Search Documents

By D. Webster

It has been found that cold work and annealing treatments greatly retard subsequent grain growth and re-crystallization in thoria-dispersed nickel and NiCr. It is suggested that this is due to cavities which form at the particle-matrix interface durilzg cold work. Some of' the cavities formed are stable at elevated temperatures and prevent the mouement of large-angle grain boundaries. The movement of these boundaries at elevated temperatures is known to start recrystal-lization and when they are pinned by voids recrystal-lization is made more difficult. TD Nichro,me had a maximun resistance to recrystallization when the initial structure was coarse-grained and had a low dislocation density. A precipitation reaction occurred between 700° and 1200° F in cold-worked TD Nichrome. It has been shown by Grant and his coworkers1-3 that a large part of the strength of dispersion-hardened materials is a result of the cold-worked structure produced during fabrication. In a comparison of the strength of cold-worked copper with and without an oxide dispersion, Grant4 has demonstrated that there is little difference in strength at room temperature. The function of the dispersion is essentially to maintain the cold-worked structure at higher temperatures than is possible in the base material. The dispersion accomplishes this by making recrystallization more difficult. The mechanism by which this is achieved is discussed in this paper. The fabrication history of the material has been found to greatly influence recrystallization behavior and this aspect is discussed in some detail. I) MATERIAL Three different thoria-dispersed materials were examined. 1) DuPont 2 pet thoria-dispersed nickel (TDNi) in 0.050-in. seeet. Thoria particle size is in the range 100 to 2500A. 2) DuPont 2 pct thoria-dispersed nichrome (20 pet Cr, 80 pct Ni) (TDNiC) in 0.125-, 0.060-, and 0.040-in. sheet. In the as-received condition these sheets have

Jan 1, 1969

By R. E. Fryxell, E. C. Duderstadt, P. K. Conn

Permeation rates for nitrogen through are-cast tungsten were measured in the temperature range 1800° to 2600°C at nitrogen pressure differentials of 1.0 and 0.1 atm. Gas chromatography was used to measure the quantities of nitrogen which permeated through 0.26-and 0.53-mm-thick membranes. Permeation rates were proportional to the difference between the square roots of the nitrogen pressure on each side of the membrane and inversely proportional to membrane thickness, indicating that atomic nitrogen was the difjusing species and that diffusion was the rate-limiting step of the process. Permeation coefficients calculated from the rates may be represented by the equation: where P is expressed in the units cu cm (stP)-mm per 1/2 sq cm-min-atm"' and 70.0 * 0.8 is the activation energy in kcal per mole of permeating species. In a previous paper' permeation rates were reported for hydrogen and for oxygen through tungsten. The permeation cells used for the hydrogen measurements were suitable for measuring nitrogen permeation under similar conditions, so the study was extended to include nitrogen. Permeation rates of nitrogen through the polycrys-talline arc-cast tungsten membranes were measured in the temperature range 1800" to 2600°C using two membrane thicknesses and two nitrogen pressure differentials. Permeation coefficients were calculated and the activation energy of the process determined. THEORY For diatomic gases which dissociate prior to diffusion, the quantity of gas which permeates through a membrane or wall at an elevated temperature where bulk diffusion is the rate-limiting step of the process is given by the equation: where: q = total amount of gas permeating a membrane, P = temperature-dependent permeation coefficient, A = area of membrane, t = time, p1 = gas pressure of high-pressure side, p2 = gas pressure of low-pressure side, and d = thickness of membrane. When bulk diffusion is the rate-controlling step, and the solubility of the gas obeys Henry's law, a further relationship is that, for any given temperature and pressure, the permeation is the product of diffusivity and the amount in solution. The permeation coefficient, P, is temperature-dependent according to the equation: where: Po = permeation constant, Q = activation energy, R = gas constant, and T = absolute temperature. EXPERIMENTAL PROCEDURES Cell Design and Experimental Apparatus. Two of the permeation cells used for the previous measurements of hydrogen permeation are shown in Fig. 1. Each consisted of a cylindrical chamber divided into two parts by a permeation membrane fabricated from high-purity (>99.9 pct W) wrought tungsten sheet made from vacuum arc-cast tungsten. The membrane in one cell was 0.26 mm thick and the other was 0.53 mm. The fabrication of these cells was described previously.' The permeation cells were mounted vertically in a high-temperature tungsten resistance furnace and the membranes and the center portions heated to test temperatures. Temperatures were measured by sighting an optical pyrometer on the edge of the membrane through a small hole in a tungsten plate which was fastened to the side of the cell. This arrangement provided an approximate black-body condition and eliminated the need for emittance corrections. Appropriate corrections were made for the quartz window through which the temperatures were measured. Argon gas flowed through the 10-liter volume of the furnace at the rate of 4.7 liters per min. An impurity

