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By A. J. Goss, M. Tanenbaum, W. G. Pfann

THE purification of two metals, antimony and tin, by zone refining is described, and a reciprocating method of passing molten zones through a straight ingot, which effects a considerable economy of time and apparatus, is discussed. Antimony has been used extensively as a doping agent in germanium and silicon. More recently, it has become important in the preparation of new semiconducting compounds such as InSb, GaSb, and AlSb. High purity is especially necessary in this latter use, since the antimony may comprise as much as 80 pct by weight of the compound. Antimony is generally available in a commercial form of about 99.8 pct purity. Column 1 of Table I is a typical emission spectra analysis of commercially available 99.8 pct antimony. Zone refining has been quite successful in increasing the purity of such samples. Columns 2 to 4 of Table I are analyses of an ingot of the antimony of column 1 after the passage of seven molten zones in an atmosphere of nitrogen. The ingot length was 9 1/2 in.; the mean zone length was 2 in.; convection was the only means of stirring. The column headings are sample locations in inches from the leading end of the ingot. The results illustrate both the merit and a limitation of zone refining. It is seen that four of the five impurities—nickel, arsenic, lead,

Jan 1, 1955

By E. L. Dougherty, J. W. Sheldon

A numerical method for computing the dynamical behavior of fluid- fluid interfaces is described. Results of studies made to assess the accuracy and economy of the method on a computer are reported. It is concluded that it is practical to obtain digital computer solutions for fluid- fluid interface problems with two space dimensions. PROBLEM DEFINITION We consider two-dimensional flow in a rectangle as shown in Fig. 1, where a fluid-fluid interface divides the rectangle into two regions. The pressure is specified along the lower boundary (the injection boundary) and upper boundary (the withdrawal boundary). There is to be no flow of fluid across the side boundaries, which are walls of symmetry for the flow, and px = 0 along these boundaries. The fluids are incompressible, the absolute permeability and porosity is constant, and each fluid has its own constant mobility. Thus, the pressure satisfies Laplace's equation in each region. Across the interface, pressure is continuous and the normal component of fluid flux is 1. These conditions are shown in Fig. 1. The velocity of a point on the interface in the direction of the normal from Fluid 1 into Fluid 2 is U,/ Q, where Un is the normal component of volumetric flux at the point on the interface, i.e., For brevity, we call the problem defined above "Problem A". Problem A is a simple example of a dynamical fluid-fluid interface problem. However, the same numerical methods which we use to solve Problem A can be extended to the solution of a large number of fluid-fluid interface problems which are mathematical models for various oil recovery processes,l hence our interest in Problem A. We define the interface by prescribing the x, y coordinates of a finite set of points. These points are called "interface mesh points" and are illustrated by triangles or asterisks in the figures. Fig. 2 is a procedural (flow) chart displaying the main steps in the solution. We comment briefly on some of these steps in this section and then give further details in subsequent sections. For mobility ratio greater than one it is well known that Problem A is unstable.*2 Small amplitude,

Jan 1, 1965

By George C. Fryburg

The oxidation of platinum at high temperatures (above 800°C) is controlled by boundary-layer diffusion, except at the lowest pressures. The rate of oxidation is determined by the rate of diffusion of oxide through the boundary layer away from the platinum. This is in contrast to the situation in tungsten and molybdenum oxidation, where the rate is controlled largely by the diffusion of oxygen through the boundary layer towards the metal. The difference in mechanism is a consequence of the much lower rate of oxidation of platinum. Evidence is presented that supports this mechanism for the oxidation of platinum. SOME years ago we reported1 a study of the oxidation of platinum in ordinary oxygen in the temperature region above 800°C, where the oxide is volatile. All the data available up to that time had been obtained with platinum crucibles or plates heated in tube furnaces. The results were widely variant and highly dependent on the flow rate of gas through the furnace: the faster the gas flow rate, the higher the measured oxidation rate. These results indicated to us2 that reaction equilibrium was being approached in the furnace and that the rate was diffusion limited. To minimize these effects, we employed1 electrically heated ribbons placed in a cooled bulb. We were primarily interested in the low-pressure region, but some experiments were performed at pressures up to 1 atm. We found a peculiar pressure dependency which was explained on the basis that the rate of oxidation was proportional to the pressure at all pressures, but that with increasing pressure an increasing fraction of the volatilizing oxide was back-reflected to the ribbon by the surrounding gas molecules. The oxide molecules are not stable at the temperature of the platinum and are decomposed on impact, the platinum being re-deposited on the specimen. Because of the limitations of space, this explanation was offered summarily without detailed support. Recently, Jaffee and associates3, 4 have suggested that the pressure dependency of our data up to 0.5 torr could be explained on the basis of a Langmuir-type adsorption of molecular oxygen followed by dissociation. Since the correct explanation of the effect of pressure on the oxidation rate is a necessary requirement to the development of the basic mechanism of the oxidation reaction, we felt that the back-reflection theory should be presented in more detail. This is the object of the present paper. RESULTS AND DISCUSSION A typical set of results showing the pressure dependency of the oxidation reaction is presented in Fig. 1, where we have plotted, on logarithmic scales, the rate of oxidation, R, vs the pressure, p. For comparison some results of Krier and Jaffee4 and of Raub and plate5 are also shown. These data were taken at atmospheric pressure using furnaces. The effect of reaction equilibrium within the furnace is apparent from the much smaller values that these observers obtained: Raub and Plate In O2 found a rate of 3.1 µg cm-2 hr-1 compared to our value of

