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By R. M. N. Pelloux

This study of aluminum-copper alloys had two aims: 1) To determine the effect of the amount and distribution of a second phase, CuAl2, on the creep-rupture strength, ductility, and fracture characteristics of the alloys. The work of Gemmell and grant' on single-phase aluminum-copper alloys provided a basis for the present study. 2) To attempt to provide a relation between the microstructure and strength of two-phase alloys deformed at comparatively high temperatures (greater than 0.45 T,). The creep behavior of the two-phase magnesium alloys Mg;Ce and Mg-A1, has been treated by Roberts. 9 In work reported by Sully and Hardy4 and by Underwood, Marsh, and Manning~ on A1-Cu two-phase alloys, and also in a portion of the work of Gemmell and grant,' aging took place during the creep tests. 'In the present work, overaged aluminum-copper alloys were subjected to creep deformation at two temperatures, 500 and 700OF. The overaging treatments to produce the precipitate dispersions were performed prior to the test, at temperatures which were the same as the ultimate respective test temperatures. Hence, the present study is concerned with the creep behavior of stable (in contrast to "underaged") two-phase A1-Cu alloys, i.e., alloys in which no depletion of the solid-solution matrix occurred during: creep. MATERIALS AND PROCEDURE A 2 and a 3 pct Cu alloy, supplied by Alcoa, were studied; Table I shows the compositions. The grain size of the specimens, 0.9 to 1.0 mm, was achieved by annealing the machined test bars for 2 hr at 1000°F, followed by furnace-cooling to 900°F, and homogenizing for 4 hr. Both compositions are in the single-phase condition at 900°F. Two types of overaged dispersions, termed "over-aged I" and "overaged 11" were prepared after the grain size and the homogenization anneals. The overaged I alloys were prepared by quenching to room temperature after homogenization, aging at either 500' or 700°F for 72 hr, and air-cooling to room temperature. The overaged I1 alloys were prepared by furnace-cooling after homogenization, to either 500' or 700°F, and holding at the necessary temperature for 72 hr. The times for furnace-cooling from 900°F to 700° and 500°F were, respectively, about 2 and 3.5 hr. The structures of the A1-2 pct Cu alloys are shown in Fig. 1 (overaged I) and in Fig. 2 (overaged 11). A comparison of Figs. 1 and 2 shows that in the overaged I alloys the precipitate particles along the grain boundaries are much more closely spaced and the grain boundaries are straighter than they are in the overaged I1 alloys. Further, the particle size and spacing in the grains are smaller than in the overaged I1 alloys. Microstructures of the A1-3 pct Cu alloys have not been shown; the structures of these alloys differed from those of the A1-2 pct Cu alloys only in that the distribution density of the particles was greater. The creep specimens had a gage section 1 in. long with a diameter of 0.155 to 0.195 in. Before testing, specimens were electropolished in a solution of 100 cc glacial acetic acid, and 30 cc of 60 pct perchloric acid, at 40' to 50°F, at 24 v. The specimens were kept refrigerated prior to testing to avoid precipitation at room temperature. Constant stress creep tests were conducted; the load was applied 75 min after heating of the specimens to test temperature had begun. EXPERIMENTAL RESULTS Creep-Rupture—Fig. 3 shows the log stress-log rupture life plotfor the overaged alloys studied, and also for the underaged A1-2 pct Cu alloy.' At 700°F, the stress-rupture life relationship is nearly independent of both the amount of precipitate (i.e., composition) and of the type of overaging treatment (i.e., precipitate dispersion). At 500°F it is apparent that the increase in rupture life that was ex-

Jan 1, 1960

By G. R. Leverant, C. P. Sullivan

To evaluate the effect of a dispersion of nondeform-able, incoherent, second-phase particles on high-strain cyclic deformation and fracture, recrystallized TD-nickel (Ni-2ThO2) and a commercially pure nickel, Ni-200, were fatigued under strain control at total strain ranges varying from 0.009 to 0.036. Relative to the Ni-200, the slip at the surface of the TD-nickel was more wavy and discontinuous due to the presence of the thoria particles. This made crevice formation (incipient cracking) within slip bands more difficult in TD-nickel than in Ni-200. Both materials cyclically hardened to a constant (saturation) flow stress which increased with increasing plastic strain amplitude. Cellular substructures were developed in both materials during cycling. The cell size in TD-nickel was controlled by the thoria particle distribution and was independent of plastic strain amplitude over the range investigated. The cell size in Ni-ZOO was larger than that in TD-nickel at similar plastic strain amplitudes and was a function of plastic strain amplitude. These results, together with the cyclic stress-strain curves for both materials, are discussed in terms of a model for fatigue strain accommodation at saturation recently proposed by Feltner and Laird. NUMEROUS fatigue investigations have considered the interrelation of slip character, dislocation substructure, and cracking in pure metals and solid-solution alloys. However, except for the studies of the low-strain fatigue of internally oxidized copper alloys1 and cast, dispersion-strengthened lead,&apos; little is known about the effects which small, incoherent, nondeform-able, second-phase particles have on cyclic deformation and cracking processes. Effects due to the particles alone are often obscured by a dislocation substructure introduced during thermomechanical processing of dispersion-strengthened metals. In the present study, recrystallized TD-nickel and a commercially pure nickel, Ni-200, were employed to evaluate the effect of a thoria dispersion on high-strai fatigue deformation and cracking at room temperature. I) MATERIAL AND EXPERIMENTAL PROCEDURE The TD-nickel was supplied by DuPont as a 5/8-in.-thick stress-relieved plate which had been subjected to a proprietary schedule of thermomechanical treatments, and the Ni-200 as 3/4-in. bar which was subsequently annealed for 2 hr at 850°C in argon resulting in an average grain diameter of 0.05 mm. The compositions of these materials are given in Table I. The microstructure of the TD-nickel consisted of elongated grains parallel to the primary working direction with an average width of 0.16 mm, Fig. l(a). Many fine annealing twins were present indicating that the starting material was in a recrystallized condition; this supposition was confirmed by the absence of of any extensive dislocation substructure, Fig. l(b). Sheetlike stringers parallel to the rolling direction were occasionally seen both within grains and at grain boundaries. Some approximately spherical particles about 2 in diam, which may correspond to exceptionally large thoria particle aggregates, were also present. The average Young&apos;s modulus of the plate material in the rolling direction was 21.8 X 106 psi which is consistent with a {100}<001>recrystalliza-tion texture3&apos;* being prominent. In transmission microscopy, the 2.3 vol pct of thoria particles generally appeared to be uniformly distributed although some clusters, 0.1 to 0.3 in diam, of larger particles were observed as previously reported for TD-nickel sheet,5 and stringering of particles was present in some areas as welt. The average diameter of the thoria particles was 450A with a calculated mean planar center-to-center spacing of 2100A, as determined by quantitative metallographic analysis.= The 0.2 pct offset yield stress was 36,000 psi which agrees with the value predicted by the modified Orowan relation7 for edge dislocations bowing between thoria particles of the size and spacing observed in the present investigation. Fig. 2 illustrates the specimen design employed for the axial high-strain fatigue testing. Adapters were screwed onto the threaded portions of each specimen so that testing could be performed in the same manner as that reported for buttonhead specimens.8 Stressing was coincident with the working direction for both materials. The gage section of each specimen was electropolished and lightly etched prior to testing. The total strain was controlled, being varied between zero and a maximum tensile strain ranging from 0.009 to 0.036. In addition to these tests, a circum-ferentially notched TD-nickel specimen was cycled over a total strain range of 0.0075. The same strain