Jan 1, 1969

By A. Totani, S. Nakajima, H. Okazaki

The phase diagram for the SnTe-SnSe system has been studied in the temperature range from 300° to 900°C by differential thermal and quenching techniques. The X-ray measurements were made on quenched specimens. High-temperature diffraction was also made to study the phase transition in SnSe. The system is proved to be of a eutectic type in which no intermetallic compound exists. The eutectic point is at the composition SnTeo.55 Seo.45. the eutectic temperature being 755°C. Solid solubility limits are SnTeo.6Seo.r and SnT eo. 3s Seo.6s at the eutectic temperature, and change almost linearly to SnTeo.aaSeo.lz and SnTeo.18 Seo.az as temperature decreases to 300°C. It was shown that the SnSe phase has a phase transition of the second order at about 540°C and that the transition temperature decreases with increase of the SnTe content. THERMOELECTRIC properties of tin telluride (SnTe) and tin selenide (SnSe) have been studied extensively in recent years. The variation of physical properties with composition could be of interest if these compounds form an appreciable crystalline solution. The purpose of present investigation is to confirm the formation of crystalline solution or intermetallic compound, if any, and to establish the phase diagram for this system. The crystal structure of SnTe is NaCl type with a cubic unit cell1 (a = 6.313A). The crystal of SnSe having an orthorh2mbic unit cellz (a = 11.496, b = 4.1510, and c = 4.4437A) is isomorphous with tin sulfide (SnS) which has a distorted sodium chloride structure. It has been known that SnSe has a phase at at 540°C; the transition has been assumed to be of the second order. As far as we know, only two studies on the SnTe-SnSe pseudobinary system have been reported. The conclusion obtained in these papers is that, in the composition regions near SnTe and SnSe, the system forms a crystalline solution of the SnTe structure and the SnSe structure, respectively, and that, in the intermediate region, both phases coexist. However, neither the variation of the solid solubility vs the temperature nor the liquidus and solidus were investigated. Hence present writers have attempted to determine the phase diagram of the system by differential thermal analysis (D.T.A.) and X-ray diffraction. EXPERIMENTAL Sample Preparation. Starting materials, SnTe and SnSe, were prepared by the direct fusion of commercially available high-purity (99.999 pct) elements. Stoichiometric amounts of each couple Sn-Te or Sn-Se were weighed into a clear fused silica ampule. After evacuation to a pressure below 10-3 mm Hg, the am- pule was sealed, and annealed at 900°C for 5 hr. The melt was quenched in water. X-ray analysis confirmed the formation of a single phase of SnTe or SnSe. The other samples, SnTel-,Sex were synthesized from these SnTe and SnSe by mixing them in the required ratio, followed by annealing at 900°C and quenching. These samples were used directly for D.T.A. For X-ray measurements, samples were annealed at 700°, 600°, or 500°C for 100 hr or at 300°C for 150 hr, and then quenched in water. It was found that the lattice constants of the SnTe phase annealed for 150 hr at temperatures above 500°C did not differ from those annealed for 100 hr at the same temperatures. However the X-ray phase analysis showed that at 300°C the annealing for 150 hr was necessary to attain a true equilibrium state. D.T.A. The solid-liquid equilibrium temperature was determined from D.T.A. measurements. The sample was sealed in an evacuated silica tube and molybdenum powders sealed in an another tube were used as a reference material. The sample and the reference tube were placed in a nickel block and were heated from room temperature to 900°C at a rate of 3°C per min and then cooled down at the same rate to 600°C. Thermocouples for these measurements were Pt-Pt. Rh (10 pct) and the error of temperature measurements was within + l0C. D.T.A. curves were obtained on a two-pen recorder and an automatic controller (PID type) was used for the program of heating and cooling. When temperature reaches the solidus from the low-temperature side, there appears an endothermic peak. The solidus temperature was determined by extrapolation of the straight portion of the starting flank of this peak to the base line. In a similar way, the liquidus temperature was determined from an exothermic peak on D.T.A. cooling curve. In the case of supercooling, if any, its degree can be estimated from the magnitude of the abrupt temperature rise. X-Ray . X-ray powder patterns were taken by a diffractometer using CuK, radiation. Since the SnSe crystal is cleaved easily, the powders become flaky when SnSe-rich samples are ground in an agate

