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By Malcolm McColl, C. A. Mead

Thin films (of mica have unique attributes that are exceptionally good for studies of high-field conduction mechamisms in thin-film insulators and the quantum mechanical tunneling of electrons from metal to metal. The principal advantages of using mica films are that the films are crystalline and the cleavage planes occur every 10Å. This property results in films whose thicknesses are integral multiples of 10Å and whose surfaces are uniformly parallel over sizable areas. Hence, very well-defined metal -mica-metal structures are possible. Furthermore, the fact that the insulator is split fro??! a bulk sample allows the index of refraction, dielectric constant, forbidden energy gap, and trapping levels and their density- to be obtained directly from measurements performed on thick samples Of mica rather than requiring that these properties be interred from the conduction characterrsties alone. In the work to he described, all the cleaving was done in a high vacuum just prior to the evaporation of metal elertrodes so as to avoid air contamination at the interfaces. Results of these studies indicate that the current through the 30 and 40Å films exhibited quantitative agreement with the theoretical voltage and temperature dependence derived by Strallon for the tunneling of electrons directly from metal to metal. Thicker films at room temperature exhibited volt-ampere curves suggesting Schottky emission of electrons from the cathode into the conduction band of mica. However, the thermal activation energy was smaller than that found from other measurements, and the experimsntal Schottky dielectric constant was larger than the square of the index of refraction. These facts would indicate that the electrons were being injected into polaron stales ill the iusulator. At low temperatures and high fields, the current through the thicker films did not exhibit the Fowler -Nordheim dependence as would be predicted by a simple extention of the theory of field emission into a vacuum. THE mechanism of electrons tunneling through insulating films has received considerable attention in the last few years due to the devices possible utilizing tunneling'-4 and the success of tunneling in the study of superconductivity.5,6 Until the recent paper by Hartman and chivian7 on the study of aluminum oxide, there had been no reported successful quantitative experimental fit to the theory. Their method of fabrication necessarily results in a polycrystalline insulator, the stoichiometry of which is nonuniform from one side to the other. This structure also introduces complications to the shape of the barrier which is set up by the insulator since the insulator possesses a spatially nonuniform band structure and dielectric constant. Due to these facts an analysis of the data in terms of a pviori barrier shape is of questionable validity. The use of muscovite mica not only overcomes these disadvantages but, as an insulating thin film, provides physical properties (dielectric constant. trapping levels and their densities, forbidden energy gap, and so forth) that are identical to the easily measured values of the bulk sample. Furthermore, it is a single-crystal insulator whose cleavage planes (10Å apart8,9) provide uniformly parallel surfaces of well-known separation. This material is therefore ideally suited to the study of electron-transport phenomena. Von Hippel10 using a 6.5-µ-thick sample was the first to observe the high-field conductivity (=5 x l06 v per cm) of mica. No attempt was made to develop an empirical formula, but Von Hippel concluded from intuitive arguments that the current was being space-charge limited by trapped electrons. Mal'tsev11 in a more recent investigation at high fields observed a dependence of the conductivity a on the field F of the form exp(ßF1/2). This dependence was attributed to the Frenkel effect,12,13 a Schottky type of emission from filled traps. No mention in the English abstract was made of the thicknesses of his samples or, and more important, of how well the value of ß fit Frenkel's theory. In 1962 Foote and Kazan14 developed a technique for splitting mica to a thickness of less than 100Å and observed a dependence of the current density j on the field of the form j = jo exp(ßF1/2) on a thin sample thought to be 40Å thick. Assuming that this was a Schottky emission process and that the appropriate dielectric constant for such a mechanism would be closer to a low-frequency value of 7.6, Foote and Kazan calculated from ß an independent thickness of the mica of 36Å. No further investigation was made of the phenomenon. However, the work reported in this paper indicates that the film measured by Foote and Kazan was probably 60Å thick, the error arising from the measurement of the very small metal-insulator-metal diode areas that were used, along with the diode capacitance and dielectric constant, to calculate the thickness. In the research reported in this paper, Foote and Kazan's technique was modified to cleave muscovite in a vacuum of 10-6 Torr, immediately after which metal electrodes were evaporated creating Au-mica-A1 diodes. Aluminum was chosen because of its strong adhesion to mica, as necessitated by the

Jan 1, 1965

G. D. Kneip, Jr., and J. 0. Betterton, Jr. (Union Carbide & Carbon Corp., Oak Ridge, Tenn.)—The authors have contributed to the theory of zone melting by considering the effects of the solidification of the final zone on the distribution curves for the finite length bar. However, they do not consider in sufficient detail the restrictions imposed by the particular metals involved. Eq. 4 has the analytical solution which is equivalent to Pfann's' equation for normal solidification of the final zone. For distribution coefficients less than one, it is apparent from this form of the equation that, as the solidification approaches completion, the concentration attains extremely large values which are inconsistent with the density of physical materials. The necessary restrictions then are that the solute concentration cannot exceed the density of the alloy, or more frequently, the solubility limit in the solid phase. Secondly, the distribution coefficient cannot be constant from 0 to 100 pet solute unless the liquidus and solidus coincide over this whole region. It would thus be more correct to impose limits on the solubility such as would be indicated by a typical eutectic diagram. Furthermore, in this case the assumption that the distribution coefficient remains constant is more likely to be realized. Eq. 4 should then be replaced by the following C,,(x) =k/L-x [ ?11 3 C11 (x)Ddx - ?11 4 Cn(x)dx= k[Cn (L-l)/k] [ L-x/l]x-1 L-l = x = L-l [kCenterlie/Cn (L-l)]1/k-1 The typical shape for the distribution curve in the final zone is indicated schematically in Fig. 12 for the simple eutectic case. The solidification proceeds according to Pfann's' expression until the concentration reaches the maximum solubility in the solid phasc. At this point, the concentration changes abruptly to the eutectic composition and remains at this value for the duration of the solidification. The width of the flat region, and the back reflection of this effect into the concentration curve on subsequent passes, depends upon the ratio of the eutectic concentration to the original concentration, upon the distribution coefficient, and upon the number of passes. Similar effects on the concentration curves in the first zone length would be expected in many systems for which the distribution coefficient is greater than one, and where the maximum solubility is not too much larger than the original concentration. The discussers agree with the authors that the assumption that the liquid is uniform in concentration should be considered with caution. Kneip and Better-ton' have shown, however, that in floating zone refining of zirconium, using induction heating, the distribution of iron agrees with theory which assumes a uniform liquid composition. Hence, in this case, the experimentally realized distribution coefficient agrees with the present phase diagram within the experimental uncertainty. L. Burris, Jr., C. H. Stockman, and I. G. Dillon (authors' reply)—The authors are happy to have received the comments of G. D. Kneip, Jr., and J. 0. Betterton, Jr., which provide additional insight into the zone refining process. It is true that the equations developed are inapplicable if the solute solubility in the solid phase is exceeded. However, this restriction on the use of the equations was clearly stated in the paper. A closer approach to

