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By L. S. Darken

IN the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be repre-sented satisfactorily by the simple equilibrium expression K - (p1)p1 (p2)p2 . (R1)r1(R2)r2 . where (P) denotes the concentration of a product and (R) the concentra-tion of a reactant in the reaction r1R1 + r2R2 + . . . Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a com-ponent is not proportional to its true mol fraction, But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple com-ponents and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satis-factorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature as ionization or the occurrence of polar and nonpolar molecules-are presumably less effective in metal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By Charles H. Jacoby, Stanley J. LeFond

Salt, or halite, has a long and most varied history. While we know the Chinese were producing salt as early as 3000 B.C., the first written reference to salt appears in the book of Job recorded about 2250 B.C., which reads: "Can nothing which is unsavory be eaten without salt?" We do not know when man first used or realized that he needed salt. Perhaps one of our early Eolithic ancestors noted a piece of salt shining along the shore of a salt lake or a bay. He may have been attracted by its shining luster and tasted it. He found that it had a tart, zesty, distinctive flavor and perhaps chewing a large piece, became ill. However, by experimentation he soon learned that taken in the proper proportions salt was a very pleasant additive to his food. He may have noticed, too, that it increased his feeling of well-being. Thus, when the curtain of recorded history rises, we find man using salt for his health's sake, seasoning his food with it, feeding it to his animals, and using it in many superstitious and religious ceremonies. These uses, however, are a far cry from the uses for salt today. The first attempts of white man to make salt in continental United States were reported in the year 1614, while the first commercial production was in 1753 from the Kanawha licks. Practically all this salt was for human consumption, preserving food, and curing hides. Prior to the coming of the white man, Indians are known to have made salt from salt springs such as those that existed at Avery Island, LA, Charleston, WV, Saltville, VA, and Onondaga, NY. In 1862 the first rock salt was mined in the US from the Avery Island salt dome. Almost immediately thereafter, rock salt was mined at Saltville, VA and then at Retsof, NY in 1885. Of the more than 39 million tons produced annually in the United States, about 58% or 23 million tons are consumed by the chemical industry in the production of chlorine, caustic soda, hydrochloric acid, sodium metal, and some 30 other basic chemicals. These basic chemicals, in turn, are used in the preparation of approximately 14,000 chemicals which range from soap and detergents, to such chlorinated hydrocarbons as DDT, BHC, carbon tetrachloride, etc. Utilization of cavities created in salt beds and domes has grown rapidly since 1947 until now the waste salt is creating an ecological problem. The uses for both dry- and solution-mined cavities range from the storage of liquid hydrocarbons to containerized storage of toxic wastes, from compressed air for the peak shaving of power to storage of nuclear wastes. Geology Mineralogy Properties: Because of its simple structure, halite, the mineralogical name for salt, was the first structure to be analyzed by X-rays. It has the following properties: Formula: NaCl (Na-39.34%. Cl2-60.66% ) Crystallography: isometric, hexoctahedral, 4/m 32/m Space group: Fm3m A0: 5.627 kX Cell contents: Na4CI4 Habit: usually cubic, rarely octahedral, massive, granular to compact Physical properties: Refractive index: 1.554 Twinning: observed on {111} Cleavage: {001} perfect Fracture: conchoidal, brittle

Jan 1, 1983

By E. R. Parker, C. F. Riisness

That grain size has a great effect on the mechanical properties of metals has been recognized for a long time. Bassett and Davis1 in 1919 did excellent work in determining the effect of grain size on the hardness of brass. About the same time Jeffries2 and Sykes3 ascertained the effect of grain size on the strength and ductility of several metals at temperatures ranging from 80°K. to their melting points. When creep was recognized as an important property of metals, those engaged in the study of this property tried to determine the effect of grain size4-9 on creep rates. Unfortunately, most of the investigations were conducted on only two grain sizes, often designated simply as "fine" and "coarse." It is well known that at high temperatures coarse-grained test bars creep less than fine-grained bars. The relation between grain size and size of test bar, however, has been frequently overlooked. In his early work, Jeffries2 showed that the number of grains in the cross section has a more important influence on the properties of the material than the actual grain size. More recently Hanson and Sandfordl0 and Pell-Walpole,ll in their measurements of the creep and tensile properties of tin, tested a wide range of grain sizes and correlated the grain size with the strength. Hanson9 later established the relation between the number of grains in the cross section and the creep rate. At high temperatures, generally a coarsegrained structure is considered superior in creep to a fine-grained structure, but it is evident that for a given bar size continuously increasing the grain size will

