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By W. E. Quist, R. Taggart, D. H. Polonis, C. J. van der Wekken

An intermediate compound that has been identified as Niab is observed to form as a decomposition product from supersaturaled Ni-Nb solid solutions during aging at temperatures between approximately 300" and 500°C. On the basis of data from electron microscopy and selected-area diffraction, the structure of this compound has been determined as fct with a = b - 3a0 and c = a, wlzere a,, is the lattice parameter of the parent solid solution. The compound consists of close-packed layers with triangular ordering, where the niobiutrl atoms are separated by two nickel atoms ([long- close?-packed directions. A nine layer stacking sequence is required to describe the proposed structure. STUDIES of the Ni-Nb binary system have been limited primarily to phase diagram determinations,'-4 investigations of high-temperature equilibrium phases,5"1 and the determination of the influence of deformation on the structure of the equilibrium compound.8 The nickel-rich portion of the binary system is reported to be of the simple eutectic type in which the maximum solubility of 12.7 at. pct Nb occurs at 1282"c.' The two-phase field below the eutectic temperature is bounded by the a fcc solid solution and an orthorhombic Ni3Nb compound. No metastable phases have been reported in previous investigations. In transformation studies of certain nickel-base commercial alloys that contain niobium, two ordered metastable compounds containing niobium have been shown to precipitate from the solid solution, both of which have been identified as y' and have the composition NisNb or Ni,Nb. One compound has been reported to have the bct DOz2 type Al3Ti structure" and the other the cubic LI2 type Cu3Au structure.9,11 In the present work on Ni-Nb binary alloys a metastable y' compound has not been detected after conventional quenching and aging treatments. An anomalous behavior was noted in electrical resistivity measurements. in alloys containing between 7 to 12 at. pct Nb when aging treatments were performed below 500°C after fast quenching from 1250°C. Transmission electron microscopy has shown that this behavior is caused by the formation of a low-temperature precipitate of unreported structure type and composition. EXPERIMENTAL METHODS Several Ni-Nb alloys, containing up to 11.5 at. pct Nb. were prepared by either levitation melting and casting in copper molds or by induction melting in alumina crucibles; both techniques employed purified helium gas as a protective atmosphere. The purity of the nickel and niobium used to make the alloys was 99.98 wt pct Ni and 99.9 wt pct Nb. The composition and homogeneity of the alloys were checked by weight measurements and by electron microprobe analysis. The induction-melted alloys were homogenized for 100 hr at 1100°C. The resistivity specimens were prepared from rods swaged to 2.5 mm and the electron microscopy specimens were cut from sheet that was rolled to 0.4 mm and thinned using a modified Bollmann technique." The elevated-temperature solution treatments were carried out in a purified helium atmosphere followed by direct quenching into a 10 pct NaCl solution at 23°C. Additional protection against oxidation of the samples during solution treatment was accomplished by using tantalum foil as a "getter" in the furnace. The specimens were aged at various temperatures in salt baths controlled to +2oC. A Leeds and Northrup K5 potentiometer was used to make electrical resistivity measurements on specimens immersed in liquid nitrogen. Electron microscopy and diffraction studies were carried out with JEM-7 and Philips EM-200 microscopes operating at 100 kv. RESULTS AND DISCUSSION Ni-Nb alloys containing between 7 and 11.5 at. pct Nb that have been solution-treated in the range 1220" to 1280°C and quenched to 23°C undergo a precipitation reaction when aged in the temperature range 300" to 500°C. Precipitation was detected by selected-area electron diffraction after aging a specimen for as little as 30 sec at 350°C) whereas the reaction was well-advanced after aging for 150 hr at 475°C. Electrical resistivity measurements were used to monitor the progress of the precipitation reaction. In the present experiments the nucleation process for precipitation required a high solution temperature and a rapid quench into brine. The presence of aluminum, iron? and carbon in amounts totaling less than 1 wt pct was found by electron diffraction to completely suppress the formation of the low-temperature precipitate that has been detected in the binary alloy. Electron diffraction techniques were used to determine the structure of the precipitates that formed during the decomposition of the Ni-Nb supersaturated solid solutions. Figs. l(a) through l(d) show electron diffraction patterns oriented to the [loo], [110], [lll], and [I031 zone axes of the matrix. Areas of reciprocal space between these sections were investigated by slowly varying the orientations of the crystal under study; this procedure revealed no reflections other than those depicted in Fig. 1. The presence of super-lattice reflections at points coincident with the matrix reflections was confirmed by the examination of an almost completely transformed structure. On the basis of the accumulated diffraction data, the reciprocal lat-

Jan 1, 1970

By W. R. Crandall

The southern gold-fields offer some of the most complex and trying problems encountered in mining; and their successful solution often means the success or failure of the particular enterprise involved. In vein-mining, where the values are scattered over large areas, making it necessary to handle a large tonnage of very low average grade, the successful solution has been found in some instances by a combined hydraulicking and milling; water under pressure being used as the mining agent, and also for transporting the broken material to the mills, and effecting in its passage a partial concentration of the product by washing out the lighter and looser dirt of the ore-mass. The placer-deposits of the South, which were the original localities from which gold was mined, have been extensively worked, and to any one now undertaking their development offer many difficulties. The antiquity of the industry in this field, which was the cradle (in fact, literally the rocker), in which the California '49-er was born, gives assurance that all the deposits available to water and natural drainage have been more or less extensively worked already, so that, as a rule, any placer-deposits yet remaining undeveloped may be considered to offer some difficulty beyond the ability of the " old-timer " to overcome.