Jan 1, 1969

By H. G. Doll

As a continuation of the earlier paper on the general subject of the SP log, a more complete analysis of certain features of the SP log in shaly sands is given. The pseudo-static SP in front of shaly sands is compared, on a theoretical basis, to the static SP in front of clean sands, as a function of the respective amount of shale and sand in the formation, and of the relative resistivities of the shale, of the uncontaminated part of the sand. and of the invaded zone of the sand. As a conclusion, the advantage of using reasonably conduc. tive mud in this case is shown. The discussion is illustrated by field examples. INTRODUCTION The discussion reported in the present paper is based on a theoretical analysis, and not on experiment. The field examples, joined to the text. are shown only as qualitative illustrations of the essential results of this analysis. Although the hypotheses made in the theoretical developments may perhaps be somewhat improved, it seems, nevertheless, that the results obtained account reasonably well for the actual phenomena, and give a fair approximation of their order of magnitude. The paper contains a mathematical analysis of a tri-dimen-sional distribution of potentials and current lines. due to spontaneous electromotive forces arising at the contact of shales and free electrolytes. as a function of the geometry and of the respective resistivities of the different media involved. It is assumed, although this hypothesis is not proven, that the emf&apos;s remain the same even if the shale occurs in very thin layers or in dispersed particles. It has already been pointed out 1,2,3 that, all other conditions being the same, the deflection of the SP log in front of a shaly sand is smaller than opposite a clean sand. When the thickness and the conductivity of a clean sand are large enough. the deflection of the SP log reaches a limiting value which is equal to the "static SP" of the clean sand. It is generally convenient to take the static SP of shale as the reference value or "base line." As a consequence, and for the sake of abbreviation, the expression. "static SP of a clean sand," is often used to designate the difference between the static SP of that sand and that of the shales, which difference is a measure of the total electromotive forces involved in the chain mud sand-shale. A similar limiting value is; also observed for the SP deflec-lion opposite a thick shaly sand, but it is smaller. just as if the total electromotive force involved were smaller in that case. This limiting value has been called the "Pseudo-Static SP" of the shaly sand. The static SP of a clean sand depends on the salinity of its connate water with respect to that of the mud, and, to a certain extent. on the differential pressure which controls the electro-filtration potentials, but it does not depend on the resistivity of the sand. On the contrary. the pseudo-static SP of a shaly sand depends not only on the salinity of its connate water and on the differential pressure, but also on the percentage of shale and on the resistivities of the shale, of the uncontaminated part of the sand, and of the zone invaded by the mud filtrate. If the three resistivities above were equal, the pseudo-static SP would be proportional to the percentage of sand in the shaly sand, and its departure from the static SP of a clean sand having the same connate water would simply be proportional to the percentage of shale. In that case, the pseudo-static SP of a shaly sand containing 10 per cent of shale would he 10 per cent less than the static SP of a clean sand. When. however. the sand is. on the average. substantially more resistive than the shale. the percentage of departure of the pseudo-static SP from the static SP of a clean sand is much larger than the percentage of shale. For that reason, the peaks of the SP log opposite shaly sands are systematically of smaller amplitude when the sands are oil-bearing than when they are water-bearing, all other conditions being the same. This feature is observed even when the sand beds are thick. and even when they do not contain a large percentage of shale. All this has already been described in all earlier publication", but mostly in a qualitative way. The present paper will analyze in more detail the action of the local SP currents which are generated inside of the shaly sands, and which are responsible for the abnormally low value of the pseudo-static SP. The quantitative computations have been extended to the general case of thin interbedded layers of sand and shale, where the resistivities of the shale and sand streaks do not have the same value: they are summarized in charts giving values of the pseudo-static SP of a shaly sand as a function of the different parameters involved. DEFINITIONS The static SP of a clean sand has been defined as the potential that would exist in the mud opposite that sand, were the SP current prevented from flowing. Such an ideal condition is represented on Fig. I-A. By analogy, the pseudo-static SP of a shaly sand can be defined as the potential that would exist in the hole, if the circuit shaly sand — surrounding shales — mud column were interrupted by the insulating plugs placed at the boundaries

Jan 1, 1950

By C. G. Dunn

IT is well known that plastic deformation alters many of the properties of a metal and subsequent heat-treatment partially or completely restores these properties.1 In the deformed or strained state, the metal is unstable and tends to change toward a condition called a "strain-free state." The transformation occurs through recovery, recrystallization, and grain growth-processes that may take place singly or in combination. The distortion of the lattice of an individual grain of a metal in a state of strain may be rather complex in nature, because plastic deformation produces: (I) dislocations within mosaic blocks; (2) elastic variations of the lattice spacings; and (3) gross alterations throughout the lattice, especially along slip planes, along composition planes between a grain and its mechanical twins, and along boundaries of deformation bands. These gross alterations are of the nature of bent planes or rotated regions of the crystal lattice and are revealed by a spread in the orientation of the grain. Although we cannot describe these strains and their formation accurately because of insufficient knowledge, we can, nevertheless, use the information as well as possible to obtain a better understanding of recovery processes. In recovery, the lattice of a grain is not made anew as it is in recrystallization, but is improved or mended in such a way that the basic structure remains unaltered. Until recently observations were that recovery produced no marked changes in the shapes of spots in Laue diffraction patterns, whereas recrystallization did, but now it is known for silicon ferrite2 that Laue spots may become quite sharp entirely through recovery. Consequently, the shape of Laue spots alone would not be a suitable test to distinguish between recovery and recrystallization. There is considerable evidence that the micro- structure usually does not change visibly during recovery. Absence of a visible change in the microstructure, therefore, provides a sufficient test of recovery in many cases. However, including this observation in a definition of recovery as a necessary condition (this is usually done) is unfortunate, because recovery may, as will become evident later, produce new grain boundaries that are visible not only in the microstructure but also in the macrostructure. For the present, therefore, let us say that a necessary condition for a process to be one of recovery is that the principal orientation or orientations of a deformed grain be essentially unchanged throughout the transformation toward the strain-free state. Several transformations may occur that fulfill this condition, and the nature of the distortion in a grain indicates what these must be if the lattice is to be mended in part or fully. Consequently, it will be convenient as well as

Jan 1, 1946

By Robert Maes, Robert de Strycker

The Fe-Ni-As phase diagram has been established by the study of about a hundred alloys, by microscopic observation, and by thermal analysis, with arsenic contents up to 50 pct. The iron and nickel arsenides present extensive solid-solution fields, owing to the substitution of nickel by iron and vice versa; the extent of the solubility field of each compound has been determined with an accuracy of ±1 pct. In the investigated range of compositions, the solidification reactions were established, and the temperatures of the invariant reaclions detevmined with a preciston of iZ°C in the most favorable and ±5°C in the least favorable cases. The isothermal lines of the liquidus surface have also been drazum, with an accuracy estimated at i5°C. Reactions in the solid state, which take place for the formation or the decomposition of certain phases , were investigated in detail. ThE constitution diagram of the Fe-Ni-As system is fundamental for the understanding of the properties of nickel speiss; these by-products of the extraction of certain nonferrous metals indeed often contain the three elements iron, nickel, and arsenic as main constituents. The Fe-Ni-As system has already been the object of earlier investigations. In 1932, Guertler and Savels-berg&apos; have presented some elements of the ternary phase diagram, for arsenic contents up to 55 pct (all percentages in this paper are given in weight percent), including the vertical section FezAs-Ni&s2. This investigation is, however, incomplete and certain anomalies suggested the necessity to verify the results published by these authors: the section Fe2As-Ni5AsZ, for example, is presented as quasi-binary, with a field of complete miscibility in the solid state, even though these compounds do not have the same structure. Recently, ~useck&apos; established an isothermal section at 800°C in the Fe-Ni-As system by X-ray diffraction and microscopic examination of water-quenched alloys. These techniques are sometimes inaccurate for the determination of the fields where alloys are liquid at the investigated temperature, and they may lead to erroneous conclusions when a compound exists at the investigated temperature but is not stable at room temperature and cannot be maintained by quenching. LIMITING BINARY PHASE DIAGRAMS The Fe-As constitution diagram has been the object of several investigations which have been reviewed by Hansen and Anderko.3 For the Ni-As phase diagram, a recent study has been effected by Yund.4 In this system, Heyding and calvert5 have determined the existence of a compound of unidentified structure at arsenic contents slightly higher than those corresponding to Ni5As2 and at temperatures lower than about 200°C; by analogy with iron and cobalt arsenides, this compound could correspond to the formula Ni2As, as suggested by Kulle-rud; although this is not definitely established. In the region of arsenic contents from 35 to 55 pct, Fried-rich7 detected anomalies in the solidification reactions; an interpretation of these anomalies was given by Hansen ,8 which assumed that the solidification reactions in practice are not in equilibrium, but are meta-stable. The main features of the Fe-Ni constitution diagram are the existence of a complete miscibility field, at least at high temperatures, for the fcc phase (which will be designated by My in the remainder of this work) and of a limited solubility field for the bcc phase (designated by Ma). EXPERIMENTAL METHODS The fundamental technique used in this investigation was microscopic observation, which allowed the determination of the reactions occurring during solidification of the alloys, and possible reactions in the solid state.