Jan 1, 1944

By C. F. Riisness, E. R. Parker

That grain size has a great effect on the mechanical properties of metals has been recognized for a long time. Bassett and Davis1 in 1919 did excellent work in determining the effect of grain size on the hardness of brass. About the same time Jeffries2 and Sykes3 ascertained the effect of grain size on the strength and ductility of several metals at temperatures ranging from 80°K. to their melting points. When creep was recognized as an important property of metals, those engaged in the study of this property tried to determine the effect of grain size4-9 on creep rates. Unfortunately, most of the investigations were conducted on only two grain sizes, often designated simply as "fine" and "coarse." It is well known that at high temperatures coarse-grained test bars creep less than fine-grained bars. The relation between grain size and size of test bar, however, has been frequently overlooked. In his early work, Jeffries2 showed that the number of grains in the cross section has a more important influence on the properties of the material than the actual grain size. More recently Hanson and Sandfordl0 and Pell-Walpole,ll in their measurements of the creep and tensile properties of tin, tested a wide range of grain sizes and correlated the grain size with the strength. Hanson9 later established the relation between the number of grains in the cross section and the creep rate. At high temperatures, generally a coarsegrained structure is considered superior in creep to a fine-grained structure, but it is evident that for a given bar size continuously increasing the grain size will

Jan 1, 1944

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 C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By H. C. Meister

THE zinc-smelting industry of the United States has grown very rapidly in recent years and bids fair to outrival that of all other countries in the future. On account of the geographical situation of the chief ore-supplies, the industry may be divided into two main groups, the eastern and the western. The eastern and older group includes the works of Pennsylvania, New Jersey and Virginia, which practically control their own ore-supply. The western group includes the works of Illinois, Missouri, Kansas, Wisconsin and Indiana, which do not control their own ore-supply, but are compelled to buy the ore in the open market. It is for this reason that the western zinc-smelting industry has been undergoing continual changes since its inception 40 years ago. During the early discoveries of lead- and zinc-ore in the lead- and zinc-districts of Wisconsin and northern Illinois, the zinc-ore (sinithsonite or " bone " as the miner calls it) had no value and was considered waste; but later, when this ore was found in large quantities, it attracted the attention of metallurgists, which finally resulted, during the early sixties, in the building of the Matthiessen & Hegeler Zinc Works at LaSalle, Ill., the pioneer zinc-works of the West. A few years later, zinc-ore was discovered associated with the lead-ore in Jefferson county, southeastern Missouri, which started the industry at Carondelet or South St. Louis. Still later, the discoveries of zinc-ore in the lead-ore region, first' at Granby and then around Joplin, lead to the introduction of the industry in the southwest Missouri and Kansas districts. At first the development of the industry was slow, but it progressed steadily and it is now one of the leading metallurgical industries of the middle West.

Jan 1, 1905

By Horace F. Silliman, Curtis L. Wilson, Eugene C. Little

The change in electrical resistance and Rockwell hardness (16-100-B) of copper alloys containing Ni2Si and Co2Si was determined by annealing the quenched solid solutions at various temperatures for various lengths of time. The rate of precipitation of Nisi, as measured by the rate of decrease of electrical resistance and increase of hardness, increased with annealing temperature up to a certain point, depending on the percentage of Ni2Si present. At these temperatures discontinuities in the rate: change occurred. Similar discontinuities in the Co2Si alloys were no The solubility of Co2Si in copper was found to be 5 per cent at 970" DISCUSSION (Robert F. Mehl presiding) R. I?. Mehl, Pittsburgh, Pa. (written discussion).—The electrical conductivity and hardness curves reported in this paper are interesting, particularly because many of the anomalies of the precipitation processes are evident from such curves. The title of the paper, however, is deceptive, for it implies that measurements of electrical conductivity and hardness are suitable to determine the rate of precipitation. Neither of these methods is suitable for a quantitative measurement of rates of reaction or of precipitation in the solid state. Electrical conductivity in some alloys shows an anomalous increase during the first stages of aging at low temperatures; it is notably sensitive to strain and to state of subdivision. I have plotted the conductivity curve representing the decomposition of the phase at 555" C. in the copper-aluminum system, given in the paper by Smith and Lindlief (Fig. 47, p. 93) as a rate of reaction curve, and compared it with the curve determined by area evaluation (Fig. 7); these two curves are not coincident. Hardness is likewise very uncertain, for it is so much dependent upon particle size. Of the various methods proposed for the study of rates of reaction and precipitation, the evaluation of volume of reaction product from the respective area of matrix and reaction product on the photomicrograph is the most trustworthy; suffering, perhaps, only from low sensitivity during the early stages. This method, used originally by Davenport and Bain and now by Smith and Lindlief, is suitable for