Jan 1, 1965

By J. Weertman

The paper of Gifkins and Snowden considers the interesting but difficult problem of determining the stress dependence of secondary (steady-state) creep at low stresses. These authors have concluded that at stresses below 250 psi (2 x 107 dynes per sq cm) the secondary creep rate of lead is proportional to the stress (viscous creep) and is not proportional to the stress raised to about a fifth power. The experimental data considered by them were obtained on tests conducted at room temperature and at 50°C. The lowest stress employed was 50 psi (3.5 X 106 dynes per sq cm). The authors pointed out the main difficulty in determining the stress dependence of creep at low stresses. The creep tests must be run for very long lengths of time. However they made no estimates of when an experimental creep rate determination must be rejected because it does not represent a true steady-state or minimum creep rate. In order to be certain that a creep curve is within the steady-state region, the total creep strain should be of the order of 0.1 to 0.2. For a creep test of a year's duration this requirement implies that a secondary creep rate smaller than about 10-3 per hr cannot be measured reliably. The corresponding creep rate for a 10-year test is 10-6 per hr. The creep rates of the tests that were considered by the authors to prove the existence of viscous creep were of the order of or less than 10-6 per hr. One can conclude reasonably that this data does not prove unambiguously that large strain steady-state creep rate of lead is proportional to the stress in the stress range of 50 to 250 psi (3.5 x 106 to 2 X 107 dynes per sq cm). Another technique can be used to obtain the stress dependence at low stress levels. The creep rate is a very sensitive function of temperature. The creep rate can be increased by very large amounts merely by increasing the temperature. We carried out steady-state creep tests on lead single crystals25 at temperatures up to 320°C. We were able to obtain creep rate data down to stresses as low as 35 psi (2.5 x 10' dynes per sq cm). Our smallest creep rate was 8 x 10-5 per hr. Thus we obtained large strain, steady-state creep rates to even lower stresses than were considered by Gifkins and Snowden. No evidence was seen for viscous creep. The creep rate was proportional to the stress raised to about a 4.5 power down to the lowest stresses. Since there is no reason to believe that changing the temperature should change the stress dependence of steady-state creep, we feel that large strain viscous creep does not occur in the stress range quoted by the authors for lead single crystals or large-grain polycrystalline samples of lead. This conclusion does not imply that viscous creep may nat occur in a lower stress range or in the same stress range for fine grain material or at creep strains very much smaller than 0.1. Support by the U.S. Office of Naval Research is acknowledged. Authors' Reply R. C. Gifkins and K. U. Snowden We thank Dr. Weertman for his discussion and although, as we hope to show, we do not agree with his reservations, we do concur in stressing the importance of ensuring that creep rates are reliably obtained. Dr. Weertman appears to be content to accept n = 1 for low stresses with fine-grained material but not for single crystals. We believe our results show that the former result cannot be accepted without also accepting the latter. We will also show that the probable errors in our minimum creep rates are insufficient to alter our conclusions, that the criterion proposed by Dr. Weertman is arbitrarily restrictive and his alternative experimental approach possibly invalid. 1) A principal result of our Fig. 1(a) is that n = 1 for polycrystalline specimens at room temperature and 50°C for stresses below -250 psi. There was evidence that crystal slip and grain boundary sliding contributed approximately equaily to the overall strain in this low-stress regime. This implies that either a) grain boundary sliding controls slip within the grains or b) both grain boundary sliding and crystal slip independently occur according to mechanisms which give n = 1. Alternative a does not seem acceptable, so we were forced to consider b. This led us to reexamine work on bicrystals by Strutt and Gifkins and plot curves Fig. l(b). Previously Strutt et al. (loc. cit.), had merged these points with others using the Zener-Holloman parameter and thus, we now believe, had been led to overlook the behavior where n = 1. Curves C and D in Fig. l(b) did appear to confirm the hypotheses that n = 1 for crystal slip at these low stresses and the sliding curve F was similarly of the expected form. It was comparatively easy to find a quantitative theory to account for n = 1 for sliding and the similarity of curves C and D to curve F (all obtained from the same set of specimens) led us to feel that the single-crystal curves were valid. 2) We believe the secondary creep rates for both the polycrystalline and single-crystal specimens to be in error by factors c2. In Fig. 6 creep curves for polycrystalline specimens of lead(1) and lead(II) are reproduced as curves a and b, respectively, and curve c is for a single crystal at 100 psi. It is clear that, although the attainment of secondary creep rate takes 2 years for a and 150 days for b, thereafter the curve is linear for periods of 7 and -1 year, respectively. The single crystal has a linear portion commencing after 20 and extending to 90 days. Creep extension was measured directly using a traveling microscope reading to 0.01 mm on gage lengths marked on the specimens; the gage lengths