Jan 1, 1957

By A. W. Bethune, L. M. Pidgeon

The equilibrium vapor pressure of zinc has been determined over the systems: ZnS(s) + Fe(s) = FeS(s) + Zn (vapor) and ZnS(s) + 2Cu(s) = Cu2S(s) + Zn (vapor) by reacting the components in an evacuated tube containing a thin copper fiber, and allowing equilibrium to be established with respect to the brass formed and the zinc in the vapor phase. The composition of the brass formed was determined and equilibrium vapor pressure values obtained from existing data. Between 850' and 1000°C, values for the first reaction ranged from 8 to 58 mm Hg; for the second reaction from 1.8 to 22 mm Hg. THE direct reduction of metallic sulphides may be indicated by an equation of the form MS + X = XS + M [1] where X is some suitable reducing agent. In the case where M is a metal of relatively high volatility, the use of vacuum will displace the equilibrium to the right at comparatively low temperatures in the face of the usually unfavorable thermochemistry. For this technique to be feasible, MS, X, and XS, must of course be nonvolatile compared to M. In this regard, zinc becomes an obvious metal both from the point of view of its volatility and the fact that most commercial ore deposits of this metal occur as the sulphide, and its direct reduction would avoid the expensive roasting process necessary prior to present day reduction methods. Two reducing agents are of interest, namely copper and iron, with the former having the added attraction of being relatively easily regenerated by oxidation in the copper converter. The possibility of these reactions has been considered before. Imbert1 patented a process whereby zinc sulphide was reduced by either copper or iron. The process as described took place at atmospheric pressure and, at the high temperatures required, the system was molten, resulting in the formation of a matte with the consequent reduction in the activities of the reactants. Peterson2 did further experimental work on these reactions and, although promising results were obtained on a small scale, attempts to increase the size of the furnace led to excessive "blue powder" formation. The early workers failed to realize the large reduction in temperature afforded by the use of vacuum and its desirable results. More recently, the direct reduction of zinc sulphide by iron has been the subject of a thermody-namic investigation by Kelley,3 and Gross and War-rington' have studied the kinetics of the reaction in the temperature range 900" to 1000°C, their experiments being conducted using vacuum and indicating that the reaction would proceed practically to completion in 1 to 3 hr, depending on the temperature. A qualitative examination of the system ZnS-Cu carried out at this University indicated that 98 pct of the theoretical zinc in the charge could be recovered in 1 hr at 1000°C when operating under reduced pressure. The purpose of this research program was to study the equilibrium of the two reactions. During the investigation, reference to the experimental work of Schenk5 was found but, due to lack of detail in the report, it was felt that it would be desirable to continue the equilibrium measurements. Selection of Method The measurement of vapor pressure of metals presents obvious problems resulting from the high temperatures which must be employed. In the present case, the production of the "reaction pressure" introduces a further difficulty since a chemical reaction must proceed before any metal vapor pressure is produced, resulting in depletion of the re-

Jan 1, 1954

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

KNOWLEDGE of the isothermal transformation behavior and the TTT chart method of graphically summarizing such information has been of invaluable aid to the ferrous metallurgist in understanding and developing heat treatments intended to provide specific mechanical properties. It is to be expected that similar lines of study directed to titanium-base alloys will be as profitable. This paper summarizes, on conventional TTT charts, the isothermal transformation products and pertinent reaction rate data for binary alloys of titanium containing 1, 3, 5, 7, 9, and 11 pct Mo, respectively. The results so presented were derived from metal-lographic examination. Some X-ray diffraction work was done to clarify certain points of question. Ti-Mo System To the authors' k.nowledge, TTT charts have only been used to describe the reaction rates of eutectoidal decompositions. It would seem that the kinetics of decomposition of any unstable solid solution might be conveniently described in this manner. The equilibrium diagram of the Ti-Mo system' is shown in Fig. 1. The similarity with the Fe-Ni system will be recognized. Additions of molybdenum serve to stabilize the /3 phase to increasingly lower temperatures. The solubility of molybdenum in the a phase is restricted to less than 1 pct at 600°C. Under normal conditions. a homogeneous ,8 structure quenched to a, temperature in the a f & field will reject a of invariant composition. The rate at which this occurs depends on the degree of undercooling and the degree of supersaturation of /3. The structural character of the rejected phase may also be expected to be related to the undercooling. Materials and Experimental Methods A sponge titanium was used which has a nominal impurity content as reported in Table I. The nominal composition of the molybdenum used is also included. The alloys were prepared in 150 g melts by arc melting in an evacuated water-cooled copper crucible of the type reported in an earlier paper.' The pancake-type ingots were forged to 1/4x1/4 in. bars and homogenized for 24 hr at 1000°C in evacuated Vycor bulbs. Specimens Vi in. thick were cut from these bars for heat treatment. The heat treatment cycles followed an invariant procedure. The specimens were soaked at 1000°C for 20 min under a helium protective atmosphere prior to quenching into a lead bath held at a temperature corresponding to a chosen degree of undercooling. After a prescribed period of time at this temperature, the specimen was removed and water quenched. A series of specimens so treated for progressively longer periods served to establish the times for initiation and completion of the decomposition of the /3 phase at a particular temperature. Although heat treatment of unprotected specimens in a lead bath does permit surface contamination by lead diffusion, this method is necessary to insure sufficiently rapid quenching rates. As long as the bath treatments were of less than 1 hr duration. the contaminated surface was not unduly deep and could be removed without excessive grinding. Metal-lographically, the contaminated zone could be readily distinguished from the pure binary alloy. Transformation Characteristics of Ti-Mo Alloys Metallographic examination showed that a supersaturated p phase may decompose by one of two processes. Alloys containing 1 to 9 pct Mo, when quenched in water from the homogeneous /3 field,

