After the box was flushed with purified argon and gettered with potassium vapor, generated from a heated steel crucible inside the box, the glass ampules were broken and the mound on the top of the alkali-metal ingot was cut off with a razor blade to yield a flat surface. To make the diffusion couple, one K ingot and one Rb ingot were pushed out of the molds together with their steel supports by screwing a metal plunger into the bottom of each mold. They were then laid on a brass cradle inside the assembling carriage (shown separately in Fig. 2) with the flat faces opposite to each

Jan 1, 1959

By Paul Gordon

The distribution coefficient, k, of interest in zone refining is generally defined as the ratio of the solid to the liquid solubilities of one element in another at the normal melting point of the solvent. In practice, distribution coefficients are frequently calculated from solubilities at temperatures well below the melting point of the solvent, e.g., at a eutectic temperature. This is done because of the general lack of accurate data on the liquidus and solidus curves in most phase diagrams. The practice is equivalent to assuming that the liquidus and solidus curves are straight lines in the temperature range between the melting point of the solvent and the temperature at which data for the solubilities are known. It is recognized that the k values so derived may be in serious error; we have found evidence in recent zone-refining operations that a case in point is silicon in aluminum. The phase diagram found in the literature for silicon in aluminum indicates a eutectic on the aluminum-rich side at 12.5 at. pct Si and at 577°C,1 and a solid solubility of silicon in aluminum at this temperature of 1.59 pct.2 It also shows the liquidus and solidus as nearly straight lines from 577°C to the melting point of aluminum (660°C)1,2 The k value obtained from this data is 0.13. This is almost exactly the same as the k value (about 0.14)' obtained in a similar way for copper in aluminum. Yet we have found by mass-spectrograph analyses* of three bars of zone-refined aluminum that copper is efficiently removed from aluminum by zone refining but silicon is not. Two of the three bars of aluminum were zone-refined in our laboratories, the other in the laboratories of AIAG Metals, Inc. The former two bars, designated bars PG2 and PG3, were 30 in. long by 1 in. in diameter during refining; each was processed in a high-purity graphite boat* and kept under refining stage of the process consisted of thirty unidirectional zone traverses at rates of about 1 to 2 in. per hr, with a zone length of 1 to 2 in. At approximately the middle of the refining period a 6-in. piece of the impurity-laden finishing end of the bar* was cut off and replaced with new start- ing material. Following refining, the purest 20-in. section of the bar (obtained by discarding approximately 2 in. of the starting end and 8 in. of the finishing end of the bar) was leveled and then analyzed. The AIAG bar was 16 in. long and about 1.2 in. in diameter; it was purified by eight passes of a 2-in. zone at a rate of 1.6 in. per hr, the bar being contained in a sintered alumina boat lined with loose alumina powder of the highest purity. Data for the silicon and copper contents of the three refined bars are given in Table I. Derived data for the efficiencies of the zone-refining operations are listed in Table 11. It is clear from these two tables that the copper is removed much more efficiently—by a factor of 10 to 50 times—from aluminum during zone refining than is silicon. For example, in bar PG3 the thirty zone passes reduced the copper content from 10 to 0.02 ppm, i.e., by 500 times, whereas the same treatment lowered the silicon content by only a factor of about 16. It seem virtually certain, therefore, that the distribution co efficient, k, for silicon in aluminum is well above that for copper and is very likely not much below unity. This also implies that the solidus line on the aluminum-rich side of the A1-Si phase diagram is very probably appreciably curved near the aluminum melting point since the phase-diagram data indicate such curvature is unlikely in the liquidus.