Jan 1, 1969

By M. T. Hepworth, T. P. Papazoglou

Hydrogen diffusion in hcp and bcc titanium in the temperature range 610° to 900°C was measured by reacting cylindrical specimens of high-purity titanium at constant temperature with small constant pressures of hydrogen of the order of a few Torr. In the range 0 to 6.7 at. pct H in hcp titanium, the diffusion coefficient D in sq cm per sec is given by: where T is in °K and R in cal per g-atom OK. Only three measurements of diffusivity in bcc titanium were made: at 900' : the diffusivity in ß titanium was found to be 1.8 x 10-4 sq crn per sec. McQUILLAN1 has studied the constitution of the Ti-H system and reported the concentration of hydrogen as a function of pressure of hydrogen and temperature. He found hydrogen absorption was reversible and rapid at temperatures above 500°C in both crystallographic modifications, the a (hcp) phase and the ß (bcc) phase, with the latter phase stabilized by hydrogen additions. Wasilewski and Kehl 2 measured the diffusivity of hydrogen in hcp and bcc Ti-H alloys. For bcc alloys, they reacted cylindrical specimens of titanium with hydrogen gas at 1 atm pressure. They measured the rate of absorption of hydrogen isothermally on specimens ranging from zero hydrogen content when above the transformation temperature to hydrogen contents sufficient to stabilize the bcc phase when below the transformation temperature. By integrating Fick's second law for a cylindrical geometry, assuming a diffusion coefficient independent of composition, they calculated diffusivities as a function of temperature. In the range 650" to 1000°C their results in bcc titanium yielded the expression: where D is in sq cm per sec, T in OK, and R the gas constant in cal per g-atom-OK. Their studies on the hcp a phase were conducted by exposing long cylindrical titanium specimens to hydrogen at a sufficiently high pressure to establish a surface layer of fl phase 80 to 120 u thick for the duration of an isothermal experiment. Concentration profiles were then determined by hydrogen analysis from chips obtained upon machining quenched specimens. The diffusivity of hydrogen was then calculated yielding the expression: The present investigation was undertaken principally to redetermine the diffusivity data on a titanium by a direct absorption from the gas phase at sufficiently low hydrogen pressures to avoid the presence of a surface bcc phase and also to check the diffusivity data at low hydrogen concentrations in the bcc stmcture. EXPERIMENTAL PROCEDURE High-purity electrolytic sponge titanium (99.9 pct) of BHN 91 was arc-melted, forged, rolled, and machined into cylinders of final hardness, upon annealing, of BHN 92. Cylindrical specimens of two sets of dimensions were used: 1.524 by 2.931 cm and 1.905 by 3.663 cm diam and length, respectively. The experimental apparatus used for annealing specimens and for admitting known amounts of hydrogen at constant pressure is shown in Fig. 1. In a typical experiment, a specimen was lightly abraded with fine-grain silicon carbide, washed with water and detergent, and then thoroughly degreased with reagent-grade tri-chlorethylene and acetone. The specimen was suspended by a Chrome1 wire in the center of a quartz furnace tube, without contact with the tube, and heated to 925°C (as measured by a thermocouple adjacent to the specimen, outside the tube) for a period of at least 4 hr under a vacuum of from 10-6 to -7 Torr as measured by an ionization gage. The furnace temperature was then adjusted to the temperature chosen for the particular diffusion study and the specimen allowed to equilibrate thermally. Hydrogen was then ad-

