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By David L. Holt

The contribution of grain boundary shear to total elongation, CS/E&apos;, has been measured in an Al-Zn eu-tectoid alloy that was quenched from above the invariant temperature, then annealed at 250° C to a grain size of&apos; 1.8 p. At 250°C, ks/E&apos; is low at both high and low strain rates, but reaches a maximum, estimated as 60 pct at an intermediate rate of 5 X 10 per rnin. Rate sensitivity, as measured by the index m = a log a/a log E&apos;, follows the same trend, and furthermore the maximum values of m and -cur at approximately the same strain rate. This result, combined with the metallographic observation that boundary migration enhances boundary shearing, is interpreted as supporting a previous suggestion that the high rate sensitivity characterizing super-plasticity is the result of combined boundary shearing and migration. It is suggested that the latter event relieves stress concentrations at triple points, and smoothes boundaries so that stress is governed largely by a viscous boundary shear. GrAIN boundary shear has been considered in relation to superplasticity in several recent papers.&apos; The problem has been to explain the high strain rate sensitivity of flow stress, and the variation of rate sensitivity with strain rate (E&apos;) and grain size (L). The requirements for superplasticity, small L and high T, suggest the reasonableness of an approach to high rate sensitivity involving grain boundary shear. Further support came from experiments on the A1-Cu eutectic alloy,&apos; where it was found that strain rate sensitivity of cast material annealed to produce an equiaxed, micron-size grain is always low; taking as an index of rate sensitivity m = a log a/a log <, m < 0.3. However, m in hot-worked alloy of comparable grain size can be as high as 0.7. In the cast and annealed material, each phase is a single crystal, the only boundaries are interphase boundaries, and it is, consequently, geometrically impossible for boundary shear to contribute to deformation in any major way. Other observations (for hot-worked material) were a-L at constant (low) strain rates and indications that the rate of recrystallization was enhanced as strain rate increased. As a result of this work, it was proposed that high rate sensitivity arises from a deformation mode of boundary shear associated with boundary migration. Migration serves to relieve stress concentrations at triple points, and smoothes boundaries so that they assume properties of fluid films. On the other hand, the low rate sensitivity observed at high and low strain rates reflects deformation of bulk material. Measurement of the variation of grain boundary shear with strain rate and m have not yet been made. Such measurements are important, especially in view of a proposal, differing in detail from the above, that high m arises merely from a transition between a grain boundary shear mode of deformation at low rates to a transgranular mode at high rates.2&apos;4 In the present work, the contribution of boundary shear to total deformation is measured and in addition metallographic observations are made on surfaces of deformed specimens to look at the interaction between boundary shear and migration. The Al-Zn eutectoid alloy was chosen for its homogeneous, fine-grained structure, which is obtained readily without hot-working. It has also been the subject of a previous phenom-enologically directed study. EXPERIMENTAL Material. Compression specimens, cross section 4 by + in., length \ in., were machined from a sand-cast ingot of composition 77.5 wt pct Zn, 22.5 wt pct Al. (The melt was prepared from 99.9 pct Zn and 99.99 pct Al.) After homogenization at 375°C for 50 hr, the specimens were quenched in brine and removed before the heat evolution that accompanies de -composition of the high-temperature phase.5&apos;6 The resulting microstructure, see Fig. l(a), was too fine for grain boundary sliding to be easily studied; coarser structures were obtained by annealing for various times at 2 50°C. Annealing was terminated by a brine quench. Final average intercept lengths between all grain boundaries (both interphase and those lying in a phase), L, were: 0.5 p [annealed for 15 min, Fig. (a)], 0.8, 1.1, and 1.8 p [Fig. l(b)l. Testing Procedure. An Instron machine was used for most of the compressive deformation. Tests were of two types: those in which crosshead velocity was changed in steps to measure m as a function of strain rate15 and tests at constant velocity to a fixed (engineering) strain of -0.2 (20 pct). Stress reached a steady-state value (a) which was plotted, on a logarithmic scale, against log strain rate (E&apos;). An alternate and equivalent evaluation of m was to take the slope of the log o vs log 6 curve. Time at temperature before testing was 15 min. Strain rates covered by the Instron (4 x lo-&apos; to 4 x 10&apos; per min) were insufficient; at a higher rate of 5 x lo2 per min a gas-operated testing machine was used, the gas driving a piston to compress the specimen at a controlled velocity.&apos; To obtain points on the log a vs log E&apos; curve at low rates, specimens were compressed by a dead weight. strain rate was an average value computed by dividing strain at the end of test by loading time. In some tests strain was measured at fractions of the loading time; creep rate was found to be reasonably constant.

Jan 1, 1969

By G. L. Oldright, F. S. Wartman, H. E. Keyes

The economic manufacture of sulfuric acid by the ordinary chamber process usually involves production on a large scale and a plant that is costly to construct. The nature of sulfuric acid makes it costly to transport any great distance. For these reasons, the metallurgist has not found it feasible, at times, to beneficiate ores amenable to leaching, and a need exists for a local process that will produce acid cheaply on a small or large scale. To leach ores containing residual sulfides, an oxidizer, such as ferric sulfate, is needed in solution. Precipitation with scrap iron is one of the cheapest methods of removing some metals from solution, giving a plant of low first cost and supplying a source of cheap ferrous sulfate. The other ingredient needed for the process is SO2 roaster gas, the addition of which, as described below, will give both ferric sulfate and sulfuric acid. Where roaster gas is a waste or obnoxious product, the expense for materials is still further lessened. The use of ferric sulfate and sulfuric acid as a solvent lends itself well to the utilization of scrap iron as a precipitant, and the stages of the process fit in well together as an economic whole. Applications The hydrometallurgist usually thinks of ferric sulfate as a partial solvent for some of the sulfides of copper alone, as most work has been done on this metal. The processes of Hannay and Christensen, for leaching unroasted galena with ferric chloride made by anodic oxidation, show the added solvent action given by "ic" salts when added to brine solutions. It was found by R. D. Bradford (in some work to be published soon by the University of Utah) that, by the addition of a ferric salt to a brine solution, the silver as well as the lead in an unroasted semi-oxidized ore could be largely dissolved. The "ic" salt in the case of silver has evidently the same effect as the case of cupric sulfate when