Jan 1, 1933

By N. L. Svensson

The model developed by Tuylor for the calculation of Polycrystalline yield strength has been applied to the case of an aggregate hawing a preferred orientation. In general this procedure requires the specification of texture by means of weighting factors applied to specific orientations. The problem to which the model has been applied is that of the yield-strength aniso-tropy of cold-rolled aluminum whose rolling texture was described as a combination of (110)[112] and (311) [112] In this case yield-strength anisotropy is defined by the rutio of yield strength measured at an angle 8 to the rolling direction to that measured along the rolling direction. The method of calculation of yield-strength ratio as a function of ? is described and the results show good agreement with experimental values. The orthotropic yield criterion suggested by Hill has been applied to the results and the strain ratio R also calculated as a function of ?. This has been compared with calculations using the method suggested by Elias, Heyer, and Smith which does not exhibit suck good agreement with observation. one deficietlcy of the method presented is that the strain ratios used by are those applying to iso-Irobic materials. The method should therefore be reg-clrded only as a first abbroximation to the prediction of anisotropy. THE problem of calculating the stress-strain characteristics of polycrystalline aggregates from the properties of single crystals has attracted attention for a number of years. The most important contributions to this study have been those due to: Sachs,' Cox and sopwith,2 Taylor,3 Kochendorfer,4 Batdorf and Budiansky,5 Calnan and Clews,6 Bishop and Hill,7,8 Kocks,9 Budiansky, Hashin, and sanders, 10 Kroner,11 Cyzak, Bow, and payne, 12 Budiansky and Wu,13 and Lin.14 While the earlier work has been largely superseded, recent developments tend to support Taylor's solution" within the restriction imposed by his assumptions. The essential features of Taylor's approach were: 1) the material is rigid-plastic; 2) each grain experiences the same strain components as the aggregate as a whole (the problem was that of uniaxial deformation with principal strain components in the ratio 3) all regions of each grain deform uniformly; 4) work hardening occurs equally on all slip systems. While Bishop and Hill7 have generally validated this approach, there has been some criticism offered. Kocks? as pointed out that since multiple slip must occur the single-crystal data must be determined from orientations arranged such that polyslip takes place. Boas and Hargreaves,15 and others, have shown experimentally that the strain distribution within grains is not uniform, the strains in the vicinity of grain boundaries being less than those in the center of the grains. Both of these criticisms can be largely offset by the suitable choice of single-crystal critical shear stress. However, for the problem analyzed below, the critical shear stress is not directly used and, consequently, these criticisms lose their importance. The more recent contributions have attempted to obtain a more complete analysis by considering an elas-toplastic material and considering interactions between grains of differing orientations. Lin14 has considered the early stages of yielding for a polycrystalline aggregate having specific regions of defined slip plane orientations. On the other hand, Budiansky and Wu13 have allowed for these interactions for randomly disposed grain orientations and have calculated the polycrystalline stress-strain curves for crystals exhibiting either elastic-ideally plastic or kinematic hardening characteristics. This work has shown that yielding commences when the macroscopic stress is 2.2 times the critical shear stress for slip in a single crystal (7,). The yield stress-strain curve then rises becoming asymptotic to a value of 3.072 7,. This is close to the value obtained by Bishop and Hill (3.06) in their confirmation of Taylor's method. This, of course, is to be expected since, at large strain values, the elastic strains are negligible and the rigid-plastic model is satisfactory. The results of Budiansky and Wu indicate that the result obtained by Taylor is 7.7 pct high at a plastic strain which is two times the elastic strain at the initiation of yield. By defining the anisotropy in terms of relative values, the ratio of yield strength at orientation ?, to that measured in the rolling direction, the effect of the discrepancy in Taylor's solution is considered to be of lesser consequence. Therefore, it is anticipated that an analysis based on Taylor's solution, which can be quite straightforward, should provide a reasonable estimation of the anisotropy of materials having a preferred orientation texture. OUTLINE OF TAYLOR'S METHOD In fee metals there are four possible slip planes (the octahedral planes) and in each there are three possible slip directions (the edges of the octahedron), that is a total of twelve possible slip systems. von Mises16 has shown that at least five independent slip systems must become operative in each grain of the polycrystalline aggregate in order to preserve continuity of strain. With this geometrical requirement as basis and the assumptions previously listed, Taylor determined the operative slip systems for a number of orientations of the tensile stress axis specified in the unit stereographic triangle. For the ith slip system, the critical shear stress