Jan 1, 1953

By L. S. Darken

A quadratic formalism is developed lor the representation of the excess free energy, and of the activity coefficients of each component of a ternary system in the vicinity of a single component selected as solvent. This formalism, in contrast to the e formalism, is thermodynamically consistent at .finite concentrations. Numerous specific systems are used as illustrations, with cross checks where possible; these systems are Fe-C-X systems in the vicinity of 1600°C and include practically all those for which reliable data are available. It is shown that this formalism is usually quite adequate to rebresent available data up to a solute concentration of 20 to 30 at. pet. It is hoped that the formalism here presented may prove useful for the treatment and tabulation of data on ternary and multi-component solutions. SINCE, as discussed in a prior paper,' we do not as yet have an adequate basic understanding of the nature of binary metallic solutions, we cannot hope to be in better position for ternary and multicomponent systems. However, the accumulation of thermodynamic data on ternary and multicomponent metallic solutions has led to an urgent need for a rational formalism for the presentation and use of such data. Notable attempts to represent the isothermal isobaric thermodynamics of ternary solutions were made by Benedict et 01.' and by Wohl.3 These attempts were directed toward developing an analytic expression adequate to encompass the entire ternary triangle, primarily for organic systems; they generally involve the power-series approach, which has been shown' to be inappropriate, in general, even for binary metallic systems. On the other hand, interest in the thermodynamics of ternary and multicomponent metallic solutions has tended to focus either on general thermodynamic relations4-10 over wide compositional ranges, or on cases where one or more components have been at rather low concentration. This latter approach has been followed by Wagner,= by chipman,11 and by Alcock and Richardson,12 and more recently in many publications by the same and other authors. It has already been shown' that the thermodynamic behavior of binary metallic systems is, in general, relatively simple only in the terminal regions. Hence, it would appear that any approach, at this time, to a simple formalism for ternary and multicomponent systems must, a fortiori, be limited to the vicinity of the major component or solvent. The present treatment is aimed to be useful for a given solvent with moderate solute concentrations ranging up to 20 or 25 at. pet and in exceptional cases to considerably higher concentrations. In order to achieve even this modest objective, it is necessary that any appropriate formalism have built into it 1) a thermodynamic consistency (at least within the desired degree of approximation), and 2) an approach at infinite dilution to Raoult's law for the solvent and to Henry's law for each solute. Let us first formulate the condition of thermodynamic consistency for a ternary system. Under isothermal isobaric conditions, we may write for the molal value G of any extensive function dG - C1 dN1 + G2 dN2 + G3 dN3 [l] where the G's are the corresponding partial molal quantities and the N's are the atom fractions. Taking component 1 as the solvent, this relation may be rewritten in terms of the independent variables N2 and N3

Jan 1, 1968

By Rollin E. Hook, Attwell M. Adair

The yield and fracture behavior of recrystallized chromiztm have been studied in order to gain an understanding of the recrystallization embrittlement-rheotropic recovery phenomenon. The duc tile-brittle tensile transition temperature of recrystallized chromium was found to vary from 225 ° to -80°C as the ratio of specimen diameter/mean planar grain size decreased. The applicability of this observation to other bcc metals is briefly discussed. Brittle fracture in recrystallized chromium was found to be initiated predominately from intercrystalline rupture nuclei. Single crystals exhibit a high degree of ductility at 23 "C. The experimental data indicate that grain boundaries play a significant part in the yield and fracture behavim. Pres training significantly reduces the transition temperature, and high temperature aging does not result in re-embrittle-ment until complete recovery or re crystallization occurs. SEVERAL theories have been used to explain the recrystallization embrittlement-rheotropic recovery phenomenon in chromium. Wain, Henderson, and ohnstone' propose a Cottrell dislocation locking mechanism due to nitrogen, and Weaver and Gross and weaver 3 propose a strain-induced precipitation mechanism involving a chromium nitride precipitate. The researches of many investigators seem to leave little doubt that brittleness in chromium is promoted by interstitial impurities. Smith and seybolt4 have shown that the ductile-brittle transition temperature is lowered as the interstitial content is reduced. weaver3 provides evidence for a 150°C reduction in the tensile transition temperature as the nitrogen content is reduced from 20 to 5 ppm. Maykuth and affee' have suggested that the amount and orientation of grain boundary impurities may be responsible for the brittle nature of recrystallized chromium. This suggestion was based on their findings that wrought iodide chromium possessing a fiberous grain structure is ductile in tension at room temperature while a recrystallized grain structure is completely brittle. Previous investigations have not studied this phenomenon sufficiently to determine its cause. Perhaps this has been largely due to previous experimental findings that brittle fracture observed in chromium has been almost entirely transgranular.' In addition McNeil and imb,' who investigated coarse-grained as-cast chromium, describe the point of initiation of fracture as cleavage, close to the (100) plane, near or at grain bound-daries, or at included particles or voids. However, Hook, Adair, and ipsitt found that fracture in coarse-grained recrystallized chromium is initiated by intergranular rupture and then propagates nearly entirely by cleavage. This result, together with their finding that room temperature ductility in bending is observed for single crystals and coarse-grained polycrystalline specimens for which the number of grains through the specimen diameter is small, suggests that grain boundaries may play an important role in the brittle behavior of chromium. The recrystallization embrittlement problem can be resolved into two questions. These are, whether the controlling mechanism is predominately one of crack initiation or crack propagation, and whether brittle fracture is initiated predominately by slip or twin induced intergranular rupture or by cleavage. The following research was designed to study the role of grain boundaries on the brittle fracture of chromium in an effort to resolve these questions. EXPERIMENTAL PROCEDURES, RESULTS, AND DISCUSSION General Procedure. All tensile specimens (except 0.04 in. diam wires) were prepared from 1/4 in. diam swaged rod fabricated from one ingot. Details of fabrication are given elewhere. The results of impurity analysis for the swaged rod and for the