Jan 1, 1926

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick&apos;s second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1&apos;5 In the second method a gas-liquid metal diffusion cell is used.&apos; The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick&apos;s second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

By T. E. Tietz, J. E. Dorn

Activation energies for creep of copper at intermediate temperatures, where crystal recovery was negligible, were determined by the simple technique of rapidly alternating the test temperature between and T2 (T2 = TI + about 10°K) throughout a constant stress creep test. The activation energy for creep H was found to be 37,000± 3,000 cal per mol, independent of stress and strain. The same creep laws as have been previously established for high temperature creep were found to be valid for creep at intermediate temperatures. But the AH was found to be lower than that for self-diffusion in the intermediate temperature range whereas it is known to be equal to that for self-diffusion at high temperatures. IT is now well established that creep at high temperatures can be correlated by the functional relationship&apos;-" e = f(?) s = constant [I] where E is the total plastic strain, f is the function that depends on the stress, ? = f e -- dt, t is the duration of test, e is the base of natural logarithms, AH is the activation energy for creep, R is the gas constant,T is the absolute temperature, and s is the stress. Thus, identical values of are achieved during creep under a given stress at two alternate temperatures at the same total strain. At the same strain therefore where subscripts refer to the two alternate temperature conditions of test. Consequently, the activation energy for high temperature creep is readily obtained with the aid of Eq. 2. Activation energies so obtained have been observed to be insensitive to the creep strain at which they are evaluated, the applied stress, grain size, minor alloying additions,&apos;-&apos; cold worked state, and the presence of thermally stable dispersions of intermetallic compounds in an a solid solution matrix Furthermore, the activation energy for high temperature creep is very nearly equal to that for self-diffusion in all cases where adequate data are available for comparison." " The apparent identity of the activation energies for high temperature creep and self-diffusion strongly suggest that high temperature creep arises from a dislocation climb process. This hypothesis is further strengthened by the fact that the energy of activation for high temperature creep is insensitive to the applied stress," and by the observations that the correlation suggested by Eq. 1 cannot be ex- tended to temperatures below those for rapid crystal recovery. When using the activation energy for self-diffusion, Eq. 1 fails to give the required correlations between creep curves at various intermediate temperatures.&apos; This suggests that the dislocation climb mechanism for creep might be superseded by some alternate mechanism in the intermediate range of temperatures. This investigation was initiated in a preliminary attempt to ascertain the type of creep law that might be valid in the intermediate range of temperatures. Special consideration, however, was given to the determination of the activation energy for creep in this range because the Becker-Orowan&apos;, " and the Mott-Nabarro10 theories for transient creep suggest that the activation energy should increase

Jan 1, 1957

By G. F. Loughlin

THE matter of grading Indiana oolitic limestone has been under a cooperative study by the Supervising Architect&apos;s office, the U. S. Geological Survey, the Bureau of Standards, and the former Indiana Limestone Quarrymen&apos;s Association. As the criteria for grading are necessarily based on a number of geologic and related factors of which those quarrying and using the stone had only imperfect appreciation, the first part of the report is a very elementary account of the origin, structure, and the chemical and physical properties of tie stone, and their relations to durability and utilization, and serves as a foundation for the second part, which discusses grading and pro- poses limits for grades established by the quamymen. Salient features of Part I of a report that has been prepared are the variations in uniformity of stone due to cross bedding, and local uncomformities; the relative prominence of weathering effects on the coarser uneven grained surfaces, and its apparent absence on fine, uniform grained surfaces, although the amount of weathering is the same on each; the attributing "crow feet" (stylolites) to solution under pressure, and the explanation that, whereas the thinnest "crow feet" have no noteworthy effect on weathering quality or strength, the thicker ones are likely to weather out rapidly and to promote splitting; the influence of fracturing on the oxidation of the original gray or "blue" to buff color above the ground water level; the interpretation of chemical analyses and the pointing out that both the gray and buff colors are due mainly to organic

Jan 1, 1929

By G. V. Jere, V. Krishnan, C. C. Patel

Standard free energy and standard enthalpy changes as a function of temperature have been calculated for the chlorination reactions of different oxides constituting columbite and tantalite. The tallies of standard lee-energy change (F) indicate the possibility of pvefeential chlorination of different oxides but the ease 0.f chlorination of columbium pentoxide at about 250°C and the chlorinating tendency of columbium pentachloride in promoting the chlorination of tantalum and other metal oxides, p7-evetzt the separation of columbiu?n and tantalum from other oxides and pom each othel.. It is likely that low temperatuves of chlorination and continuous 1err2oval of columbium pentachloride from the ..eaction zone may help partial separation of columbium from tantalum as well as from titanium. The standavd enthaply change (AH?) values shotr that 1ou.-temperature chlorination around 300" to 500°C is likely to sustain the chlorination , without external heating. COLUMBIUM (niobium) and tantalum metals, their alloys and interstitial compounds are finding extensive uses in nuclear reactors and high-temperature equipment.la-3 These metals also find uses in chemical process plants, electrical rectifiers and capacitors and as "getters" in electronic tubes.la With the development of Kroll process of reduction of volatilized titanium tetrachloride by magnesium for the production of titanium metal, chlorine metallurgy is receiving greater attention. Chlorine metallurgy has several advantages, the foremost amongst them are: the ease of chloride formation, separation of the different constituents of minerals by selective chlorination, and the reduction of the chlorides in vapor phase to the respective metals. Recently, Si-bert, Kolk, and Steinberg4 have considered a number of methods for the preparation of columbium metal and the most promising is found to be the halide reduction. Since the minerals columbite and tantalite are comparatively abundant in nature, the future of the metallurgical processes depends on the utilization of these minerals for the production of columbium and tantalum chlorides by chlorination. In this paper, an attempt has been made to interpret thermodynamically the chlorination of individual oxides constituting columbite and tantalite, with the help of the recent thermodynamic data.5-8 For this purpose, standard free energy and standard enthalpy changes of the chlorination reactions of the oxides with chlorine, both in absence and presence of carbon as the reductant, have been calculated as a function of temperature and represented graphically. Similar calculations for the reactions employing carbon tetrachloride and carbonyl chloride as chlorinating agents have also been incorporated in this paper. REPORTED WORK ON CHLORINATION Cuvelliezg has patented a process for the separation of columbium and tantalum from their concentrate, wherein 75 pct Cb05 is claimed to be chlorinated at 1050°C in the course of 7 hr using chlorine or chlorine containing nonreducing gases, the products of reaction being CbC1, or CbOC1,. At this temperature, Ta,05 is claimed to remain unaffected. It is further claimed1° that at higher temperatures, the proportion of Ta205 chlorinated increases while that of Cb205 diminishes. During the studies on the action of chlorine on individual metal oxides, Kangro and Jahn" have observed that Ta,05 is not chlorinated even at 1200" in the stream of chlorine, while 75 pct of Cb,05 is converted into CbOC1, around 900 to 1100°C. The chlorination of Cb205 by chlorine in the presence of carbon, investigated by Lind and Ingle,&apos; and