Jan 1, 1967

John P Hammond '59, President T C Frick '58, Past President Basil Kantzer '60. President-elect George R Gray '58, Vice-President Earl M Kipp '58, Vice-President G M Stearns, Treasurer Joe B Alford, Executive Secretary 800 Fidelity Union Bldg Dallas, Texas

Jan 1, 1957

By C. F. Riisness, E. R. Parker

THAT grain size has a great effect on the mechanical properties of metals has been recognized for a long time. Bassett and Davis1 in 1919 did excellent work in [ ] determining the effect of grain size on the hardness of brass. About the same time Jeffries2 and Sykes3 ascertained the effect of grain size on the strength and ductility of several metals at temperatures ranging from 80°K. to their melting points. When creep was recognized as an important property of metals, those engaged in the study of this property tried to determine the effect of grain size 4-9 on creep rates. Unfortunately, most of the investigations were conducted on only two grain sizes, often designated simply as "fine" and "coarse." It is well known that at high temperatures coarse-grained test bars creep less than fine-grained bars. The relation between grain size and size of test bar, [ ] however, has been frequently overlooked. In his early work, Jeffries2 showed that the number of grains in the cross section has a more important influence on the properties of the material than the actual grain size. More recently Hanson and Sandford10 and Pell-Walpole,11 in their measurements of the creep and tensile properties of tin, tested a wide range of grain sizes and correlated the grain size with the strength. Hanson9 later established the relation between the number of grains in the cross section and the. creep rate: At high temperatures, generally a coarse-grained structure is considered superior in creep to a fine-grained structure, but it is evident that for a given bar size continuously increasing the grain size will

Jan 1, 1944

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By Juan Sodi, John F. Elliott

The standard free energy of ReS2 has been measured in the range of 1050° to 1250°K using H2/H2S mixtures and a slight variation of the method described by Hager and Elliott.1 The result is: The experimental method and apparatus were modified slightly for this study. Measurements on Cu2S were made to verify the application of the method to the work on ReS2. THE EXPERIMENTS AND RESULTS Briefly, the experimental method consisted of exposing a chip of copper or rhenium at a known temperature for 8 hr to a slowly flowing gas stream at the same temperature in which Ph2S and PH2 were known. The chip was withdrawn quickly from the hot furnace, and subsequently it was inspected for the presence of a sulfided surface. In the experiments described here, there was no ambiguity in any case as to the presence or the absence of the sulfide. At a given temperature, gas compositions for sulfidization were explored systematically until two compositions were found whose values of ?G°, Eqs. [I] and [2], were within approximately 100 cal of each other, one of which was sulfi-dizing and the other was not. These are termed the "straddle" compositions and it is assumed that the equilibrium composition lies between them. The chief modification to the apparatus, which is shown schematically in Fig. 1 of Ref. 1, was to support the metal specimen on a small alumina boat which could be moved along the reaction tube, 6 mm ID, by platinum wires. An appropriate seal at each end of the reaction tube permitted the sample to be moved from the cold end of the tube into the hot zone in 2 to 3 sec, and the sample could be withdrawn equally rapidly. Thus, it was possible essentially to quench the specimen from the reaction temperature with the reaction gas or helium flowing and without danger of breaking the reaction tube. The usual practice at the end of the experiment was to switch the gas system to the helium tank, flood the reaction chamber with helium, and pull the sample out of the hot zone. The purpose of the modification was to permit study of the sulfidization of copper without the complication of the back-reaction between the gas and the specimen as the latter cooled during slow withdrawal of it from the hot zone; this was a problem in the earlier work.&apos; A further improvement located the tip of the temperature-indieating thermocouple and the specimen precisely at the hottest part of the furnace. A carefully calibrated thermocouple, with its tip at the position of the specimen and with other conditions duplicating those of an actual experiment, showed that in the temperature range of 900° to 1122°C the temperature of the specimen differed from that of the tip of the indicating thermocouple by less than 0.5°C. The two positions were 0.5 cm apart. The reaction gas was prepared from ultrahigh-purity hydrogen (<l ppm O2, <0.5 ppm H2O) and CP grade hydrogen sulfide (99.5 pct H2S). High-purity helium (99.995 pct He) was used. All of these gases were purchased from the Matheson Co. All flow meters were recalibrated by the soap-bubble method with hydrogen, H2S, helium, and several gas compositions used during the study. These calibrations gave a linear relationship with a slope of 1.0 for the plot of log flow rate vs log pressure drop across the flow meter, in accordance with the Hagen-Poiseuille equation. The analysis of the gas was determined in the same manner as was reported previously. Good checks were obtained between the composition of the gas established by the flow-meter settings and by chemical analysis of the gas taken after the mixing bulb and ahead of the furnace. The pressures of H2S, H2, S2, and HS in the equilibrium gas at temperature were calculated from the following data :3 The pressures of the species S and S8 were negligible for the conditions of the experiments.3 There was no sign of vaporization of ReS2 either by weight loss or deposits in the reaction tube. Thus it is not possible to account for the apparent volatility of the compound reported by Juza and Biltz.2 The inlet gas composition and the calculated equilibrium ratio of PH2 S/PH2 for the "straddle" points of each experiment are shown in Table I. The specimens of metal for the experiment were small clippings of annealed copper (99.9+ pct) sheet 0.005 in. thick that was obtained from Baker and Adamson and of "high-purity" rhenium (99.9+ pct) sheet 0.005 in. thick that was purchased from Chase Brass and Copper Co. A specimen was removed from the apparatus; inspected for the presence of the sulfide, and then stored in a sealed vial. A fresh clipping was used in each measurement. The condition of the surface of each specimen after the experiment is noted in Table I.