Jan 1, 1968

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack&apos; find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

By J. Walter Snavely

PRESENT-DAY processing in many industries, calcining, sintering, briquetting, beneficiation and nodulizing, increasingly calls for the handling of large volumes of hot bulk materials. Various types of conveyors have been employed. This discussion will cover the factors governing their selection. For temperature ranges up to 400°F, or approximately 200 °C, a wide range of conveyors is available. Special constructions of rubber conveyor belts, steel conveyor belts, vibrating and shaker conveyors, apron conveyors, and drag chain conveyors, all are used successfully. As temperatures go well above 400 2F, however, choice of conveyors is narrowly limited. This paper will consider the problem of handling bulk materials only where the temperatures exceed 400°F. The arbitrary selection of 400 °F as a dividing point undoubtedly can be challenged, as special conveyor belting constructions are available which are suitable for temperatures in excess of 400°F. However, when the relatively short life of such belts and the cost of their replacement, with the attendant down time, are balanced against the reliability and long service life of the properly designed steel constructed units to be discussed, there is little question in any operator&apos;s mind that the special belts are more expensive to use. Because the conveyors under study are for the handling of bulk materials, inevitably including a high proportion of fines, obviously wire mesh belts cannot be included for consideration. Even though this type of conveyor is widely used at high temperatures, i.e., for carrying glassware through a lehr, it is unsuited for the conveying of bulk materials, and therefore will be excluded from further discussion in this paper. Preliminary to the study of the conveyor itself is the determination as to whether the material is to be cooled while it is being handled, or whether the processing requires retention of all heat and the maintenance of a given temperature range. In the majority of cases cooling is incidental to or part of the handling process, when the handling, for example, follows completion of sintering, roasting, calcining, refining, or some other process. To meet such operating conditions successfully, the conveying medium used must have: 1—a construction capable of withstanding maximum initial temperatures of the material being handled. 2—a construction providing efficient heat transfer for cooling. 3—a construction providing dependable operation and long life with minimum service requirements, and 4—a construction providing controlled and efficient conveying. Under the usual conditions of cooling during the handling, the construction selected to withstand the initial maximum temperatures does not necessarily involve using alloys, as excellent results can be achieved with normal carbon steels and cast irons, when they are properly applied and proportioned. The earliest and simplest type of conveyor for handling very hot materials is the cast steel drag chain conveyor, still widely used for handling hot cement clinker, as illustrated by Figs. I and 2. Because of the rugged and generous proportions of the chain link design, low carbon steels are entirely suitable for the links. The pins, however, must be alloy steel. The simple, rugged construction of this type of conveyor makes it readily capable of withstanding high initial temperatures, even though the chain is operating buried in the material. The drag-chain type of conveyor has advantages and limitations. Although the efficiency of the heat transfer is relatively poor, the life of the conveyor is reasonably long, and because of its crude simplicity it does not require much servicing. However, as a conveyor, it is limited in capacity, and largely limited to horizontal runs. Furthermore, because of the crude design, heavy weight, and the chain operating at the temperature of the material, greatly reducing permissible operating chain pulls, this type of conveyor is limited to relatively short centers. Another type of conveyor that has been used for very hot materials is the cast pan conveyor. Because of its very generous proportions the cast pan, which is made of either cast iron or malleable iron, can withstand initial maximum temperatures. It also provides efficient heat transfer for cooling. Further, it is on efficient conveyor construction, which can be used for inclines. Because the chain employs rolling friction instead of sliding friction, and is not in the maximum temperature zone, much longer centers are possible. It is this type of conveyor that is frequently used in the casting of various metal pigs, pig iron, and aluminum; it is obvious, therefore, that very high initial temperatures are being handled. With this kind of conveyor the return run is frequently sprayed with water to accelerate heat transfer. The build-up of residual heat in the very heavy cast pans is thus overcome. The outboard roller steel pan conveyor is an improved pan conveyor&apos; which provides high rates of heat transfer and substitutes formed steel pans for the heavy cast pans. It is a very efficient conveying medium. The details of this particular construction are clearly shown in Fig. 3. An early application of this type of conveyor is shown in Fig. 4. In this case the conveyor units are handling roasted phosphate rock at average temperatures of 1000" to 1500°F, and frequent maximum temperatures as high as 1900°F. Several widths are used. The capacity of the unit at a speed of 50 fpm is approximately 30 tph per inch of width at peak loadings, average capacity being about 1/3 of peak loading. The assembled conveyor is shown in Fig. 5, with views of both the top and the underside to show all the construction details. In particular, the following general design principles were carried out in this construction:

Jan 1, 1954

By E. T. Turkdogan

The activity of sulfur was determined as a function of composition of ferrous sulfide by equilibrating with hydrogen sulfide-hydrogen gas mixtures at 670° , 800°, and 900". The present results supplement the available data over the composition range from 36.6 to 39.5 pct S. The X-ray lattice spacing measurements made are in accord with the available data and indicate that the limiting composition FeSl.008 may be taken for the iron-iron sulfide equilibrium. The growth rate of ferrous sulfide on iron was measured by reacting iron strips or blocks in hydrogen sulfide-hydrogen gas mixtures. Owing to the slow approach to equilibrium between the gas phase and the surface of the sulfide layer, The sulfidation experiments were carried out for several days. It is shown that the growth rate ullimately proceeds in accordance wilh the parabolic rate law. From the parabolic rate constants and the thermodynamic data on iron sulfide the self-difiusivity and chemical diffusivity of iron in ferrous bisulfide are evalualed. The self-diffusivity of iron thus derived zs found to increase with increasing sulfur content. THE ferrous sulfide known as "pyrrhotite" is a non-stoichiometric phase having a wide composition range from about 50 to about 58 or 60 at. pct, depending on the sulfur activity. RosenQvistl studied the thermodynamics of this phase over wide ranges of temperature and composition. Hauffe and Rahmel&apos; and Meussner and ~irchenall~ studied the parabolic rate of sulfidation of iron in sulfur vapor. By using markers, these investigators showed that the iron cations were the predominant diffusing species in iron sulfide. This is confirmed decisively by the self-diffusivity measurements of condit4 who showed that the self-diffusivity of sulfur in ferrous sulfide is several orders of magnitude lower than the self-diffusivity of iron. Although much has been learned from these studies about the Fe-S system, further research on this subject was considered desirable for better understanding of the physical chemistry of iron sulfide. This work was confined to the study of the kinetics of sulfidation of iron in hydrogen sulfide-hydrogen gas mixtures. The results of this study are given in two consecutive parts. Part I, the present paper, is on the parabolic rate of sulfidation of iron and the diffusivity of iron in ferrous sulfide. The second paper, Part 11, is on the kinetics of the surface reaction between hydrogen sulfide and ferrous sulfide. EXPERIMENTAL Three types of experiments were carried out: i) equilibration of ferrous sulfide with gas of known E. T. TURKDOGAN, member AIME, is Manager,Chemical Metallurgy Division, Edgar C. Bain Laboratory for Fundamental Research, U. S. Steel Corp., Research Center, Monroeville, Pa. Manuscript submitted March 6. 1968. ISD sulfur potential; ii) X-ray studies of ferrous sulfide; and iii) measurements of the parabolic rate of sulfidation of iron. Equilibrium Studies. About 1 g of iron powder or foil. contained in a small recrystallized alumina crucible ind suspended from a calibrated silica spring, was reacted with a hydrogen sulfide-hydrogen mixture of known ratio until no further change in weight was observed. %hen the gas composition was changed and the new state of equilibrium was established after several hours of reaction time. The composition of the sulfide was obtained from the initial weight of the sample and the weight after equilibration. X-Ray Studies. The lattice parameters of some of the equilibrated samples were determined using the General Electric XRD-5 diffractometer with a cobalt tube (no filter) set at 40 kv apd 10 ma; the CoK, radiation was taken as 1.79020A. Observed 220 and 311 diffraction peaks of silicon served as an internal comparison standard to correct for possible misalignment of the goniometer. The lattice parameters of the sulfide phase were calculated from the corrected Bragg angles of the 110 and 102 peaks. Rate Studies. In the initial experiments attempts were made to measure the parabolic rate of sulfidation by measuring the gain in weight of a thin iron strip, -0.05 cm thick, suspended from a silica spring in the reacting atmosphere. The preliminary experiments showed that this technique was not reliable for the measurement of the parabolic growth rate of the iron sulfide layer. In the subsequent experiments the data on growth rate were obtained by measuring, on a microscope stage, change in the thickness of the sample after reaction for a specified time in a hydrogen sulfide-hydrogen mixture of known sulfur activity. For each reaction time a new sample was used. Precision-machined iron blocks, 0.5 by 2 by 5 cu cm, were de-greased and annealed in hydrogen for several hours prior to the sulfidation rate measurements. The experiments were carried out at 670°, 800°, and 900°C in gas mixtures having the ratios, and 1.0 for periods of times from a few hours up to 8 days. Apparatus and Materials. A vertical globar tube furnace with a 3-in.-long uniform temperature zone was used. The glass tube fittings were fused on the zircon reaction tube, 1.5 in. diam. The temperature was measured with a Pt-10 pct Rh/Pt thermocouple placed in the hot zone of the furnace inside the reaction tube (an alumina thermocouple sheath was used). A separate thermocouple was used for the temperature controller which maintained the furnace temperature constant within about 2°C. Anhydrous liquid hydrogen sulfide and oxygen-free dry hydrogen from gas tanks were used in preparing the gas mixtures by the constant head capillary flow-meters. In all cases volume flow rate was 1000 cu cm per min at stp, corresponding to a linear velocity of about 6 cm per sec at 800°C; under these conditions