Jan 1, 1963

By F. I. Stalkup

Vapor-liquid phase equilibrium experiments have been conducted in a static equilibrium cell on mixtures of a light, 45 API stock- tank gravity reservoir fluid and a rich hydrocarbon gas containing approximately 55 mole per cent of intermediate hydrocarbons. Both apressure-vs-composition study of the gas and a simulated reservoir fluid, and a multiple-batch contact simulation of the condensing-gas-drive oil recovery process were performed. In the latter experiments equilibrium gas and liquid compositions were analyzed. Also, conventional, "condensing-gas-drive", long-tube displacement experiments of the reservoir fluid and gases of various richness were performed. The results of these experiments could not be satisfactorily interpreted by the conventional pseudo-ternary-diagram representation of multicom-ponent phase behavior. The results seem to be explained better by considering a bubble-point surface and a dew - point surface joined in a plait-point locus. Portions of the plait-point locus cannot be "seen" directly by the rich hydrocarbon gas because of curvature of the dew-point surface. In such a system, continuous injection of the rich gas over stationary reservoir fluid might form a zone of contiguously miscible compositions from pure rich gas to pure reservoir fluid by: (1) saturating the reservoir fluid with injected gas to the bubble-point surface; (2) creating by mass transfer with fresh injected gas a path of contiguously miscible compositions along the bubble - point surface to the plait-point locus; and (3) creating by mass transfer with additional injected gas a path of gas compositions along the dew-point surface up to the point where direct miscibility results between dew-point fluid and the injected rich gas. INTRODUCTION The use of the pseudo-ternary-phase diagram to illustrate miscible displacement phase behavior has been discussed by several authors.5,7 Such a representation of phase behavior is not rigorous, but the ternary diagram nevertheless gives a qualitative picture of what actually occurs in a miscible displacement process. Fig. 1 is a typical illustration of miscible displacement phase behavior by a ternary diagram. The multicomponent hydrocarbon system is divided into three pseudo-components: a light fraction containing methane and nitrogen, an intermediate fraction containing ethane through hexanes plus carbon dioxide, and a heavy fraction containing heptane and heavier components. A two-phase region is bounded by a dew-point curve and a bubble-point curve, which are joined at the critical point. The concept deduced from such a representation for miscible displacement by a condensing-gas-drive process is as follows: a rich gas G, which lies to the right of the limiting tie line through the critical point C, is injected into the reservoir and contacts reservoir fluid L, saturating the reservoir fluid to give bubble-point fluid L1 and equilibrium dew-point gas GI. Continued injection of rich gas changes the composition of the saturated liquid L1 through a series of liquid compositions lying along the bubble-point curve, until the critical composition C is reached, at which point direct miscibility with the rich gas is achieved. Some equilibrium gas with compositions lying along the dew-point curve from G1 to C is also formed in this process. Thus, continuous injection of rich gas forms a

Jan 1, 1966

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.' The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By F. D. Rosi, C. A. Dube, B. H. Alexander

WHEN a deformed polpcrystalline metal is heated to a sufficiently high temperature, a recrystallized structure develops which consists of small, essentially stress-free grains. This transformation is referred to as primary recrystallization. Under certain conditions, on prolonged annealing of the specimens, a type of grain coarsening occurs in which a small number of grains commence to grow at various points by devouring the neighboring finegrained primary structure, which, in itself, exhibits a marked stability toward normal grain growth. This grain coarsening process has been referred to by Burgers' as "secondary recrystallization" or "exaggerated grain growth." Although much work has been done on recrystallization and growth processes, present knowledge of the factors which determine the occurrence and growth of secondary grains is inadequate for the advancement of a theory which accounts for the observed characteristics of this recrystallization phenomenon. In this respect, it would be important to make measurements of the velocity of growth of these large secondary grains. The early work of Feitnecht2 on aluminum showed that the size of secondary grains increased with temperature and time, suggesting that such measurements would be possible. More recently, Burgers1 found that the growth velocity of these grains in aluminum was constant over a large time interval, as is generally found for the growth velocity of primary grains in a uniformly deformed test piece.3-5 It is reasonable to expect that the determination of the activation energy of the secondary growth process might lead to a better understanding of the underlying atomic mechanism. This investigation, therefore, is one of a series primarily designed to measure the growth velocity of secondary grains at various temperatures for silver, copper, and aluminum. It is hoped that these studies along with those of orientation relationships, will establish a sound basis for theorizing as to the origin and nature of the secondary transformation. Experimental Procedure The metal used in the present investigation was high-purity silver (999.9 fine), which was supplied in the form of cold-rolled plates 0.250 in. thick. These plates were annealed at 500°C for 1 hr and then straight-rolled to a thickness of 0.04 in. in three reductions of approximately 45 pct, followed in each case by an anneal at 450°C for 1/2 hr. The 0.04 in. sheets were given a final reduction of approximately 50 pct, which resulted in a thickness of 0.02 in., thereby insuring two-dimensional crystal growth. Individual specimens of this material about 1x3 cm were used for all heat treatments, unless otherwise noted. The annealing was carried out under an atmosphere of argon in an Inconel tube furnace whose temperature was controlled to within -+2°C. Metallographic examination of the secondary transformation was accomplished by mechanically polishing the specimens on one side to approximately one half their thickness through 2/0 metallographic emery paper, and then electrolytically polishing in a solution of potassium ferrocyanide and sodium cyanide. With a current density of approximately 20 amp per sq dm, the time required to obtain a satisfactory surface varied from 3 to 5 min. Standard potassium bichromate was used to etch the electrolytically polished surfaces. A heavy etch with this solution produced a sharp contrast between the secondary grains and the fine-grained primary structure, darkening the latter while leaving the large secondary grains bright. All area measurements of the secondary crystals were made with a planimeter on enlarged tracings of the grains.

Jan 1, 1953

By Paul M. Tyler

YEAR after year, the kaolin industry of the United States has been setting new production records and making better products. High-grade paper, pottery, and rubber clays are produced in this country mostly in the South. Georgia alone contributes over 70 pct and South Carolina almost 20 pct of the total domestic output. Residual kaolin is mined in North Carolina, highly plastic but naturally sandy Tertiary (Eocene) potting clays are worked in north central Florida, and good white clays are produced in several other states, but the main sources of kaolin or china clay have been numerous deposits in the Tuscaloosa (Upper Cretaceous) formation. This formation of generally sandy sediments is called the Middendorf member in older geologic reports and corresponds in age with some of the New Jersey clays. As shown in fig. 1, it crops out almost continuously in a generally southwesterly direction across South Carolina and Georgia and into Alabama. Clay is mined from this formation in all three states but the principal producing centers lie within about 10 miles of a straight line drawn between Aiken, S. C., and a point about 10 miles south of Macon, Ga. The white kaolins of the South were recognized and used prior to the Civil War but suitable treatment processes were not introduced until World War I when imports, chiefly from England, were curtailed. Although imports of high-grade clays were resumed after 1918, the domestic industry managed to treble its prewar production record during the early 1920's and has continued to grow. Whereas the 1909 to 1913 average total production in the United States was only 132,104 short tons valued at $705,352 f.O.b. mines, the output in 1948 was 1,-568,848 tons worth $19,756,738. Paradoxically, it seems in retrospect that the early failure of the American industry to meet foreign competition was due to the superior quality of our sedimentary clays in their natural state. Kaolin, of course, is the principal decomposition product of feldspars which originate in acidic igneous rocks such as granite, aplite, alaskite, granodiorite, quartz porphyry, etc. English china clays occur in residual deposits and before they can be marketed they have to be treated to remove accompanying quartz, mica, and other impurities. Notwithstanding the relatively crude methods employed, the final product is a beneficiated clay which is subject to a certain amount of technical control as to quality and uniformity. Although the naturally concentrated deposits in Georgia and South Carolina contain some of the finest crude white kaolin in the world, even it can be made better by suitable treatment. In recent years well over half of the high-grade china clay produced in the United States has been used in making paper. Some qualities of paper clays are still produced by the dry process, or air flotation, but the paper industry's specifications have grown so exacting that wet processing was adopted and more refined methods had to be perfected. Notwithstanding notable advances in clay-preparation technology during the past decade, or possibly because these advances have implemented and encouraged technologic changes in consuming industries, demand has grown for products of higher uniform quality than can be obtained from even the best natural deposits without rigidly controlled fractionation. Largely as a result of the wide adoption of machine coating for paper, the clay industry has been obliged not merely to eliminate virtually all mineral impurities but also to segregate the clay substance itself into narrow particle-size ranges. By extraordinary coordination of sales effort and production technology, several Georgia companies manage to market a wide variety of specialized joint products but the commercial success of many producers depends upon their mining only the best parts of their deposits and then skimming the cream of this almost pure clay in order to obtain a maximum yield of kaolinite finer than about 2 microns in maximum particle size and possessing low viscosity as well as the more familiar attributes of suitable color and brightness, or reflectance. To the casual visitor from another mineral industry, the kaolin mines and plants may appear to be