Jan 1, 1969

By J. C. Martin

Stmplified equations are developed for the flow of fluids in gas drive reservoirs in which the effects of gravity can be neglected. The results show that the pressure distribution is governed by a nonlinear heat flow type of equation, and the saturation distributions are related to the pressure by the same equations QS those developed by Muskat for the average pressure and saturations in gas drive reservoirs. Unrler certain conditions the equation for the pressure can be approximated by the linear form of the heat flow equatlon. This equation tk analogous to the equation for the pressure in single-phase compressible flow The analysis reveals that the equation for the pressure in n~ultiphase flows can be obtained directly from the equation for the pressure in slngle-phase flows by simply replacing the single-phase compressibility by the total compressibility and the single-phase mobility by the sum of the mobilities of all the fluids present. Perrine&apos;s method of pressure buildup analysis for multiphme flows is based on these same substitutions. Thus, the development presented in this paper constitutes a theoretical justification for Perrine&apos;s method of pressure buildup analysis. One of the most difficult problems associated with the production of oil is the determination of the flow of the fluids within the reservoirs. One purpose of this paper is to present the development of simplified equations for the flow in gas drive reservoirs. The other purpose is to present some of the needed theoretical foundation for the methods currently being used in the analysis of multiphase pressure buildup data. The analysis presented in this paper makes use of a partial linearization of the equations governing multiphase flows. It is felt that the process of linearizing or partially linearizing the nonlinear equations of multiphase flows can lead to useful results since this process has proved extremely valuable in the study of other fields of science and engineering where nonlinear equations are encountered. Pressure buildup data of shut-in wells have been used for many years to estimate the static reservoir pressure. These data have also been used in studying the aver- age permeability both away from and close to the well-bores. The majority of the buildup data are obtained from wells producing two or three fluids. As yet the theoretical foundations for the methods of buildup analysis used in connection with rnultiphase buildup data have not been established. A number of methods of analysis of pressure buildup data have been developed." Most of these methods apply only to single-phase flows, and almost all of the theoretical analysis is confined to single-phase flows. Perrine&apos; developed a method of analysis for rnultiphase flows from the method for single-phase flows of Miller, Dyes, and Hutchinson.&apos; He did this by simply replacing the single-phase compressibility by the multiphase compressibility and replacing the single-phase mobility by the sum of the mobilities of the fluids in the rnultiphase flows. Obviously, such a procedure lacks a certain amount of theoretical justification, and such practices can lead to erroneous results. Fortunately, Perrine&apos;s results have a theoretical justification, and this justification is presented in the following discussion. It is assumed that gravitational effects and the cornpressibility of the rock can be neglected. Under these assumptions the equations governing the simultaneous flow of gas, oil and water in porous media areo* The preceding equations can be expanded into the following expressions.