Jan 1, 1965

By C. G. Dunn, J. L. Walter

Either (100) (001] or (110) (0011 oriented secondaries, or both, depending on annealing atmosphere and material composition, grew in a matrix of 2-dimensional grains. The growth dependence of secondaries of(hkl) orientation in the iron and 0.6 pct Si-Fe is explained in terms of surface energy driving forces and the dependence of these driving forces on both (hkl) orientation and amount of oxygen at the surace. (100) [001] grains grow when suflicient oxygen is present at the gas-metal interface to make y100 the lowest (hkl) surface energy. When little or no oxygen is present at the gas -metal interface, making Y110 the lowest surface energy, (110) (001 1 grains grow. When Y100 and y110 are approximately equal but lowest among (hkl) surface energies, both (100) (0011 and (110) (0011 grains grow simultaneously. An excess of surface oxygen produces complete grain growth inhibition in high-purity iron; i.e., a 3-dimensional grain structure is retained over long annealing periods. However, a small amount of silicon in the iron reduces the growth inhibiting tendency of oxygen without altering the (hkl) surface energy relationships. Some information on annealing twins is presented. SECONDARY recrystallization in high-purity a iron, cold rolled to strip a few mils thick, was reported recently.' The present paper provides additional information on this subject, also furnishes similar information on both zone-refined iron and a high-purity 0.6 pct Si-Fe alloy, and treats the more important surface phenomena that determine to a large extent whether one or more secondary recrystallization textures will appear during annealing. Previous studies on high-purity 3 pct Si-Fe2,3 have shown the importance of (hkl) and impurity-atom dependent gas-metal surface energies on the formation of secondary recrystallization textures in high-purity material. For example, either (100) or (110) oriented grains may have the lowest surface energy depending on the amount of oxygen at the gas-metal interface, and hence the highest driving force for growth if other growth factors are the same. Another important phenomenon in high-purity material is stabilization of the matrix structure; neither impurities nor a strong matrix texture seem to be necessary when recrystallization and normal grain growth occur, developing a stable two-dimensional type grain structure. The average grain size in such a structure is usually between one and two times the specimen thickness. Consequently, most of the grains have grain boundaries terminating at exposed surfaces, and this results in gas-metal interfaces (or hkl surfaces) as well as

Jan 1, 1962

By H. H. Kellogg, T. R. Ingraham

Three anhydrous zinc sulfates have been identified. They are: ZnSO,(a), stable below 1007°K; ZnS04(/3), stable above 1007OK; and ZnO.ZZnSO,. The decomposition pressure of each sulfate has been measured and the following relations calculated from the results: The measured data have been combined with the known themzodynamic properties of ZnS, ZnO, Zn, SO,, and SO, to yield univariant and bivariant phase diagrams for the system Zn-S-0. The application of these diagrams to problems of roasting zinc concentrates is discussed. PRESENT knowledge of the equilibrium chemistry of the system Zn-S:O, so essential to scientific control of zinc-blende roasting, is deficient in several respects. A basic sulfate of zinc has been reported by many investigators, but its composition is in doubt and its thermodynamic properties have not been measured. Our scanty knowledge of the properties of the normal sulfate at roasting temperatures is based on old and inexact studies. A crystal transformation in the normal sulfate, involving a sizable heat effect, has been noted by several investigators but has never been quantified. The studies reported herein were designed to fill these gaps in knowledge and to make possible a reasonably complete thermodynamic description of the system Zn-S-0 at roasting temperatures. The results make possible a far more exact understanding of zinc roasting chemistry than was hitherto possible. EXPERIMENTAL The principal experimental technique employed was the measurement of the total gas pressure developed from decomposition of either ZnSO, or ZnO2ZnS0, in a closed system. The apparatus employed was essentially the same as that described by Warner and lngrahaml and Flengas and tngraham.' The unusual feature is a flexible Pyrex bellows used to separate the reaction gas mixture (S03, SOz, and 02) from the mercury in the manometer and thus prevent corrosion of the mercury by SO3. The bellows operates without evidence of hysteresis and, barring accidents, may be used for several months. The response of the bellows varies from manometer to manometer, but is generally of the order of 0.6-cm displacement for a l-cm change in pressure. The response for all manometers has been linear over the range 0 to 1 atm. To prevent condensation and polymerization of sulfur trioxide, the bellows-manometer was maintained at 100.0" * 0.5" by a circulating bath of silicone oil. The connecting tubing between the manometer and the furnace was maintained at 100.0" * 0.2"* also, with a stirred air bath. The open end of the manometer was connected with a chamber which was maintained at a known pressure. The pressure could be varied so that readings of the height of the mercury column, measured with a cathetometer, could be made with both rising and falling mercury column. By using the average of the readings, any error due to sticking of the mercury column was minimized. The sample was placed in a 2-in.-long platinum boat formed into the shape of a half-cylinder. The sample was prepared as a fine powder and pressed against the inner wall of the platinum boat. A silica thermocouple well, covered with a platinum sleeve, was placed lengthwise along the center of the boat. The temperature of the sample was read on a calibrated Pt-10 pct Rh theirnocouple. The temperature profile of the furnace was constant within ± 0.2 C over the length of furnace occupied by the sample. The horizontal furnace used to contain the sample and the quartz reaction tube was electrically heated, with the control thermocouple placed 1/4 in. from the windings. A Brown Pyro-O-Vane temperature controller with a 3-sec response time was used to maintain the furnace temperature. Before beginning a run, the apparatus, including the bellows manometer, was thoroughly washed in sib with acid and distilled water to remove any