Jan 1, 1968

By Pradeep K. Rohatgi, David N. French, Surendar M. Jain, Clyde M. Adams

The effect of solute concentration and diffussivity on dendritic solidification of dilute binary aqueous solutions has been investigated; chlorides of sodium, potassium, lithiurn, and hydrogen were used as solutes. Dendrite spacings were measured in spherical droplets and in unidirectionally solidified specimens. In the droplets, the freezing rate is uniform over the entire specimen and remains constant from the beginning to the end of solidification. In the unidirec-tionally frozen specimens the freezing rate varies within a given volume of liquid during the solidification cycle; in addition, it varies with location uithin the specimen. Mass transport analysis has been used to calculate the supersaturation, AC, supercooling, AT, and transcerse growth velocity, V , of ice dendrites during solidijication from the dendrite spacings measured in the droplels. The ice dendrite spacing in a given solute increases lineary with the solule concentralion at a fixed freezing rate. The ualues of AC, AT, and V increase with an increase in solule concentration. The value of AT in the aqueous solution is of the same order of magnitude as in Al-Cu alloys of the same concentration; the dendrite spacings in Al-Cu alloys also increase with an increase in solute concentralion. For the jamily of aqueozrs solulions incestigaled, the dendrite spacing increases linearly with solute diffusivity at fixed values of concertralion and freezing ,rate. The values of ?C and ?T decrease, whereas the value of V increases with an increase in solule diffusicity. The measured dendrite spacings , L, can be expressed by the relatiun: L = K;(dfa/db) 4 K2C +K3D - K4 where dfs/d? is-change in fraction solid with time (freezing rate), C is solute concentration, D is solute diffusivit K1 = (14 * 4)pmin1'2, K2 = (70 ± 10) pl (moles)- K3 = (24 r 3) . l05 psec (cm)-~. K. = -132 ± 10) 1. FREEZING of solutions is almost always an ehunmix-ing" process because the composition of crystallizing solid generally differs from that of the parent liquid. " Solute concentration and transport are therefore in]portant considerations in solidification of solutions. The influence of these factors on the dendritic solutions produced from metallic solutions is of practical significance since the properties of the solid aggre-gate are often strongly influenced by dendrite spacing.''' Alexander and Fthines3 found that dendrite spac- ings generally increase with solute concentration in several metallic systems. Michael and Bever1 have observed an increase in a aluminum dendrite spacings in dilute A1-Cu alloys. Rohatgi and AdamsJ have reported a linear increase in a aluminum dendrite spacings with increasing copper contents up to 28 pct in A1-Cu alloys. Bolling and Tiller"' have theoretically examined the effects of solute concentration and diffusivity on the growth of cells and dendrites. Their analysis of dendritic growth assumes a steady-state growth and the maximum possible velocity for dendrite propagation. In addition, the quantitative analysis is restricted to dendrites of rotational symmetry and is therefore not directly applicable to the plate-shaped dendrites of ice obtained in the present study. There are practically no experimental observations of the effect of solute diffusivity on dendrite spacings in metallic systems. The reason appears to be the lack of experimental data on solute diffusion coefficients in liquid metallic solutions. The present work is concerned with the effect of solute concentration and diffusivity on dendritic solidification of dilute aqueous solutions: the solutes examined are potassium chloride. sodium chloride, lithium chloride. and hydrogen chloride. There were several reasons for selecting these solutes. The variation of dendrite spacing with freezing rate in these solutiolls is similar to that observed in A1-Cu alloys.8 These aqueous solutions have almost identical phase diagrams at dilute concentrations. Fig. 1. and the diffusion coefficients show very little variation with solute Concentration.9,10 Dendrite spacings were measured as a function of freezing rate. solute concentration. and solute diffusivity. Dendrite spacings were measured in two different types of freezing systems. droplet and unidirectional, respectively. In the droplet freezing system

Jan 1, 1970

By R. E. Ogilvie, E. T. Peters

The X-ray Kossel-line method has been used preaioz~sly for measuring lattice parameters to accuracies of 1 part in 100,000.5 A second application of this method is described for determining the crystallographic orientation of a randomly positioned single-crysta1 spherical volume that can he as small as 50 µ in diameter, within accuracy limits of ±1/2 deg. The theory, experimental procedure, and interpretation of Kossel-line patterns and an experimenta1 verification of the predicted orientation relationship of the cph k and fee a Cu-Si phases are presented. This orientation relationship can be described as (111)a, (00.1)k; [110]a [11.0]k. In addition, the lattice parameter of the a phase was found to he a. = 3.62154 ± 0.00014Å. The Kossel-line method when used in conjunction with electron microanalysis is shown to he capable of providing a complete chemical and structural analysis of a given crystal. THE most easily accomplished methods for determining the orientation of a single crystal are variations of the Laue X-ray diffraction method. Although certain materials can be oriented to within ± 1 deg accuracy by observation of exterior macroscopic features, such as etch pits, cleavage faces, or growth features, the Laue method is generally preferred for routine laboratory application. Both back-reflection and transmission patterns are coordinated by appropriate reference charts and are plotted in terms of reflection plane poles (normals) on a stereographic projection. Orientation is deduced by relating the pole distribution (which is fixed by the crystallographic symmetry of the specimen) to two specified external reference directions. The Laue method has several limitations. 1) Orientation can rarely be determined to better than ±l deg accuracy. Principal errors involve inaccuracy in specimen-to-film distance, measurement confidence of individual Laue spots, and stereographic plotting. 2) Because of the indeterminacy of the X-ray wave length diffracted to a given spot, it is not possible to determine supplementary crystallographic data, such as interplanar spacings and lattice parameters. 3) The method is generally limited to specimens of cubic symmetry or to specimens of high symmetry and known structure. 4) The relatively large cross-sectional area of the incident X-ray beam generally precludes the measurement of relative grain orientation in a polycrystalline material.* _____ Several of these limitations can be overcome by application of the Kossel-line method, which has been previously employed for precision lattice-parameter determinations.'-= For this method, a point source of divergent monochromatic X-rays is generated within the crystal by means of an incident electron beam. The divergent X-rays which fulfill the Bragg law are diffracted by the specimen and are recorded on a film placed either in transmission or back reflection. Analysis of the film yields a direct measurement of orientation and lattice-spacing values to an accuracy of ±1/2 pct. As analyses can be obtained from spherical specimen volumes as small as 50 µ in diameter, the method provides a means for structural analysis of second-phase or impurity precipitates within a given matrix. The primary limitation of the Kossel-line method is the requirement for an electron microanalyzer or similar apparatus capable of producing a finely focused electron beam. This paper is designed to present the theory, experimental procedure, and geometrical interpretation of Kossel patterns. The experimentally determined orientation relationship between the k and a phases occurring in the Cu-Si system and a precision measurement of the a lattice parameter are presented as a practical application of the method. THEORY OF KOSSEL LINES Divergent X-ray beam photography utilizes an effective point source of characteristic X-rays which, when diffracted from a single crystal, form numerous diffraction and absorption cones that are recorded on film.7 The cones generated from a source lying within the crystal are called Kossel lines.' Although the X-ray scattering from a divergent point source contained within a crystal is described in terms of Laue dynamical theory,9 the directions of the diffracted spectra can be ade-