By J. E. Hanlon, J. D. Wolf

The relaxation peaks observed in plastically deformed materials at low temperatures have been reviewed by sack1 and Niblett and wilks. 2 In particular, the dislocation-relaxation in columbium has received considerable study.3-6 The present work deals with the lower-temperature dislocation-relaxation peak (referred to by Chambers and Schultz as the a peak) in columbium and Cb-5 pct Zr. The columbium and Cb-5 pct Zr specimens were machined to 3/8-in.-diam by 7-in.-long rods from bars hot-extruded at 1200°C. The internal friction and resonant frequency of the samples were measured in torsion at kilocycle frequencies at a maximum strain amplitude of -10-6. The interstitial content of both materials was approximately 70 ppm N and 200 ppm 0. The dislocation-re laxation peaks were measured in the hot-extruded state and after successive anneals. Fig. 1 is a compilation of the data. The resonant frequencies for the columbium and Cb-5 pct Zr samples were, respectively, 5.5 and 6.5 kc. Other workers have noted that the dislocation-relaxation peaks in columbium are not characteristic of a single relaxation time. As can be seen in Fig. 1, the zirconium addition further broadens the spectrum of relaxation times. The magnitude of the modulus defect as computed from resonant-frequency data also reflects this extension. The occurrence of the low-temperature a peak at a position 20°K higher in Cb-5 pct Zr as compared to pure columbium, in the hot-swaged state, suggests a decrease in the average dislocation mobility for the alloy. The authors do not feel that these data are sufficient to permit an interpretation in terms of any detailed models.

Jan 1, 1967

University of New Mexico, Albuquerque, N M Requests for publications should be addressed to the Librarian of the University Papers of the Geological Series of the University are bound in volumes: Vol 1, vol 2, pt 1, and vol 2, pt. 2, and vol. 3 are out of print, but separates of the following papers may be had at a uniform cost of 25 cents each. Vol. 1? No. 1, Geology of the environs of Albuquerque (1898); 2, Occurrence of copper and lead in the San Andreas and Caballo Mountains (1898), 3, Geological reconnaissance in western Socorro and Valencia counties (1898); Geology of the San Pedro and Albuquerque districts (1898). , Vol 2: No. 1, Geology of the Albuquerque Sheet (1900); 2, Miscellaneous economic papers by Herrick (1900); 3, Geological reconnaissance in western Socorro and Valencia counties (1900); 4, Geology of the White Sands of New Mexico (1900); 5, Identifi¬cation of an Ohio coal measure&apos;s horizon in New Mexico (1900); 6, Cyanide process in New Mexico (1900). Vol. 3. No 3, The oil situation in New Mexico (1920), 4, Geology of Sandia Mountains (1922); 5, Oil and gas m New Mexico in 1923.