Jan 1, 1969

By B. Chalmers, Stefan Wojciechowski

Rotary oscillation of the mold has been used to produce mechanical stirring of the melt during unidirectional solidification. Al-Cu alloys (1 to 4 wt pct Cu) were solidified to study the influence of alloy composition, temperature at which intensive cooling was initiated, and intensity of stirring on the temperature distribution in the sample, the resulting structure, and the copper microsegregation at the columnar to equiaxed transition. The Proposed explanation for the equiaxed solidification in stirred castings consists of the melting off of dendrite fragments, their partial remelting in hotter liquid, and the subsequent growth of the surviving part when the temperature of the melt is lowered. This may result in the formation of a crystal network, which can stop the growth of the columnar crystals and produce the equiaxed zone. It has long been known and many times affirmed that ultrasonic vibrations or relative motion of liquid and solid can significantly reduce the length of the columnar zone and refine the grains in the equiaxed zone in ingots and castings. Because of the technological importance of these phenomena many investigations have been conducted in which ultrasonic energy or mechanical vibration,1-6 electromagnetic stirring,7"10'17 magnetic stirring,"'12 or mechanical stirring13'14 were used to produce the relative liquid-solid motion. More recently, the question of the importance of natural (or thermal) convection has been raised.15-l7 Several possible mechanisms have been suggested.l,8,18-20 They can be divided into two main groups. The first group includes such nucleation hypotheses as nucleation frequency enhancement due to cavitation at the mold wall or other surfaces; cavita-tion in the body of the liquid resulting from the pressure wave, or an agglomeration mechanism, which involves the formation of nuclei by the accretion of subcritical nuclei. The second group considers the grain-refining action to be due to crystal multiplication phenomena such as the removal of the dendrite fragments by viscous forces or by a high-pressure cycle following cavitation or by a melting-off process. Sbme recent investigations give good experimental support to the melting-off proposa1.21-23 The purpose of the present study was to examine the effect of mechanical stirring during the unidirectional solidification on the structure of alloy samples and on the solidification variables. The motion of the liquid was produced by rotary oscillation of the mold around its vertical axis.