Jan 1, 1965

By R. A. Wood, R. I. Jaffee, H. R. Ogden, D. N. Williams

The tensile properties, creep resistance. and thermal stability of highly alloyed Ti-Al-Zr alloys were examined. On the basis of these studies, the Ti-7Al-1ZZr composition was selected for more complete evaluation. The alloy was found to be weldable and free from excessive directionality. In addition, it developed maximum properties without requiring heat treatment other than an annealing operation in the alpha field. The alloy was recommended for scale up and is presently being investigated on a production-level basis. One of the more attractive properties of titanium alloys is their ability to withstand stress at moderately high temperatures, and a considerable amount of effort has been devoted to increasing the maximum service temperature of titanium alloys. This work has suggested that the optimum alloys for high-temperature service will be single-phase a (close-packed hexagonal) alloys containing significant amounts of aluminum. However, the maximum amount of aluminum which can be alloyed with titanium is between 6 and 8 pct,l since at high-aluminum contents an embrittlement reaction occurs in the anticipated service temperature range, 800" to 1100°F. It has been shown that the embrittlement reaction involves decomposition of the high-aluminum a phase to one or more new phases.' Since this reaction does not occur at intermediate or low-aluminum contents, it was felt that intermediate Ti-A1 alloys might be strengthened by a-soluble ternary additions without inducing the embrittlement reaction. The first alloying addition considered was tin, which shows extensive solubility in a titanium and has moderate strengthening tendencies. Unfortunately, it was soon apparent that tin also promoted the embrittlement reaction, and that to obtain a stable alloy, the aluminum content had to be reduced as the tin content was increased. The second alloying addition considered was zirconium, which is similar to tin in its effects on titanium. This element did not contribute to the embrittlement reaction and, in fact, appeared to increase the maximum amount of aluminum which could be alloyed with titanium without inducing instability. This paper describes an investigation of the Ti-A1-Zr a alloy region. Alloys containing from 4 to 12 pct A1 and from 6 to 15 pct Zr were examined. The properties of these alloys are described and the bases for selecting an optimum composition is outlined. This composition, Ti-7A1-12Zr, is presently being scaled up in tonnage quantities, and is being evaluated extensively throughout the industry. In addition to presenting the basis for its selection, this paper presents a description of the properties developed in laboratory material as determined during the alloy investigation. These properties suggest that this alloy can fill an important position in applications requiring light weight, fabrica-bility, weldability, and strength to 1000oF or higher. EXPERIMENTAL PROCEDURES Titanium alloy ingots were prepared by inert electrode arc melting under an argon atmosphere. Alloying elements used were 110 Bhn titanium sponge, high-purity aluminum, and reactor-grade zirconium. Pancake-shaped ingots were prepared weighing approximately 300 g. The composition of the ingots was checked by weight measurements before and after melting. The pancake ingots were forged at 2000°F to approximately half their original thickness to give a flat plate roughly 1/2 in. thick. This plate was then rolled at 1800' to 1600°F to 0.250 in. thick. All of the alloys examined fabricated well. However, alloys containing 15 pct Zr tended to overheat due to exothermic oxidation, and scaling was excessive. As might be anticipated from its effect in decreasing the ß transus, increased zirconium appeared to improve fabricability somewhat, especially during rolling at lower temperatures. Except for a limited study of heat-treatment response, all alloys were examined in the a-annealed condition. Prior to heat treatment the a and ß tran-sus temperatures were determined by metallo-graphic examination of samples quenched after annealing at 50-deg intervals in the transformation region. These data are shown in Fig. 1. Recrystal-lization appeared to occur in about 1 hr in the range 1300º to 1500ºF. Therefore, alloys were annealed for 1 hr at 1550ºF (4 and 5 pct Al), 1600ºF (6 through 7-1/2 pct Al), or 1650°F (8 or more pct Al). This produced an equiaxed a grain structure. In most alloys, a "ghost" structure was visible after the a-annealing treatment, as shown in Fig. 2. This structure apparently resulted from the acicular