Jan 1, 1963

By F. R. Scauzillo

Equilibrium data which should be useful in the design and/or evaluation of glycol dehydration units were prepared from an analysis of various published data and the correlation of these data by the use of the thermo-dynamic equilibrium ratio. The equilibrium ratios of water are used to solve the glycol absorber problem; such solutions are necessary to define the number of trays and the glycol circulation rate needed to meet drying requirements. Activity coefficients were obtained which relate directly to the equilibrium ratios of water in the water-TEG-natural gas system. These activity coefficients have been used to calculate the equilibrium dew points for aqueous TEG concentrations of 60 to 99.9 weight per cent for the temperature range of 40° to 120° F. They also provide a means of calculating equilibrium ratios for water in the water-TEG-natural gas system; this applies to any desired TEG concentration and to the temperature range from 40° to 120°F. INTRODUCTION During the last several years, the drying of natural gas with aqueous triethylene-glycol (TEG) solutions has become very prominent. Most users of TEG as a drying agent have been satisfied with the performance of TEG solutions at the conditions used; however, there always has been some discussion of the drying ability of TEG solutions at conditions not commonly encountered such as temperatures below 50° or 60°F, but more particularly temperatures above 100°F, and pressures above 1,000 psia. Today, when higher wellhead temperatures such as 120°F are more commonly encountered many are skeptical of TEG's ability to dry sufficiently well to provide dew points around 32°F, which is generally the maximum tolerable when attempting to dry a gas to contract specifications of 7 Ib/MMscf. These views probably have evolved to some extent from the days when suppliers would not guarantee dew-point depressions in excess of 65° to 75 °OF. Also, the feelings about TEG drying may have arisen from the lack of information about the equilibrium relation of water in the drying operations. Porter and Reid' have reported equilibrium data for a 95 per cent TEG solution, while Townsend2 reported equilibrium data for 95, 98 and 100 per cent TEG solutions. Townsend also presented a calculational method which obtains activity coefficients in the liquid phase and, subsequently, the equilibrium water content of a saturated gas over glycol from published3 atmospheric dew points. Wise, Puck and Failey' presented activity data for the water-TEG system at atmospheric pressure. In the past, the equilibrium ratios published for water in a 95 per cent by weight aqueous TEG solution have been used indiscriminately by many for all concentrations of TEG encountered in gas drying operations. Since essentially all such gas operations require the use of more concentrated TEG solutions, a study was undertaken to correlate the existing equilibrium data for aqueous TEG and gas systems and to provide some means of calculating the equilibrium ratio of water in the natural gas-water-TEG system where TEG concentrations were other than 95 per cent. The data presented herein consider only the equilibrium drying ability of the TEG solutions and do not consider the effect of temperature and pressure on the tray eficiency of contactors. In other words, this paper is concerned primarily with the development of the equilibrium relationship between water in the dried natural gas and the water in the lean TEG entering the top tray of the absorber. BASIC EQUILIBRIUM RELATIONS A relationship which relates the K value of water in the natural gas-water-TEG system to the vapor pressure of water at the system temperature, the total pressure of the system and the activities of the liquid and gas phases has been evaluated. It is well known that, for any component of a mixture at equilibrium between a gas phase and a liquid phase,