Jan 1, 1897

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By P. A. Beck, S. Kohara, M. N. Parthasarathi

IT has been shown1,3 that many observed phenomena related to annealing textures in f.c.c. metals can be adequately accounted for, at least in a qualitative way, by considering the orientation dependence of the boundary mobility, without any hypotheses concerning preferred orientation of nuclei. It was noted1 that this approach is particularly successful in the common cases of primary recrystallization in highly cold-worked polycrys-talline metals, where nuclei occur in great abundance, and that in the other extreme case, where the number of nuclei is very limited, or even only a single crystal is grown, the orientation dependence of boundary mobility has only a small effect, or none at all, on the orientations resulting from annealing. Recently Dunn described examples3-6 where observed secondary recrystallization textures apparently cannot be accounted for on the basis of oriented growth alone, but also require oriented nuclei, or at least the absence of nuclei in certain orientation ranges. In general, the great difficulty in correlating the preferred orientation of recrystallized grains with that of nuclei is inherent in the fact that nuclei are by nature very small, and that they are usually identifiable as "nuclei" only after growth, i.e., after they have already been subject to growth selectivity. An investigation was carried out by Liebmann and Lücke,' and also a very similar one by Graham and Cahn,' to obtain quantitative information on the orientation depend- ence of boundary migration rates in the recrystallization of slightly deformed aluminum single-crystal rods or plates, in which artificially nucleated recrystallized grains of predetermined orientation were grown. Liebmann and Lücke foupd maximum boundary mobility for boundaries across which the misorientation corresponded to a rotation of 40 deg around a common [Ill] axis, in accordance with earlier conclusions.9,1 Also, they confirmed that such an orientation relationship predominates among crystals growing into slightly extended single crystals from presumably random artificial nuclei. On the other hand, Graham and Cahn found no preferred orientation among crystals grown in a similar manner. It is not as yet known how these observations may be reconciled with each other. The view has been expressed in various papers5'10,21 that selective growth based on the orientation dependence of boundary mobility is not in itself sufficient to account for the formation of sharp re-crystallization textures, such as those often observed in highly deformed polycrystalline metals after annealing. The present work was undertaken to ascertain whether or not it is possible to obtain a sharp re-crystallization texture in a case where random nuclei are assuredly present in large numbers. It was previously found1' that high-purity aluminum crystals rolled 80 pct on the (110) plane in the [1T2] direction, when suitable precautions are taken, may be annealed for periods of about 1000 sec at 350°C without recrystallization. It was also found that the reluctance to recrystallize in this case is due to the scarcity of material in sufficiently deviating orientations to serve as nuclei. By using such a matrix,

Jan 1, 1959

By J. Szekely, V. Stanek

Heat and gas flow interactions in nonisothermal packed beds were examined in the paper. A study was made of the response of the system to a step or pulse change in the inlet gas temperature, with a fixed value of the overall pressure drop across the bed. Under these conditions the heat flow and fluid flow transients are coupled because the convective heat transfer rate is alfected by the mass flow rate of the gas which, in turn, for a fixed pressure drop will depend on the temperature profile in the system. The Problem was stated in terms of differential equations, which were integrated numerically. The parameters used in the computation were so chosen to reflect the operation of the stack region of blast furnaces and sinterbeds. The computed results showed that the pressure drop-flou1 relationships and the rate of progress of the temperature fronts (waves) were strongly interrelated and were also markedly affected by variations in particle size and in void fraction. MANY metallurgical processes involve the contact of solid particles with a gas stream in a packed bed arrangement under nonisothermal conditions. Examples are shaft furnaces, regenerators, pebble heaters, and the sinter process. Although the heat and mass transfer aspects of packed bed processing have been extensively studied, the associated flow phenomena and in particular the effects of nonisothermality on the flow, have received little attention to date. :In fact, most of the previous workers considered the flow rate of the carrier gas time invariant and independent of the heat or mass transfer processSzekely and carr2 have shown that the pressure drop-flow relationships in nonisothermal packed beds may be strongly affected by the temperature profile within the system. These authors have devised a method for relating the pressure drop to flow for a given temperature profile. thus providing an extension of the Ergun equation to steady nonisothermal systems. Finally, in a recent paper willmot3 examined the response of regenerators to externally imposed changes in the gas flow rate. Both these investigations were somewhat specialized since, in general, neither the temperature distribution nor the gas flow rate may be regarded as truly independent variables, thus the heat transfer and the fluid flow problems have to be solved simultaneously. The work reported here is divided into two parts: in Part 1 the general formulation is given and a detailed discussion is presented of fixed bed systems. Part is devoted to systems in which a gas and particulate solids are contacted in a counter flow arrangement. FORMULATION Consider a nonisothermal fixed packed bed, extending from through which a gas is flowing. The problem is to develop a relationship between pressure drop and gas flow (with the gas flow being the dependent variable) and to evaluate the rate at which a change in the gas temperature, imposed at the inlet, travels through the system. Let us consider an infinitesimal section of the bed and establish differential heat, mass, and mechanical energy balances over this region. In addition, relationships are needed describing the temperature dependence of gas density (equation of state) and the temperature dependence of viscosity. These may be written as: where c, and are constants. It is noted that in this formulation we neglected any temperature gradients within the solid particles, thus assuming these to be either sufficiently small or of sufficiently high thermal conductivity to meet this condition. The justification and consequences of this assumption will be mentioned in the discussion.