Jan 1, 1969

By R. L. McCarron, G. R. Belton

The diffusivities of oxygen and sulfur in liquid iron have heen determined hy a capillary technique in which the surface concentrations of the solutes were established by means of appropriate H2/H2 and H2S/H, gas mixtures. Total diffusate and concentration profile results are shown to be in good accord, yielding for- 1560 and Supporting results at 1660°C are also presented. The conditions necessary to avoid gas transport control in this type of experiment are discussed. IN spite of their importance in understanding the kinetics and mechanisms of refining reactions, the dif-fusivities of oxygen and sulfur in liquid iron are not well established. Accordingly, as a first step in studies of rates of solute absorption from the gas phase into liquid iron, new measurements of these diffusivities have been made and are presented in this paper. The only published results for the diffusion of sulfur in pure liquid iron are those of Kawai.&apos; He used a diffusion couple technique in which two cylindrical specimens, one containing sulfur and the other with negligible sulfur concentration, were joined together and held in a refractory capillary. After an experiment, the sample was quenched and the concentration distribution of the solute determined. Kawai recognized that significant changes in solute distribution occurred during melting and freezing and he attempted to correct the concentration profiles for these effects to give a sulfur diffusivity of 4.6 x 10-6 sq cm per sec at 1560°C. The method of correction, however, was not rigorous and the uncertainty in this result cannot be easily assessed. Koslov et a1.2 have reported the diffusivity of oxygen in iron as 7.8 x 10"3 sq cm per sec at 1660°C. This value appears to be unreasonably high but, unfortunately, details of their experiments are not available. Shurygin and Kryuk have used the rotating disc method for a study of oxygen diffusion in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was determined by measuring the decrease in weight of the disc. On the assumption that the rate of dissolution was controlled by the diffusion of oxygen in the iron, the diffusion coefficient was computed to be 5.2 x sq cm per sec at 1550°C. However, the Levich equation, which was used to interpret the rate data, was originally de- rived for the case of mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s equations. Recently, Novokhatskiy and Ershov, using an identical experimental method to that of Shurygin and Kryuk, obtained a diffusivity for oxygen in liquid iron of 1.22 x 104 sq cm per sec at 1550°C: no reasons were offered for the disagreement. Schwerdtfeger5 has also recently studied the diffusivity of oxygen in liquid iron. He reacted shallow melts of liquid iron, 0.5 to 1.0 cm deep and contained in high-purity alumina crucibles, with appropriate H20-HZ-He mixtures. The total sample was analyzed, without sectioning, to obtain the average concentration of diffusate. A value at 1610°C of D = 12(3) x 10-5 sq cm per sec was obtained from the results of twenty experiments.= Oxygen profile measurements, which were carried out in three additional experiments using long capillaries and the semiinfinite boundary conditions, indicated a diffusivity about half that computed from the shallow bath experiments. Possible sources of error in Schwerdtfeger&apos;s study will be discussed later in this paper. EXPERIMENTAL TECHNIQUE The essential arrangement of the diffusion cell is shown in Fig. 1. The liquid iron was contained in an alumina capillary, 3 to 4 mm diam and 3 to 9 cm long, which was supported by a hollow alumina pedestal and this whole assembly was held within a movable alumina reaction tube. This tube, which was about 7 mm in bore

Jan 1, 1970

By D. G. Westlake

The electrical resistance of a series of V-H alloys (0 to 3.5 at. pct H) has been measured over the temperature range G° to 360°. Interstitial impurities made contributions to the residual resistivity, but not the ideal resistivity. The contribution of hydrogen in solid solution is expressed by Ap = 1.12 microhm-cm per at. pct H; but the contribution of precipitated hydride was negligible. A portion of the so1vu.s for the V-H phase diagram is presented. The solubility limit is given by In N (at. pct H) = (5.828 i 0.009) - (2933 i 44)/RT. Comparison of critical temperatures joy hydride precipitation and published critical temperatures for hydrogen embrittlement suggests the two are related. ThiS study was initiated as part of an investigation of the mechanism by which small concentrations of hydrogen embrittle the hydride-forming metals at low temperatures. It has already been shown that, in the case of hcp zirconium, a reduction in ductility accompanies the strengthening resulting from precipitation of a finely dispersed hydride phase.&apos;&apos;&apos; Our attempts to detect a similar precipitation of a second phase at low temperatures in V-H alloys by transmission electron microscopy have been thwarted because we have been unable to prepare thin foils that are representative of the bulk material with respect to hydrogen concentrati~n.~&apos;~ The present investigation establishes the solvus of the V-H system at subambient temperatures. Subsequently, we hope to be able to determine whether the embrittlement temperature is related to the critical temperature for precipitation of the hydride in a given V-H alloy. veleckis5 has proposed a partial phase diagram for the V-H system based on extrapolations of the pressure-composition relations he measured at higher temperatures. Kofstad and wallace&apos; conducted a similar study of single-phase alloys but did not attempt to establish the phase diagram. Zanowick and wallace&apos; and ~aeland&apos; have studied a portion of the phase diagram by X-ray diffraction, but they investigated no alloys in the hydrogen concentration range 0 to 3 at. pct, the range of interest to us. EXPERIMENTAL PROCEDURE The vanadium was obtained from the Bureau of Mines, Boulder City, Nev., in the form of electrolytic crystals. The analyses supplied with them listed 230 ppm by weight metallic impurities, 20 ppm C, 100 ppm N, and 290 ppm 0. The crystals were electron-beam-melted into an ingot that was rolled to 0.64 mm. Strips, 60 mm long and 4.2 mm wide, were cut from the sheet, and both rolled surfaces were ground on wet 600-grit Sic paper to produce specimens 0.4 mm thick. They were wrapped in molybdenum foil, vacuum-encapsulated in quartz, and annealed 4 hr at 1273°K. The specimens were annealed in a dynamic vacuum of 2X lo-&apos; Torr for 30 min at 1073°K for dehydrogenation, and charged with the desired quantity of hydrogen by allowing reaction with hydrogen gas at 1073°K for 2 hr and cooling at 100°K per hr. Purified hydrogen was obtained by thermal decomposition of UH3. Sixteen specimens were studied: two contained no hydrogen and the others had hydrogen concentrations between 0.5 and 3.5 at. pct (hydrogen analyses were done by vacuum extraction at 1073°K). Electrical resistances were measured by the four-terminal-resistor method on an apparatus similar to the one described by Horak.~ The specimen holder was designed so that both current and potential leads made spring-loaded mechanical contact with the specimen. The potential leads were 30 mm apart, and the current leads were 55 mm apart. The current was 0.10000 amp. We used the following baths for the indicated temperature ranges: liquid nitrogen, 77°K; Freon 12, 120" to 230°K; Freon 11, 230" to 290°K; and ethanol, 290" to 340°K. Temperatures lower than 77°K were achieved by allowing the specimen to warm up after removal from liquid helium. Temperatures above 77°K were measured by a calibrated copper-constantan thermocouple (soldered to the specimen holder) and below 77°K by a calibrated carbon resistor. The temperature of the bath changed less than 0.l0K between duplicate measurements of the resistance. RESULTS AND DISCUSSION Typical plots of resistivity p vs temperature T are shown in Fig. 1. In the interest of clarity, only five curves are presented and the data points have been