By Cyril Smith

THE following table, which is composed of data given in the author's first paper on the thermal conductivity of copper alloys1, contains the results which have been obtained by previous workers on the thermal conductivity of the copper-tin, the copper-phosphorus and the copper-tin-phosphorus alloys (the phosphor bronzes). TABLE 1.-Previous Investigations Composition, Per Cent. by Weight Thermal Conduc¬ Investigator tivity, Cal/Sq. Cm./ Copper Tin Phosphorus CM./Sec.. °C. Hardebecka 95.0 5.0 0.176 (20° C.) Grossmanb 90.1 9.9 0.105 75.5. 24.5 0.059 24.9 75.1 0'.139 (13° C.) 9.7 90.3 0.131 0.0 100.0 0.142 Griffiths and Schofieldc 91.7' 8.0 0.30 0.108 87.2 12.4 0.40 0.087 (20° C.) 90.0 10.0 Small amt. 0.100 Donaldsondd: 87.8 1 11.3 0.35 0.128 Pfleiderere 99.4 1 0.63 0.250 (30° C.) 98.0 1.98. 0.125

Jan 1, 1930

By Samuel S. Adams

Potash, the generic term for a variety of potassium-bearing minerals, ores, and refined products (Table I), owes its importance as an industrial mineral to the potassium requirement of growing plants. The term "potash" originally referred to potassium carbonate produced by the leaching of wood ashes. This process, for which the first U.S. patent was issued in 1790, was the basis for the largest United States chemical industry in the early nineteenth century. The agricultural use of potash soon eclipsed the chemical applications following the German discovery in 1840 that potassium is essential to plant growth. The initial discoveries of large deposits of soluble potassium minerals, essential for agriculture applications, were made in 1857 in Germany and in 1914 in the United States. More than 90% of the 20.4 million short tons K2O produced in the world in 1970 (Eilertsen, 1971 ) was derived from marine evaporite deposits and approximately 90% was used in fertilizers. The potassium content of an ore, mineral, or product is customarily expressed as % K,O, a unit of measure which is neither a natural nor synthetic compound of potassium (1 .O% K is equivalent to 1.2046% K,O) . Geology Potassium, the seventh most abundant element in the earth's crust, is present in silicate minerals in igneous, sedimentary and meta- morphic rocks. Potassium is also a major constituent of many surface and subsurface brines (Table 2). Economic potash deposits are essentially restricted, however, to widespread, thick accumulations of marine chloride evaporite deposits. These deposits yield high grade, large tonnage ore bodies, many of which are amenable to low cost mining and beneficiation. The products from these deposits are, moreover, ideal for use in fertilizer because of the high relative solubility of the potassium chloride and sulfate evaporite minerals. World potash production and reserves for such de- posits so vastly overshadow other sources of potassium that the following discussion will be limited largely to potash deposits in marine evaporites with brief reference to certain potash-rich brines. Approximately 85% of current domestic production is from bedded salt deposits and much of the balance is from brines. Marine evaporite deposits are accumulations of salt minerals deposited in structural sedimentary basins through the evaporation of sea-water or mixtures of seawater and other brines. The salt minerals are precipitated in assemblages and sequences of assemblages as determined by the compositions of the brines and the solubility relations in the salt systems (D'Ans, 1933). The evaporation of seawater normally yields carbonate minerals as the first precipitates (Table 3). Further evaporation and concentration of the brine leads to the precipitation, in succession, of sulfate, chloride, and supersaline mineral assemblages including the salts of potassium and magnesium. The common minerals, ores, and products of potassium deposits are listed in [Table 1]. Many potash deposits contain accessory evaporite minerals together with a variety of detrital and authigenic silicates (Braitsch, 1971).