Jan 1, 1962

By K. R. Evans

The yield and fracture characteristics of a Ti-8 pct A1 alloy have been examined at room temperature as a function of exposure temperatures to 1700°F. Em-brittlenzent of the alloy is observed to occur following exposures below 1280°F, the critical temperature for formation of ordered Ti3Al particles. Presence of Ti3Al particles results in an increase in the yield and flout stresses which, for a given exposure time, are a maximum at the critical temperature. Embrittlement is attributed to the occurrence of plastically induced fracture controlled by the increase inflow stress. This interpretation is compatible with the decreasing ductility and increasing crack popagation rates observed with increasing exposure time below the critical temperature. Slip line observations and measurements of the gain size dependence of the yield stress indicate that the slip character of the alloy is not influenced by exposure treatments below the critical temperature. ThE potential usefulness of Ti-A1 alloys in structural applications has prompted considerable interest in studies of their microstructure and mechanical characteristics. The relatively recent surge of interest in the system and at the same time its complexities are indicated by the fact that despite numerous recent efforts14 there has not even been general agreement upon a phase diagram for the system. However, most of the Ti-A1 alloys of commercial interest range in aluminum content from 5.0 to 8.5 wt pct where most investigators achowledge the existence of the ordered Ti41 phase. Goldak and parrs confirmed the existence of Ti41 from X-ray diffraction analysis of the stoichiometric composition while Blackburn6 has determined its presence in commercial Ti-8 pct A1 alloys by electron diffraction analysis and dark field transmission microscopy. The embrittlement of Ti-8 pct A1 alloys was initially reported by Crossley and carew7 who showed that aging in the temperature range of 750" to 1110°F resulted in extreme brittleness. This behavior was later confirmed and correlated by Soltiss to the presence of long-range order in the commercial Ti-8 pct Al-1 pct Mo-1 pct V alloy (Ti-8-1-1) which exhibited anomalous creep and yield strength behavior at 950°F. This investigation was designed to study the mechanical characteristics of a binary Ti-8 pct A1 alloy in order to further examine the nature of the embrittlement behavior reported for the alloy system. EXPERIMENTAL PROCEDURE A Ti-8 pct A1 binary alloy was obtained from the Wah Chang Co. in the form of 0.050 in. sheet. The chemical composition of the alloy is given in Table I. Heat-treatment of the alloy was conducted in evacuated vycor capsules for the tensile sDecimens (1.25 bv 0.25 in. gage section) and in evacuated stainless steel jackets for the crack growth-rate panels. All specimens were annealed at 1700°F for 24 hr and water quenched before an exposure at elevated temperatures. Tensile testing was conducted at room temperature in an Instron testing machine equipped with a pushbutton control for instantaneous control of the cross-head motion. In this manner the change in stress, Aa, accompanying an increase in strain-rate by a factor of 10 was measured immediately after yielding. The crack growth-rate panels used were 3 by 18 in. with a precrack 0.33 in. long cut into the center of the panel. The panels were cycled at a maximum gross stress of 40,000 psi at a maximum to minimum tension stress ratio of 20. Cycling of the specimens was continued until the crack propagated the width of the panels. The crack length was intermittently measured during slow crack growth. EXPERIMENTAL RESULTS Correlation of Embrittlement to the Critical Temperature for Ordering. Blackburn6 has found that the critical temperature, T,, for the formation of Ti41 in a Ti-8 pct A1 alloy with an interstitial content on the order of that given in Table I is approximately 1245°F. The relationship between the ductility of the binary alloy used in this investigation and T, was estimated from tensile tests on specimens which were exposed for 24 hr at various temperatures followed

Jan 1, 1970

By Floyd E. Bliven

A century ago, Thomas Carlyle sketched the Emblem of the Wasting Candle in one of his papers. "Terar Dum Prosim" he wrote under the candle-" May I be wasted so that I be of use." The application of his reasoning is an excellent guide for a discussion of the scrap problems of today. The General Electric Co. has addressed itself to the need of proper and careful preparation of scrap metals for many years. A supervisor of salvage directs this work in each of the works. Generally he is an engineer and has had broad factory training. He gives general direction to the collection, preparation and disposition of scrap materials. He operates the extensive facilities which each works has provided for the centralization and control of scrap accumulations, and also initiates studies leading to the reduction of scrap accruing from machining and assembly operations. r We recognize that each industry, each factory, each locality faces a different set of conditions. Irrespective of size, in a plant employing 20 men or a large works with 15,00 employees-certain fundamental principles can be applied for organization and the collection of scrap. The manufacture of electrical apparatus is a highly complicated intricate business. In one area we make electronic tube and adjacent buildings house the manufacture of steam turbines. Both are instruments for power-different in size and in many cases serving different fields of application. Unlike the great industries that build automobiles, trucks, or engines where repetitive operations, once solved, set the stage, electrical manufacturers&apos; plants are large jobbing shops. Therefore, we must carefully plan every step in handling the scrap that "in so wasting to produce the finished motor or locomotive-we can return this product to reprocessing and ultimate use." ESSENTIALS FOR SALVAGE EFFICIENCY The essential steps for an efficient salvage department are: I. Selection of Personnel.-An able foreman would be a man of broad experience and understanding-one who commands the respect of the entire foreman group as well as that of his own men. In the interest of clean scrap, it is necessary to acquaint the foremen in the separate manufacturing units with the need of careful segregation in the shop and the best methods of obtaining it. At least 40 per cent contact time should be devoted for this purpose. 2. The physical equipment of the salvage department should be devised and selected to handle complete, at one point, all scrap operations. Bulky materials as produced by some large shops can be economically placed in salable shape at the divisional point. Because salvage

