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By Clarence Zener

THE internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites,4,5 localized weak regions introduced by cold-working,6,7 grain boundaries and possibly twinning planes.8.9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, 3-s in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff.10 EXPERIMENTAL METHOD The experimental method used has previously been described in Institute papers.5,6.9 The measure of internal friction adopted here, I/Q, is (p) X the logarithmic decrement, a measure used by some writers, and is also (I/2p) X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the fundamental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. EXPERIMENTAL RESULTS The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°°C. As shown in Fig. i, the internal friction increased by only a factor of 2 from room temperature to 300°°C., then by a factor of 100 during the next :too' interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction ~ e-HI/RT [I]

Jan 1, 1942

By B. W. Levinger

THE lattice parameter of the ß form of pure titanium has been measured at elevated temperature.', ' No attempt was made, however, to correct the parameter obtained to room temperature. In the course of phase diagram studies at Armour Research Foundation and elsewhere, the variation of ß-phase lattice parameter with composition has been established in a number of binary and ternary systems involving titanium. It was possible to extrapolate in these instances to 100 pct Ti to find the apparent lattice parameter of ß titanium at room temperature. Table I lists the results thus obtained. The suggested value for the lattice parameter of ß titanium is the average of the extrapolated values 3.276 ±0.003 kX. This suggested value gives an interatomic distance in ± titanium of 2.837 kX and hence a Goldschmidt atomic diameter (coordination number 12) of 2.925 kX. The latter agrees closely with the value of 2.93 given by Hume-Rothery." From the data of Adenstedt and coworkers' it was possible to determine by extrapolation the mean coefficient of linear expansion for /3 titanium in the range from room temperature to 1000°C. This value, 10.1x10-8 per degree C, compares with about 11x10-8 for a titanium in a similar range." It was thus possible to calculate the parameter at 900 °C. The value of 3.305 kX agrees well with 3.3065 given by Eppel-sheimer.' The majority of values reported in the literature7-', ' were given as Angstroms. In at least one case, ref. 8, it was shown that they actually represented kX units. The source of this confusion appears to be that a large number of tables of X-ray emission spectra list wavelengths as Angstroms and give values in kX units. The accepted conversion factor for kX units to Angstroms (10.' cm) is 1.00202. Thus the parameter of ß titanium suggested corresponds to 3.282A. References J. H. de Boer, W. G. Burgers, and J. D. Fast: Proc. Acad. Amsterdam (1936) 39, p. 515. 2D. S. Eppelsheimer and R. R. Penman: Nature (Dec. 2, 1950) 166, p. 960. 3 W. Hume-Rothery: The Structure of Metals and Alloys (1945) London. Inst. Metals. 4 H. K. Adenstedt, J. R. Pequignot, and J. M. Raymer: Trans. ASM (1952) 44, p. 990. 5 Gmelins Handbuch der Anorganischen Chemie. Titan, Verlag Chemie, Weinhein (1951). 8 P. Pietrokowsky and P. Duwez: Trans. AIME (1952) 194, p. 627; Journal of Metals (June 1952). 7 P. Duwez and J. L. Taylor: Trans. ASM (1952) 44. D. 495. 8 M. Hansen, E. L. Kamen, H. D. Kessler, and D. J. McPherson: Trans. AIME (1951) 191, p, 881; Journal of Metals (October 1951). 8 Unpublished Research, Armour Research Foundation.

Jan 1, 1954

By R. G. Treuting, W. C. Ellis

The twinned state is characterized by a lattice of coincidence sites. Imperfections are required at stable lateral twin interfaces. Twinned regions can occur with relative ease in the diamond cubic IN recent contributions1,2 on the origin and growth of cubic annealing twins, attention has been directed to the orientation relations between such twinned components and their parent matrix. There are some aspects of twinning which may be illuminated by a more detailed consideration of the twinned state" alone. As an extreme example, the dense twinning in cast ingots of germanium,&apos; as contrasted with the rarity of twins in cast face-centered cubic metals, is yet to be accounted for. It has been this that has led us to the present work, which, it will be noted, uses methods and constructions in many respects similar to those of Kronberg and Wilson.&apos; In the cubic systems, a 70" 32&apos; rotation about a <110> axis is angularly equivalent, as to twinning, to the more usually considered 180" rotation about a <111> axis. Figs. 1 and 2 show a (110) projection of a twinned face-centered cubic lattice and a twinned diamond cubic lattice. In both figures, the two adjacent planes A and B, shown by the larger and smaller circles, are sufficient to represent the entire array. In each case a section of lattice, the original atom sites of which are shown by open circles, has been rotated as indicated through 70" 32&apos; to bring an original. [112] direction into coincidence with the [112] diiection. The latter is the intercept on the (110) projection of the (ill) plane normal thereto, the twinning plane. In the face-centered cubic case the rotation can be performed about an axis passing through an atom-site; the mirror plane then is also a composition plane containing atoms common to both twinned and untwinned lattices. The diamond cubic lattice may be construed as two interpenetrated face-centered lattices. Its (111) planes recur in a sequence of alternately short and long interspacings. Consequently a mirror plane for twinning cannot be a composition plane, but must be the bisector of one of the spacings. When the longer spacing is selected, the closest distance of approach across the mirror plane in the [ill] direc- tion is identical with that in the untwinned structure. In each case periodically recurring (ill) planes (parallel with the twinning plane) are found, on which there is coincidence of atom sites of the pre-twinned and twinned orientations; these are indicated by the cross-hatched circles. In the face-centered lattice there is such coincidence every third (ill) plane; in the diamond cubic lattice, on two adjacent planes in every six. At the twinning interface in the latter, there is on each side of the mirror plane a (ill) plane of atoms common to both twin components. Conceivably, there is little influence on a plane of atoms about to be adhered to such a pair of coincidence planes, whether it be laid down in a normal or in a twinned position with respect to the previously formed structure. Slawson% as attributed the high incidence of twinning in diamond to this boundary state. Further examination shows that the motion of intermediate planes can consist of various pairs of equal and opposite translations, for example of (ill) planes in the [l&apos;;i2) direction, the familiar twinning shear, indicated in the small schematics in the figures. Since the translations form a system of shears of alternating sign between coincidence planes, twinning could take place by such a mechanism over an extended region without extensive shear; in fact, in this case any atom moves but the distance in the [1i2] direction. One alternative construction for the face-centered cubic lattice leading to the same end result is illustrated in Fig. 3. The plane (711) with respect to the pretwinning orientation (the twinning plane of Fig. 1) is given, the twinned region arbitrarily bounded by <110> and <112> directions. The coupled shear is identical to that of Fig. 1. The "rotational" movement about coincidence sites generating the same twinned position could consist as shown of the translation a,/d% for each atom of a group of three in the B layer in a different one of the three <112> directions, and a similar translation of the underlying three atoms in the C layer in either the same or the opposite sense. This is not dissimilar to Kronberg and Wilson&apos;s construction for their 22" rotation of three adjacent (111) planes.