Jan 1, 1975

By C. Dean Starr

The physical basis of the equation correlating electrical conductizlity and temperature coefficient of resistance of solid solution alloys has been inzlestzgated and the nature of the constants evaluated. It is shaun that the same form of correlation is valid irrespective of the magnitude of the temperature coefficient. However, the effect of therma1 expansion and change in resistivity with temberature nust be considered when the magnitude of the temperature coefficient of resistance is near zero. In a comprehensive literature survey conducted at the Armour Research Foundation in 1950, it was found that a linear relationship exists between the electrical conductivity, K, and the temperature coefficient of resistance, a, for solid solution alloys. This was expressed by the equation where B, a constant, depends on the solvent metal but not the solute. A continuing investigation by Hansen, Johnston, and Parks showed this equation was generally appropriate for Cu, Ag, Au, Pd, Pt, and Co base binary solid solution alloys as well as for many ternary alloys of copper over a range of conductivities and temperature coefficient of resistances from 0.02 to 0.60 reciprocal pohm cm and-0.00015to0.004Q per 0 per "C respectively. Eq. [I] was not always valid for alloys that exhibited a change in state (magnetic to nonmagnetic) or for alloys that had a temperature coefficient of resistance near or below zero. For example, in nickel alloys, a simple linear curve as predicted by Eq. [l] was not obtained when the conductivity was plotted against the temperature coefficient of resistance. Hansen suggested that deviations observed were caused by transitions from a ferromagnetic to a nonmagnetic state. Subsequent and more extensive data by ronin on Ni-Mn alloys confirmed Hansen's postulate. While both states independently showed a linear relationship between K and a, the value of B was different for the two states. In some copper and gold base alloys, as well as the platinum and palladium alloys investigated by Hansen, the conductivity did not extrapolate to zero at zero a as demanded by Eq. [I]. This deviation can be readily corrected by simply adding a constant to Eq. [I.] whence Eq. [2] shows the K decreases as a decreases but that K has a positive value when a = 0 which is observed for commercial solid solution alloys as well as the experimental alloys tested by Hansen. While other methods of correlation of electrical properties have been made such as the one by Starr and Wang3 who found a linear relationship between resistivity and temperature coefficient of resistance for Ni-Cr-Al-Cu alloys, the data, in general, can also be correlated by a form of Eq. [2]. Thus, Hansen's empirical equation has considerable merit. The objective of this paper is to determine the physical basis for this equation and to examine the region near zero a in more detail. ELECTRICAL CONDUCTIVITY VS TEMPERATURE COEFFICIENT OF FU3SISTANCE The resistance of a metal or alloy is defined as

Jan 1, 1963

By Yves Dardel

The literature concerning the remelting of alunlinum and its alloys is very rich. Unfortunately the majority of the papers on this subject have no scientific value, for the theories or explanations are too often in opposition to the laws of physical chemistry. Furthermore only a few of the methods of purification are considered in the literature. Hence it has seemed necessary to the author to sketch a general theory of the purification of secondary aluminum. The purpose of the purification is to eliminate the impurities that the charges, and the atmosphere of the furnaces bring into the bath during the successive remelt-ings. Indeed scrap as well as metal can be used when soiled with oil, greases, water, or others, if it has been sufficiently dried and contains oxides. At the melting point of the metal, the oils and greases are decomposed into their constituent elements H², O2, H²O, co², CO, CH,, and others. These gases are added to the corresponding gases in the atmosphere of the furnace. The impurities introduced into the metal during the remelting will accordingly be the products resulting from the action of these gases on the liquid bath. The quantity of hydrogen that is soluble in aluminum and its alloys is given by the relation of sieverts3 as a function of its partial pressure PH2 in the atmosphere m = K vPH² [I] where K is a constant, which depends only upon the temperature and increases with it. The experiments of Rijntgen and Braun4, RÖntgen and M611er5, Bircum-shaw6 and Winterhagerl have rendered it possible to determine the value of K, when the temperature is less than 1.000°C. One obtains: log K = - 4,702.5T + o 238 [2] Besides its usual significance, the term Ph~ represents also the internal pressure of dissolved hydrogen, since in the equilibrium, that is1 when no gas exchange Occurs between the two phases, the Pressures of hydrogen in the metal and in the atmosphere must be equal. Eq I shows that when the partial pressure of H2 increases the amount of dissolved hydrogen in equilibrium increases, and that, if the contrary Occurs, the quantity of H² should diminish. However, if for any reason the diffusion of hydrogen is hindered and the total amount of dissolved gas remains constant while the temperature decreases, the internal pressure of H² increases until it reaches the value of the hydrostatic pressure. At this point, bubbles of hydrogen appear in the bath and escape out of it. The amount of hydrogen in the metal is then limited by a a depending On the hydro- static pressure, which is practically equal to one atmosphere. Indeed hydrogen does not accumulate in the form of a hydride appearing as a separate solid phase. However1 even the mechanism of the solubility is not yet elucidated. One does not know exactly as yet, whether the