Jan 1, 1951

By Paul M. Tyler

YEAR after year, the kaolin industry of the United States has been setting new production records and making better products. High-grade paper, pottery, and rubber clays are produced in this country mostly in the South. Georgia alone contributes over 70 pct and South Carolina almost 20 pct of the total domestic output. Residual kaolin is mined in North Carolina, highly plastic but naturally sandy Tertiary (Eocene) potting clays are worked in north central Florida, and good white clays are produced in several other states, but the main sources of kaolin or china clay have been numerous deposits in the Tuscaloosa (Upper Cretaceous) formation. This formation of generally sandy sediments is called the Middendorf member in older geologic reports and corresponds in age with some of the New Jersey clays. As shown in fig. 1, it crops out almost continuously in a generally southwesterly direction across South Carolina and Georgia and into Alabama. Clay is mined from this formation in all three states but the principal producing centers lie within about 10 miles of a straight line drawn between Aiken, S. C., and a point about 10 miles south of Macon, Ga. The white kaolins of the South were recognized and used prior to the Civil War but suitable treatment processes were not introduced until World War I when imports, chiefly from England, were curtailed. Although imports of high-grade clays were resumed after 1918, the domestic industry managed to treble its prewar production record during the early 1920's and has continued to grow. Whereas the 1909 to 1913 average total production in the United States was only 132,104 short tons valued at $705,352 f.O.b. mines, the output in 1948 was 1,-568,848 tons worth $19,756,738. Paradoxically, it seems in retrospect that the early failure of the American industry to meet foreign competition was due to the superior quality of our sedimentary clays in their natural state. Kaolin, of course, is the principal decomposition product of feldspars which originate in acidic igneous rocks such as granite, aplite, alaskite, granodiorite, quartz porphyry, etc. English china clays occur in residual deposits and before they can be marketed they have to be treated to remove accompanying quartz, mica, and other impurities. Notwithstanding the relatively crude methods employed, the final product is a beneficiated clay which is subject to a certain amount of technical control as to quality and uniformity. Although the naturally concentrated deposits in Georgia and South Carolina contain some of the finest crude white kaolin in the world, even it can be made better by suitable treatment. In recent years well over half of the high-grade china clay produced in the United States has been used in making paper. Some qualities of paper clays are still produced by the dry process, or air flotation, but the paper industry's specifications have grown so exacting that wet processing was adopted and more refined methods had to be perfected. Notwithstanding notable advances in clay-preparation technology during the past decade, or possibly because these advances have implemented and encouraged technologic changes in consuming industries, demand has grown for products of higher uniform quality than can be obtained from even the best natural deposits without rigidly controlled fractionation. Largely as a result of the wide adoption of machine coating for paper, the clay industry has been obliged not merely to eliminate virtually all mineral impurities but also to segregate the clay substance itself into narrow particle-size ranges. By extraordinary coordination of sales effort and production technology, several Georgia companies manage to market a wide variety of specialized joint products but the commercial success of many producers depends upon their mining only the best parts of their deposits and then skimming the cream of this almost pure clay in order to obtain a maximum yield of kaolinite finer than about 2 microns in maximum particle size and possessing low viscosity as well as the more familiar attributes of suitable color and brightness, or reflectance. To the casual visitor from another mineral industry, the kaolin mines and plants may appear to be

Jan 1, 1951

By D. J. Schmatz

DISCUSSION OF RESULTS The qualitative correlation between low-temperature ductility and prior high-temperature creep strain in nickel obtained in this investigation confirms the result obtained on high-purity brass by Chen and Machlin. However, the quantitative effect is much smaller in nickel. Comparison can be made on the basis of a prior high-temperature strain that is a certain percentage of the total high-temperature elongation to rupture. In the research of Chen and machlin, the prior high-temperature strain of 1/2 pct equaled 8.5 pct of the total high-temperature elongation at rupture. For nickel, in our experiments, 8.5 pct of 21.2 pct equals 1.8 pct. For eh = 1.8 pct, the loss in ductility in percent equals x 100 = b.5 pct. That is, for equivalent bo Formation of Beta Manganese-Type Structure in Iron-Aluminum-Manganese Alloys D. J. Schmatz IRON-aluminum alloys have gained much interest in the past few years for use as a base material for elevated-temperature alloys because of their excel- high-temperature strain the loss in low-temperature ductility is 8.5 pct for nickel as compared to 60 pct for pure a, brass. It is also interesting to note the observation that in nickel the low-temperature fractures, even at the most extreme high-temperature pre-strain, were partly trans crystalline and partly intercrystalline. In the case of a brass, these fractures were completely intercrystalline. According to the data on the percent of the grain boundary area that is cracked, at 22 pct high-temperature elongation, about 12.5 pct of the grain boundary area does not carry load. Thus, the inter-crack areas are carrying a stress that is about 11 pct higher than the nominal stress. A simple model predicts that the overall elongation, which is primarily the elongation in the bulk of the specimen, will correspond to the nominal stress when the stress in the intercrack area equals the tensile strength. Quantitatively this model predicts the equation The form of this equation will agree with that found if the strain-hardening exponent, n, equals unity. Actually this model is too gross an approximation to yield good quantitative results. The question naturally arises as to whether in ordinary hot-working, such as hot-rolling, intercrys-talline cracks are introduced that affect the low-temperature properties. It appears that the answer is that such a possibility cannot be overlooked, if the hot-working induces tensile stresses at temperatures above the equicohesive temperature and if the material tends to be notch sensitive at low temperature. ACKNOWLEDGMENT This research was supported by the Aeronautical Research Laboratory, Directorate of Research, Wright Air Development Center, United States Air Force. REFERENCES lC. Zener: Fracturing of Metals, 1948, Cleveland, ASM. 'H. C. Chang and N. J. Grant: Mechanism of Intercrystalline Fracture. AIME Trans., 1956, voL 8, p. 544; lownal of Metals, May, 1956. 'E. S. Machlin. CreepRupt ure by Vacancy Condensation, AIME Trans., 1956, vol. 8, p. 106; lownd of Metals, February, 1956 'C. Chen and E. S. Machlin: On a Mechanism of High-Temper at ure Inter-crystalline Cracking, lownd of Metals, July. 1957. p. 829. Alloys lent oxidation resistance. Binary alloys of aluminum in iron are ferritic and consequently have poor hot strength. Alloys of iron-aluminum-manganese were made in an attempt to produce an austenitic alloy containing sufficient aluminum to retain the oxidation resistance of binary alloys of iron-alumi-