Jan 1, 1968

By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.&apos;&apos;2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3&apos;4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970

By J. B. Clark, A. J. McEvily, R. L. Snyder

The nonuniform distribution of precipitate particles has been recognized as a leading factor contributing to the relatively low fatigue resistance of aluminum alloys. The structure of many of these alloys is characterized by narrow precipitate-free zones adjacent to the grain boundaries. Alloys with such zones exhibit a tendency for brittle inter crystalline fracture. The interrelation between this type of structure and mechanical properties was investigated in an Al-10 wt pct Mg alloy. It was found that deformation during fatigue occurs preferentially along these zones and cracks initiate there. In Al-10wt pct Mg, the zones were found to be supersaturated even after extensive general precipitation and are due to the absence of proper precipitate nuclei in the region near the grain boundaries. Cold working the alloy prior to aging improves the mechanical properties by inducing precipitation within the zones and also by jogging of grain boundaries. The mode of fracture is changed from brittle inter crystalline to more ductile trans granular fracture. THE process of fatigue is highly structure sensitive, with the strength of the whole often dependent upon some localized discontinuity, either geometrical or metallurgical in nature. Much has been learned about the role of geometrical discontinuities, e.g., notches, in fatigue, but with the exception of the effects of inclusions or the shapes of carbides, relatively little is known about the specific effects of discontinuities in metallurgical structure such as nonuniform precipitation. In most age-hardening aluminum alloys, metallo-graphic studies have shown that the extent of precipitation adjacent to grain boundaries is much less than that which occurs in the interior of the grains. The width of these almost precipitate-free regions, which are sometimes called denuded zones, and the extent of solute depletion within them, are dependent upon the particular alloy and its aging treatment. It has been observed1 that these zones are relatively soft with the result that plastic deformation takes place preferentially within them. It has also been shown 2-4 that there exists a tendency for intercrys- talline cracking in fatigue when such zones are present. It is of interest to note that Broom et al.2,3 were able to reduce the incidence of this type of failure in an A1-4 wt pct Cu alloy by stretching the material 10 pct prior to aging. In the present study, the effects of precipitate-free regions on the fatigue properties of an A1-10 wt pct Mg alloy were studied in detail, and the effects of deformation prior to aging on the nature of the precipitation process as well as on fatigue properties were also investigated. MATERIAL AND PROCESSING An A1-10 wt pct Mg alloy was selected for this study, because it was known that well-defined precipitate-free regions along the grain boundaries are readily obtained in this alloy after aging at 200oC.5 The starting materials were 99.998 pct A1 and singly sublimed magnesium of about 99.9 pct purity. The aluminum was induction melted in a graphite crucible, and then the magnesium addition was immersed until dissolved. Chlorine gas was then bubbled through the molten alloy for 4 min to degas the melt, after which the melt was cast at a pouring temperature of 730" to 760°C into a cold, graphite-coated, tapered steel mold. Since A1-Mg alloys are difficult to homogenize,5 special care was taken to obtain a uniform composition. Two-in. cubes were cut from the ingot and heated at 446°C for 30 min. These cubes were then hot forged approximately 35 pct in each of the three cube directions and homogenized for 16 hr at 446°C. Sheet specimens were then obtained by pressing 40 pct and rolling 35 pct per pass with reheating between reduction steps to a final thickness of approximately 0.10 in. The sheet was then solution treated for 16 hr at 446°C and water quenched. The age hardening behavior of this material at 200°C was then determined, and the results are shown in Fig. 1. The age hardening of this alloy when subjected to cold work prior to aging is also shown in this figure. Preliminary work indicated that extensive deformation after quenching was required to affect drastically the precipitate-free regions in this alloy, and a rolling reduction of 50 pct was chosen. For purposes of comparison the following three conditions were studied: a) Solution treated, quenched, and aged 20 hr at 200°C

Jan 1, 1963

By G. Bruggeman, K. G. Kreider

Grain boundary dij]usion coefficienls were measured in tungsten between 1400° and 2200° C and can be expressed by the equation sq cm per sec This activation energy confirms some eavlier estimates made .from tungsten sintering experiments. Grain boundary diffusion was found to occur in sub-bozrndavies having -misorientations of less than 10 deg. The actiuation energy for this subboundavy diffusion is equal to that for dijjusion in incoherent grain boundaries with in the limits of error. This is shown to be consistent with the dislocation model of Low-angle boundaries wheve diffusion occlcvs along- the dislocation &apos;YPipes" comprising -tile boundary. RECENT investigations of the sintering of tungsten powders all report activation energies which are considerably less than the activation energy for tungsten volume diffusion. Kothari&apos; reports a value of 100 * 5 kcal per mole, Hayden and Brophy&apos; obtained 90 kcal per mole, and Vasilos and smith3 found 110.7 kcal per mole from their sintering studies. Since most determinations of the activation energy for volume diffu-sion4-&apos; fall between 120 and 160 kcal per mole (the true value seems most likely to be nearer 150 kcal per mole), the conclusion is drawn that the mass transport leading to densification during sintering is accomplished by grain boundary diffusion. This interpretation is consistent with various diffusion models of the sintering process. 10-12 Vasilos and Smith calculate diffusion coefficients from their data which fit the equation D * 1.36 x 10* exp(-llO,700/HD However, no direct measurements of tungsten grain boundary diffusion have been made. Furthermore, considerable disagreement exists between the directly measured values of tungsten volume diffusion.&apos;-&apos; In order to corroborate the inferred results of the sintering experiments concerning grain boundary diffusion and to provide accurate diffusion data essential to the analysis of the kinetics of creep, oxidation, precipitation, and so forth, the present work was undertaken to measure self-diffusion in single-crystal and polycrystalline tungsten between 1400" and 2200°C. It is within this temperature range that tungsten sintering is done, the re crystallization of tungsten occurs, and the widest application of tungsten as a high-temperature material will probably be made. EXPERIMENTAL PROCEDURE Radioactive WlE5 was produced by irradiating tungstic acid in a neutron flux of 1.2 x 1012 neutrons per sq cm per sec for 36 hr. A 2-week waiting period was allowed for the decay of w"~ also produced by the irradiation. (w"~ has a half-life of 24 hr.) The half-life of the remaining isotope was determined to be 75 days confirming the presence of w lE5 and the absence of any undesired radionuclide. Specimens 4 in. in diam and $ in. thick were cut from polycrystalline swaged tungsten rods (recrystal-lized) and from Linde single-crystal rods. Chemical analyses of these materials appear in Table I. Actually upon closer examination, the single-crystal specimens were found to consist of several subgrains separated primarily by tilt boundaries in which the misor-ientation ranged from 3 to 10 deg. Thus, it was possible to measure boundary diffusion coefficients in these low-angle subboundaries as well as in the incoherent boundaries of the polycrystalline specimens. The two faces of each specimen were ground flat and parallel within 0.0001 in. The radioactive tungstic acid was dissolved in concentrated ammonium hydroxide, placed on the ground flat of the specimen, and evaporated to dryness. The oxide was then reduced in hydrogen at 1000°C resulting in a layer of wlE5 approximately 1 p thick. The diffusion anneals were performed in vacuum in a tantalum resistance furnace. Time at temperature ranged from 10 hr at 1400°C to 2 hr at 2200°C. The penetration profile was determined by measuring the residual activity after successive removal of surface layers by grinding on metallographic polishing paper. Extreme care was exercised to insure that sections were always taken normal to the diffusion direction; this was verified repeatedly by checking that front and back surfaces of the specimen remained parallel. The activity was measured with an end-window Geiger-Mueller counter. The sides and edges of the specimen were well-shielded to eliminate possible effects due to surface diffusion. The weight of the