Jan 1, 1943

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement, breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By Kenneth P. Katen

INTRODUCTION Though the use of continuous mining machines consolidated the operations of cutting, drilling, blasting, and loading in one machine that would theoretically provide uninterrupted production, it was soon realized that the face haulage and roof support operations remained as major impediments to continuous production. The ability to provide not only continuous cutting and loading, but also continuous haulage and roof support (see Fig. I), was the basis for the introduction of mechanized longwall systems in this country from Europe in 1951. The early systems employed friction props for roof support, but were to become obsolete shortly after introduction of the first hydraulically powered, self-advancing supports in 1960. Since then, use of the longwall technique has grown to the point where it is currently providing more than 5% of the annual output of underground coal mines in the United States. The shortwall system had its origin in Australia, but was first introduced into this country in 1962 following the development of powered roof supports. It, too, provides for continuous cutting, loading, and roof support (see Fig. 2), but has not experienced the widespread popularity of longwall due to its inherent inability to easily provide for continuous haulage. While there are in the neighborhood of 100 longwall systems currently in operation in this country, there are only a handful of short- wall operations providing production of slightly more than 907 184.7 t/a (1,000,000 stpy). Both of these systems provide uninterrupted roof support for face operations by means of hydraulically powered steel roof supports. In each case, the coal removal consists of open-end cuts made from the narrow end of a large rectangular pillar (panel) which has been blocked out by continuous miners developing entries around its perimeter. However, this is the extent of the similarities between the two systems. It is hoped

Jan 1, 1981

By A. Lubinski, J. L. Logan, W. S. Althouse

A4ost gas twells and flowing oil wells are completed and treated through a string of tubing and a packer. Changes in temperature and in pressure inside or outside the tubing will: (I) if free motion of the tubing inside the packer is permitted, increase or decrease the length of the rubing; or (2) if free motion is prevented, induce forces in the tubing and on the packer. If pressure inside the tubing is greater than outside, the tubing may buckle helically even in the presence of a packer-to-tubing tension. The tubing will always buckle, and much more severely, if free motion is permitted. The buckling may be prevented by pulling the tubing in sufficient tension. The prediction of these forces and tubing movement has here to fore been based upon calculations that did not inciude helical buckling. This paper preseitts means with which these length or force changes can be calculated while taking into account the effect of helical buckling. To avoid damaging formations, failure of remedial operations, or damage to the tubing or packer, application is made to practical problems involving calculations of the required length of seals, amount of sluckoff or tension, and prevention of permanent corkscrewing. INTRODUCTION Leakage of a packer may result in costly failures of such operations as squeeze cementing, hydraulic fracturing, etc. To avoid such failures, the authors are often asked questions pertaining to the length of necessary seals, the amount of necessary slackoff, etc. Published work&apos; does not take into account helical buckling of tubing. Investigation of helical buckling was prompted by the fact that allowance must be made for this phenomenon in order to provide relevant answers. In the past, theoretical work on helical buckling was confined to conditions for which such buckling does not The mathematical treatment of behavior in a buckled condition, given in the Appendix, is novel. Assumptions upon which this investigation is based are listed and discussed in a special section. The following are a few of the many kinds of problems which may be solved with this paper. 1. Consider a packer in which tubing may move. Such movement will occur after pressures and temperature are changed. The paper provides means for: (a) calculating the amount of such movement and, therefore. the required length of seals; and (b) calculating the necessary amount of initial slackoff, for which there is no danger of unsealing the packer, if the length of seals is given. Such calculations, as well as those which follow, tully take into account the fact that part of the movement ib due to elastic helical buckling of the lower part of the string. This buckling may occur even in tubing under tension. Insufficient initial slackoff for a given length of seals, or insufficient length of seals for a given slackoff, may result in costly failures. A field case of such a failure will be given further in this paper. 2. In the case in which tubing cannot move in the packer, changes of pressure and temperature result in tubing-to-packer forces and forces in the tubing above the packer, both of which may be calculated. This knowledge is important because, if these forces are too large, the) could damage the packer or the tubing. 3. For wells in which wireline tools are to be run through the tubing, the paper provides means to keep the tubing from buckling, thereby permitting free passage of tools. 4. In deep wells, mainly in the presence of large casing, tubing may become "corkscrewed", i.e., take a permanent helical set. A field case is described further in the text. Using this paper, one may calculate in advance conditions under which permanent corkscrewing would occur, and then take preventive steps. HELICAL BUCKLING Consider a string of tubing, freely suspended in the absence of any fluid inside casing, as shown in Fig. I(a). Now consider an upward force F applied at the lower end of this tubing. This force compresses the string; and if the compression is large enough (which is always the case in actual problems), the lower portion of the string will buckle into a helix, as shown in Fig. 1 (b). The lower end of the tubing is subjected to a compression F. This compression decreases with the distance from the bottom and becomes nil (neither compression nor ten-