Jan 1, 1960

By Arthur Mitchell

POSSIBLY in no other of the non-ferrous mining districts of this country has the use and develop-ment of mechanical loaders been carried to such an extent as in the "lead belt" of Southeast Missouri. It has become apparent to the four mining companies in the district that it is imperative to apply satisfactory mechanical methods to the chief remaining stage of the entire operations-mining, milling, smelting and refining-in which manual labor is still largely used to handle material in process. With increasing wages and with the reduction of the metal divisor by the extension of mining into lower-grade orebodies, the shoveling cost per ton of lead produced has become relatively so large that in an effort to reduce it there is ample justification for considerable capital expenditure. Hand shovelers load about 18 tons of ore per shift and the average grade is less than five per cent. lead. Further, the ore is relatively heavy, about 21 cu. ft. to the ton when broken, and is often so coarse and so closely compacted after shooting that it requires much more block-holing, sledging, and muscular effort to shovel than, for example, does the cherty and more granular ore of the Joplin district or the finer ore in the headings of a drift mine. No mining company desires to pay for mere back muscles if it be economically feasible to avoid it, and labor saving machinery should be susceptible of operation by older employees, who are no longer capable of the more strenuous manual occupations.

Jan 4, 1923

By P. G. Meikle, C. T. Holland

The effect of the condition of friction upon the ultimate unit compressive strength as determined between the compressed faces of precisely machined coal specimens and specially prepared testing platens has been examined. Reductions of 30 to 40% in the ultimate unit compressive strength of these model coal pillars have been verified when lubricants areused between the faces as compared to non-lubricated faces. Increase in unit compressive strength due to confinement at each of three levels of friction appears to follow generally the widely accepted "1/2 power law", i.e. S - C (L/T)1/2 where S is the unit ultimate strength, C is a constant dependent on the coal being tested and the coefficient of friction acting at the compression surfaces and L and T are the least width and thickness of the specimen, respectively. Results suggest that the surface condition of both the specimen and platens should be mentioned in detail in conjunction with compression testing, for although the term (L/T)1/2 is adequate for all practical purposes, the coefficient C is directly dependent on the condition of interfacial friction, all else remaining constant. One phase of the investigation of the confining effect of friction on the ultimate unit compressive strength of small coal specimens has recently been completed at the School of Mines of West Virginia University. The efficient control of ground is of fundamental importance to successful mining operations and the design of support pillars has always presented the mining engineer with a difficult and intriguing engineering problem. Since about the turn of the century, many investigators have performed extensive laboratory tests on small coal specimens in efforts to solve some of the perplexing problems of strata control and pillar action in coal mines. A detailed review of this work would serve no purpose here, but a brief mention of the more significant contributions is in order. Muller16 was perhaps the first to illustrate the effect of confining pressure on the strength of coal specimens in compression. His work has recently been more carefully expanded by the experiments of Murrell17 in Great Britain. Rice and Enzian l9 observed that as the size of cubical test specimens increased, the unit compressive strength decreased. These observations were later supplemented by Lawall and Holland, 13 by Greenwald4,5 et a1 at the U. S. Bureau of Mines, by Gaddy3 as well as by Steart,22 Millard15 et a1 and Evans2 et al. Gaddy3 seems to have been first to quantify this relationship with his equation: S = K/vd , where S - ultimate unit compressive strength (psi), K = a constant dependent on the coal, and D =edge dimension (in inches). Holland7 concluded that the strength of coal as affected by lateral dimensions and thickness could be expressed as where K = a coefficient dependent upon the coal, L = least width of pillar (in.) and T = thickness of pillar (in.). Data supplied by this formula have been compared to the estimated stresses in pillars that had been standing for long periods in coal mines and in the cases so far studied the results indicate that the formula predictions are sufficiently accurate for engineering purposes (Holland11 ). This equation therefore is believed to be the simplest and most accurate tool available at the present time for approximating the strength of a coal pillar (over a specified range of L/T) in situ. However, Holland7,9 has indicated that friction between the coal pillars and the top and bottom rock

Jan 1, 1965

By L. H. Sjodahl, J. B. Conway

of each particle on grain boundary movement is proportional to the area it occupies on the grain boundary and this increases with the square of the particle radius. In contrast to the impression gained by Tiwari the effectiveness of a particle, as a grain boundary obstacle, increases rapidly as the particle size increases. The counterbalancing factor in a dispersion of constant volume (e.g., those considered by Zener) is of course the rapidly diminishing number of particles, a situation which does not exist in thoria dispersed materials where the volume fraction of thoria remains constant. Although it has been assumed that the Zener approach is valid for the sake of the above argument, it is open to the following objections: 1) It assumes that the effect of many small particles along a grain boundary is cumulative and does not take into account the possibility of each small particle being overcome separately. In this case the boundary will not be able to move forward until the largest particle on the boundary has been overcome. This means that the rate controlling factor will be the rate at which a few relatively large particles are overcome with the remaining small particles playing a negligible role. 2) When the dispersion consists of very small particles the interparticle spacing is usually small compared to the grain size and most particles are located away from grain boundaries where they can play no part. The most efficient dispersion, from a purely geometrical viewpoint, is one where the particle spacing is equal to the grain size so that all the particles are on grain boundaries. Tiwari's second point that voids cannot prevent re-crystallization seems to be unfounded as several workes20-23 have shown that voids alone can retard grain boundary movement and recrystallization. To further convince Tiwari, Fig. 17 shows a void in deformed TD Nichrome holding back a recrystallization interface. Tiwari's explanation for the effect of voids on recrystallization, i.e., they reduce local strain energy and hence lower the driving force for recrystallization may be valid in itself but is irrelevant to the present case where even complete recrystallization after ONE of the more recently proposed expressions for describing stress-strain behavior is that due to Voce.1,2 This equation is usually written: s =s8 ?(s8?so)e??/?c [l] where s is the true stress, ? is true strain, cC is a constant called the characteristic strain, s8 is the asymptotic stress approached at high strain values, and so is the threshold stress at which the plastic deformation begins. While this expression has not been universally accepted as yet it does contain certain features which are consistent with experimental stress-strain behavior. In a more recent publication Hsu, Davies, and Royles3 employed the concept of generalized strain proposed by seth4 and identified a method for linearizing the stress-strain plot. In this approach the generalized strain was given by: where 7 is the generalized strain, 1 is the instantaneous length, 1, the datum length, and n is a constant called the "coefficient of strain measure". A value of n was said to exist which would yield the linearity: s —s+ S[.-(tf] [3] In recent studies of both these approaches, it has been found that while the Voce equation and the gen-