Jan 1, 1952

By F. R. Hensel

Up to the present time few attempts have been made to produce hard nonmagnetic materials by heat treatment of austenitic steels. The usual result has been to cause them to pass into the martensitic stage, thus destroying to a great extent the typical austenitic properties, since this involves a transition of a portion of the iron from a face-centered to a body-centered type of atomic arrangement. High-strength nonmagnetic materials such as might be provided by properly hardening austenite are required in the electrical industry for different machine parts. In Europe nonmagnetic retainer rings for restraining the end-turns of the rotor windings in turbo-alternators have been developed as a special application of high-strength austenite. In testing1 a 28,000-kva. three-phase Siemens turbo generator running at 3000 r.p.m. at full load current, the losses in the short-circuit test were 450 kw. for the magnetic ring and 286 kw. for the nonmagnetic, and the difference should be attributable to the magnetic ring. The differences in temperatures during the same test are given in Table 1 and these show the advantage of a nonmagnetic over a magnetic retainer ring.

Jan 1, 1931

By F. Weinberg

Lead single crystals have been deformed in tension over the temperature range of 4.2°K to the melting point. Changes in flow stress resulting from temperature cycling and strain rate cycling have been measured as a function of temperature for crystals of different orientations and purity. It was found that the flow stress ratio, after correcting for the temperature dependence of the shear modulus, decreased progressively with temperature above approximately 0.5Tm. The activation energy calculated from the high-temperature portion of the curve was found to be markedly higher than that of self-diffusion. For single glide crystals, the corrected flow stress showed an increase above 0.5 Tm before decreasitzg with temperature. This increase is attributed to static recovery occurrittg during temperature cycling. THE temperature dependence of the flow stress, based on temperature cycling and strain rate cycling, has been extensively investigated,&apos; and on the basis of these results dislocation models of the work-hardening process have been proposed. In general, the flow stress is divided into two parts, ts, the short-range interaction term, which is only effective at low temperatures and which decreases with increasing temperature, and TG, the long-range stress term, which is independent of temperature after allowing for the temperature dependence of the shear modulus. The observations demonstrating that tG/µ is independent of temperature were generally carried out at low temperatures to minimize recovery effects. Several investigations have been reported on flow stress measurements at high temperatures2"5 which demonstrate that TG/µ does not remain constant at temperatures above 0.5Tm (where Tm is the melting temperature of the material in OK). Specifically, Hirsch and warrington3 carried out temperature cycling tests at two strain rates on single and polycrystalline aluminum up to 0.8 Tm and on polycrystalline copper. For aluminum they found that the flow stress ratio (the flow stress at temperature T2, divided by the flow stress at the reference temperature T1 in one temperature cycle) dropped progressively with increasing temperature above 0.5Tm. From the slopes of the high-temperature portions of the curves, they determined an activation energy for the deformation process of 1.6 ev (at best) which they considered was in agreement with the activation energy of self-diffusion, 1.35 ev. Calculations of the activation volume demonstrated that the deformation was not controlled by dislocation climb. They proposed a mechanism in which the rate-controlling process at high temperatures was due to the rate of move- ment of vacancies away from jogs, i.e., that of self-diffusion. Results of Lucke and Buhler4 on single crystals of aluminum confirmed this conclusion. They measured the critical resolved shear stress of aluminum over a wide range of temperature and strain rates. They found that the temperature dependence of the critical resolved shear stress was similar to that of the flow stress ratio, as determined by Hirsch and Warrington, and from their data calculated an activation energy for high-temperature deformation of 1.35 ev identical to that of self-diffusion. More recently Gallagher5 has carried out a detailed investigation of the temperature dependence of the flow stress ratio of copper, silver, and gold. In all cases, he found that the flow stress ratio, after adjusting for the shear modulus temperature change, drops at high temperatures. The activation energies he determined were found to be appreciably higher than the activation energy of self-diffusion of the material being considered. The flow stress ratio was found to be dependent on the orientation of the material, and, in addition, an anomalous increase in the flow stress ratio for copper, oriented for single glide, was observed above 0.5Tm. The purpose of the present investigation was to measure the critical resolved shear stress, the flow stress ratio, and the strain rate sensitivity of lead, primarily as a function of temperature. The results should indicate whether, following Lucke and Buhler, the critical resolved shear stress of lead has the same temperature dependence as the flow stress, and, following Hirsch and Warrington, whether the activation energy for high-temperature deformation in lead is the same as that of self-diffusion. Lead deforms as a normal fee material,6&apos;7 is available in high-purity form, can readily be grown as single crystals, and, for this investigation, has the very considerable advantage of having a low melting point, 327°C. The observations of the critical resolved shear stress of lead have been published elsewhere.&apos; EXPERIMENTAL PROCEDURE The experimental procedure was essentially the same as that used in the critical resolved shear stress measurements.&apos; Single crystals of 99.999 pct (59) and 99.9999 pct (69) lead were deformed in tension with a table-model Instron in a silicone oil bath above room temperatures and in a cooled methyl alcohol or liquid-nitrogen bath below room temperatures. The test specimens were rectangular in section, 0.65 by 0.33 cm, and had a 5-cm gage length. The specimens were grown as single crystals with tapered ends, which fitted into matched tapered grips for testing. To obtain the flow stress between two temperatures, specimens were first deformed approximately 1.0 pct at the higher temperature. The test was then stopped, the load relaxed, the oil bath removed without disturbing the specimen, the grips and specimen cooled with a fan and then immersed in liquid nitro-