Jan 1, 1963

By Y. C. Liu

THE existence of mechanical twins in bcc metals has long been known. With recent intensive interest in the mechanism of twin formation and its role in plasticity and crack initiation, a study of the general Characteristics of twin intersection appears pertinent. The scope of the present note will be limited to the crystallography of the twin intersections of (112) twins, without consideration of its mechanism, movement of atoms, crystal structure, or the strain energy involved at such an intersection. The twinning elements of (112) twins are considered to be K1 = {112}, n1 = (111) and K2 = {112}, n2 = (111) with a twin shear of 0.707. The crystallographic features of twin intersections have been worked out in detail by Cahn.1 The present work applies the general principles postulated by Cahn to the intersections of (112) twins. The basic conditions for the twin intersection are: 1) The trace of crossing (A) and the secondary (C) twins in the planes of the crossed twin (B) must be parallel. 2) The direction (n1) and magnitude (s) of shear must be identical in the crossing and secondary twins. Also the sense of shear must be the same. These two conditions have to be fulfilled in order to maintain geometrical continuity at the twin interfaces. Fig. 1 shows the perspective representation of how these two conditions are fulfilled at the intersection. This type of intersection will be named Type-I. It is the purpose of this note to point out the existence of another type of intersection, Type-II, as shown in Fig. 2. In this type of intersection, the crossing twin A remains straight and the crossed twin B has been bent. The two conditions laid down by Cahn must also be met. This leads to the following corollary conditions: 1) The interface between twins B and C must be parallel to the twin habit of crossing twin A. 2) n1c must be parallel to n1A. 3) The twin shear (s) of twin C must be exactly equal to and in the same sense as that of crossing twin A. Thus, in order for the Type-II intersection to take place, the twining elements of secondary twin C must fulfill the above three conditions with respect to crossing twin A. Let K1 of crossed twin B be (112). All indices of the matrix can therefore be converted into new in-

Jan 1, 1963

In accordance with the usual custom, manuscripts to be presented at the next meeting of the Institute must be in the hands of the, Secretary before July 1, 1917. Manuscripts to be properly distributed in advance of the meeting must be in the hands of the Secretary before June 1, 1917. At the last meeting of the Institute 45 papers were presented, and 42 of them were actively discussed. This experience makes us believe that advance distribution is the best possible means of getting a good discussion of papers and of securing for them the interest of the members of the profession. It will be impossible, however, to give the papers proper distribution if they bare not received before June 1, 1917.

Jan 4, 1917

By L. F. Mondolfo, W. T. Collins

A study of the relationship between undercooling for nucleation and structure in Sn-Cu alloys with 0.1 to 5 pct Cu has shown that in hypereutectic allojls the halo of tin that surrounds the primary crystals of Cu3Sn5 is larger, the larger the undercooling for nucleation o,f the tin. This increase of halo size results in a decrease of coupled eutectic, and, in alloys far from the eulectic composition, may produce its complete disappeavance, with the formation of a divorced eutectic structure. This was confirnred by the excrrnination of other alloys in which divorced eutectic slructuves are formed, and leads to the conclusion that they ave only an extrenle case of halo forrtzalion , which results when the two phases freeze one at a time and solidification of the first is completed Defove the second starts. It was also found that under proper conditions of nucleation all types of eutectic structures can be formed in the sartte system , and therefore divorced eutectics, like normal and anomalous, are not characteristic of the syslett~, but are mainly controlled by nucleatiorz. Dizlovced eutectics are formed when the phase that tutcleates the eulectic vequires a large undevcooling for ils nucleation and when the cotnpositiorz of the alloy is far from the eutectic., on the side of the primary phase that does not nucleate the other phase. It is recommended that the tevm "divorced" be used in preference to degenerate because it is more desct-iptice of the morphology and mode of forinalion of the structures. ThE variety of structures found in eutectic alloys has been extensively investigated and classified. The most accepted classification is the one by ~cheil,' in which three different types of eutectic were distinguished: 1) normal, 2) anomalous, 3) degenerate (divorced). ATornlal eutectics are typified by the simultaneous growth of the two phases ("coupling") by which the two phases appear as interpenetrating crystals. The presence of a crystallization front, in which the two phases grow side by side, creates the eutectic grains, with the boundaries where the fronts meet. The presence of eutectic grains is the .distinguishing feature of a normal eutectic, according to Scheil. Straumanis and Brakss2 examined the Cd-Zn system and showed that there was a crystallographic relationship between the phases. Later, others4 also investigated additional systems and found definite crystallographic relationships in the coupled eutectics. The anornalous eutectic shows much less coupling than the normal; the two phases are intimately mixed but 'grow without a uniform crystallization front—a consistent crystallographic relationship— and the eutectic grain is conspicuously absent. As in the normal eutectics faster rates of growth result in a finer structure, but there is not the typical uniform spacing of normal eutectics. The degenerate eutectic shows no coupling; in fact the two phases attempt to minimize their area of contact and to form separate crystals. It has been suggested5" that slow cooling may favor this type of structure. Scheil believes that normal eutectics are formed when the two solid phases are present in more or less equal proportions, whereas both anomalous and degenerate eutectics form when one of the phases is present only in small amounts. spengler7 extended much farther this qualitative relationship between the eutectic type and the ratio of the two phases, and added a relationship to the melting point of the constituents. On this basis he proposed two equations for determining into which of Scheil's classifications an alloy belongs. The first equation is: where TI is the melting temperature of the lower-melting component, Tp of the higher-melting component, and Te the eutectic temperature. The second equations is: where is the volume percent of the lower-melting phase and $2 of the higher-melting phase at the eutectic composition. If 0 and/or 4 are in the range 0.1 to 1, a normal eutectic is formed; if in the range 0.01 to 0.1, anomalous; if less than 0.01, degenerate. Although the examples given by Spengler show a good agreement with the formulas, chadwick found that the Zn-Sn eutectic is normal to all growth rates, even though the volume ratio is 12/1, and Davies9 reports that the A1-AlgCo2 eutectic is normal, with a volume ratio of more than 30/1. Many more discrepancies of this type can also be found. Neither Scheil nor most of the other investigators have considered nucleation as a factor in the formation of divorced eutectics. Daviesg states that divorced eutectics form when neither phase acts as