Jan 1, 1969

By C. Atkinson

A method is described for the numerical solution of the diffusion equation with a composition-dependent diffusion coefficient and applied to the radial growth of a cylinder; the radial growth of a sphere, and the symmetric growth of an ellipsoid. Sample applications of the method are made to the growth of particles of proeutectoid ferrite into austenite. RECENTLY&apos; we described a method for numerical solution of the diffusion equation with a composition-dependent diffusion coefficient for the case of the growth of a planar interface. In this paper we extend this method to describe the radial growth of a cylinder, the radial growth of a sphere, and the symmetric growth of an ellipsoid. In the latter case, limiting values of the axial ratios of the ellipsoid reduces the problem to one of a cylinder, a sphere, or a plane depending on the axial ratio. A check on these limiting values is made in the results section. In all of these cases we consider growth from zero size. A natural consequence of this assumption as applied to the sphere, for example, is that the radius of the sphere is proportional to the square root of the time. This is consistent with the condition that the radius is zero initially, i.e., grows from zero size. It may be argued that it is more realistic to consider particles which grow from a nucleus of finite initial size; even in this case the analysis of this paper is likely to be applicable. This can be seen if a comparison is made of the work of Cable and Evans,2 who consider a sphere of initially finite size growing by diffusion in a matrix with a constant diffusion coefficient, with the results of Scriven3 for growth from zero size. This comparison shows that the rates of growth in each case differ trivially by the time the particle has grown to about five times its initial size." This investigation is a generalization of those of Zener,4 Ham,5 and Horvay and cahn6 to the situation often encountered experimentally, in which the diffusion coefficient varies with concentration. First let us consider each of the cases separately. I) GROWTH OF SPHERICAL PARTICLES FROM ZERO SIZE In this case the differential equation in the matrix depends only on R, the radius in spherical coordinates, and can be written: ? 1 <^\ ^13D . , dt U\dRz + R 3Rj + dR dR [ J where C is the composition, t is the time, and D is the diffusion coefficient which depends on c. The boundary conditions will be: c = c, at the moving interface in the matrix, c = c, at infinity in the matrix (and at t = 0, everywhere in the matrix), c = X, is the composition in the spherical particle. Each of the above compositions is assumed constant. In addition there is the flu condition at the moving interface which can be written: , dR0 ~/3c dt \dR/H =Ra where R,, which is a function of t, is the position of the moving interface. We make the substitution q = RI~ in [I] reducing this equation to: & - m - *ws) »i where we have written D = D,F(c) or simply D,F, and Do = D(c,). Thus F[c(q0)] = 1 where q, = ~,/a is the value of the dimensionless parameter q evaluated at the interface. Multiplying Eq. [2] by dq/dc and integrating, we find: where the lower limit of the integral has been chosen so that dc/dq — 0 as c — c,, thereby satisfying the boundary condition at infinity. We require, then, to solve Eq. [3] subject to the condition c = c, when q = q, (this follows from putting R = R, at the interface) together with the flux condition which can be rewritten in terms of q as: Eqs. [3] and [4] together with the condition c = c, at q = q0 enable us to find 77, and the concentration profile c = c(q). Numerical Method. We treat Eq. [3] in the same way as we did the corresponding equation for the planar interface problem&apos; i.e., by dividing the interval c, to c, into n equal steps so that: cr = ca -rbc [5] where r takes the values 0, 1, ... n and we call no,, q1, ... nn the values of n corresponding to the compositions c,, c,, ... c,.