Jan 1, 1969

By F. G. Smith

A few years ago, the writer encountered a problem that, at first, seemed to be due to peculiar conditions affecting grain growth. Large cups made from heavy metal failed in the first drawing operation in the process of making seamless tubes. The metal, as cast, appeared to be sound and strong; it rolled successfully and withstood the first cupping operation, but on the first draw it failed, with a crystalline fracture. The failure appeared in the slightly worked part of the bottom of the cup, and microscopic examination revealed exceptionally large grains. Knowing the general conditions governing recrystallization of brass, which were later published by Mathewson and Phillipsll an investigation was outlined with the idea of including various conditions under which new grains might form, and which would include the effect that a previous anneal might have upon the anneal following. These conditions were produced by annealing specimens of brass at five different temperatures, indenting them with a 10-mm. ball under four different pressures, and then reannealing at each of the five temperatures five specimens each of which had been annealed at one of the five temperatures. Preparation of Specimens The material used was cartridge brass 0.400 in. thick, having the following composition: Copper 66.60 per. cent., zinc 33.35 per cent., lead 0.02 per cent., iron 0.03 per cent. This was rolled with 35 per cent. reduction after a 700" C. anneal. Fig. 1 shows the structure of this original bar on which all subsequent anneals were made. Pieces 1 in. (2.5 cm.) wide and 3 in. long were prepared and annealed for 1/2 hr. at 450°, 550°, 650°, &apos;750°, and 850" C. Each of these pieces are indented under the Brinell test with a 10-mm. ball at 500, 1000, 2000, and 3000 kg. pressure. Then, sets of five pieces from each of the original anneals were reannealed at 450°, 550°, 650°, 750°, and 850" C.

Jan 1, 1921

By C. H. Mathewson, E. M. Thalheimer

In planning the present experiments, we have made a particular effort to secure that adjustment of working conditions which would render the forthcoming tests most serviceable by way of indicating the comparative properties of the three different commercial grades of copper used. More specifically, we have endeavored to obtain certain definite information with respect to the relative behavior under test of ordinary electrolytic copper and furnace-refined lake copper containing (a) a moderate percentage of arsenic and (b) a rather large percentage of arsenic, in addition to the usual content of silver and other impurities. These comparisons were made systematic and comprehensive by testing throughout a series of (eight) reductions running from 0 to 70 per cent. in the case of cold-rolled metal, and throughout a series of (15) temperatures running from 100&apos; C. to 1,000" C. in the case of annealed metal. In other words, a survey of properties similar to that made by Grard,&apos; in the case of electrolytic copper, was here repeated (with modifications) and extended to two other commercial varieties of copper. The great importance of copper both as a material of construction and as the base of our most important alloys (aside from steel) has led to innumerable investigations of its properties, particularly in commercial forms. Naturally, the merits of furnace-refined lake coppers us. those of the very pure electrolytic product have furnished the subject of much experimental work and animated discussion, wherein the effect of arsenic has by no means been overlooked. In the literature of the past 10 years,