Jan 1, 1965

By Lawrence Adler

MINE hoist ropes have hitherto been selected by successive approximation, a process both tedious and inexact. The proposed expression is a readily solved synthesis of existing data and the following standard equation:1 [ ] For convenience, a glossary of all terms appears on page 564. Since rope weight (Wr) and bending load (B) are functions of unit rope weight (Wo), which in turn is a function of rope strength (T), W, and B can be expressed in terms of T. Wr as a Function of T: A study of the curve in Fig. 1, unit rope weight vs strength, yields Eq. 2:

Jan 5, 1957

By N. Brown

IT has been observed that a hexagonal-close-packed crystal will undergo the same macroscopic displacements as an isotropic material if the basal plane is perpendicular to the axis of twist.&apos; Other orientations may produce both bending and twisting, but this analysis will be confined to pure torsion of a right circular cylinder. The z axis, the axis of twist, and the specimen axis are coincident. The displacements are given by Uq = rz, Ur = Uz = 0 [1] where 4 is the angle of twist per unit length. This requires rotational slip, as discussed by Frank&apos; and Wilman, which may be observed readily. The relative rotation of adjoining slip planes is simply produced by a movement of a planar grid of screw dislocations."." The screw dislocations are of the same sign and they move radially inward. For hexagonal-close-packed metals, the grid is hexagonal and the screw dislocations lie in the < 2110 > directions. The displacement of a point is the resultant of two displacements produced by intersecting screws sweeping over the point. The dislocations must pass over the point (r, o) in such a manner that its resultant displacement corresponds to the observed macroscopic displacement. If 6&apos; is measured from the [1010] direction, then for 0 < ? < ~/3, only the [1210] and 121101 type screw dislocations are needed to produce the required displacement. If n1 screws of type [1210] and n2 of type [2110] pass over a point, then, in order that Ur = 0 n, sin ? - n2 sin (/3 — 6&apos;) = 0. [2] If the tangential displacement is to be independent of 0, then n1 cos ? + n2cos (/3 —?) = N [3] where N is independent of ? and thus depends only on r. Nb is the tangential displacement where b is the Burgers vector. Since U? is a linear function of r, then N must be a linear function of r. If a2 is the outer radius and a, is the inner radius to which the plastic deformation has extended, then N = Nm2 r-a1 [4] This function meets the conditions that at

Jan 1, 1956

By J. B. Clark, A. S. Yue

PfANN1 has shown that when a cylinder of molten binary alloy freezes directionally, the solute distribution can be described analytically by cg=k(l-g)k-1 [1] in which Cg is the solute concentration in the solid at the point where a fraction g of the original liquid has frozen and Co is the initial solute concentration. The term k is the effective distribution coefficient of the solute and is defined as the ratio Cx/CL where Cl is the solute concentration in the main body of the liquid. Both the slope and the intercept at -log (1 - g) = 0 of a logarithmic plot of Eq. [I.] provide a measure of k. Under conditions of freezing where diffusion in the solid is negligible and the solute concentration in the liquid is uniform, the effective distribution coefficient k, derived as above, is equal to the equilibrium distribution coefficient taken from the phase diagram. However, under ordinary freezing conditions, even though solid-state diffusion is negligible, the solute rejected from the freezing solid does not have sufficient time to diffuse uniformly throughout the main body of the liquid. A concentration gradient is formed in a boundary layer in front of the advancing solid-liquid interface as pointed out by Rutter and Chalmers.&apos; Thus, under these conditions, the concentration of the freezing liquid in the boundary layer is higher than that predicted from the equilibrium phase diagram and consequently the effective distribution coefficient k, obtained from directional freezing experiments, is larger than the equilibrium distribution coefficient. The symbol k will designate the effective distribution coefficient in the discussion which follows. In this paper, the determination of the effective distribution coefficient is demonstrated for several dilute binary alloys and a polynary magnesium alloy. The effect of freezing rate on the value of the derived k is presented in detail. An example for the calculation of the solidus in a dilute binary solution using the experimentally determined effective distribution coefficient is given. MATERIALS STUDIED Binary magnesium alloys of copper, nickel, and zinc containing approximately 0.10 wt pct solute and a polynary alloy containing approximately 0.10 wt pct each of several elements were selected for study. The spectrographic analyses of these alloys are given in Table I. The analyses are believed accurate to within +5 pct of the stated value. EXPERIMENTAL PROCEDURE Extruded rods of the alloys, 3/8 in. in diam and 11 in. long were used for directional freezing studies. The alloy rods were melted horizontally in a high-purity graphite boat by a Nichrome-wound tube furnace which moved parallel to the length of the rod. The boat was supported inside a Vycor tube suitably connected to provide a protective atmosphere of dry SO2. For an experimental run, the following procedure was used. The alloy rod was cleaned in dilute HNO, and dried. The graphite boat containing the alloy rod was placed within the Vycor tube and the tube connected to the gas train&apos; The &apos;ystem was purged for 20 min with dry argon and then a flow of dried SO, was maintained for the duration of the run. The movable furnace was positioned and either all or a desired portion of the alloy rod was melted. After attainment of steady-state temperature gradients the molten bar was solidified from one end to the other at a controlled rate by pulling the furnace along the length of the bar at the desired speed. At the conclusion of the run, the directionally frozen alloy rod was analyzed spectrographically at 1 1/4-in. intervals.