Jan 1, 1968

By R. S. Wagner, W. C. Ellis

A new mechanism of crystal growth involving oapor, liquid, crnd solid phases explains many observations of the effect of implurities in crystal growth from the vapor. The role of the impuuitq is to form a liquid Solution with the crystalline tnalerial to be grown from the vapor. Since the solution is n prefevred site for deposition firorti the uapor, the liquid becorrles supersaturated. Crystal growth occurs by precipitatzon from the supersaturated liquid crt tlie solid-liquid zntevfnce. A crystalline defect, such as a screw dislocation, is not essetztial for VLS (vapor -liquid-solid) growth. The concept of the VLS mechanism is discussed in detail with reference to tire controlled growth of silicon crystals using gold, platinum, palladium, nickel, silver, or copper as an implurity agent. RECENTLY a short communication&apos; described a new concept of crystal growth from the vapor, the VLS mechanism. In this paper we present a detailed description of the process and its application to the growth of silicon crystals and we discuss its relevance to existing concepts of .&apos;whisker" crystal growth. Crystal growth from the vapor is usually explained by a theory proposed by Frank2 and developed in detail by Burton, Cabrera, and Frank.3 In this theory a screw dislocation terminating at the growth surface provides a self-perpetuating step. Accommodation of atoms at the step is energetically favorable, and is possible of much lower supersatu-ration than required for two-dimensional nucleation. Crystals of a unique form resulting from aniso-tropic growth from the vapor are "whisker" or filamentary ones. Such crystals have a lengthwise dimension orders of magnitude larger than those of the cross section. For most filamentary crystals both the fast-growth direction and directions of lateral growth have small Miller indices. The special growth form for a whisker crystal implies that the tip surface of the crystal must be a preferred growth site. sears4 proposed that, according to the Frank theory. a whisker contains a screw dislocation emergent at the growing tip. Such an axial defect provides a preferred growth site and accounts for unidirectional growth. The hypothesis was extended by Price. Vermilyea. and Webb," still implying the presence of a dislocation at the whisker tip. They postulated that impurities arriving at the fast-growing tip face become buried while those arriving on the surface of slow-growing lateral faces accumulate and thereby hinder growth. These considerations led to a whisker morphology. There is increasing evidence that most whisker crystals grown from the vapor are dislocation-free. Webb and his coworkers6 searched for an Eshelby twist7 in zinc? cadmium, iron. copper, silver, and palladium whisker crystals. They found unequivocal evidence for an axial screw dislocation in only one element, palladium. However, not every palladium crystal examined contained a dislocation. Observations with the electron microscope have failed to show dislocations in whisker crystals of zinc, silicon.9 and one morphology of AlN.10 Since many whiskers are completely free of dislocations, an axial dislocation does not appear to be required for whisker growth of many substances. A significant advance in understanding whisker growth has been a recognition of the need for impurities. This requirement has been clearly demonstrated for copper,11 iron,13 and silicon9-1 whiskers. For silicon, detailed studies proved conclusively that certain impurities, for example, nickel or gold, are essential. Another pertinent phenomenon which has received little attention is the presence of a liquid layer or droplets on the surface of some crystals growing from the vapor. Crystals in which this has been observed include p-toluidine,14 MoO3,15 ferrites,16 and silicon carbide.&apos;" The liquid layers or globules were considered to be metastable phases, molecular complexes, or intermediate polymers originating from condensation of the vapor phase. The possibility has been suggested that the halide being reduced is condensed at the tip18 or adsorbed on the surface11 of a growing metal whisker, for example copper. The literature on whiskers discloses illustrations of rounded terminations at the tips. These appear. for example, on crystals of A12O3,19,20 sic,21 and BeO.22 For BeO, Edwards and Happel suggested that during growth of the whisker the rounded termination consisted of molten beryllium enclosed in a solid shell of BeO. A recent paper9 on the growth of silicon whiskers contains many observations pertinent to an understanding of the mechanisnl of whisker growth. These observations are summarized as follows. 1) Silicon whiskers are dislocation-free. 2) Certain impurities are essential for whisker growth. Without such impurities the silicon deposit is in the form of a film or consists of discrete polyhedral crystals.

Jan 1, 1965

By A. E. Jenkins, O. C. Roberts, D. G. C. Robertson

Using an inverted-cone coil at 450 kHz, it has been possible to levitate iron (FeS), cobalt (CoS), and nickel (NiS) sulfides. Important nontransition metal sulfides such as ZnS, PbS, and Cu2S have proven impossible to levitate although Cu-Fe-S ternary alloys containing 30 wt pct S and up to 10 wt pct Cu, and Cu-Co-S and Cu-Ni-S ternary alloys containing 30 wt pct Cu have been levitated. The levitation technique has been used in preliminary experiments on the vaporization from liquid sulfides and the reaction of liquid metal-sulfur alloys with oxidizing atmospheres. The course of the reactions with pure oxygen were followed using highspeed photography and two-color pyrometry. ELECTROMAGNETIC levitation is now established as a basic laboratory technique in high-temperature research but its application has been restricted mainly to metals and alloys. Applications have included alloy preparation,&apos; metal purification,2&apos;3 determination of liquid metal densities and emissivities,4,5 and studies of metal supercooling,4 alloy thermodynamics,6 and vaporization phenomena.7-9 The application of the technique to compounds has not been considered previously. The successful investigation of the reactions between dilute iron alloys and oxidizing atmospheres10&apos;1 has prompted the current physico-chemical studies involving levitated metal sulfide drops and flowing inert or oxidizing atmospheres. This paper presents the results of such a study and provides a basis for future studies involving a wide range of other compounds of metallurgical interest. The successful levitation of many metal sulfides and mattes provides a method of studying the oxidation reactions fundamental to flash-smelting and similar pyrometallurgi-cal operations under closely controlled laboratory conditions. In addition the system allows the use of a controlled atmosphere (e.g., a gas stream of a certain H2/H2S ratio) with a particular chemical potential to study the relevant thermodynamic equilibria or the mass transfer processes between the atmosphere and the levitated drop under conditions where the hydrodynamics of the system can be closely defined. The optimum frequency for the levitation melting of metals in an inverted-cone coil type inductor is within the radio frequency range 400 to 500 kHz. At frequencies lower than 10 kHz the rate of heat generation is usually insufficient to melt the levitated charge&apos; or where melting is achieved, "dripping" from the charge is encountered.&apos;&apos; At frequencies above 2 mHz the levitation force decreases. Metals, alloys and preheated elemental semiconductors such as germanium and silicon, have been levitated but the levitation of only a few metal compounds has been reported. Jostsons13 and the authors have levitated liquid titanium-oxygen alloys containing 50 at. pct 0 while clark14 has reported the levitation of mixtures of FeS and MnS for short periods. With a "cold crucible" inductor sterling15 has melted ferrites by preheating them by induction in a 4 mHz field and melting at a lower frequency. However this second type of inductor has been designed purely for the melting of materials without contamination; there is only a small gas film between the charge and the inductor and the electromagnetic levitation effect is of secondary importance. For this reason further discussion will be restricted to the use of the coil type inductor. The assessment of the suitability of a particular metal compound for levitation is based upon the following two criteria: i) thermal stability, and ii) physical "levitability". In this paper these two criteria will be considered separately. The thermal stability of a solid or liquid metal compound with respect to a gaseous environment depends upon its chemical reactivity with that environment or, in the case of an inert atmosphere considered here, its volatility. The physical criterion as to whether or not a particular compound can be levitated is based upon a comparison between those physical properties of the compound determining "levitability" which are defined by the fundamental equations of levitation theory as developed by Okress et a1.,16 and the properties of the metals. Since it is not practical to cover the vast field of metal compounds, further discussion will concentrate on the metal sulfides but the treatment would be applicable to any metal compound. THE THERMAL STABILITY OF METAL SULFIDES The temperatures usually encountered during levitation in inert atmospheres cover the range 1400" to 2000°C. The stabilities of the condensed states of the sulfides under these conditions are considered in relation to the periodic classification by reference to Table I. Two general classes of sulfides emerge. The solid sulfides of elements of group IIB and of groups further to the right are volatile while those sulfides of group IB and of groups further to the left are nonvolatile solids. The sulfides described as volatile may be dismissed as unsuitable for levitation. The stabilities of the more favorable nonvolatile sulfides under the anticipated conditions must be studied more closely From Table I it is seen that the alkali metal sulfides exist as liquids in the temperature range of in-