Jan 1, 1917

By G. F. Comstock

The subject of transverse fissures in steel rails has been discussed very thoroughly in recent years from various points of view and the final opinions expressed may be roughly classified into two groups: That these fissures are the result merely of fatigue of the steel and are independent of the quality of the metal. That the quality of the metal and the mill practice must have something to do with them. The first point of view was most ably and logically presented by J. E. Howard,&apos; and in the discussion of this paper, as well as in several other preceding publications, Dr. P. H. Dudley, Consulting Engineer of the New York Central Lines, has strongly defended the other opinion.2 The steel makers of the country have naturally rallied under Mr. Howard&apos;s banner, hoping to place the entire blame for these failures upon the railroads with their high wheel-loads, hard steel, heavy traffic, and sometimes inferior road-bed; while the railroad men, on the other hand, have been busy accumulating statistics and records in the effort to find an actual reason in the rails themselves that would account for the seemingly haphazard occurrence of transverse fissures under varying conditions and at widely separated points. The view that these fissures were due merely to normal fatigue under alternating stresses seemed most reasonable to the writer until quite recently, because from work done in this laboratory, as well as the work of other investigators, of the problem, no structural differences, in the vast majority of cases, were found between metal at the nuclei of transverse fissures and metal at similar positions in the same rails or in other rails that had not developed fissures. Within the last year or two, however, since the method of etching polished sections for the microscope with a oupric chloride solution has been tried systematically on lengthwise sections, passing through the nuclei of transverse fissures, evidence

Jan 1, 1920

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.&apos;-&apos; Komatsu and rant&apos; in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov&apos;s analysis12 of the distribution of spheres of varying size. DeHoff&apos;s analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965

By S. Shapiro, J. A. Ford

The crystallo graphy of several grains of the lamellar Ni-Ni3 B eutectic solidified under conditions appvoachirt equilibriun has been examined.. A preferred interlace relationship has been observed in this system which may be described as: A detailed study of this interface by means of an atomistic model reveals the interface Plane to be puckered and more accurately describable as: Analysis of the atomic configuration on these planes reveals that this interface conforms to the orientation criteria proposed for directionally solidified lanzellar eutectics. In addition, a model is proposed to help explain the growth of a "puckered" interface. DURING the past several years an increasing number of unidirectional solidification experiments on eutectic alloys have been reported in the literature. The primary emphasis, in most cases, has been the effect of growth variables on microstructure. Some authors have, however, studied the crystallographic orientations and interfacial relationships resulting from these experiments. Four crystallographic studies have been published;&apos;-4 in each of these there is a factor which tends to prohibit the extension of the observations beyond the particular system. In the Al-CuA12 system, the approximately equal volume fractions of the phases have resulted in sorrie controversy as to which phase constitutes the matrix. In the Mg-Mg,Sn eutectic the presence of several interconnecting lamellar systems2 complicates the analysis. The two remaining eutectics. 1nSb-b and Al-Ali, are both rodlike (the latter exhibits a plate morphology at low solidification rates): the matrix in each of these alloys is the simpler (fcc) phase. Studies of nucleation in eutectic alloys indicate that the more complex constituent is the nucleating -.phase.&apos; For the purpose of an analysis of interface crystallography it was deemed desirable to study a lamellar system in which the matrix was the more complex and, presumably. the nucleating phase. Recently it has been shown that there is a eutectic in the Ni-B system between Ni3B and i; preliminary investigation by the authors indicated that the matrix in this eutectic is the boride phase. The structure of Ni,B is reported to be orthorhombic, the compound being isostructural with cementite. This eutectic is therefore analogous to that between austenite and cementite. Furthermore, the Ni-B system is not susceptible to a competing eutectic reaction as occurs in the Fe-C alloys; nor does it exhibit a eutectoid decomposition. For these reasons the study of the interfacial relationship in the Ni-Ni3B eutectic was undertaken. PROCEDURE Ingots of nominal composition 3.5 and 3.6 wt pct B were induction-melted in boron nitride crucibles within a graphite susceptor under a boric oxide slag; a dynamic argon atmosphere was maintained over the melt to prevent rapid oxidation of the susceptor. The raw materials used were 99.97 pct Ni from Huntington Metals Division of International Nickel Co. and 99.8+ pct B chips supplied by the United Mineral and Chemical Co. The analyses of the starting materials are listed in Table I. The melt was held at 1500cC for 2 hr to insure complete reaction and allowed to cool to room temperature. The castings were chemically analyzed for boron and were metallographically examined for uniformity. The metallographic samples were mechanically polished through 0.1 p A1,0, and etched with Carapella&apos;s reagent. Each master casting was cut up to make several specimen blanks which were remelted, in boron nitride crucibles, to form ingots of 1/2 to 3/4 in. in diarn by 7 in. long. These ingots were unidirectionally solidified using a modified vertical Bridgman technique. The rate of solidification was assumed to be equal to the uniform rate at which the crucible-susceptor assembly was withdrawn from the induction coil. This rate was varied from 1.18 to 2.21 cm per hr. In order to perform these experiments it was found necessary to redetermine the eutectic composition. This was accomplished by the zone-melting technique described by Yue and lark.&apos; An ingot of 4.5 wt pct B was zone-melted in a horizontal boron nitride boat 7-1/2 in. long with a 112-in.-square cross section. A