Jan 1, 1970

By S. A. Levy, J. D. Wood, J. F. Libsch

A study of the preparation and characteristics of a sevies of Fe-C-N alloys has been conducted. X-ray, microhardness, and metallographic data from a series of single-phase alloys produced by controlled nitriding of carburized foils are reported. The existence of a, y&apos;, and E carbonitride has been confirmed and it has been found that y&apos; is the hardest of these three phases. These results have been used to interpret the structures observed in nitrided steels. ThIS paper represents the second phase of a three-part study concerning combined nitriding and induction hardening. The first part&apos; reports the engineering properties (depth hardness, fatigue, corrosion, and tempering resistance) obtained when seven different steels were subjected to the combined surface hardening treatment. The present paper concerns the nature of a series of single-phase alloys prepared by controlled nitriding of carburized foils. The objective was to simulate the various layers present in the as-nitrided steels. A third paper will report data concerning induction hardening of the foils and will attempt to set forth a mechanism for the high hardness obtained with the combined treatment. Studies of nitriding generally fall into three categories. The first were performed with bars using conventional nitriding procedures, thus yielding a nitrogen gradient and a series of phase layers near the surface.2-6 Such studies were complicated by the presence of the nitrogen gradient, for it was difficult to correlate microhardness and X-ray data with chemical composition. There were always complications due to penetration of the X-ray beam which yielded data influenced by underlying layers. Similar difficulty was experienced in taking hardness readings on a tapered specimen or in isolating various layers by machining. A second group of investigations was primarily concerned with establishment of regions in the Fe-N7,9,10 or the Fe-C-N phase diagram.8 These were performed with powder specimens which were nitrided in am-monia-hydrogen mixtures to produce a series of single-phase specimens. Unfortunately, the powder specimens were not amenable to either microstruc-ture or microhardness study. The third was essentially a compromise of the first two. Bose and Hawkes," using 0.005-in.-thick iron foils, were able to obtain microhardness, microstruc-ture, composition, and X-ray data on Fe-N alloys of eutectoid composition by equilibration in ammonia-hydrogen mixtures at 1290°F. To obtain a better understanding of the nitriding process and the characteristics of the phases in ni-trided plain carbon steels, the present investigation was undertaken. The investigation was patterned after that of Bose and Hawkes with the exception that nitriding was performed at 930°F (below the eutectoid temperature), as in the case of conventional nitriding. In addition to gaining some understanding of the source of high hardness of nitrided and induction-hardened steels, found in a previous study,&apos; this investigation was concerned with the possibility of controlling the phases present in a nitrided case through the use of ammonia-hydrogen mixtures. Knowledge of the properties of each phase and the conditions necessary for its production could make it possible to avoid undesirable surface layers in nitriding. EXPERIMENTAL PROCEDURE Specimen Preparation. A specimen thickness of 0.005 in. was selected to insure that a uniform nitrogen concentration could be obtained in a reasonable length of time by equilibration in an ammonia-hydro-gen atmosphere. The starting material was a vacuum-cast ingot of pure iron, the major impurities of which were: C, 0.003 pct; 0, 0.014 pct; S, 0.004 pct; N, 0.003 pct.* &apos;Compositions are quoted as weight percent except as noted. The ingot was heated to 1500°F in a nitrogen atmosphere and forged to a slab 0.25 in. thick. The material was then reduced to 0.005 in. by alternately cold rolling and annealing in a nitrogen atmosphere at 1600°F. This material was divided into five groups of specimens which, after carburizing, yielded the following carbon contents: 0.003, 0.28, 0.36, 0.46, and 0.74 pct C. The carburizing was performed by the Leeds and Northrup Research Laboratories, using a controlled "carburizing potential" which yielded a uniform carbon concentration throughout the cross section.