Jan 1, 1970

By E. C. Smith

THE CHAIRMAN.-Mr. Earle Smith- has kindly offered to make some remarks in connection with segregation in the product, Mr. Smith: E. C. SMITH,* Cleveland, Ohio-I will start this off by a story of the code days of the American Iron and Steel Institute. In those days, Republic did not have a big strip mill, and the question came up of the check analysis of rimmed steel. I suggested that they let me be the chairman of the Committee on Accumulating the Information on the Variation of the Composition of the Ingots of Rimmed Steel. Somebody wanted to know why I wanted to be the chairman. I said, "We don't make any of the big ingots of rimmed steel, and no matter who makes them they are so bad that you don't dare publish the information. So if I collect it and hide it you can't charge me with having done anything that really disrupted the commercial situation. So, everybody furnished me with a rather complete story as to the horrible variations in big rimmed ingots. I took it out to my house and put it away, and it is still there. Now, segregation in the big ingot is no longer an "-academic-matter-as far as II am concerned. ¬I am in a situation like that of the German who was told in 1936 about the coming war. He said: "Until it is your throat that is going to be cut, you don't pay any attention to what is happening to the other man." That is the way with the problem that we have in front of us. Recently I have been told that the comptroller was questioning the payment for certain articles of stamped steel that had been made from rimmed steel, because upon check analysis of the rimmed steel it had been determined that these stamped articles were not within the compositions that were included in the specification, and therefore he as the comptroller had no alternative. It was not meeting the specification; therefore, no payment. So I would say to all of you: You can very seriously consider this matter of segregation now and on into the future on the basis of the fact that it is actually going to cost your companies, which are making these products, money unless there is some new idea about the infallibility of quantitative chemists who analyze some of these products or lawyers who read specifications. I don't know which man is going to be the major factor in the future. If the National Bureau of Standards could in some way show the specification writers the variation between good chemists analyzing for what they expect to be umpire results, the writers would certainly realize that some of the specifications to which we have calmly signed our names as being O.K. are well, as one man said to me, they might be filled by the devil, and they, certainly could be filled by the Lord, but they could not be filled by mankind. I would like to inject two or three things into a segregation study which I want you to think about, because I would be a little surprised if there is very much discussion of them. In the first place, we generally make steel in the United States in the basic open hearth, and I do not think there has been nearly enough consideration given to segregation within the bath before it moves into the ladle. I am sure that any of the people who handled the 9400 series of the NE series when it contained the 0.60 per cent silicon have more respect than they had previously for the segregation that is within the ladle; that is, before the metal reaches the ingot mold, the frozen ingots and the segregation in them. Another point to which I think we ought to give serious consideration is the segregation of iron oxide in the ingot-iron type of material, where the distinction between that and the steel segregation is that it is actually segregating iron oxide. Normally we are segregating some form of carbon or sulphur, or something like. that, with the stamping steel industry now coming down into the ranges of chemistry, where the segregation of iron oxide will be just

Jan 1, 1944

By J. G. Y. Chow, S. B. McRickard

The tensi1e properties of Ferrovac iron have been studied from 4° to 300°K. The stress required for macroscopic yielding was found to he constant below approximately 50°K. The effect of mechanical twinning on this low -temperature stress plateau was investigated. The onset of twinning occurs in this iron between 130° and 150°K and depending on its previous thermal history the twinning-stress curue may drop below or remain above the vield-stress curves as the temperature is lowered. Twinning has been shown to initiate slip in quenclzed iron at low temperatures. In no instances, however, did the onset of twinning alter the continuity of the yield stress -tempwature curve. Our data shows that carbon inhibits twinning and slip at low tem-peratures. This observation nay be used to explain the ductile-to-brittle transition in iron. The effect of fast neutron irradiation on yielding and embrittlement in iron and Fe-C alloys is offered as supporting evidence for this viewpoint. THE mode of yielding in iron at low temperatures was studied in an attempt to find an expression based on a single mechanism to describe the thermal dependence of the yield stress of iron. There are two types of inflections observed in the variation of the yield stress with temperature in iron and Fe-C alloys. The first is associated with ductile behavior and consists of a region extending 50" to 100°K above absolute zero in which the yield stress is independent of temperature. The second is observed in more brittle materials such as Fe-C alloys and irradiated iron and consists of an abrupt discontinuity in the yield curve as the temperature is lowered through a ductile-to-brittle transition point. The temperature dependence of the yield stress for iron with four grain diameters as found in this study is shown in Fig. 1. To varying degrees all the curves appear to flatten or approach an asymptotic value as the temperature is lowered below 50°K. Several other investigators1,2 have observed a plateau in the yield stress of iron and steel at low temperatures and in 1956 Louat3 presented a theory which contained an explanation for this behavior. In a subsequent exchange with Erickson and Low4'5 who attributed the plateau to the onset of mechanical twinning Louat8 showed that twinning first occurs in iron and steel tested in tension at temperatures as high as 140°K which is well above the observed plateau in yield stress. Furthermore he pointed out that both twinning and slip are basically dislocation processes and that with modified parameters his original theory still applied when deformation is initiated by twinning. Variables which affect the ductile-to-brittle transition in iron are test temperature, strain rate, composition and grain size.7 LOW,8 Hahn et al.,9 and Hull10 have provided evidence which links brittle fracture at a given temperature with the specimen grain size and the onset of twinning. In fact, Hull equates the brittle fracture stress to the twinning stress. On the other hand brittle fracture has been observed in the absence of twinning and priestnerl1 has given a fracture criterion which is valid whether or not fracture is preceded by extensive twinning. The data presented here clarify the role of twinning in the low-temperature deformation of iron. Strong evidence is given that the amount and distribution of interstitial impurities such as carbon are of