Jan 1, 1970

By R. E. Reed-Hill, W. H. Hartt

High-purity magnesium single crystals, oriented with basal plane parallel to stress axis, were deformed in tension at room temperature so as to form second-order (1011)- (1012) twins. Investigation by optical and replica electron microscopy revealed that these twins can support very large internal strains approaching 1000 pct and that fracture follows as a direct consequence of these strains. At low strains the basal plane within (10i1)- (10i2) twins rotates with increasing deformation until it becomes approximately parallel to the twin boundaries. This rotation is not consistent with deformation by basal slip in the double twin, but may be rationalized in terms of nonbasal slip. Observations also indicate that basal slip in the primary (1011) twin, prior to second-order twinning, may contribute to this rotation. Deformation markings that are difficult to interpret in terms of slip on previously observed systems were noted in the twin bands. A possible means of rationalizing these markings is to relate them to grain boundary shear. The fracture associated with these twins is thought to initiate by formation of voids at the twin boundaries. These grow into microcracks, with ultimate fracture occurring by tearing of the interconnecting regions. THE significance of deformation and fracture along second-order (10i1)-(10i2) twins in polycrystalline magnesium1-' and many magnesium alloys4 was discussed in a previous paper.5 It was noted that this double twinning mode effectively controls the room-temperature deformation and fracture of magnesium single crystals, oriented with the basal plane parallel to the tensile axis. Reed-Hill and Robertson6 observed that, although these crystals may fracture at a macroscopic strain of less than 1 pct, shear strains up to 1000 pct could occur within (1011)- (10i2) twin bands. They concluded that the fracture was "ductile" and resulted from concentrating the deformation into a very small volume. The present research was undertaken to obtain a better understanding of the deformation and fracture associated with these twins. EXPERIMENTAL TECHNIQUES The experimental procedure involved straining high-purity magnesium single crystals in tension at room temperature. Specimens were oriented so that the applied stress direction was within 2 deg of the [1010] crystal axis. The specimen cross section was rectangular with faces closely parallel to (1210) and (0002). The specimen preparation and testing procedures have been described in detail elsewhere.5 Second-order (1011)- (1072) twins nucleated during straining were studied using optical and replica electron microscopy techniques. For the latter, cellulose acetate-carbon double replicas were employed. Observations were made on the (1210) crystal surface, which is the plane of shear for twins of this type. In addition to the single crystals, some investigations were carried out on longitudinal polycrystalline specimens. These were obtained from high-purity magnesium plate with a texture in which the basal planes of the grains tended to be nearly parallel to the specimen axis. All. polycrystalline specimens were annealed prior to testing in order to produce a coarse grain structure, permitting Laue back-reflection X-ray photographs to be obtained from grains of interest. EXPERIMENTAL RESULTS a) Deformation Within ( 101 l )-( 1072) Twins. Fig. 1 is an optical micrograph demonstrating the extent of the plastic deformation that can occur in (1011)-(10i2) twin bands. Notice at the lower left corner of the photograph the large displacement of the dark band (a polishing step) where it crosses the twins. The shear strain in the twin band at this position was computed to be 700 pct, using the ratio of step width to twin thickness. It was previously shown5 that (1011)- (1012) twin bands are often composed of small, separate twins aligned close to the macroscopic habit plane. Fig. 2 is an electron micrograph from near the upper end of the twin band in Fig. 1. This illustrates that the twin habit often does not coincide exactly with the macroscopic band habit, but may be inclined at a slightly smaller angle to the matrix basal plane. Figs. 3 through 6 are electron micrographs of the twin band in Fig. 2 illustrating successive steps in the development of deformation inside the band. A twin band such

Jan 1, 1969

By AIME AIME

Council.* PRESIDENT OF THE COUNCIL. ROBERT W. HUNT CHICAGO, ILL. (Term expires February, 1907.) VICE-PRESIDENTS OF THE COUNCIL. WILLIAM P. BLAKE TUCSON, ARIZ. THOMAS F. COLE DULUTH, MINN. IRVING A. STEARNS WILKES-BARRE, PA. (Term expires February, 1907.) HENRY AL HOWE NEW YORK, N. Y. J. B. GRANT DENVER, COLO. JAMES D. HAGUE NEW YORK, N. Y. (Term expires February, 1909.)

Nov 1, 1906

By L. E. Welch, C. W. MacGregor

THE past 20 years has seen a revolutionary change in the testing of materials at elevated temperatures. This has largely been brought about by the practical importance of the creep problem in the design of equipment for operation at high temperatures. The short-time tension test carried out at elevated temperatures has consequently assumed in many cases only a secondary role compared to the long-time creep test. In many problems, however, a knowledge of the short-time high-temperature properties of a metal is essential. To mention a few cases in which this is so, we might include all hot-forming operations such as rolling,' forging, etc., the welding problem if residual stresses are to be computed, the development of new alloys for high-temperature service where, in the initial stages, time does not permit of long duration creep tests, and others. Usually a knowledge of the short-time properties is desired, if only to serve as a background against which to compare creep behavior. In conducting short-time high-temperature tests, it has been almost the universal practice to determine stresses based on the original area and strains referred to the original gauge length which is usually chosen as 2 in. It has. been pointed out 1,2 that one of the reasons that the true significance of certain tensile properties is not understood, which perhaps curtails their usefulness, especially when the material is applied [ ] under conditions differing considerably from the test conditions, is that true physical stresses and strains are not determined. It is essential to have a knowledge of true stresses, and strains in order to correlate the values present in the tension test with those existing, for example, in hot metal-forming operations and in the general problem of the yielding and failure of metals under combined stress conditions. Stress and strain values based on the original dimensions of the test piece do not exist physically except in the early stages of the test. Since at the present time there is very little information in the literature on true stress-strain relations in the short-time high-temperature tension test it is proposed in the following pages to describe a