Jan 1, 1970

By G. R. Speich, D. J. Mack

The transformation of was studied by isothermal methods. At all temperatures, the ß transforms quickly to fine grained ß" which develops silver-rich striations. At higher temperatures the striations disappear, the final structure being Widmanstatten a in ß&apos;. At lower temperatures, the striated ß" is consumed by pearlite nodules of a + ß&apos; which in turn form the Widmanstatten a in ß&apos;. The transformation is unlike any previously reported for a eutectoid. AS part of a general program of study on the eutectoid reaction, the Ag-Cd eutectoid seemed particularly attractive because the ß phase which undergoes the reaction is another of the typical "electron compounds," AgCd, having the disordered body-centered cubic structure. This work deals with the eutectoid which occurs at 50.5 wt pct Ag, and not with the eutectoid which has been reported at 42.9 pct Ag.&apos; There has been no work reported specifically on the Ag-Cd eutectoid which was studied. The only information available on this eutectoid is that work done in the determination of the phase diagram. For the most part, the terminal portions of the diagram, Fig. 1, are well established; however, the region from 40 to 60 pct Cd is still somewhat in doubt. The X-ray evidence&apos;..&apos; in this region is in conflict with the results of thermal analysis. X-ray analysis3 does not show a polymorphic transformation at about 240°C as indicated by thermal analysis.1,5 Even the X-ray evidence, within itself, is confusing in this region of the diagram. One investigator2 reports the ß phase as hexagonal close-packed and has found three phases in the one-phase ß field. Other X-ray investigators"&apos; &apos; report the ß phase as body-centered cubic. The authors believe that much of the confusion resulted from incomplete homogenization of the alloys. It was found that it takes almost a week to produce a completely homogeneous two-phase structure at 370°C. Another possible source of error is the volatilization of cadmium from the surface and cracks of the specimen during annealing with the possible formation of a cadmium-poor phase. The only metallographic data available on this eutectoid alloy are those of Durrant1 and Fraenkel and Wolff.5 his information is very limited. The phase diagram chosen as most nearly correct is that in the Metals Handbook," which is almost identical with the phase diagram suggested by Durrant.1 Materials and Procedure The alloy was prepared from high purity silver (999.5 plus fine) and high purity cadmium (0.02 Pb, 0.005 Cu, trace Fe). The metals were melted in carbon under a nitrogen atmosphere. Some cadmium was lost by volatilization but by remelting several times and adding cadmium a 200 g ingot of approximately eutectoid composition was obtained. Because the CdO fumes are quite toxic, the exit gas from the furnace was led through a water trap to condense the CdO. The ingot was homogenized at 650°C for 24 hr, no attempt was made to prevent decadmiumization. This resulted in a narrow decadmiumized rim on the ingot which was removed. Filings for analysis were obtained from cross sections of the ingot. Silver was determined by the Volhard thiocyanate method,? cadmium by difference. The ingot analyzed 50.8 pct Ag at the top of the ingot and 50.7 pct at the middle and at the bottom of the ingot. This alloy was only slightly hypo-eutectoid compared to the accepted value of 50.5 pct Ag and was used for the isothermal studies. It was felt that further attempts to adjust the composition might be futile because of the volatility of the cadmium. The ingot was sectioned to specimens approximately 3/4 x 3/4 x 1/8 in. These specimens were "austeni-tized" for 3 hr in air at 650°C to yield homogeneous ß and then quenched into a salt bath held at constant subeutectoid temperatures where the transformation

Jan 1, 1954

By L. Weyher, H. L. Lovell

This discussion is restricted to a very specific application of the cyclone - its use as a hydro-cyclone in the cleaning of fine coal. It is hoped that the development of the present data will assist in the further elucidation of existing qualitative models, and also in an enhanced application of the hydrocyclone and provide a base for further research. Discussed are the mechanisms of gravity separation in hydro-cyclones, test procedures, experimental observations, and industrial applications from these studies. Within the general area of unit operations, a considerable effort has been expended in theoretical and empirical research associated with cyclone operations. The motivation involves the industrial requirement for devices and techniques to manipulate small particles at low operating costs, a situation required in coal preparation. There are good reasons why the cyclone helps to satisfy this demand, because it combines operational simplicity (no moving parts) with versatility and high throughput capacity per unit area. The cyclone is one of the most widely applied tools in the process technologies. There are areas for potential cyclone application which have been only meagerly explored or not considered at all. This discussion is restricted to a very specific application of the cyclone - its use as a hydrocyclone in the cleaning of fine coal. It represents an initial presentation of a more comprehensive report. Coal preparation can appropriately claim the hydrocyclone since most of its predominant industrial uses have originated in this area and have spread into other applications, including the broad field of ore dressing, the petroleum industry, chemical processing, nuclear engineering and food technology. There is one operational principle common in all cyclones: A fluid is tangentially introduced into a cylindrical or conical container under pressure. A predominantly irrotational flow field1 is established within the cyclone (Fig. 1). The uniqueness of this flow is indicated by the variation in tangential velocity across the cyclone radius, which reaches a maximum a short distance from the center and decays toward the cyclone wall. In contrast, the tangential velocity in a centrifuge increases uniformly toward the wall. Usually two products are discharged from the cyclone. They differ in that one discharge consists predominantly of that portion of the feed fluid which moves along the wall axially away from the feed inlet, while the other consists predominantly of fluid spiralling along the central regions of the cyclone, in an axial direction opposite to that of the wall current. Fig. 2 indicates these discharge points schematically. The latter product may be termed the vortex-product, since it is discharged with the central vortex-current. In the case of conical cyclones, the former product may be referred to as the apex-product. Although the names "over- and underflow" are widely used, many cyclones are operated from extreme angular positions thus the proposed terms are less ambiguous. The cyclone feed fluid can be laden with solid particles or nonmiscible fluid drops. Such a feed component is discharged from the cyclone, after some residence time, into the one or the other product. Yet, the orifice through which a particle will leave the cyclone is dependent upon a number of factors. These factors, in a statistical sense, determine the path of the particle within the cyclone. Thus, different separation phenomena are possible and different process results attainable by the controllable variation of the particle path. It is then, to attain a fuller understanding of this particle path, to which this study is ultimately directed. It is anticipated that the detailed study of the data being developed will allow further elucidation of existing qualitative models. However, the development of a quantitative description of cyclone operation in terms of a mechanism is not currently feasible. The flow conditions in a cyclone are not fully understood even for a pure fluid, without the added complexity of the inclusion of multiple size-density particles. It is hoped that the development of the present data will also assist in an enhanced application of the hydro-cyclone and provide a base for further research. Some practical applications drawn from the data are suggested. Cyclone operations have been classified according

Jan 1, 1967

By J. A. Putnam, A. D. K. Laird

In laboratory research on the behavior of oil, gas and water in porous materials, no direct method has been devised to measure saturation without disturbing the flow. Indirect methods involving various forms of radiation have been developed for measuring one or two components. The X-ray absorption method for two components has been described previously1-3. The possibility of three component measurement has also been mentioned1. Since two component measurement still requires considerable care to insure accuracy, the fact that three components can be measured satisfactorily is not generally appreciated. The fraction of the energy of an X-ray beam of one wavelength transmitted through a material is given by the transmission factor. in which 1 is the beam&apos;s path length through the fluid. p is the fluid density, and 1,. is its mass absorption coefficient. Eq. 1 implies that all parts of the beam pass through equal amounts of the fluid. Practical applications are, therefore, limited to systems in which the fluid is distributed so that I varies negligibly over the cross-section of the beam. Typical variations of the transmission factor with X-ray tube potential arc shown in Fig. 2 from which experimental points have been omitted for clarity. The X-ray absorption of low pressure gases in a core is practically zero so it cannot he distinguished from that a vacuum by instruments that will differentiate between liquids. The transmission factor of a gas in a core is. therefore, unity. Consequently, the saturation of only one gaseous component can be found. If two fluids completely fill a core, their two saturations add to unity and, therefore, only one value of the transmission factor, T, is needed to determine both of them. When two liquids do not completely fill the core, their saturations do not add to unity and transmission factors at two wavelengths must be measured. At one of these wavelengths, 7 for one liquid must be different from T or the other liquid. The change of T for one liquid us the wavelength is changed between the two values must be different from the corresponding change of T in the other liquid. The two values of fluid saturation will also give that of the gas because the three saturations must add to unity. In Fig. 2 it can be seen that there are many large differences of T between various oil solutions and water solutions at any one potential, and between potentials for any one solution. Consequently, conditions for optimum accuracy of measurement of the saturations of a gas and two liquids can be chosen. Once the operating potentials have been selected, however. it is more convenient to cross plot the data from Fig. 2 on transmission factor-solution concentration coordinates for the chosen potentials, as shown in Fig. 3. Fig. 3 was used to plan the experimental procedure for Core N-38-1. Since the voltage control at 45 kv was good, the slopes of the curves in Fig. 2 at this potential would cause little error. At low potentials, however, the voltage control was not good, so 33 kv was chosen because the small slopes of the curves made voltage control less critical. The lowest strength beam that could be measured reasonably at 33 kv corresponded to a minimum T factor of 0.385. Fig. 3 shows that both 4.80 weight per cent of cadmium chloride in water and 24.0 per cent of iodobenzene in crystal oil had this T value, and, consequently, were indistinguishable to the X-rays at 33 kv. Thus, at 33 kv, the liquid saturation was given by the same curve regardless of the relative amounts of oil and water solutions present. This simple calibration curve from which the gas and liquid saturation can be read, is shown in Fig. 4. Fig. 3 also shows that at 45 kv, T for the aqueous solution is 0.610. and that T for the oil solution is 0.220. These values were transferred to Fig. 4 to give the triangular calibration plot from which the brine and oil saturations can be found, after the gas saturation has been determined at 33 kv.