By L. L. Newman

As soon as the Congress recognized the alarming rate at which our domestic oil resources were being depleted during the war, it took action to step up the rate of research and development which the Bureau of Mines had been conducting for several years on the production of synthetic liquid fuels from coals. Under Public Law 290, approved April 5, 1944, funds were authorized for the Bureau to proceed with research, development, design and construction of demonstration plants for the hydrogenation of coal, the synthesis of oil from carbon monoxide and hydrogen, and the distillation of oil from shale. During the latter part of 1944, when it became evident that the collapse of Germany was near, a Technical Oil Mission was organized to study the Ger- man techniques of synthetic oil production. Since the cost of hydrogen or synthesis gas is one of the major factors of expense in the operation of hydrogenation or synthesis gas processes, the Bureau of Mines considered it of prime importance to include on the mission gas engineers whose instructions were to examine closely the methods employed by the Germans in solving the problem of providing low- cost hydrogen or synthesis gas for their very extensive operations on synthetic liquid fuels. The Solid Fuels Mission and the Utilities Mission, as well as the Army and Navy Missions, also included teams for the study of German gas production. Although their objectives naturally differed from those of the Technical Oil Mission and from each other, it was recognized that there was considerable overlapping of their fields of investigation. Duplication of effort, however, was largely avoided through the close cooperation between the group leaders of these missions. For example, although I went to Europe as a member of the Technical Oil Mission, my first German assignment was actually made by Dr. Harry F. Yancey, leader of the Solid Fuels Mission- to investigate the brown-coal gasification methods in central Germany. The art of gasification in the United States and England, and to a large extent in the proximity of the coking-coal regions of Germany and the rest of continental Europe, depends essentially on two stages of operation; namely, carbonization and intermittent water-gas generation. As far as the United States is concerned, complete gasification in a single stage of operation is rarely practiced, except in gas-producer operations where the product is a relatively lean gas consumed close to the point of manufacture, and for water-gas production with anthracite as a generator fuel. Complete gasification of bituminous coal has been the subject of numerous investigations. Many relatively simple modifications of the water-gas generator have been tried to permit the direct gasification of low-cost bituminous coal instead of high- cost coke and anthracite for the production of water gas. Although varying degrees of success have been achieved and the water gas produced generally has been higher in calorific value, in only a few isolated in- stances has there been any sustained use of bituminous coal for water-gas production for public utility uses after the shortages of anthracite and coke have been lessened.

Jan 1, 1946

By P. A. Beck, Hsun Hu

As described by means of quantitative pole figures, the annealing texture of highly rolled aluminum consists of the four retained components of the rolling texture near (123) [121], rather more sharply developed, and of a cube texture component. Local reorientation corresponds fairly well to 40 rotation around a [111] axis. In copper strip rolled 96 pct, the annealing texture is mainly the cube texture, with the four twin orientations as minor components. The annealing texture of highly rolled brass strip consists of four components of the (225) [734] type. REVIEWS by Wassermann,&apos; Barrett,&apos; Dunn,3 and Richards&apos; give detailed accounts of the numerous publications dealing with annealing textures in rolled polycrystalline metals. Although a considerable amount of information of an empirical nature has been available for many years, even relatively recently the state of recrystallization-texture theory was considered uncertain. The reviews referred to above deal mainly with the description of experimental results, without developing generally applicable principles, suitable for explaining the observed annealing textures. The investigations of Burgers and Louwerse5 and Barrett6 showed that in deformed single crystals of aluminum the orientation of the recrystallized grains deviates drastically from that of the deformed matrix. According to Barrett and to Beck and Hu,7 the relationship between the two orientations can be best described as a rotation of about 40° around a [111] axis. Recent investigations led to similar orientation relationships for various face-centered cubic metals with a simple texture, regardless of whether the annealing process was recrystallization (strain-free grains growing in a highly deformed large crystal of aluminum&apos; or copper: or in deformed cube texture copper") or coarsening (strain-free grains growing at the expense of an essentially strain-free, fine grained, polycrystalline matrix of single orientation texture copper,&apos;" aluminum,&apos; or nickel-iron). Barrett" pointed out the possibility that this orientation relationship may be a result of the orientation dependence of the rate of grain boundary migration. More recently, considerable evidence became available in favor of this view.12,13 In apparent contradiction to the above results, it has been known for a long time that the recrystallization texture of polycrystalline metals is often similar to the deformation texture. This was found, in particular, for the fiber textures obtained by wire drawing, compression, or compression rolling.&apos; Following a suggestion by Barrett,2 Kronberg and Wilson and Beck and Hu7 described a mechanism by which a [Ill] fiber texture, resulting from plastic deformation, may be retained upon recrystallization, even though the orientation of individual recrystallized grains differs from that of the local area of the matrix in which they grow. This mechanism assumes that the reorientation corresponds to a rotation around the [1ll] axis, which is also the fiber axis. The present investigation was undertaken to examine in detail the orientation relationship between deformation texture and recrystallization texture in rolled face-centered cubic metals, using the quantitative methods of texture determination that have recently become available.", &apos;" Quantitative pole figures for the rolling textures of such metals were reported recently." Quantitative pole figures for annealing textures are given in the present paper. It was planned to investigate whether or not the orientation relationship previously found for the recrystallization of deformed single crystals, and for coarsening of single-orientation texture material, is capable of accounting for the observed, often complex, annealing textures in rolled polycrystalline metals. The question whether local reorientation is predominant, even in the early phases of the annealing process, was to be studied with high purity aluminum. by making use of an oxide film and sensitive tint illum-