Jan 1, 1961

By W. F. Carew, F. A. Crossley

The stress for rupture in 500 hr at 1000° F has been reported to be about 13,000 psi higher for Widmanstitten than for equiaxed microstructures for the Ti-7A1-3Mo alloy.1,2 Also, limited data indicated Widmanstatten and equiaxed micro-structures to have approximately the same creep resistance at 1000°F.&apos; Recently, data have been obtained which show Widmanstatten structures to be significantly more creep resistant than equiaxed structures at 1000°F, see Fig. 1. These data represent several ingots and several heat treatments of the solution treat and age type. The thermal history and tensile properties corresponding to the creep data are given in Table I. The creep data were taken from creep-rupture tests. The associ- ated rupture data are given in Table 11. It may be noted that total creep deformations are considerably greater for equiaxed structures. Previous evaluations of stability indicated that all of the structures tested are stable with respect to exposure to stress at elevated temperature.1,2 For a minimum creep rate of 10-4 in. per in. per hr the difference in stress levels is indicated to be about 17,000 psi. Holden,et found an irreversible contraction upon heating three a-ß titanium alloys in the equiaxed condition above their ß-transus temperatures. The alloys were: Ti-6Al-4V, Ti-155 A (5Al-1.3Cr-1.5Fe-1.2Mo), and C-130 AM (44-4Mn). The net contractions in length between the original equiaxed and the final Widmanstatten structures measured at room temperature were: 0.4, 0.4, and 0.7 pct, respectively. The greater creep and rupture resistance of the WidmanstStten structure of the Ti-7Al-3Mo alloy may be associated with the phenomenon

Jan 1, 1959

By David Mitchell

THE production of fluorspar is one of the smaller nonmetallic indus-tries in the United, States with a capital investment-about $10,000,000. Shipments from United States mines1 in 1936 totaled 176,231 short tons valued at $3,111,268, an average price of $17.65 per ton. The United States produces about 40 per cent of the world&apos;s fluorspar, of which about 90 per cent comes from the Illinois and Kentucky deposits along the Ohio River.2 Further detailed information on the fluorspar industry in the United States is given by Hatmaker and Davis.28 Fluorspar is marketed according to the following relative quantities and specifications: Consump- Specifications, Per Cent Use Form tion in 1936, Per Cent CaF2 SiO2 Fe2O3 Metallurgical Gravel 79 +85 -5 or lump Ceramic.. Ground 10 +95 -3 -0.1 Acid Ground 11 +98 -1 The concentration of the coarser sizes presents relatively little diffi-culty, good recoveries being obtained with jigs and tables. However, sizes smaller than about 10 mesh cannot be successfully treated by ordinary gravity separation methods and so have been accumulating as

Jan 1, 1938

By G. H. Cady, L. C. McCabe, D. R. Mitchell

While running certain float-and-sink tests, unit coal calorific values were determined for gravity fractions of a series of Illinois coals from several districts in the southern part of the state. When these values were plotted against specific gravity what appear to be characteristic curves of somewhat different shape were obtained for each district represented. This in itself seems noteworthy. The shape of the curves seems to indicate that the lightest fraction of the coal, which inspection shows to be largely vitrain, suffers the least deterioration in storage. It was also observed that on dilution curves established with dry ash and B.t.u. values the fractions of 1.35, 1.40 and 1.50 sp. gr., which constitute the greater weight per cent of a given coal sample, fall more frequently on a straight dilution line than do the lighter or heavier fractions of the same sample. In most instances there is a marked steepening between the 1.35 and the fraction of lighter gravity. In general the curve increases in steepness between the fractions of 1.50 and 1.70 specific gravity. The variations in the unit coal-specific gravity curves as well as those observed in dilution curves which appear to be pertinent to this problem are: (I) variation in coal substance with change in specific gravity, (2) variation in kind and quantity of mineral matter with the specific gravity of the fraction, (3) factors of analytical procedure which tend to introduce error in analysis, particularly in high-ash and high-sulfur fractions. DISCUSSION (A. C. Callen presiding) E. Stansfield, ? Edmonton, A1ta.-—The necessity of avoiding oxidation in grinding and in drying should be emphasized. My assumptions as to pure coal coincide with t,he author&apos;s but most of my curves are nearly straight lines. The low sulfur content

Jan 1, 1934

By Robert A. Haney, Stephen J. Gigliotti, James L. Banfield

A series of investigations were made by the Mine Safety and Health Administration to evaluate the performance of various face ventilation systems as part of a program to reduce frictional ignitions of methane and to develop face ventilation systems that could be used with the line brattice more than 10 feet from the face. Tests were conducted in a full-scale laboratory model of a face area. Systems tested included unassisted blowing and exhaust line brattice, diffuser fan and spray fan systems. Systems were evaluated at air quantities ranging from 1.4 to 7.0 m3/s (3,000 to 15,000 cfm), and brattice-to-face distances from 1.5 to 9 meters (5 to 30 feet.). Tests were designed so that systems could be evaluated for the location of the high-point methane concentration in the face area, methane dilution capacity, and face ventilation index. The methane dilution capacity is the total amount of methane a system can dilute to 1.0 volume-percent. The face ventilation index is the efficiency at which the available face air volume is being used.