Jan 1, 1949

By L. D. Clark, S. S. Saluja

A physical law, governing the rupture of rock by confined explosive charge correspondent to current expressions for determining weight of charge to rupture rock burden, W, was developed in the form Q = cVw3 by two early investigators performing unique experiments with ice. The coefficient C, is found by trial blast. Recent physical tests conducted with rock, synthetic materials and ice to establish the validity of the theory on which it and other related formulae are based indicated: (a) that failure under hydrodynamic impact pressure is by tension rather than shear as was assumed; (b) that the fundamental law of mechanics, enabling the determination of Q = cvw3, modified to the form P = R x Sa x Wb is valid when low velocity explosives are used; (c) that rock breakage under the action of low velocity explosives is entirely due to explosion gas pressure, as was believed; (d) that under the action of high velocity explosive it is due to the joint effects of scabbing and gas pressure; and that further possible modification could make the above equation also applicable to these joint mechanisms. shape could be easily frozen and because large loads would not be required. They found: (a) that the not unfamiliar shearing equation for metals was applicable to ice where P = load in lb; S = periphery of pressure surface, in.; W = burden, in.; K = modulus of rupture by shear in lb per in.2; and (b) that "the form of cavity produced by the application of gradual pressure is similar to that obtained by blasting in rock under similar conditions of free face and pressure surface!" This similarity in crater shapes leads to the conclusion that rock would rupture by shear, as did ice, and its behavior under the force of a blast could be governed by such a relationship as P = S x W x K. Three important interrelated empirical expressions were derived and rock, charging and spacing coefficients C,, C, and e were established and substantiated by trial blasts. In checking the accuracy of the main assumptions, duplication of the ice tests, substituting rock, suggested that K is not constant and that P = K x W x S, though valid for ice, does not necessarily hold for homogeneous limestone.' Conclusions from this later work raised questions making continued investigation desirable because such conclusions do not destroy the practical value of the empirical equations or theory. Further study for the establishment of the relationship between load, burden and periphery of the pressure surface and possible application of these to the mechanism of rock blasting was undertaken by the authors of this paper. MECHANICAL TESTING - EXPERIMENTAL PROCEDURE Certain inconsistencies in the results of the aforementioned tests repeated on three types of limestone suggested these inconsistencies be attributed to rock inhomogeneity. It was also suspected that the loading speed, which could not be held uniform, may have contributed. The earlier work with both rock and ice

Jan 1, 1964

By D. B. Masson

THE martensitic transformations occurring in ,B AgCd as a result of cold working at room temp.. a-ture and cooling below room ten1erature have been reported by Masson and Barrett.1 These authors found that simple cooling to 127°K caused body-cen-tered-cubic AgCd containing 53.0 at. pct Ag to transform to an orthorhombic structure, while mechanical deformation at room temperature was found to induce a hexagonal structure. Furthermore, they observed that the temperature at which martensite first appeared on cooling, Ms, and that at which the transformation was complete, MI, as well as the corresponding temperatures for the reversion on heating, As and Af, could be ascertained to ± 1°K, although they report these temperatures only for the alloy containing 53.0 at. pct Ag (51.96 wt pct). In the work reported here the temperature range of the transformation on cooling was studied as a function of composition, and further consideration was given to the relationship between the original bcc structure and the transformation-induced hexagonal and orthorhomic structures. EXPERIMENTAL PROCEDURE All samples studied were in the form of annealed 300-mesh powder and were prepared from the constituent metals in the manner described previously.1 The compositions in weight and atomic pct are listed in Columns 1 and 2 of Table I. Method of determination of transformation temperature was the same as utilized previously1—measurement of the intensity of X-rays diffracted by the transformation product. A diagram of the low-temperature sample mount is shown in Fig. 1. This mount was made to fit a GE model XRD-3 X-ray diffraction unit. The powder sample was varnished to a flat surface on a copper sample holder at A. This sample holder was soldered to a brass rod, B, which was in turn soldered to a second copper rod, C. Rod C could be cooled to 78°K by inserting it into a reservoir of liquid nitrogen, D. A heater coil of nichrome wire was wound at E on the sample holder, and by varying the current through the heater a thermal gradient could be maintained along brass rod B. Sample temperatures from 78°K up could be attained and held as long as needed. The sample holder and nitrogen reservoir were insulated by Styrofoam, F, and the sample itself was protected by two radiation shields, G. The X-ray beam entered and left the sample chamber through windoys in the supporting container at H and I. Sample temperatures were measured by a calibrated copper-constantan thermocouple varnished to the sample holder just out of the beam at A. The low-temperature structure had been found to possess orthorhombic symmetry1 and the expected positions of the diffraction maxima were known. Therefore the sample was aligned in the X-ray beam and the Geiger counter of the spectrometer set to receive the most intense orthorhombic reflection without an adjacent interfering cubic reflection. This