Jan 1, 1953

By G. H. Kesler, J. E. Oberele, C. E. Dryden, J. H. Oxley

Heat-transfer rates were measured in a model of a multifilament vapor-deposition bulb fo the preparation of high-purzty metals. Local transfer coefficients for heat transfer frow the filaments to the circuates process stream were determined as a functiol of gas flow rates and bulb, inlet, and filament, geowzetvies. These results a-e then convertted to n mass-t7,ansfer basis to provide a method of correlating vapor-deposition rates and to predict the performance of commercial urzits. The firm1 cor?,elating equation for mass transfer was found to be- wheve k, is the mass-transfer coefficient; D, is bze gas difficsivity : P is the system pressure; R is the gas constant; T is the gas temperature; Df, DB, and Di ave tlze diameters of the filament, bulb, and inlet, respectively; k is the gas conductivity; C, is the specific heat of the gas, M is the wzolecular zleight of the gas; Npr . N,,, NRe a7&apos;e the Prandtl, Schmidt, and Reynolds numbem of the system, respectively; LB is the height of the bulb; and SB and Sf are the total suyiace area of the bulb and filaments, respectively. ONE of the more conventional methods of preparing very high-purity metals is the vapor deposition of the metal upon heated filaments. The reactions which can be employed in such a process generally fall into two classes: 1) Pyrolysis of a volatile metal compound. Generally because of their instabilities, metal iodides are used; however, other metal halides and hydrides have been employed. These processes are frequently carried out under vacuum conditions, and the filaments are maintained at high temperatures. 2) Hydrogen reduction of a volatile metal compound. A metal chloride is normally the preferred feed for these processes, but other halides are sometimes used under special conditions. These hydro- gen-reduction processes are usually operated at atmospheric pressure. Many of the current processes for the production of semiconductor materials are actually vapor-deposition processes. However, the vapor-deposition process itself is relatively old, and almost all metals can be prepared in a state of very high purity by the use of vapor-deposition techniques. Loonam has recently given an excellent review of the iodide process for metal deposition,&apos; and Owen has started some detailed studies with a carbonyl system.&apos; A more general treatment of all vapor-deposition processes has been outlined by Powell, Campbell, and Gonser.3 Despite the fact that vapor-deposition techniques have been employed since 1890, there is a surprising lack of fundamental information regarding the transport characteristics of even the simplest deposition system, the heated filament. The purpose of the investigation described in this paper was to extend some of the earlier data obtained at Battelle to predict deposition rates and the uniformity of deposition in large-diameter, multifilament deposition bulbs under forced convection conditions.4&apos;5 A number of other investigators have already presented a simplified treatment of the deposition process under non-flow conditions, i.e., pure diffusion.6"9 To obtain information on the transport characteristics of a deposition bulb, a model of a typical plant deposition unit was constructed, and local heat-transfer coefficients from the filaments to a circulating air stream were determined under various conditions of air-flow rates and bulb, inlet, and filament geometries. These results were then converted to a mass-transfer basis, and consequently provided a method to correlate experimental vapor-deposition rates and to design commercial deposition units. EXPERIMENTAL WORK Description of Model. The apparatus which was used in this work was a scaled model of one type of deposition bulb. It was constructed of Lucite and was easily altered to give several combinations of diameter of bulb liner, inlet size and location, number of filaments, and outlet geometry. The model is shown in Figs. 1 and 2. The bulb shell was made octagonal for convenience in construction and observation, and the bulb liners were cylindrical. Air, introduced through one of several different jet inlets, was used as the test fluid in these model studies. Filaments for deposition of metal were simulated by metal rods 1/4-in. in diam. Two of the rods could be heated by passing electrical current through them ¦ while the remaining rods could not be heated. This procedure minimized the amount of heat which was

Jan 1, 1962

By W. D. Forgeng, R. L. Folkman, D. C. Hilty

The solubility of oxygen in molten Fe-Cr alloys has been determined at 1550° , 1600°, and 1650°C for alloys containing up to alloyshasbeenabout 50 pct Cr and found to decrease as chromium increases to 6 pet and then to increase gradually. Phase relations in the Fe-Cr-0 system at steelmaking temperatures have been evaluated and two previously unreported oxides have been identified. OPERATIONS in the melting and refining of chromium steels are dependent to a major degree on the reactions of chromium and iron with oxygen and are primarily directed toward controlling and modifying these reactions to secure maximum advantage in the utilization of chromium. Although fairly effective practices have been developed empirically, understanding of the specific reactions is limited. Moreover, the ability of molten steel to dissolve oxygen that subsequently precipitates as oxide inclusions during solidification is well known, so that clarification of the effect of chromium on the nature and mechanism of formation of these inclusions is desirable. Study of the problem indicated that increased knowledge of the fundamental Fe-Cr-0 system is essential to further technical and economic improvement. Consequently, an investigation of the influence of chromium on the solubility of oxygen in molten iron and of phases and phase relations in the Fe-Cr-0 system was undertaken at the Metals Research Laboratories of the Electro Metallurgical Co. as part of a general program on the effective utilization of chromium in chromium steel production. Experimental Procedure All of the experimental runs made during this investigation were carried out in the rotating crucible induction furnace which has been described in detail in a previous publication.&apos; In review, the principle underlying this furnace is that rotational forces in the crucible cause the molten metal to assume a concave shape in such a manner that the slag is contained in the molten metal cup, thereby minimizing slag/crucible contact and subsequent reaction. Practically all of the heats were melted in commercial-quality magnesia crucibles of the type usually furnished for laboratory induction furnaces. All of the runs were made under an argon atmosphere after the furnace chamber had been degassed. Bath temperatures were controlled by Pt—Pt-10 pct Rh thermocouples. The basic furnace charge consisted of a premelted 12 to 15 lb electrolytic iron slug which had been cast to a shape convenient for fitting into the rotating furnace crucible. A typical analysis of the electrolytic iron slugs is given in Table I. For certain runs, it was desirable to melt down charges containing high initial chromium contents. In these cases the chromium was added to the electrolytic iron during the premelting operations. Chromium was added to the rotating furnace bath in the form of electrolytic chromium of the analysis given in Table 11. In all of the constant temperature runs, the standard procedure was to melt down the electrolytic iron or alloy slug under vacuum, admit argon to slightly greater than atmospheric pressure, and adjust rotational speed to develop a well formed "cup" on the bath surface. The melt was then saturated with oxygen by an addition of ferric oxide and the temperature of the bath adjusted to within +5°C of the desired level. At this point the heat was permitted to come to equilibrium prior to sampling or further addition. This time interval was varied from 15 min to 2 hr but generally was about 20 min. After sampling, the desired chromium addition was made and the bath again equilibrated prior to subsequent sampling. This cycle of addition and sampling continued for the duration of the run which lasted from 4 to 8 hr. At the end of this period, power was shut off and the bath allowed to solidify in the furnace. Quenched metal samples were taken from the equilibrated melts by means of the "Taylor sampler" which has been described by Taylor and Chipman.&apos; Before being submitted to chemical analysis, all samples were carefully examined for surface slag occlusions and cold shuts. Later in the study, each sample was radiographed and examined metal-lographically in cross-section to determine the presence of internal defects. On the basis of these examinations, sound and apparently clean specimens were selected from the Taylor samples for chemical analysis.