Jan 1, 1942

By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

It is known that stoichiometric NiTi transforms to a structure of lower symmetry near room temperature. The present investigation deals primarily with the changes in the electrical and magnetic properties which occur at the transformation. The effects of composition and various heat treatments on electrical properties are also discussed. In recent investigations by Purdy and Parr,' Wang et a1.,2 Dautovich and Purdy,~ Dautovich et a1.,4 and the authors, ~,' NiTi has been observed to undergo a martensitic phase transformation from the ordered CsCl (B2) structure to one of lower symmetry. The crystal structure of the low-temperature modification is still not completely worked out. This transformation occurs near room temperature for the stoichiometric composition. The thermodynamic, elastic, crystallographic, and microstructural characteristics of this transformation for some compositions have been previously reported.'-= In the present investigation, the changes in the electrical transport properties and magnetic susceptibility of NiTi when it undergoes the martensitic phase transformation have been measured. The approximate composition range covered is 48 to 52 pct Ti.* *All compositions are given in atomic percent._____________________ EXPERIMENTAL PROCEDURES AND RESULTS 1) Sample Preparation. The NiTi alloys were prepared from iodide titanium (>99.92 pct Ti) and vacuum-premelted carbonyl nickel (>99.95 pct Ni) by repeated arc melting under gettered argon and casting in a water-cooled copper mold. After the cast buttons were hot-forged at 800" to 950°C, the oxidized surface was removed by grinding and etching. Samples were cut from the worked polycrystalline buttons. After fabrication, the samples were annealed 1 hr at 900°C and water-quenched. The composition of the alloys was assumed to be the same as in the initial feed. This assumption was supported by material balance checks on 100-g arc-melted buttons which demonstrated quantitative recovery to within k0.02 pct. The oxygen content of the alloys was '150 ppma (weight) and the carbon content was 30 to 50 ppm. 2) Electrical Resistivity and Hall Effect. The electrical resistivity was measured over the composition range 48 to 52 pct Ti for temperatures varying from 4.2"K to 900°C. The high-temperature and many of the low-temperature experiments were carried out using conventional 4-probe dc techniques.7 The Hall coefficient and ac resistivity were measured at 20 cps using the apparatus shown schematically in Fig. 1. The equipment is basically an ac potentiometer: The resistive or Hall voltage of the sample is balanced by a comparison voltage provided by a dividing network across a standard series resistance. The off-balance signal is amplified by a Tektronix 122 amplifier and detected by a Princeton Applied Research (PAR) phase-sensitive detector. The precision of the resistivity and Hall coefficient measurements is i0.1 and i3 pct, respectively. The uncertainty in the data is increased by i2 pct from the precision limits because of uncertainty in dimensions and possible end effects. The temperature dependence of the electrical resistivity and Hall effect for a stoichiometric (50.0 pct Ti) NiTi sample are illustrated in Fig. 2. Above 75"C, this sample has essentially the B2 structure, while below about 0°C it is completely in the low-tempera-

Jan 1, 1968

By Frederick N. Rhines, Robert F. Mehl

Relatively few data have been collected on the rates of diffusion in ternary solid solution systems. In general it does not seem worth while to gather extensive data for such systems until the factors that determine the rates of diffusion in binary systems are better understood. But the rates of diffusion in a ternary system of limited solid solubility, in which the terminal solid solution is in equilibrium with an intermediate phase and may thus be represented as a quasibinary system, represents a case of special interest. In this case, where by reason of the association of the two solute metals in an intermediate phase a special attraction of the two solute atoms may be safely assumed, some interaction of these atoms during simultaneous diffusion in the solvent lattice might be expected. It has frequently been proposed that molecular solid solutions exist in quasibinary and in other ternary (and binary) solid solutions. There is no direct evidence for such solid solutions; arguments based upon the supposed anomaly in certain physical properties1 are hardly important; unexpected density relationships have proved deceptive;2 suggestions of molecular solid solutions have been made on the basis of solution laws in their application to certain systems, but without result;3 attempts to find lattice parameters in the solid solution Al-MgZnz, which cannot be calculated from the separate effects of magnesium and zinc and might therefore be taken as evidence for a molecular aggregation, have given negative results.* Fundamentally, methods for the determination of the state of molecular aggregation in solution depend upon the kinetic behavior of the particles constituting the system. If it could be shown that the two solutes in a quasibinary ternary system diffuse in molecular proportions, despite a radical difference in the separate rates of diffusion of each solute when diffusing alone in the solvent lattice, some basis for the concept of molecular solid solution would be afforded. Freche5 examined the rates of

Jan 1, 1940

By Frederick N. Rhines, Robert F. Mehl

Relatively few data have been collected on the rates of diffusion in ternary solid solution systems. In general it does not seem worth while to gather extensive data for such systems until the factors that determine the rates of diffusion in binary systems are better understood. But the rates of diffusion in a ternary system of limited solid solubility, in which the terminal solid solution is in equilibrium with an intermediate phase and may thus be represented as a quasibinary system, represents a case of special interest. In this case, where by reason of the association of the two solute metals in an intermediate phase a special attraction of the two solute atoms may be safely assumed, some interaction of these atoms during simultaneous diffusion in the solvent lattice might be expected. It has frequently been proposed that molecular solid solutions exist in quasibinary and in other ternary (and binary) solid solutions. There is no direct evidence for such solid solutions; arguments based upon the supposed anomaly in certain physical properties1 are hardly important; unexpected density relationships have proved deceptive;2 suggestions of molecular solid solutions have been made on the basis of solution laws in their application to certain systems, but without result;3 attempts to find lattice parameters in the solid solution Al-MgZnz, which cannot be calculated from the separate effects of magnesium and zinc and might therefore be taken as evidence for a molecular aggregation, have given negative results.* Fundamentally, methods for the determination of the state of molecular aggregation in solution depend upon the kinetic behavior of the particles constituting the system. If it could be shown that the two solutes in a quasibinary ternary system diffuse in molecular proportions, despite a radical difference in the separate rates of diffusion of each solute when diffusing alone in the solvent lattice, some basis for the concept of molecular solid solution would be afforded. Freche5 examined the rates of