By S. K. Mitra

A refinement of the Seeger model for intersection process is investigated which is in better agreement with experimental observations than the original. It is shown that, in single crystals, the strain hardening in Stage II is mainly due to the short-mnge interactions when intersection is the rate-controlling process. It is also demonstrated that the creep curves, as predicted by this theory, are in good agreement with the experimental observations. MOTT: Cottrell? and Seeger have developed an approximate theory for plastic deformation of single crystals over the range of variables where the strain rate is controlled by the rate of intersection of dislocations. Although it is now generally agreed that the low temperature deformation of many pure metals is controlled by the intersection mechanism, various dictates of the over-simplified Seeger model are not in good agreement with all the experimental facts. It is the purpose of this paper to reveal that by appropriate extensions of the Seeger model, particularly those suggested by Basinski: a much more reliable theory results. The refined model to be presented here will be shown to account, in a satisfactory way, for the effect of stress, temperature, and strain on the creep rate under constant stress and for the effect of temperature and strain on the flow stress in constant strain-rate tests. EXPERIMENTAL METHOD To Check the theoretical deductions, both creep and tension tests were conducted on single crystals of high-purity Al (99.994 pct Al) so oriented that both the active slip plane and the Burger&apos;s vector of the operative dislocations on that plane made angles of about 45 deg to the tension axis. Single crystals of aluminum (5/8 in. by 1/10 in. by 8 in.) were grown in a graphite mold under an inert atmosphere using the Bridgman method. The chemical composition of the aluminum is given in Table I. A common seed was used for all crystals and their orientation is shown in Fig 3. The extensometry consisted of two differential transformers with matched outputs mounted so as to measure the extension in a 2 in. gage length. The amplified difference in output of the two transformers was recorded by a potentiometer. The amplification was calibrated before each run so that one chart division of the recording potentiometer indicated a 105 shear strain on the specimen. Stresses were measured to the nearest 1 x l04 dynes per sq cm. ACTIVATION VOLUME The concept of Basinski that the activation volume is not constant but is a function of the force that aids thermal fluctuation in effecting the cutting of dislocations will be adopted in this section. The force acting due to an applied shear stress on the dislocation being intersected is where L is the mean spacing between the forest dislocations, is the Burger&apos;s vector and T is the back stress. A detailed discussion about the origin of back stress will be taken up later in this report. As shown by Basinski, the activation energy, U, that must be supplied by a thermal fluctuation in order to effect intersection, is equal to where x is the distance through which the dislocation must be translated for complete intersection, and Fm is the maximum force encountered in intersection. When the applied stress is decreased abrupt ly F also decreases and the activation energy increases correspondingly as documented in Eqs. [ 1 ] and [2]. The Seeger equation for the strain rate when the deformation is controlled by rate of intersection of where the shear strain rate (per sec) N = the number of points per unit vol at which intersection can take place

Jan 1, 1962

By Peter R. Morris

The effecl of preferred orienlation on X-vay dzffvaction measurements of retained austenzte was investigated for four precipitation-hardening staznless steels in sheet form. A method is preserzted for estimating the ervor in measurement associated with a given samplirig direction. The method was used to select an "optimum" sampling direclion in order to minimize errors in measurement due to preferred orientation. hleasuremenls of retained austenite content employing lhe proposed sampling direction are conzpaved to measuretnents enzploying the more commonly used normal direclion for a series of sawzples. THE first application of X-ray diffraction to the measurement of retained austenite in steels is due to Sekito, 1 who employed a photographic technique in which the (111) reflection from a thin strip of gold affixed to a cylindrical sample was employed as a standard. Averbach 2 introduced the "direct comparison" method in which the ratios of observed to calculated random intensity are assumed proportional to the austenite and/or martensite contents. Averbach&apos;s work forms the basis of most subsequent X-ray diffraction methods for the determination of retained austenite. Subsequent improvements are due to: Averbach and Cohen,3 who employed a sodium chloride crystal to monochromate cobalt radiation; Averbach et a1.,4 who introduced a bent sodium chloride monochromator; Mager,&apos; who used a bent quartz crystal to monochromate chromium radiation ; Littmam, who first used a geiger counter diffractometer for this purpose; Beu and Beu and Koistinen, 11,12 who studied effects of absorption factor, surface preparation, sample geometry, integrated intensity vs peak height, choice of radiation, monochromator, and filter. The possibility of errors in measured values due to orientation effects was noted by Miller,13 who suggested examination of a surface other than the plane of rolling. Lopata and Kula 14 have developed an experimental technique in which the preferred orientation is measured in each sample. They illustrated the method for a sample containing 42 pct retained austenite. Application of their technique to the 1 to 15 pct range typical for the precipitation-hardening stainless steels does not appear feasible. EXPERIMENTAL PROCEDURE The nominal compositions of the precipitation-hardening stainless steels investigated are listed in Table I. Ingots were solution-treated, hot-rolled to approximately 0.2 in., and reduced to 0.050 in. by a suc- cession of cold rolling and annealing operations. After this treatment the 17-4PH sample was in the marten-sitic condition, while the 17-7PH, PH 14-8Mo, and PH 15-7Mo samples were in the austenitic condition. Samples of 17-7PH and PH 15-7Mo steels in the mar-tensitic condition were obtained by heating to 1750&apos;F for 10 min and holding at -100°F for 8 hr. A sample of PH 14-8Mo steel in the martensitic condition was obtained by heating to 1700°F for 1 hr and holding at -100°F for 8 hr, followed by aging at 950" for 1 hr. POLE FIGURE DETERMINATIONS Samples were thinned to 0.003 to 0.005 in. by etching in a solution containing 250 ml reagent-grade phosphoric acid (85 to 87 pct H3PO4), 250 ml technical-grade hydrogen peroxide (30 to 35 pct H 2 O 2), and 50 to 100 ml reagent-grade hydrochloric acid (37 to 38 pct HCl). The specimens were placed in an "integrating" sample holder which provided a 1-in. oscillation in the plane of the sample. The diffractometer was aligned to measure the intensity diffracted by planes of the particular {hkl} type being studied. The sample was Set for a given latitude angle, a, measured from the plane of the sheet, and diffracted intensity recorded as the longitude angle, 0, measured in the plane of the sheet from the rolling direction, was increased from 0 to 360 deg. After a 360-deg scan of B, a was incremented by 5 deg, and the process repeated. Random standards obtained by spraying suspensions of powdered iron (bcc structure) and nickel (fcc structure) in lacquer were used to correct observed intensities for absorption and geometrical effects. Zirconium-filtered molybdenum radiation was used to determine the transmission regions of the (111) (0to 45 deg), (200) (0 to 60 deg), and (220) (0 to 45 deg) austenite and (110) (0 to 45 deg), (200) (0 to 50 deg), and (211) (0 to 35 deg) martensite pole figures. Vanadium-filtered chromium radiation was used to

Jan 1, 1968