Jan 1, 1965

By G. S. Upadhyaya, A. D. McQuillan

HERE would appear to be a simple relationship between the group number in the periodic table of the early transition metals and the maximum amount of hydrogen which they can absorb.' Thus group IIIA metals (Sc, Y, and La) yield a trihydride in which the metal atoms are on a fcc lattice and the hydrogen atoms occupy both tetrahedral and octahedral interstices. Group IVA metals (Ti, Zr, Hf) form dihy-drides in which the metal atoms are on either a fct or cubic lattice, but in which only the tetrahedral interstices are occupied by hydrogen atoms. In group VA (V, Nb, Ta) the hydrogen-saturated metal attains a composition slightly below that of a monohydride under normal conditions. Finally the metals of group VIA (Cr, Mo, W) do not dissolve appreciable quantities of hydrogen. The manner in which hydrogen solubility disappears on alloying a group VA metal with one from group VIA has previously been investigated.2 It is necessary, in order to obtain a general picture of the reactions of alloys of the early transition metals with hydrogen, to examine a system containing metals from groups IVA and VA in which there must be a change from a fcc to a bee hydride phase. The system chosen for investigation was the pseudobinary system between titanium hydride and niobium hydride. Metallic alloys were prepared by melting iodide-prepared titanium with zone-refined niobium in an argon-atmosphere are-furnace. To ensure homogeneity each alloy was cold-swaged and then heated at 1250°C in a high-vacuum furnace until metallo-graphic examination confirmed its complete homogeneity. Small weighed specimens of the alloys were charged with hydrogen using gaseous hydrogen generated by heating titanium hydride. The apparatus has been described elsewhere.3 Throughout the charging process the hydrogen pressure was kept at about 1 atm while the specimen, initially at 800 °C, was slowly cooled to 150°C over a period of days. The total amount of hydrogen absorbed by each specimen and the room-temperature crystal structure of the hydride powders were determined. The X-ray investigation indicates that the fee hydride phase arises from alloys extending in composition from titanium to 67 at. pct Nb. After a two-phase field lying between 67 and 74 at. pct Nb in which the fee and bee hydrides coexist, all alloys richer in niobium yield a distorted bee hydride. Data derived from parameter measurements are presented in Fig. 1. The atomic volume per metal atom has been plotted against the composition of the initial metallic alloy in order to facilitate comparison of the effects of hydrogen addition in the two phases of different crystal structure. The amount of hydrogen absorbed by each alloy at saturation in terms of the hydrogen to metal ratio and alloy composition is given in Fig. 2. Over the whole range of the fee hydride phase the hydrogen content remains constant, while in the distorted body-centred hydride phase, the hydrogen content increases with increasing titanium content reaching a hydrogen/metal ratio of 1.4 at the boundary of the two-phase region. It seems likely, therefore, that the maximum hydrogen content of the fee hydrides is limited to a hydrogen/metal ratio of 2 because hydrogen atoms

Jan 1, 1962

By Lars Rossemyr, Terkel Rosenqvist

The equilibrium Mn + 2 IiCl = MnCl2(g) + H2 has been studied at 1090°C for pure manganese and for Mn-Si alloys. For this reoction a standard free energy of Fo1363, = - 19,700 i 300 col ioas found. Combined with other thermal data, the standard free energy of the reaction Mn(s, ß) + Cl2 = MnCl2(g) was derived: Fo=- 56,140 + 9.78 T log T - 40.10 T For the formation of the various manganese silicides the following free energies were obtained. 5 Mn + 3 Si - M1z5Si3 ?F°1363 = -41,500 i 1500 cal Mn + Si - h.lnSi ?F°1363= -10,000 i 500 cnl Mn + 2 Si = MnSiz ?F°1363= -11,500 ± 500 cal In the search for a method suitable for the study of thermodynamic properties of certain alloy systems, it was found that the heterogeneous equilibrium between the alloy and a gas mixture consisting of hydrogen chloride, hydrogen, and volatile metal chlorides has considerable advantages. In addition to giving thermodynamic information about the alloys, such measurements may be used to derive thermodynamic data for the volatile metal chloride itself. The present paper gives some results which were obtained for manganese silicides and manganous chloride. Similar studies are presently being carried out for the iron silicides. The phase diagram of the Mn-Si system is rather well known,' but no information exists to the authors' knowledge about the thermodynamic properties of manganese silicides or about the chemical activities in molten Mn-Si alloys. At elevated temperature, manganese may react with hydrogen chloride according to the equation: Mn(s, ß ) + 2 HC1 = MnC1, (g ) + H2 [ 1] with the equilibrium constant The value of K, may be determined from measurements of the gas composition in equilibrium with pure manganese. When this value is used in connection with measurements on manganese alloys, the chemical activity of manganese in the alloy may be derived. Initial calculations showed that around 1000" to 1200°C the equilibrium constant K1 has a value of a few thousand, i.e., the reaction is shifted far to the right. In order to study this rather unbalanced gas composition, a flow method was used in two slightly different modifications. For all experiments with manganese silicides and for some experiments with pure manganese the apparatus shown on Fig. 1 was used. A bed of the metal or alloy was placed in a tube furnace. The refractory tube had an internal diameter of 14 mm and the bed was 75 mm long. Electrolytic manganese of high purity and silicon, 99.95 pct Si, were used as raw materials. All alloys were prepared by melting weighed amounts of the elements in a high frequency induction furnace in argon atmosphere. The melting was done in a silica crucible which was placed inside a graphite shell. The alloys were crushed to - 10 +40 mesh and analyzed chemically. Also, for the pure elements, the same size fraction was used. A controlled gas mixture of purified hydrogen and from 3 to 12 pct HC1 was passed through the bed where it reacted with manganese according to Eq. [I]. The volatile manganese chloride was collected in a condenser placed in the cooler part of the furnace tube. The gas mixture before and after the furnace was sampled and analyzed by absorption of

Jan 1, 1962

By Cyril Smith

ALTHOUGH alloys of copper and silicon were examined several years ago,1 and their excellent mechanical properties were shown, it was not until C: B. Jacobs2 introduced manganese in small quantities to the alloys that they became of commercial importance. A few years ago The American Brass. Company took over the patents and commenced to manufacture the alloy under the name "Everdur." The present study of the constitution of the ternary system was undertaken in order to reach a fuller understanding of the behavior of the alloy. REVIEW OF PREVIOUS WORK ON, THE BINARY SYSTEMS There have been no papers published dealing with the constitution of the ternary system, although some tests of the mechanical properties have been described,3 which indicate that there is a change insolubility with temperature.

Jan 1, 1930