Jan 1, 1940

By Henry A. Stiff, and Lawrence E. Davis

The authors previously presented a method for predicting the tendency of oil field waters to deposit calcium sulfate. The present paper gives a similar method for calcium carbonate. Methods for predicting calcium carbonate scaling tendencies in fresh waters have been available for some time, but these could not be used for brines. By experimentally deriving the value of the K term in the Langelier equation, a method has been developed which applies to waters of high salt content. A statistical study is included which shows that the experimentally derived values of K are in good agreement with actual conditions. Several applications of the final equation to production practice are given. INTRODUCTION The authors previously presented a method for predicting the formation of calcium sulfate scale in oil field waters.' Although calcium sulfate deposition is important in production operations, the majority of scale problems involve calcium carbonate. The present communication discusses a method by which the formation of this type of scale in oil field waters can be predicted. Calcium carbonate precipitation is caused by a shift toward carbonate in the carbonate-bicarbonate-carbon dioxide equilibrium. When equilibrium shifts in the other direction, the precipitate goes back into solution. Since there is usually considerable delay between the establishment of an equilibrium and the precipitation or solution of calcium carbonate, unstable conditions exist in which a water will precipitate or dissolve calcium carbonate on standing. Tillmans? who did a major part of the early work on carbonate scaling, pointed out that the condition of equilibrium not only indicates the tendency of a water to scale but also is an indication of its corrosive properties. Previously precipitated calcium carbonate combines with iron to form a dense crust which inhibits corrosion. If the water tends to dissolve carbonate, the scale becomes porous, and electrolytic corrosion takes place. Tillmans1 work was extended by several investigators until in 1934 Langeliers developed an equation setting forth the conditions of carbonate equilibrium. By the use of this equation the pH of a water at equilibrium can be calculated. If the actual pH is higher than the calculated pH, the water has a tendency to form scale. If it is lower. the water has a tendency to be corrosive. Langelier's equation can be expressed in a simple form as follows: SI = pH-pCa-pA lk-K where: SI is the stability index. A positive index indicates scale formation. A negative index indicates corrosion. pH is the pH of the water sample, as actually determined. pCa is the negative logarithm of the calcium concentration. pAlk is the negative logarithm of the total alkalinity. K is a constant, the value of which depends on the total salt concentration and the temperature. This equation has been shown to apply to waters with totaI solid concentrations as high as 4.000 ppm. In fact, control of fresh water treatment by means of this equation has been standard text-book practice for a number of years. Nomographs have been worked out so that the stability index of a fresh water sample can be determined in a matter of minutes. Most oil field waters, however, contain well over 4,000 ppm of salts and for this reason the usual application of Langelier's equation can not be made. By an empirical method we have extended the application of the Langelier equation to waters of high salt concentration. By the use of this equation the tendency of oil field waters to deposit calcium carbonate can be predicted.

Jan 1, 1952

By David Cole

DAVID COLE, EL PASO, TEXAS (communication to the Secretary*).-I have read with great interest Dr. Gahl's painstaking paper giving us the details of development of flotation at Inspiration, and it seems to me that he has covered the ground so completely that there is little to discuss or criticize in connection with his subject. While it was in operation, the test mill in which the campaign was carried on was the Mecca of mill men and metallurgists. There was much to interest students of milling methods in addition to the flotation experiments, and readers of Dr. Gahl's paper will miss the information they hoped to get when the "pilot" mill results were. finally compiled, and I hope that the following remarks outlining from a distance some of the things that happened there will bring forth the rest of the story of the performances recorded in these important experiments. Prior to the use of flotation methods in concentration it had long been recognized that the "unavoidable" losses of sulphides were in the slime which is inevitably produced in the grinding operations required to free the minerals to be separated. Classifying the feed prior to its final stage of treatment had long been in style in milling. This assisted the sand-handling machines and resulted in lowering the tailings made by them, but at the expense of the slime-handling department; and while little was expected of the latter, the wisdom of complicating the process by hydraulic classification was being seriously questioned. Indeed, at the