Jan 1, 1967

By P. R. Celmer, Leonard R. Weisberg

THE principle of fractional crystallization has been successfully used to prepare high-purity (99.999 pct) Ga. Hoffman and Scribnerl removed single crystals of gallium solidifying in a gallium melt, while Zimmerman2 grew single crystals from the melt by the Kyropolous technique. In contrast, attempts at purifying gallium by zone refining have been less successful. ichards, reported that despite the passage of 40 zones through a gallium ingot, there still remained 5 to 70 ppm each of Cu, Fe, Ca, Mg, Si, Al, and Ag. Previously, Detwiler and Fox4 detected only one impurity, Pb, segregating in zone-refined ingots. These surprising results prompted an investigation of the factors controlling impurity segregation in gallium. Possible reasons for this were insufficient diffusion of impurities in the melt; recontamination of the melt by its oxide film which is not affected by the passage of the zone; reaction of gallium with the boat; sudden freezing of gallium following supercooling, especially since gallium easily supercools to and trapping of impurities at grain boundaries. Impurity segregation tests were carried out by directionally freezing gallium using the Bridgman rnethd, modified in that the molten gallium is lowered out of a furnace into a slush of dry ice and trichloroethylene, thus minimizing supercooling. Since the gallium is contained vertically, the oxide film is in contact only with the tail end of the melt. It was found that Teflon makes an excellent crucible for gallium since it is quite pure, non-reactive, translucent, flexible, machinable, and is not wet by gallium. The gallium crystals could be grown at various speeds, and the melt could be vigorously stirred by a Teflon rod moving through the gallium in a vertical reciprocating fashion. Single crystals could be grown by placing a solid Teflon plug at the bottom of the melt drilled out in such a way to cause the solidifying gallium to follow a winding path. Thus, even if many crystals are originally nucleated, only one grain will predominate. The grain structure of the gallium crystals was revealed by an etchant composed of equal volumes of HC1, HNO3 and HF, diluted with water to half strength. Emission spectrographic analyses were carried out on samples removed from the front and tail ends of the resulting gallium ingots. Typical results of this study are summarized in Table I. The rate of freezing in all three cases was about 1 in. per hr. It can be seen that even though stirring of the melt does help, it is even more important to grow a single crystal of Ga in order to obtain good segregation of impurities. The effect of crys-tallinity on the segregation of impurities was previously observed6 in the directional freezing of germanium; however, in this case, the effect was much less pronounced. This dependence of impurity segregation on the crystalline perfection of Ga may be related to its thermal conductivity which is the most anisotropic of all metals.7 The anisotropic thermal conductivity can cause the solid-liquid interface to be nonuniform, thus leading to trapping of impurities during freeing, and therefore reduced segregation. In conclusion, it is indicated that zone refining of gallium would be more successful if seeding and similar precautions are taken to insure single crystal growth. The authors are indebted to Mr. H. H. Whitaker for the spectrographic analyses and to Drs. B. Abeles and F. D. Rosi for helpful advice and encouragement throughout the course of this work. This research was supported by the Electronics Research Directorate, Air Research and Development Command, under Contract No. AF33(616)-5029. REFERENCES &apos;J. 1. IToffmon and B. T. Scribrer: I. Research h&apos;atl. Bur. Standards, 1935, "01. 15, p. 205. &apos;W. Zirnmerman: Science, 1954, vol. 119, p. 41. %J. L. Richards: Nature, 1956, vol. 117, p. 182. &apos;D. P. Detwiler and W. M. Fox: I. Metals, 1955, "01. 7, p. 205. 5P. W. Bridgman, Proc. Am. ilcod. Sci., 1925, vul. 60, pp. 305,385,423. "S. L1. Christian: private c ommuni cation. &apos;K. W. Powell: roy. Sac., 1951, vol. 209, p. 525. &apos;W. G. Pfann: Zone Re fining, p. 20. John Wiley and Sons, Inc., New York, L058.

Jan 1, 1962

Jan 1, 1967

By Patricia J. Rand, Kailish Narayan

Atlantic Richfield Co. began operating a commercial uranium solution mining project in April 1975, in Live Oak County, Tex., 10 miles southwest of the town of George West. The operation is designed to produce 250,00 lb of U308 per year and is jointly owned by Atlantic Richfield Co., Dalco, and U.S. Steel. The proprietary process employed in this operation consists of injecting an alkaline leaching solution into the ore-bearing formation through a pattern of injection wells. The uranium-bearing solution is then removed through producing wells using submersible pumps in central production wells. The produced solution is pumped through a pipeline to the plant area where the uranium is extracted. The barren solution is refurbished and returned to the pattern area for reinjection. The injection field and plant site are located in the drainage of Spring Creek, a small intermittent stream tributary to the Nueces River. Land use in the area is primarily agricultural cattle ranching and farming---but several producing gas fields are present in the areas as well. A nine month enviromental baseline study was conducted on the property beginning in Feb. 1975. Plants and animals of the Clay West area were identified and representative terrestrial and aquatic communities were analyzed. Physical and chemical parameters of the soils were described and analyzed. The surface and underground waters were analyzed chemically; radionuclides, heavy metals, nutrients, and pesticide concentrations were measured in the creek sediments; bacteriological measurements were made in creek water and sediments; radionuclide and chemical levels in plants and animals, both terrestial and aquatic, were measured. These studies, though not required by existing, state or federal laws, were considered necessary to assess the existing conditions before operations began on site. The in-place leaching technique for uranium mining eliminates the enviromental disturbances associated with open pit or underground mining. No grinding and crushing of ore is needed, nor are large tonnages of waste tailings produced. Surface subsidence is not expected since less than 5 lb of uranium is present per ton of rock and even complete removal of such small amounts should not cause subsidence. Solution mining has fewer environmental problems than conventional mining. Members of the Texas Water Quality Board recognized the differences which exist and have recently formulated new environmental control procedures which apply specifically to solution mining. Some of the solution mining activities which are of particular concern are discussed in the following pages. Process Description The produced uranium-bearing solution is pumped through a pipeline from the pattern area to the plant area. The first pattern area consists of a nest of 125 fluid injection, production, and monitor wells [(Fig. 1)]. Injection wells have 4-in. casings and are spaced 50 ft apart on a square grid. Production wells have a 6-in. casing and are located in the center of each square. A block flow sheet of the plant is given in [Fig. 2]. The produced solution goes through parallel trains, each consisting of a carbon column and an ion exchange column in series. The carbon column removes any sand present in the produced solution and the ion exchange column extracts the uranium. The depleted solution is treated with chemicals and returned to the field for reinjection. The uranium retained in the ion exchange column is removed periodically with a sodium chloride solution. Uranium-bearing solution from the ion exchange column is passed through a charcoal column for removal of impurities and then to a precipitation tank where the uranium is precipitated as yellowcake slurry. The yellowcake slurry is clarified, filtered and dried to produce a granular yellowcake product. Environmental Considerations Sources of waste solutions to storage reservoirs, the backwash reservoir and atmospheric discharges are shown in the block flow sheet [(Fig. 2)]. These waste solutions pose a relatively small problem and are adequately controlled by conventional means. There is one area, however,