Jan 1, 1961

By D. E. Mikkola, G. E. Poquette

X-ray diffraction was used to study the growth of antiphase domains in quenched (or "disordered&apos;? Cu3Au annealed in the range 300" to 385°C. Measurements of the long-range order parameter indicate that a high degree of order is established rapidly at these annealing temperatures. Average domain sizes obtained by Fourier analysis of the superlattice peak profiles show that antiphase domain growth is analogous to classical metallurgical grain growth (i.e.,fol-lows a D2 US kt relation). The activation energy for the growth process, 44 kcal per mole, indicates diffusion control. The anisotropy in the observed effective domain sizes from seven different superlattice peaks can be best accounted for by a configuration involving antiphase domain boundaries on {100 } and (111 ) planes, where the (100) boundary is the low-energy type, {lOO} Type I. The disappearance of the (111) antiphase domain boundary during domain growth is dif-fusion-controlled with an activation energy of 48.5 kcal per mole. On the other hand, the behavior of the parameter representing the amount of (100) Type I boundary indicates that there may be a conversion of the higher-energy boundary types to (100) Type I boundary during the growth process. THE order-disorder transformation in the alloy Cu3Au has been the subject of numerous experimental investigations over the past 40 years, most of which have involved measurements of convenient physical properties such as resistivity and hardness as a function of heat treatment. The interpretation of these data is difficult because measurements of this type have the disadvantage that they yield total changes resulting from several different atomic processes which may be occurring simultaneously. The present study was undertaken to establish by means of X-ray diffraction the kinetic behavior of one of these atomic processes, namely antiphase domain growth. In the completely ordered state Cu3Au has an L12 structure which can be described as an fcc type arrangement of atoms in which the gold atoms occupy the corner sites and copper atoms the face-centered sites. Three other equivalent unit cells can be formed by allowing two gold atoms to occupy opposite face-centered sites and copper atoms to occupy the remaining corner and face-centered sites. These four different unit cells are crystallographically related by a shift of 1/2<110>. Quenching from above the critical temperature (392°C) to room temperature retains the "disordered" structure-a "random" arrangement of copper and gold atoms having the fcc structure. Annealing the disordered alloy below the critical temperature causes ordering to occur through the nucleation and growth of ordered regions at different points throughout the crystal. These small ordered regions, each based on one of the four types of unit cell, grow by consuming the disordered material until they impinge to form a domain structure in which the domains are antiphase by a shift of 4(110). The boundaries between domains are called antiphase domain boundaries (APDB) and they have been found to lie primarily on &apos; {100} planes in highly ordered Cu3Au. Two types of APDB can occur on ( 100) planes. An example of an (001)1/2[110] shear type APDB is shown in Fig. I. Because of the layer of copper atoms separating the domains in this case, there are no near-neighbor violations across the boundary and it has a low surface ener This type of APDB will be referred to as {lOO} Type I. Fig. 2 shows an (001): [011] climb type APDB, (100) Type 11. This type of APDB can be described as resulting from removal of a (200) plane followed by a shift of 1/2<110> to bring the separated regions together. Near-neighbor violations across (100) Type I1 APDB make it a high-energy boundary. There are numerous other possible APDB configurations; however, it is only worth noting that shear type APDB can be produced on the (111) plane by motion of a normal fcc dislocation with Burgers vector 1/2<110> through the ordered structure. A (111); [110] shear type APDB is shown in Fig. 3. Again, because of the near-neighbor violations this type of APDB has a higher energy than the (100) Type I APDB.