Jan 10, 1916

By T. K. Redden

Protective coatings based on the formation of a surface coating of nickel aluminide (NiAl) were applied to the nickel-base superalloys IN 100, SEL 15, and U-700. Coated specimens were exposed to an oxidizing environment at temperatures between 1600 and 2200 F for times up to 1000 hr. The oxidation resistance and stability of the coating were evaluated by weight gain measurements, metallographic examination, and X-ray diffraction study of surface oxides and coating. The composition of the coating and diffusion zone was determined by electron microprobe traverse of samples before and after high-temperature exposure. Intermediate phases formed in the coating and diffusion zone were identified by X-ray diffraction in situ and after electrolytic extraction. The outer coating was found to consist of the inter-metallic compound, NiAl, while the diffusion zone contained MC, M23C6 or M6C carbides, and a phase in a matrix of NiAl + Nidl. Oxidation resulted in formation of an A1203 n'ch scale containing some Tz02. Depletion of aluminum during oxidation resulted in degradation of the outer coating to Ni3Al and the nickel alloy matrix. Diffusion of aluminum into the base metal was found to be slight and did not influence coating life significantly. The o formed in the diffusion zone during coating decomposed during elevated-temperature exposure to form stable carbide phases characteristic of the base metal. Diffusion zone phase changes were found to have no effect on the life of the aluminide coating in the oxidizing envzron?nent. THE oxidation resistance of many high-strength nickel-base superalloys is inadequate for extended exposure at temperatures above about 1600°F. In addition, some applications for these materials require that they be exposed to environments containing sulfur compounds and sodium salts which can cause surface attalk known as sulfidation or hot corrosion. In order to provide the necessary corrosion resistance to the high-strength alloys, protective coatings based on an aluminizing process have been developed. These processes, usually based on a pack cementation technique, result in the formation of a NiAl-rich outer coating layer either during the coating process or by a subsequent diffusion treatment. The performance of the aluminide coatings is affected by interactions between the coating layer and the base metal both during the coating process and during subsequent exposure at elevated temperatures. Knowledge of these interactions is required to guide the development of coatings capable of longer life and improved reliability. Goward et al.' recently reported the metallurgical factors which influence coating per- formance on MAR-M200. The present work is concerned with correlating the interactions and performance of coating compositions on several representative materials. EXPERIMENTAL PROCEDURES Materials. Three cast nickel-base superalloys which are used for turbine buckets in air-breathing engines were studied: IN 100, U-700, and SEL 15. Their chemical compositions are given in Table I. The alloys were vacuum-induction-melted and cast to slabs approximately 0.3 in. thick from which rectangular specimens 0.25 by 0.5 by 1 in. were machined. Coating Procedures. The machined specimens were coated by CODEP processes which were developed at the author's laboratory. These are based on pack cementation in various media to deposit either aluminum or aluminum in combination with titanium. The coating process which deposits only aluminum is designated CODEP-C, while the CODEP-D process deposits titanium in combination with aluminum. The CODEP-D process was applied only to IN 100. Both CODEP processes are applied at 1950" or 2000°F for 4 hr without need for a subsequent diffusion treatment. An outer coating about 1 mil in thickness is produced by these processes. Test Procedures. Coated specimens were exposed to static oxidation for periods ranging from 24 to 1000 hr at temperatures of 1600" to 2200°F. Terminal weight gain measurements and visual examination were used to evaluate oxidation resistance. including oxide spalling and coating failure. Both as-coated and exposed specimens of each alloy were studied by metallographic examination, electron microprobe analysis (EMA), and X-ray diffraction analysis either of the exposed surfaces or of phases extracted from the coating and diffusion zone. RESULTS As-Coated Condition. The microstructures of as-coated conditions were generally similar, irrespective of base materials or the particular coating process. They are typified by IN 100 coated by CODEP-D as shown in Fig. 1. The predominately single-phase outer layer, area A, Fig. 1, was identified by X-ray diffraction as the intermetallic compound NiA1. The NiAl zone extended inward to the original base metal interface. The diffusion zone, area B, Fig. 1, included carbide phases, a lamellar phase oriented perpendicular to the base metal surface, and a matrix phase consisting of a mixture of NiAl and Ni3Al. The phases in the diffusion zone were electrolytically extracted using a 10 pct HCl in methanol solution at approximately 1.3 amp per sq cm. The extracted phases were found to be M6C, MC, or M=C6 carbides and o as shown in Table I1 for each of the alloys. The d spacings from a typical diffraction pattern are

Jan 1, 1969

By C. K. Eilerts

Finite difference equations were programmed and used to integrate the second-order, second-degree, partial differential equation with variable coefficients that represents the transient linear flow of gas-condensate fluids. Effect was given to the change with pressure of the compressibility factor, the viscosity, and the effective permeability and to change of the absolute permeability with distance. Integrations used as illustrations include recovery of fluid from a reservoir at a constant production rate followed by recovery at a declining rate calculated to maintain a constant pressure at the producing boundary. The time required to attain such a limiting pressure and the fraction of the reserve recovered in that time vary markedly with properties of the fluid represented by the coefficients. Fluid also is returned to the reservoir at a constant rate, until initial formation pressure is attained at the input boundary, and then at a calculated rate that will maintain but not exceed the limiting pressure. The computing programs were used to calculate the results that would be obtained in a series of back-pressure tests made at selected intervals of reservoir depletion. If effect is given to the variations in properties of the fluid that actually occur, then a series of back- pressure curves — one for each stage of reserve depletion — is required to indicate open-flow capacity and related flow characteristics dependably. The isochronal performnce method for determining flow characteristics of a well was simulated by computation. INTRODUCTION The back-pressure test procedurel is based on a derivation of the equation for steady-state radial flow of a gas, the properties of which are of necessity assumed to remain unchanged in applying the test results. The properties of most natural gases being recovered from reservoirs change as the reserve is depleted and pressures decline, and the results of an early back-pressure test may not be dependable for estimating the future delivery capacity of a well. The compressibility factor of a fluid under an initial pressure of 10,000 psia can change 45 per cent and the viscosity can change 70 per cent during the productive life of the reservoir. There are indications that the effective permeability to the flowing fluid can become 50 per cent of the original absolute permeability before enough liquid collects in the structure about a well as pressure declines to permit flow of liquid into the well. The advent of programmed electronic computing made practicable the integration of nonlinear, second-order, partial differentia1 equations2.3 pertaining to flow in reservoirs. Aronofsky and Porter4 represented the compressibility factor and the viscosity by a linear relationship, and integrated the equation for radial flow of gas for pressures up to 1,200 psi. Bruce, Peaceman, Rachford and Rice5 integrated the partial differential equations for both linear and radial unsteady-state flow of ideal gas in porous media. Their published results were a substantial guide in this study of integration of the partial differential equation of linear flow with coefficients of the equation variable. The computing program was developed to treat effective permeability as being both distance-dependent and pressure-dependent. In this study all examples of effective permeability are assumptions designed primarily to aid in developing programs for giving effect to this and other variable coefficients. The accumulation of data for expressing the pressure dependency of the effective permeability is the objective of a concurrent investigation. FUNDAMENTAL DIFFERENTIAL EQUATIONS DIFFERENTIAL EQUATION OF FLOW Linear transient fluid flow is represented by the partial differential equation,