Jan 1, 1978

By Frederick T. Williams

THE purpose of this paper is to discuss the relative merits of the large 31/8 in. machine and the small 21/4-in. tappett machine in driving development-headings ; and although the . data here presented were obtained from cross-cut headings alone, experience has shown that the results are equally true in drifting, raising and winning. Recently we drove two parallel cross-cuts through the same formation, using a 3k-in. machine at the breast of one cross-cut., and a 2k-in. machine of the same make at the breast of the other. The results of this work afforded an ideal comparison, since in both cases the headings were advanced through rock practically of the same hardness and breaking-properties ; the amount of sludging was equal, and there was no difference in the condition of the steel or the machines, in the air-pressure or in the experience of the operating-crews. Some operators in the Cripple Creek district contend that there is ground which cannot be handled with the small machine, the holes being too small to contain enough powder to pull the ground, etc. The results obtained in working the property of the Portland Gold Mining Co., however, show that the ground worked by them does not fall in this class. During a period of two years there have been driven, with the small machine, 4 miles and 308 ft. of development-headings, through a diversity of ground, including Pike&apos;s Peak granite (a coarsely porphyritic type of granite), highly indurated, andesitic or phonolytic breccia, true massive andesite, trachytic phonolyte, tuffas, and along dikes of decomposed basalt and hard phonolyte; in every instance a satisfactory record was made. The headings here described were driven through highly indurated, andesitic breccia, having a hardness of from 5.2 to 7.2

Mar 1, 1906

By B. C. Craft, Murray F. Hawkins, John R. Rayne

A reservoir mechanism of sulfur recovery by the Frasch process is presented. Improving the economic, of recovery appears to be largely a well, rather than a reservoir problem. A most important factor is the limitation of the lateral extraction of .sulfur about the wells due to the almost vertical .flow of the injected hot water. Model studies are described which confirin the mechanism of sulfur recovery by presently used methods. Studies on a five-spot system indicate improved econo171ics regarding recovery, recovery rate, therinal efficiency, and well spacing. INTRODUCTION Sulfur mining by the Frasch process is one of the most important methods of sulfur production. Developed by Herman Frasch in 1894, it enjoyed a rapid growth and presently supplies 40 per cent of the world&apos;s sulfur and about 80 per cent of the U. S. sulfur." The Frasch process of mining the underground native sulfur deposits involves melting the sulfur in place by introducing super-heated water into the sulfur bearing formations, and producing the sulfur as a liquid. Many problems are encountered in mining these native sulfur deposits, and sulfur production depends chiefly upon the nature of the sulfur deposit and the underground thermal efficiency of the heat transfer system. THE RECOVERY MECHANISM Sulfur is typically found in salt dome cap rock as crystal aggregates occurring within the cavities, seams, and pores of limestone and gypsum formations.&apos; Sulfur-bearing limestone is typically cavernous, vugular, and fractured. Porosity averages about 20 per cent and sulfur saturation averages approximately 25 per cent by weight.1,15 Vhe sulfur bearing formations are very heterogeneous in nature and physical characteristics vary widely within small distances. Total cap rock thickness may vary from 50 to more than 1,000 ft, and net productive thicknesses from a few feet to a few hundred feet. In most cases the upper portion of the limestone formation is barren of sulfur, varying from 5 to 200 ft in thickness.1,15,33 The immediately overlying sediments and the underlying dense anhydrite formation provide permeability barriers to the flow of water from the cap rock section.&apos;" Sulfur wells are drilled with conventional oilfield drilling rigs. Fig. 1 illustrates the casing program of a completed sulfur well. The cap rock sections are drilled with core bits and continuous core logs are recorded. After coring, the cap rock section is underreamed to a diameter of 9 7/8 in. The bottom of the 8-in. casing is welded closed and rests on the bottom of the drill hole, which extends through the cap rock to a few feet above the bottom of the sulfur-bearing formation. The 8-in. pipe contains 5 ft of 3/4-in. perforations on 6-in. centers and 15 ft of 1-in. perforations on 1-ft centers. The 20-ft perforated section is set opposite the lower 20 ft of the sulfur-bearing formation. The 4-in. sulfur pipe is set inside the 8-in. water line on a seat ring at the top of the 5-ft section of 3/4-in. perforations. The mining water, heated to about 330°F under a pressure of 250 psi, is forced down the annulus between the 8-in. and 441-1. pipes and through the 1-in. perforations to the sulfur-bearing formation. Compressed air, at 400 psi pressure, is supplied through a 1-in. air line near the bottom of the well to provide air-lift of the liquid