Jan 1, 1933

By Horace Pops

Martensitic transformation has been studied during cooling and heating in ß-phase Cu-Zn alloys to which small additions have been made of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, and Sb. The start and finish of the martensitic reaction and the variation of transformation temperature with third-element content were determined by electrical-resistivity measurements from alloys which had either constant zinc contents or constant values of electron concentration. All of the third elements, except nickel, lowered the transformation temperature if the results were plotted along the lines of constant zinc contents in each ternary system. A significant difference in the rate of lowering of the transformation temperature per atomic percent of the third element was observed for elements which had the same nominal valence. No systematic variation of transformation temperature with the valence of the third element was observed. It is suggested that the observed increase in transformation temperature for nickel-bearing alloys is due to the transfer of electrons from the conduction band of the alloy to virtual bound states. However, electron concentration is not the most important factor controlling the instability of the 0 phase. The transformation temperatures of the ternary alloys can be predicted from the following approxilnate expression: Ms (°K) = +3280 - 80 Zn + 8 Ni - 30 Ag - 12 Au - 140 Cd -90 Ga- 145 In - 80 Ge -175 Sn - 120 Si - 150 Sb MOST binary ß -phase alloys based upon the noble metals copper, silver, and gold are unstable at low temperatures and transform spontaneously by a martensitic reaction. This transformation has been studied recently in the ordered bcc ß&apos;-phase Cu-Zn binary al1oys1,2 where the transformation temperature is below the room temperature and decreases with an increase in zinc content. It has been reported that the transformation temperatures can be raised above room temperature by small additions of a third element such as silicon3,5 or gallium,4,5 but no quantitative study has been made. The transformation temperature of different binary alloys can be altered by third-element additions. For example, it was shown that nickel and copper may have a large effect on the Ms temperature of CU-Al6 and Au-cd7 alloys. The present investigation was made to determine systematically the influence of various third elements on the martensite-transformation temperature of Cu-Zn ß-phase alloys. Since these alloys have an electronic origin,&apos; alloy compositions were chosen so that the transformation temperatures could be determined at constant zinc contents or at constant values of electron concentration. I) EXPERIMENTAL PROCEDURE Ten ternary alloy systems were obtained by adding nickel, the noble metals silver and gold, and some B-subgroup elements to a Cu-Zn matrix. These are arranged according to their rows and columns in the Period Table as follows: Each ternary alloy was prepared by melting and casting weighed quantities of high-purity metals (99.99+ pct) in sealed quartz tubes under a partial pressure of helium to make a 4-g ingot. The molten alloys were shaken vigorously and then quenched in water. Since the weight loss was negligible, the compositions of the ingots after casting and annealing were assumed to be the same as the nominal compositions. The ingots were homogenized after casting in helium-filled Vycor tubes for 24 hr at temperatures between 750" and 810 C and quenched into brine. Metallographic examination revealed that all alloys were homogeneous, poly crystalline ß-phase alloys, and that the grain size was in the range 1 to 5 mm. Electrical-resistivity measurements were made to determine transformation temperatures of the ternary alloys during continuous cooling or heating. Transformation temperatures of the ternary alloys can be determined by electrical-resistivity measurements since the resistance of the martensitic phase is much higher than that of the 0&apos; phase. The technique has been described previously in connection with a study of Au-Zn alloys.9 The reproducibility of transformation temperature was approximately ±6°C. II)RESULTS A hysteresis was always observed in electrical-resistivity curves and was usually less than about 12°C.

Jan 1, 1967

CONTENTS PAGE. WHITE, DAVID.-Environmental Conditions of Deposition of Coal. Discussed by E. C. Jeffrey, George H. Ashley, Reinhardt Thiessen, S. W. Parr, David B. Reger, Wilbur A. Nelson, James F. Kemp, E. S. Moore, Homer G. Turner, David White, A. C. Noé, W. A. I. M. van Waterschoot van der Gracht 2 THIESSEN, REINHARDT.-The Constitution of Coal. Discussed by Edward C. Jeffrey, Reinhardt Thiessen, Ralph H. Sweetser, David White 12 TURNER, HOMER G.-Microscopical Structure of Anthracite. Discussed by E. S. Moore, Edward C. Jeffrey, Reinhardt Thiessen, H. J. Rose, James F. Kemp, David White, Clarence A. Seyler, A. C. Noé 14 JEFFREY, EDWARD C.-Coal in Relation to Coke. Discussed by H. J. Rose, David White, E. S. Sinkinson, S. W. Parr, James F. Kemp, Edward C. Jeffrey, Reinhardt Thiessen, Chas. R. Fettke 17 FRANCIS, W., and WHEELER, R. V.-The Resolution of Coal by Oxidation. Discussed by Edward C. Jeffrey, S. W. Parr, E. S. Sinkinson, Reinhardt Thiessen, David White 23 TIDESWELL, F. V., and WHEELER, R. V.-The Constitution of Coal. Discussed by David White, A. C. Fieldner 24 JOLLY, J., and WHEELER, R. V.-Organic Sulfur Compounds in Coal. Discussed by S. W. Parr 25 SINNATT, F. S.-Selective Combustion in Coal. Discussed by J. D. Davis, A. C. Fieldner, Geo. S. Rice, W. M. Grant, H. J. Rose, S. W. Parr, David White 25 COBB, JOHN W.-Nitrogenous Constituents of Coal. Discussed by S. W. Parr, H. J. Rose, Reinhardt Thiessen 28 PARR, S. W., and HOBART, F. B.-Coal and Oxygen. Discussed by J. D. Davis, W. T. Thorm, Jr., S. W. Parr, H. J. Rose, A. C. Fieldner, F. F. Jorgensen, David White, W. M. Grant 30 FIELDNER, A. C., and DAVIS, J. D.-Modern Views of Chemistry of Coals of Different Ranks as Conglomerates. Discussed by S. W. Parr, David White, Reinhardt Thiessen, A. C. Fieldner, Clarence A. Seyler 32 EBY, J. BRIAN.-Contact Metamorphism of Some Colorado Coals. Discussed by Geo. C. McFarlane, W. T. Thom, Jr 35 WHITE, DAVID.-Progressive Regional Carbonization of Coals. Discussed by A. C. Fieldner, Homer G. Turner, W. A. J. M. van Waterschoot van der Gracht, A. C. Noé 37 THOM, W. T., JR.-Moisture as a Component of the Volatile Matter of Coal. Discussed by A. C. Fieldner, S. W. Parr, Clarence A. Seyler, W. T. Thom, Jr., R. D. Hall 39