Jan 1, 1965

By A. E. Dwight, Paul A. Beck

Known CsCl-type phases in transition metal alloys are shown to be formed preferentially at an electron concentration of approximately 6; a tetragonally distorted version of the CsCl structure is stable at -e/a = 6.5. The relationship of the distortion to electron concentration is verified by experimental data for the quasibinary systems Time ,Os) , Ti(Re,Ir), and Ti(Re,Pt) and the ternary system Ti-Ru-Rh. It was noted some years ago1j2 that the occurrence of CsC1-type ordered structures in equiatomic binary alloys, AB, of transition metals correlates with the location of the component elements in the periodic table. One of the components, A, must be to the left and the other component. B, must be to the right of the chromium group. It was pointed out2 that the CsCl structure does not occur in CrFe. is metastable in VFe,3 and is stable in TiFe up to high temperatures, and that this progressively increasing stability may correspond to an increase in electron transfer between the two components and to a correlated decrease of the magnetic moment associated with the iron atoms. Such a decrease was in fact later demonstrated by Nevitt. 4 The binary CsC1-type phases that are formed by a transition metal with either another transition metal or a lanthanide are listed in Table I. Thirty-three of these phases occur at an average electron concentration (average number of electrons outside of closed shells) of e/a = 6. The five phases that are formed at an electron concentration of e/a = 5.5 appear to be borderline cases. This is suggested for instance by the fact that TiRe is bcc. without any long-range order, while TiTc (at the same electron concentration) has a CsCl ordered structure. Six of the undistorted CsCl phases formed by transition metals with one another have an average electron concentration of e/a = 6. 5. Table I. With the exception of Zr4,Rhs4 and Hf48Rh52. the B component in these phases is a first long-period transition metal, i.e.. iron or cobalt. TiNi. with an electron concentration of e/n = 7, appears to undergo transformation at around room temperature to a more complex ordered struct~re.~ The five other CsCl structures known to occur at e/a = 6.5 have either scandium or a lanthanide metal as the A component; the difference in the elec-tronegativity and in the e/a ratio between the component elements is in these phases very large, A(e/a) - 7, and they may be expected to have a rather strong ionic bond component. Presumably the ionic bond stabilizes the CsCl-type structure at the equiatomic composition and it overrides the electron concentration requirement. When the B element is not from the first long period and the A component is not a rare earth metal. equiatomic (AB) alloys of transition metals with an average electron concentration of e/a = 6.5 in most cases have a crystal structure closely related to the CsC1-type, but slightly distorted tetragonally, Table I. This was first found6 for VRu, NbRu. and TaRu. It was noted6 that the undistorted CsCl structure is also stable in the three systems. but at a lower electron concentration, near e/a = 6. In these systems this requires a deviation from equiatomic stoichiometry. which is otherwise ideally suited for the CsC1-type structure. A similar situation was later found in the Ti-Rh7 and the Ti-Ir systems. 8 The Ti-Rh alloys undergo a second distortion and become orthorhombic when the rhodium content becomes somewhat larger than 50 pct. As mentioned previously. TiRe does not have the CsC1-type ordered structure. In order to investigate how close TiRe is to the borderline of stability of the

Jan 1, 1970

By I. Fatt

Relative permeability and relative electrical resistivity curves are obtained for networks of tubes with a tube radius distribution by means of a network of resistors used as an analog model. These curves are similar to those obtained from real porous media. The effects of pore size distribution and network structure on relative permeability and resistivity are demonstrated. INTRODUCTION Study of the dynamic properties of networks of single size tubes in paper IT' of this series has shown that the network model has flow properties similar to those observed on real porous media. The comparison of properties of single size tube networks with those of real porous media cannot be carried far because very few porous media have uniform size pores. The capillary pressure curve from most porous materials such as soil, sandstone, and sintered glass indicate that these materials have pore size distribution similar to those shown in Figs. 5-1, 9-1, and 10-I.† To properly test the network model, it is therefore necessary to compare the dynamic properties of real porous media with those of networks of tubes in which the tube radii are distributed accord- ing to the distributions in the aforementioned figures. A network in which the tube sizes are distributed cannot be treated in the same manner as a network of single size tubes. In the single size tube network, the relation between tube geometry, flow resistance, and tube volume did not have to be known if the assumption was made that whatever relation did exist was the same for all tubes in a particular network. In a network of distributed tube size, the relation between tube geometry and flow resistance must be known or assumed in order to replace the tubes by equivalent electrical resistors. Relation of Tube Geometry to Flow Resistance The interchangeability of tubes and electrical resistors in the network model is possible because of the analogy between Poiseuille's law and Ohm's law. Poiseuille's law for a cylinder is q= pr4/8µl ?P.........(1) where q is the volumetric rate of flow, µ is the viscosity, ?P is the pressure gradient, r is the tube radius, and 1 is the tube length. Ohm's law is I=1/R?E..........(2) where I is the flux and is equivalent to the volumetric rate in Poiseuille's law, R is the resistance, and ?E is the voltage gradient. Both laws give the flux as a function of the potential drop and the resistance of the medium. By analogy then, 1/R=pr4/8µl ?P...........(3)