Jan 1, 1957

While coal was mined in New Mexico in 1860, production was on a small scale during the period considered here, and Table 77 contains all the data found. [ ]

Jan 1, 1942

By Leonard Grimshaw

THE idea of bonding two dissimilar ferrous metals, and making use of both, is an old one. Tips have been brazed onto tool shanks for many years. The bonding of larger pieces to form whole bars and sheets has also been accomplished, but has received little attention in the technical literature, although a number of patents have been issued covering various methods for its accomplishment. There are three main motives behind the manufacture of composite steels. One is that the physical properties of one steel may supplement those of another; a useful, but at the same time, hard, brittle steel may be backed by a soft ductile one, or a stainless steel may be backed by a steel possessing greater strength. Another motive is direct lowering of cost; an expensive steel may be backed by a less expensive one, bringing down the cost of the piece as a whole. The third motive is an indirect lowering of cost, as when a useful steel is backed by a steel that is easier to machine, so that machining cost on a finished product is lowered considerably. Often more than one of these motives lead to a decision to use a com-posite steel.

Jan 1, 1936

By E. S. Machlin

An extension of the thermodynamic theory has been made for the case of irreversible growth processes occurring by the motion of an interface. The theory is applicable to such diverse phenomena as diffusion, growth in recrystallization, continuous grain growth, growth of carbides, etc., growth of eutectoid products, growth in solidification, recovery, "slipless" flow, etc. THE publication of a recent book1 has served to focus attention on a very powerful means of treating certain irreversible processes. This method which has been formally described as the thermodynamic theory of irreversible processes is applicable to processes which involve an approach to equilibrium and for which the deviations from equilibrium are small. The irreversible processes can be classified into three groups: chemical reactions, transport processes (diffusion, heat and electrical flows), and relaxation phenomena involving a degradation of internal energy to more stable states. The limits of applicability of the theory can be precisely defined1,2 for each type of irreversible process. For example, in a chemical reaction at constant temperature and pressure, the Gibbs free energy released per mol in the process should be less than the thermal energy, RT. Another type of irreversible process, which sometimes involves a combination of the first two of the above-mentioned groups, is treated in this paper. This process is one characterized by the motion of an interface separating two regions having different values of free energy and may be briefly described as a growth process. Prigogine2 and Herring3 have treated special cases of this type of process. Previous conscious applications of the theory in metallurgy have been limited to the field of diffusion, one of the transport processes. Darken,4 Bardeen,5 Prigogine2 and others have made significant contributions in this respect. Some other applications of the theory are described in this paper. The Theory The thermodynamic theory of irreversible processes is based on the work of Onsager,6 DeDonder,7 Prigogine2 and others. A resume of the theory has been given by Prigogine2 and DeGroot.1 A brief description of the theory follows, although for a complete understanding the reader is urged to read the references. It is first assumed that the change in entropy, even for a system removed from equilibrium, is given by dS = [dU + pdV - Si µi, dn, - Sk Pk dxk]T-1 Using this expression, the irreversible entropy production in the system is calculated by subtracting the contribution to the change in entropy of the system by transfer of heat, work, or matter from the surroundings. Thus, for example, the irreversible entropy production of a system at constant temperature and pressure is given by dtS = — — dG (DeDonder7) Now it has been shown by Prigogine,2 DeDonder,7 and DeGroot1 that the rate of irreversible entropy production diS/dt, when calculated in the manner suggested, can be written as a sum of products of conjugate forces XK and fluxes Jk, i.e., d,s/ = Sk Jk Xk [I-1] dt The assumption is next made that a linear relation exists between a given flux and the forces, obtained from Eq. I-1, i.e., Ji = Sk Lik Xk (i = 1, 2, . . . n) [I-2] Generally, there is a degree of freedom in choice of the fluxes and forces. However, for all the choices consistent with Eq. I-1 the Onsager8 relations, based on the principle of microscopic reversibility, namely, Lik = Lki, are valid. The coefficients Lik, depending upon the choice of the conjugate fluxes and forces, may be more or less dependent upon the parameters defining the state of the system. In general, the proper choice of fluxes and forces utilizing Eq. I-1, makes the coefficients Lik independent of time. Also, because many of the three classes of irreversible phenomena have already been treated,1,2 a proper choice can be made by analogy. In any case, the validity of Eq. 1-2, from whatever choice made using Eq. I-1, must be tested by experimentation. The theory, thus, comprises the following steps: 1—The irreversible entropy production is calculated to yield Eq. I-1. 2—The terms in Eq. I-1 are grouped