Jan 1, 1956

By E. L. Claridge, K. S. Lee

Areal sweep efficiency of oil displacement by enhanced-viscosity water exhibiting pseudoplastic behavior was measured in a Hele-Shaw model representing one-quarter of a five-spot pattern. The pseudoplasticity of polymer solutions and the velocity distribution in the five-spot pattern produced a condition under which the mobility ratio between the displacing and the displaced fluid could not be assigned a single value. Instead, the movement of the displacement front is governed by local mobility ratios which are also time dependent. The areal sweep at breakthrough with polymer solutions was poorer than the sweep obtained with Newtonian fluids of comparable viscosity. However, the areal sweep at 1 PV throughput was greatly improved as compared to flood water without polymer. It was also demonstrated that, even after the oil-cut had declined to a low value during a regular waterflood, switching to polymer flood efficiently swept out the oil remaining in the model. INTRODUCTION The behavior of fluid displacements in isotropic porous media for various patterns of injection and production wells has been extensively investigated.1-7 These investigations all concerned Newtonian fluids, i.e., the viscosity of each fluid was constant regardless of flow rate. The generally unfavorable influence on areal sweep efficiency of higher mobility of the displacing fluid as compared to the mobility of the displaced fluid has been established for both miscible and immiscible fluids. The principle was also established that a close correspondence exists between miscible and immiscible flood front behavior,2, 3 although oil recovery in a waterflood at unfavorable mobility ratio may be less than that observed in a miscible displacement at the same mobility ratio. This is true even when oil recovery is expressed on the basis of movable oil. The reason is that oil saturation only slowly achieves its final value behind the water-flood front in accordance with the Buckley-Leverett8 simultaneous flow relations. It is convenient to use miscible displacements for laboratory simulation of waterflood frontal advance since the interfacial tension forces which are negligible in proportion to viscous forces on a reservoir scale9 are thus made nonoperative in the laboratory model. For miscible displacements, the Hele-Shaw type of model adequately represents a porous medium so long as the appropriate scaling rules5-10 are observed in its design and operation. During simulation of waterflood front behavior in the laboratory by using miscible displacements, the behavior of connate water may ordinarily be disregarded since it is usually indistinguishable from flood water in this process. However, when the flood water is deliberately thickened to improve the mobility ratio between water and oil. the effect on the sweep efficiency due to generation of a connate water bank during the process must be considered. In a uniform porous medium, such a bank is generated11 and efficiently displaced by injection of thickened water.l2 The oil originally in-place at the start of the waterflood is then displaced by connate water followed by thickened water. If the flood water must be thickened to obtain a favorable mobility ratio, the mobility of the oil phase is appreciably less than that of the connate water. Hence, the oil phase is inefficiently displaced by the connate water bank, and a considerable proportion of the oil comes in contact with and is displaced by the thickened waterflood front&apos; A recent study 12 of five-spot displacements using miscible Newtonian fluids in which connate water banks of various sizes were simulated shows that, for connate water banks as large as 40 percent of 1 PV, major improvements in sweep efficiency resulted from use of a thickened

Jan 1, 1969

By C. S. Matthews, P. Hazebroek, H. Rainbow

It ha been suggested that lormation fractures created by well stimulation treatments will adversely affect sweep-out efficrency in injection operations. Fluid-flow model studies involving vertical fractures of various lengths and fluid systems of various mobility ratios have been carried out to study this subject. In addition, limited data have been obtained on one model containing a horizontal fracture. It was found that relatively long and highly conductive fractures (not generally obtained fracturing operations) were required to affect the sweep-out efficiency substantially. In a given case in the field an approximate distinction can be made between the presence of long conductive fractures and shorter or less conductive ones. This is done with pressure build-up analyses along with data on the relationship of fracture length and conductivity to well productivity. This type analysis shows that usually the fractures induced are either short or of limited conductivity and therefore do not damage sweep-out efficiency. INTRODUCTION Improved well productivity and in-jectivity can frequently be exploited in injection operations. Higher total throughput can yield improved economics. On occasion, the achievement of an increased productivity or injectivity in specific wells can bring about a more uniform sweep of the reservoir. Higher rates can be exploited particularly in water floods of "depleted" reservoirs where a rapid "fill-up" is desired and where low pressures contribute to low well productivity. The creation of fractures local to the wellbore is an excellent means for achieving these objectives. Even though fracturing has been employed in some floods with success,1"3 there still seems to be some reluctance to employ this tool for fear of undue damage to the flood pattern and ultimate recovery. We therefore need to examine the influence which fractures of varying length may have on flood performance and then determine the length of fractures which obtain in the field with conventional fracture treatments. A substantial influence of fractures on the recovery obtained at breakthrough of the injected fluid has been presented by Crawford and Collins for equal fluid mobilities for the line-drive pattern.4,5 In addition, the influence which a fracture has on the production performance after breakthrough and on the ultimate recovery warrants consideration in reaching a conclusion concerning the use of induced fractures in flooding operations. This report presents this type of data for the five-spot injection pattern for several fluid mobilities. In arriving at some conclusion concerning the fracture lengths obtained in field operations we must examine the performance characteristic most affected by the fracture. This is the change in the flow system as reflected in the change in productivity and pressure build-up behavior. A study of these changes is also presented in this report. RESERVOIR ANALOGS The X-ray shadowgraph technique, employing miscible displacement in porous models, has been used in the study of the influence of fractures on pattern sweep-out efficiency. The X-ray shadowgraph procedure is described in detail in an earlier report8. Fractures were represented by leaving the proper portion of the model surface exposed to either injection or production. This assumes the fracture resistance to be negligible compared to that of the formation. Actually the flow resistance in propped fractures obtained in the field is sometimes not negligible so that the results with this model indicate the maximum influence of the fracture. Two types of models were necessary to represent vertical fractures in a five-spot flood. These pattern elements are illustrated in Fig. 1. In studying the influence of the horizontal fracture, only one well spacing length to thickness ratio of 50 was used. The pool unit of a Carter Electric Analyzer was used in studying the influence of fractures on productivity and build-up behavior. The square drainage system of a well was represented by a network of 576 elements of equal volume and resistance. One-fourth of this drainage area was studied as a model unit using a network of 144 condensers and resistors. Vertical fractures were represented by a shunt directed from the well perpendicular to the drainage boundary. Horizontal fractures were represented by a circular shunt. Resistance of a shunt was varied in representing different conductivities for the fractures. FRACTURE DIRECTION AND LENGTH The direction at which a vertical fracture extends into the formation and its length and conductivity influence the sweep behavior. The two