Jan 1, 1957

By C. F. Baes, H. H. Kellogg

The effect of dissolved sulphur on the surface tension of liquid copper has been measured by a sessile-drop method at 1120°C. Sulphur is highly "surface active" in liquid copper; the surface tension lowering is about 650 dynes per cm for a sulphur content of 0.6 pct. The degree of adsorption of sulphur on the liquid copper surface has been calculated, and various models of the surface layer have been tested against the results. THE science and technology of surface chemistry and physics at room temperature are relatively advanced, and the engineer possesses a background of information that allows him to predict and control many phenomena—such as frothing, emulsifica-tion, wetting of solids by liquids, flow through capillaries, adsorption, mineral flotation, penetration of porous bodies by liquids—which are related to the behavior at interfaces. Surface phenomena in high temperature systems are probably of equal importance to the metallurgist and ceramist, but at present are incompletely understood. Frothing of liquid slags, penetration of refractories by liquid metals and slags, infiltration of powder metallurgy "skeletons" by liquid metals, bonding of metals to ceramic oxides in the manufacture of "cermets," wetting of one metal by another for purposes of soldering and welding, are but a few of the many phenomena of metallurgy that are controlled by surface behavior. Concerning the most elementary of surface properties—the gas-liquid surface tension—the existing data on liquid metals are inadequate. For the surface tension of "pure" metals the results of different investigators differ by 10 or 20 pct. The role of surface-active agents in liquid metals is relatively unknown, and it is not unlikely that the discrepancy in the values for the surface tension of pure metals is due to the presence of traces of surface-tension-lowering impurities in the samples. Based on analogy to room-temperature systems, the highly surface-active impurities in liquid metals should be elements or compounds of limited solubility in the liquid metal and possessing considerably weaker in-termolecular bonding forces than the metal itself. The nonmetals of the V, VI, and VII groups of the periodic table might be expected to act in this way. The experimental work in this paper represents a study of the surface tension of pure liquid copper in hydrogen at 1120°C, and the effect of dissolved sulphur (which is a strongly surface-active agent in liquid copper) on the surface tension of copper. The Gibbs equation has been applied to the results and an attempt made to correlate the surface tension behavior with two models of the interfacial layer. The sessile-drop method for surface-tension measurement at high temperatures which was used in this investigation has been described by several investigators.1,2 It involves the measurements of the dimensions of a stationary liquid drop on a horizontal surface. From these dimensions and the liquid density, the surface tension of the liquid may be calculated either by means of various approximate formulas, or more accurately by means of the Bash-forth and Adams tables.- or liquid drops which exhibit a contact angle greater than 90°, by far the simplest dimensions to measure are those indicated in Fig. 1, i.e., the diameter of the maximum horizontal cross section (2X) and the maximum height (Z) above this plane. In order to calculate the contact angle and the volume of the drop, the diameter at the base of the drop (2a) and the total height (h) also must be measured. Upon investigation of the literature, the authors failed to discover a concise statement of the accuracy of the method when used in conjunction with the Bashforth and Adams tables, hence a careful examination of the tables was made and the curve shown in Fig. 2 was constructed. The "error factor," plotted as the ordinate, is the factor by which the

Jan 1, 1954

There were present twelve- Directors, the Secretary and the Assistant Secretary of the Institute, and fifteen guests. A committee of three was appointed to draft a suitable resolution of memorial of the services of Joseph Esrey Johnson, Jr. The committee consists of Joseph W. Richards, Chairman, J. V. N. Dorr and Allen H. Rogers. William R. Walker was elected a Director in place of J. E. Johnson, Jr., and Edwin Ludlow was elected a member of the Executive Committee in his stead. George C. Stone was appointed Chairman of the Committee on Membership in place of Mr. Johnson. The following resolutions were then adopted: RESOLVED, That a special business meeting of the Institute be and the same hereby is appointed to be, held at the office of the Institute, No. 29 West 39th Street, Borough of Manhattan, City of New York, on the 27th day of June, 1919, it 8.30 o'clock in the P. M. to consider and take action upon the proposal to change the name of the Institute to "American Institute of Mining and Metallurgical Engineers, Incor-porated," and the further proposal to extend the corporate purposes of the Institute so that it shall, in addition to its other powers, be empowered to promote the arts and sciences connected with the economic production of the useful minerals and metals, and the welfare of, those employed in these industries, by all lawful means.

Jan 6, 1919

By Frederic P. Dewey

The Bureau of the Mint of the United States Treasury maintains 13 ofEces for the purchase of gold-bullion, and this paper describes an investigation to establish the reasonable differences in the assay-results at the various institutions which may be commercially allowable in the settlements between them. Beginning with the comparative assay of proof-gold at the Philadelphia mint and the Utrecht mint, which shows 0.00002 as the closest agreement now possible, nine tables of comparative results, taken from the regular work of the service, are given..These tables begin with very fine gold, produced in an electrolytic refinery, showing close agreement in the assay-results, and follow through decreasing gold fineness and increasing amounts and complexity of base metals to very impure and complex bars produced at cyanide-mills, some of which give widely-varying results. Next is given a series of results on samples, prepared and sent out to various laboratories in the service, to test the influence of different metals and various combinations upon the agreement of the assay-results ; 11 samples were sent out and each one was assayed from 44 to 71 times, making a total of 623 assays. To these ire added 107 assays of identical samples of coin-gold. On a previous occasion,' I have endeavored to show the degree of accuracy that may be expected in the ordinary everyday analysis of various materials, and on another occasion,2

Jan 1, 1910