Jan 1, 1982

The Institute maintains a dual relationship with students: (1) an individual relationship with a Student Associate; and (2) a relationship with local organizations of students, known as Affiliated Student Societies or Student Chapters. 1. The conditions of Student Associateship are set forth in Section 8, .Article 1 of the By-laws of the Institute (see p. 45 and following pages) During 1934, sundry amendments were made for the purpose of improving the student relationship. Post-graduate students are now eligible; and the associateship can be maintained, with the payment of the regular dues of $2 per gear, for 18 months following graduation in June. A Student Associate is given a subscription to MINING A ND METALLURGY: he is accorded the privilege of getting special publications such as "The Porphyry Coppers" and "Ore Deposits of the Western States" at the reduced prices applicable to Members; he has the privileges of the Engineering Societies Employment Service and the Engineering Societies Library; and he is not only invited but urged to attend all meetings of the Institute, its Divisions and its Local Sections. The Institute wants to extend the hand of professional fellowship to students following mineral industries curricula.

Jan 1, 1936

The 114th (New York) Meeting of the Institute will be held in the third week of February, 1917. The Committee on Papers and Publications has set Dec: 1, 1916; as the closing date for the receipt of manuscripts intended for this meeting. Manuscripts must be received by the Secretary on or before this date. If they are sent through members of the technical committee they must be sent to those committees enough in advance of the time to be forwarded and in the hands of the Secretary by the time specified. While Dec. 1, 1916, is the final closing date, it is a great advantage to get papers in as much before that time as possible as it enables them to be submitted in proof form to their authors. Papers received on or before Nov. 1, 1916, will, as far as possible, be published in the January Bulletin or earlier, thus giving good distribution among the members in advance of tile meeting. The Institute&apos;s records show that the discussion of papers is very rnuch better when they are distributed somewhat in advance of the meeting instead of in the Bulletin which goes out immediately preceding the meeting.

Jan 9, 1916

By J. H. Scaff, W. G. Pfann

The effects of impurities on the electrical properties of silicon are discussed in a companion paper by Messrs. Scaff, Theuerer, and Schumacher.&apos; It was shown that an ingot of silicon which contained boron and phosphorus in certain concentrations consisted partly of p-silicon and partly of n-silicon2 and that the common boundary between these regions was the source of a photo-voltage. These features were ascribed to the segregation of boron and phosphorus during solidification of the ingot. Because of different rates of segregation the first portion of the ingot to freeze contained a molar excess of boron over phosphorus and hence was p-silicon. The last-solidified region contained a molar excess of phosphorus and was n-silicon. This paper is concerned with the microscopic examination of such ingots. The microstructures are rather unusual in certain respects and their study has helped to show how the segregation of minor elements modifies the electrical properties of silicon. The microstructures of ingots prepared from two lots of silicon, designated 1 and 2, will be described. These lots were obtained from the Electro Metallurgical Co. Both contain 99.8+ pct silicon, but they differ in impurity analysis. For each lot will be shown the microstruc-ture of a slowly cooled ingot, for which the time of solidification is 6 min., and that of a rapidly cooled ingot, for which the time of solidification is 2 min. The ingots were prepared from 45 g charges of silicon. When an alloy freezes a cored structure is generally produced because of insufficient diffusion to remove concentration differences established during freezing. As a result of coring the first portion of a crystal to freeze is usually poorer in solute than equilibrium requires, while the last material to solidify is richer. In a columnar grain, growth is principally unidirectional and coring can produce a concentration gradient along the entire grain. By carrying the picture of the coring process from a single grain to an entire ingot in which columnar grains are aligned more or less radially, one can easily see that a composition gradient could be established between the outside and center of the ingot. This, to a considerable extent, occurs during the solidification of a slowly cooled ingot of silicon. Slowly Cooled Ingot In slowly cooled ingots of both lots of silicon, columnar grains which are approximately radial in direction and longest at the top of the ingot enclose a region in which the shapes and align- ment of the grains are considerably less regular. The central region is last to solidify and contains cavities and inclusions. The sketch of Fig 1 illustrates some of these features, as well as others which will be described below. If a polished section of an ingot is etched in a mixture of 2 parts of 20 pct HF and 98 parts of HNO3 the p-n barrier becomes visible. The overall shape of the barrier in a slowly-cooled ingot is roughly oval, as may be seen in Fig 1. The proportion of n-silicon, that is, the region enclosed by the barrier, is considerably greater in ingots of lot 1 than in those of lot 2. A sample about 34 x 1/8 X 1/8 in. was cut from a slowly cooled ingot of lot 1 with its long direction extending from the top of the ingot to the porous region. Thus its upper half was psilicon, its lower half n-silicon. A longitudinal face was polished and etched in the acid mixture. The areas of interest are identified in Fig 2. A band of parallel markings extends across the sample in the columnar region. These striae are roughly parallel to the upper surface of the ingot and cross grain boundaries with only slight deviations. They are quite distinct in the n-silicon,

Jan 1, 1950