By Robert H. Richards

The extent to which sizing by sieves should be carried, as a preliminary to the separation, by jigging, of minerals of different specific gravities, has been a matter of controversy for many years. The subject has been investigated by several authorities, yet the ground does not seem to have been completely covered, nor are the questions involved entirely settled. For my present purpose I shall refer to but three investigators—Rittinger, Munroe, and Hoppe. In seeking additional light, I have gone over part of the old ground which has been considered satisfactorily settled; and since these preliminary tests have thrown light on some points, they have been included in this paper. In the investigations here described, I have confined myself, for several reasons, wholly to small sizes—grains of 0.1 inch in diameter and less. Rittinger&apos;s work was mainly done upon larger sizes, and there is much need among millmen of information concerning the smaller sizes. Moreover, these sizes brought the investigation within the means at my disposal. The laws that have been claimed as the laws of jigging by the several authorities are: 1. The law of equal-settling particles. 2. The lam of interstitial currents. 3. The law of acceleration. 4. The law of suction. The first of these has been considered by investigators, generally, to be the most important of all, and the larger part of the work of jigging is thought to be governed by it. But that it does not cover the whole of jigging is clear to all; and to account for the increased efficiency which we may call the extra jigging-catch, the other three laws have been advanced. The investigation described in this paper was undertaken to determine, as far as possible, to what extent each of the four laws con-

Jan 1, 1895

By L. C. Graton

THE Federal taxes on incomes and excess profits are of course heavy. In 1917, the value of the mineral production of the United States was a little in excess of $5,000,000,000. The total of Federal taxes for that year, for the mineral producing companies, as computed by themselves, amounts, according to tentative compilations, to about $207,000,000, and the total for the comprehensive group of mineral and metal indus-tries to about $766,000,000, which figures represent respectively 9.5 per cent. and 35.1 per cent. of the total tax paid by all corporations. Be-cause of greater complexities in applying the revenue laws to mineral properties than to most other industries, opportunity is afforded for wide differences of view. The taxes indicated above, therefore, are not final

Jan 11, 1919

By D. L. Albright, R. W. Kraft

High-purity materials have been used in producing as-cast, controlled, colony, and degenerate solidification structures in the Fe-FeS eutectic. Experiments disclosed that this eutectic can be classified as normal and has a natural morphology composed of rodlike iron particles dispersed in a matrix of iron sulfide. The metallography of the various structures was studied, and a preferred crystallography was revealed in the controlled specimens produced by unidirectional solidification. The orientation effects found in these latter specimens are an [001] fiber texture in the -mowth direction of the bcc iron bhase and a texture corresponding to bicrystalline behavior in the hexagonal iron sulfide, with the growth direction near to (2111) poles. The observed texture of the iron phase is considered as indirect evidence that the alloy un-dercooled by at least 75°C before solidification. The unidirectional solidification of binary eutectic alloys has produced materials which exhibit a structure and properties markedly dependent upon the solidification process. In many cases a controlled microstructure with pronounced metallographic and crystallographic anisotropy can be experimentally achieved by proper regulation and balance of the growth rate of the alloy, the chemical purity of the starting materials, and the thermal gradient in the liquid at the liquid-solid interface. The purposes of this investigation were to produce various micro-structures in the Fe-FeS eutectic for subsequent study of their magnetic properties and to correlate the different structures with the solidification conditions in order to obtain a better understanding of the structure of eutectics. The Fe-S equilibrium diagram exhibits a eutectic composed of nearly pure iron and stoichiometric iron sulfide (FeS1.00), with the eutectic reaction occurring at 988°C and 31.0 wt pct S.1 Calculations indicate that this eutectic should solidify with about 9.5 vol pct Fe and 90.5 vol pct FeS, which in turn suggests2 that the micros tructure will consist of a rodlike iron constituent dispersed in a matrix of FeS. This characteristic has in fact been revealed some years ago.3 Thus, controlled solidification of this alloy might yield a material whose micromorphology would consist of very small ferromagnetic iron particles, rod-like in shape and aligned parallel to one another, supported in a matrix of antiferromagnetic FeS. Such specimens, because of the magnetic characteristics of the two phases, would be interesting subjects of study as magnetic materials. Hence the magnetic properties were considered in detail and are reported elsewhere.4 EXPERIMENTAL PROCEDURE The specimens of Fe-FeS eutectic were prepared from ultrapure iron (99.99+ pct) and high-purity sulfur (99.999+ pct). The iron was estimated to contain 60 ppm impurities (99.994 pct Fe) after zone purification.5 The ingots of iron were cut into chips, and the lumps of sulfur were ground into powder. In order to redice any nometallic impurities which might have accumulated during handling, the iron chips were annealed for 5 hr at 750° ± 10°C in a dry hydrogen atmosphere. Immediately after this treatment the chips were blended with the sulfur powder in eutectic proportions; the mixture was tamped into transparent fused quartz tubing and then vacuum-encapsulated under a pressure of 40 to 60µ of Hg. Because FeS expands upon solidification it was necessary to re-encapsulate the initial capsules so that oxidation reactions would be avoided when the inner tube cracked during solidification. For purposes of homogenizing the blended mixtures before solidification, the double capsules were heated to 750° ± 20°C and held for 20 hr; after this treatment the reacted product was weakly agglomerated. Each sample was then loaded into an apparatus for very rapid melting and freezing; this was accomplished by passing a molten zone through the specimen, using induction heating and a traverse mechanism. The resulting specimens solidified in the shape of the quartz tubing. Two sizes of specimens were used in this work, 18 mm diam by 100 mm long and 5 mm diam by 30 mm long. Metallographic examination of several ingots of both sizes after the above consolidation indicated no lack of compositional homogeneity and a random "as-cast" structure, because the travel rate was so rapid that unidirectional solidification was not achieved. Unidirectionally solidified specimens were resolidified in the apparatus shown schematically in Fig. 1, This equipment consisted of a kanthal resistance furnace mounted on the carriage of a zone-melting unit so that the heating element could traverse the length of the sample at a selected rate of speed. Large specimens were solidified with the mechanism tilted at ap-

Jan 1, 1967