Jan 1, 1954

By Klaus Schwerdtfeger

The rules of solution of oxygen from H2O-H2-He gas and of nitrogen from N2-H2 gas in shallow melts of liquid iron were measured at 1610o and 1600o C, respectiuely. Concentration profiles were detemined in the liquid iron. Tire rate data indicate that the solution process is controlled by diffusion in the iron melt. The diffusivities for oxygen and nitrogen in liquid iron, as calculated from the present data, are DFe-o = (12 ± 3) < 10-5 sq cm per sec and DFe-N = 11 ± 2) X 10-5 sq cm per sec at the temperatures employed. AN attempt was made by Shurygin and Kryukl to measure the diffusivity of oxygen 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 measured. Assuming that the rate of dissolution of silica is controlled by diffusion of oxygen in the iron, the oxygen diffusivity was computed from the rate data giving Dfe-0 = 6.1 X 5 sq cm per sec at 1600°C. Although this value seems to be of the right order of magnitude, there is no proof of the correctness of the assumptions involved in the interpretation of these rate data. The oxygen concentration in the iron at the iron-iron silicate interface was taken to be that in equilibrium with the silica-saturated silicate melt. That is, it was assumed that no concentration gradient existed in the liquid silicate. This is a questionable assumption, unless it is proved that the thickness of the silicate layer is very much smaller than that of the diffusion boundary layer in the iron. Furthermore, Shurygin et al.1 used the Levich equation2 to interpret their rate data. This equation was derived for 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 derivations. In the present work the diffusivities of oxygen and nitrogen in liquid iron were measured at 1610" and 1600oC, respectively. EXPERIMENTAL METHOD Iron melts contained in high-purity gas-tight alumina crucibles were reacted with H2O-H2-He gas for the determination of the oxygen diffusivity and with N2-H2 gas for the determination of nitrogen diffusivity. At the end of the reaction period, the samples were quenched in a cold H2-He gas stream at the top of the furnace. Oxygen or nitrogen contents in the iron were determined by chemical analysis. Two different types of diffusion experiments were perforxed. To determine concentration profiles, a few rate measurements were made using 4-cm-deep melts. The solidified samples were sliced into discs and each disc was analyzed for oxygen or nitrogen. In another series of experiments, oxygen or nitrogen was diffused into shallow melts (about 0.5 to 1 cm in depth) and the total sample was analyzed to obtain an average concentration of the diffusate. In most experiments, 4- to 5-mm-ID alumina crucibles were used. Some experiments were also made in smaller (3 mm) and larger (7 mm) diam crucibles. This variation in diameter caused no difference in the reaction rate, within the limits of experimental uncertainty. To promote the establishment of a stable density profile in the melt, all the samples were suspended in the lower end of the hot zone so that the top of the melt was hotter by a few degrees. Molybdenum wire resistance heating was used. The reaction tube of the furnace was a gas-tight recrystal-lized alumina tube. In most experiments the furnace was heated by an ac power supply. To check the possibility of inductive stirring, some experiments were carried out in a dc operated furnace, with essentially the same results. The temperature of the furnace was controlled automatically in the usual manner. The temperature was measured with a Pt/Pt-10 pet Rh thermocouple and is estimated to be accurate within ±5°C. The iron used was prepared by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zir-conia crucible. The main impurities are: Si 0.004 pct P, S <0.002 pct Cr 0.005 pct N 0.001 pct Zr 0.002 pct O 0.003 pct Mn 0.004 pct C 0.002 pct The gas composition was controlled by constant pressure head capillary flowmeters. Oxygen was removed from the gas mixture by passing it through columns of platinized asbestos (450°C) and anhydrone. Selected H2O contents were obtained by passing the purified gas through oxalic acid dihydrate-anhydrous oxalic acid mixtures held at constant temperature in a water bath. Water vapor pressure data for the oxalic acid dihydrate-anhydrous oxalic acid equilibrium were taken from the 1iterature.3 The flow rate used was about 1.5 liters per min. The whole system was checked for tightness at regular intervals.

Jan 1, 1968

By Earl Bardwell

(Butte Meeting, August, 1913.) THE structural relations existing between cuprous oxide and copper were first systematically studied by Heyn1, who suggested that a study of the microstructure of refined copper might be substituted for the analytical methods in vogue for determining the oxygen content of copper coming .;from the refining furnace. Hofman, Green and Yerxa,2 in their paper A Laboratory Study of the Stages in the Refining of Copper, working along the lines suggested by Heyn, showed that a study off the microstructure could be made to yield a correct estimate of the oxygen content of the specimen of refined copper under examination. In order to determine the oxygen content of the specimen of refined copper under examination a photomicrograph was first made. From the relative areas of copper and eutectic, the percentage of cuprous oxide and the corresponding percentage of oxygen were then readily calculated. It was found that the values for oxygen thus obtained corresponded closely with the analytical results. With the idea of utilizing, this method of determining the oxygen content of each charge dipped from the refining furnaces at the Boston & Montana Reduction Plant, the physical testing laboratory was equipped with suitable apparatus for carrying out the work. It may be of interest to describe certain of the methods which have been worked out in, this connection and give such data as have been obtained bearing on the effect of the oxygen content of refined copper upon its conductivity.

Jan 7, 1913