Jan 1, 1970

ALABAMA Aldrich.-Lloyd, T W Anniston.-Carrington, F G Gerber, A B Heimrod, A A. White, H E Ashland.-Barton, J C Sturdevant, J C Bessemer.-Abbott, C E Ball, T L Hines, H K Hodgkin, W -0. Salmon, H S Thompson, N E Birmingham.-Adams, J H Adler, J. E Aldrich, T H Aldrich, T H, Jr. Ball, E M

Jan 1, 1923

G. K. BURGESS, ? Washington, D. C.-At the Bureau of Standards it was decided, in order to study the high-aluminum end of these curves, that efforts should be made to prepare pure aluminum, and the promise of getting aluminum, practically free from the two elements that have such great effect in very small quantities, namely, silicon and iron, and which

Jan 12, 1919

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST&apos; PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F..RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY K. KENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y

Jan 6, 1914

By A. K. Bhasin

A. K. Bhasin, (Development Engineer, Marcona Corp., San Francisco, Calif)-The author suggests the use of the term "consistency" for apparent viscosity and accordingly calls his viscometer a "consistometer." However, he goes on to refer to "consistency" as a combination of plastic viscosity, yield stress, and stability (p. 104, col. 2, line 6). Unfortunately, such conflicting terminology is encountered too often in rheological

Jan 1, 1973

The following list of US companies, mines, and mills engaged in uranium production was compiled by the Health and Safety Analysis Center, Mine Safety and Health Administration, in Denver, Colo. The list includes those companies reporting to the Center in 1978. Thanks to D. K. Walker, Chief of the Health and Safety Analysis Center, for providing the information to MINING ENGINEERING.

Jan 10, 1978

By H. R. Deeth, C. J. Koenig

ABOUT ten years ago nepheline syenite was introduced to the ceramic industry and the material has now found application in the various branches of the industry, namely, as a vitrifying agent in white-wares and as a source of alumina and alkalies in glasses, glazes, and porcelain enamels. Spence1 described the early mining and processing developments regarding this material. Since the time of his article many research papers have appeared relating to the usage of nepheline syenite but little has been published relative to subsequent mining and processing methods. A complete indexed review of the literature was issued recently by Ohio State University.2 Since "Lakefield" nepheline syenite from Blue Mountain, Ontario (Fig I); is the only commercial ceramic-grade nepheline syenite now being marketed on this continent, discussion is limited to this operation carried on by American Nepheline Limited, Lakefield, Ont., and its subsidiary in the United States, American Nepheline Corp. at Rochester, N. Y. THE DEPOSIT Blue Mountain is a long ridge rising to an elevation of about 350 ft at its highest point above the surrounding country and extending for about six miles in a northeasterly direction across Methuen township, Peterborough County. The rock of the Blue Mountain central alkaline intrusive is fine grained, light colored and of even granitic texture. The solidified mass consists predominately of the minerals albite, nepheline and microcline in order of abundance. The average mineralogical composition for the deposit obtained by a study of 112 samples taken regularly over the whole formation is as follows:3 [VOLUMETRIC MINERAL PER CENT Albite54 Microcline20 Nepheline22 Muscovite2 Mafics2 (Biotite, hastingsite, magnetite) Total100] The mineral nepheline (or nephelite) belongs to the feldspathoid group but is lower in silica content than are the feldspars. It is a silicate of soda, potash, and alumina (NaKAl2O32SiO2). Its presence with albite (Na2O A1203 6SiO2) and microcline (K20 A12O3 6SiO2) gives the Blue Mountain deposit an alkali content of 15 pct and an alumina content of approximately 24 pct. While this huge alkaline mass is somewhat variable mineralogically, it has a uniform chemical composition. When the iron, mostly in the form of magnetite, is removed during processing, a remarkably uniform finished product is obtained. Geological surveying has disclosed many million tons of nepheline syenite in the Blue Mountain deposit. Diamond drilling in the area where mining is now being carried out indicates a block of about one million tons.

Jan 1, 1947

By F. R. Hensel

PURE silver and silver-lead alloys have been studied as to their suitability for bearings.1-8 A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materials.† The silver-rich end of the diagram as reported in the literature9-11 was found to be sketchy and it was necessary to carry out considerable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. TEST MATERIALS In the beginning of the work, only fused alloys were investigated. Later, research [TABLE I. Composition of Fused Silver thallium Alloys Tested for Antifriction Properties PERCENTAGE ALLOY No.OF THALLIUM 15330.48 153406 231 HT2.04 2312.10 232 HT3.83Balance 2324.07Silver 233 HT5.86 2336.38 2349.84 234 HT10.07] was carried out on electroplating methods and diffusion processes. In preparing the fused alloys, care was taken to exhaust the toxic fumes caused by the thallium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in. diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr2O7, 8 c.c. H2SO4, and 100 c.c. H2O. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C. show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475°C. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not result in complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1945