Jan 7, 1925

By J. H. Westbrook

IT is always of interest to document the origin of real microstructures which closely approach various idealized morphologies. Such instances constitute excellent bases for experimental studies of the effect of microstructure on properties. Typical examples include the eutectoid steels (lamellae) used by many investigators and the two phase Cu-Cr alloys (spheres) recently employed by Hibbard and Hart The present note describes a structure with cylindrical particles. In a study of certain alloys in the Cr-C system, an alloy was arc melted whose composition was very close to the aCr-Cr,C, eutectic (3.2 wt pct C, according to the latest phase diagram published by Bloom and Grant2). The alloy was not analyzed but previous experience with the melting technique employed indicates good correspondence between intended and analyzed compositions with negligible tungsten contamination from the electrode. The phases present in the alloy were identified by X-ray powder patterns as a chromium and Cr,C,. Typical micrographs, presented in Fig. 1, show unmistakable evidence of the cylindrical geometry of the carbide phase. The eutectic grains are randomly oriented and, consequently, only a few show the true fibrous nature of the carbide particles, most being cut so as to show slightly elliptical cross sections. Within any particular grain, remarkable uniformity is to be observed with respect to the size, shape, spacing, and orientation of the carbide particles. Length to diameter ratios have been estimated from the micrographs to be at least 250:1, with diameters of about lp. This alloy may be of further interest from different viewpoints. On the one hand, it might be used to check the applicability of the equations derived by Fullman3 for computing true particle dimensions of cylindrical particles from opaque random sections. On the other hand, it might be possible to extract the carbide particles from this alloy and repack them in a ductile matrix to form a synthetic structure of the type discussed by Metcalfe et al.4 With the large l:d ratio and the small diameter of the carbide fibers, it is likely that the interdefect distance in each fiber is sufficiently great to permit realization of a large fraction of the presumed high strength of the carbide. References 1W. R. Hibbard, Jr. and E. W. Hart: Dispersion Hardening of Copper-Chromium Alloys. AIME Trans., 1955, vol. 203, p. 200; Joun-nal of Metals, January 1955. 2D. S. Bloom and N. J. Grant: The System Chromium-Carbon. AIME Trans.. 1950. vol. 188. p. 41; JouRnal of Metals, January 1950. aR. L. Fullman: Measurement of Approximately Cylindrical Particles in Ooaaue Samples. AIME Trans.. 1953, vol. 197, p. 1267; Journal of Metals. ~ebtember 1953 4 A. G. Metcalfe, C. H. Sump, and W. C. Troy: Fiber Metallurgy. Metal Progress, 1955, vol. 67, p. 81.

Jan 1, 1958

By Carl F. Dietz

(New York Meeting, February, 1912.) THE problem of drying ores is one that most mill-engineers are sooner or later called upon to meet, and it may be timely to point out sortie of the difficulties resulting from such operations from purely a metallurgical and economic stand-point. We mean, in the following pages, to discuss primarily the effect of such operations on. the ore itself, without particular reference to the mechanical or cost features of the subject; That an appreciable tonnage of the ore fed to the usual form of drier, either rotary or stack, is lost, is fairly well appreciated, but we believe that only a few mill-managers know just. what their drier-losses amount to, and we have found that in most cases they console themselves with the fact that the drier-smoke is not very much discolored, and it is generally believed that the draft is not sufficient to carry away more than a. negligible percentage of the values. The drying of ores is becoming an important factor. since the more general application of magnetic, static, and dry-table treatment. Its importance in the field of metallurgical operations warrants a close examination into its effects. This subject has been repeatedly brought hone to us, and while the drier-losses, in every case examined, have considerably exceeded even the most generous estimate, an attempt at a recovery of these values is rarely made. We have found that the losses resulting from drying-operations can be effectively recovered, at a low cost, and believe that the publication of the results of a number of investigations along these lines will be of interest and benefit to the profession at large. To dry an ore quickly and effectively, it must be brought into actual contact with hot gases or air. The rapid drying is effected by the fact that the hotter the gas the hungrier it is

Jul 1, 1912