Jan 1, 1970

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

c axis compression behavior of beryllium single crystals at three purity levels under hydrostatic pressures up to 27 kbars was determined. Extensive non-basal slip, observed by two-surface trace analysis and transmission electron microscopy, occurred under a hydrostatic pressure of about 12 kbars (175 ksi) for the high-purity (twelve-zone pass) material and at about 19 kbar (275 ksi) for the lower-purity (zone-leveled) material. Prismatic loops with a (c + a) Burgers vector were observed in association with second-phase parti- A principal factor limiting the use of beryllium is its brittle behavior when tested at the usual strain rates (E = 10-4 sec- 1) at temperatures below about 200°C and under impact conditions at temperatures in excess of 200°C. It has been proposed&apos; that the brittle-ness of beryllium is associated with the lack of a sufficient number of independent slip modes and the absence of a slip mode with a Burgers vector out of the basal plane [presumably (c + a) pyramidal slip mode] and to the ease with which beryllium cleaves on the basal and second-order prism planes. The absence of pyramidal slip has been attributed to a high Peierls-Nabarro stress associated with the motion of dislocations with a (c + a) vector and the ease with which cleavage occurs on the basal and second-order prism planes. The experimental evidence in support of the proposed explanation for the brittleness of beryllium is far from complete; for example, that the ductile-to-brittle transition in polycrystalline beryllium is associated with the operation of profuse (C + a) slip has not been unequivocally established. The occurrence of (c + a) slip ({1122}(1123)) has been experimentally established2-5 under conditions where basal and prism cleavage are restricted in a c axis compression test. In these investigations (C +a) slip was found in high-purity beryllium single crystals tested in c axis compression* at 200°C and in Be-4.4 pct Cu and Be-5.2 pct cles in the lower-purity materials tested. The loops were related to surface "extrusions" observed on many of these same specimens. Nonbasal dislocations operating on (1122) planes with a (c + a) Burgers vector were observed. The presence of c and a dislocations together with (c + a) dislocations suggests that the (c + a) dislocations dissociate presumably on unloading or after failure of the test crystals to c and a dislocations. terial, (c + a) slip has only been observed near the the fracture4 surface in room-temperature c axis compression tests. Fracture in these tests occurs without measurable plastic flow, as determined with a strain sensitivity of 10"6. Since it has been shown for many metals that the application of hydrostatic pressure suppresses fracture,?-&apos; it was felt that studying the behavior of unalloyed beryllium single crystals stressed in c axis compression under a hydrostatic pressure would reveal whether (c + a) can occur if fracture was prevented, and that it might elucidate the role of (c + a) slip in the ductile to brittle transition. Evidence that (C + a) slip is associated with increased ductility in a high-pressure environment has been found in stress-strain tests on poly crystalline beryllium.10 The present paper describes a study on the influence of a hydrostatic pressure environment on the occurrence of (c + a) slip in beryllium single crystals. Material of two purity levels was tested in c axis compression over the pressure range ambient to about 27.5 kbars.* 1) MATERIAL PREPARATION AND CHARACTERIZATION Two lots of low-purity single-crystal beryllium were used. The first lot was "ingot secondary refined grade" and designated lot A. The second lot (lot B) was produced by a two floating zone pass zone-leveling operation in an argon-filled sealed quartz apparatus on a 1-in.-diam by 12-in.-long bar of Pechiney secondary refined-grade vacuum-cast and hot-extruded material. The high-purity material (lot C) was made by traversing twelve floating zone passes through a similar bar of Pechiney secondary refined-grade vacuum-cast and hot-extruded material. In a series of spark cutting and lapping procedures,11 single-. crystal specimens some 0.12 in. sq by 0.30 in. high were made with the sides Parallel to the first- and second-order prism planes and the basal plane within 3&apos; of arc of the top and bottom surfaces of the specimen. Such an accurate orientation is necessary because of the large difference in resolved shear stress

Jan 1, 1970

By R. W. Carpenter, J. C. Ogle

It is possible, by using pack-rolling instead of conventional rolling, to reduce a number of metals to thicknesses of 2µm or less. Such thinfoils are generally made at room temperature without intermediate annealing. In addition, pack-rolled foils fail by developing pinholes at thicknesses near 2µm instead of developing the shear cracks usually observed in cold-rolled ductile metals. This paper presents the results of a general investigation of the deformation substructure and texture developed in copper and iron pack -rolled from 130 to about 2µm thickness. Electron microscopy showed that in both metals a fine (0.2 to 0.5?µ m) deformation subgrain structure formed during pack-rolling; in neither case was this substructure grossly different from substructures formed during conventional rolling. The deformation texture formed in pack-rolled iron was quite similar to usual bcc textures; however, in the case of copper, the cube texture was stable during pack-rolling and the normal copper deformation texture was unstable. It is shown analytically that the constraining pack induced a large hydrostatic pressure in the foils during pack-rolling. The pinhole failure mechanism is attributed to the presence of the large hydrostatic pressure during pack-rolling; this strongly suppressed the growth of shear cracks. The stability of the cube texture in copper is also probably due to the unusuul stress distribution developed during pack-rolling. EXPERIMENTS at several laboratories have shown that very thin foils of the common structural metals and many of the rare earths can be made by "pack-rolling". 1-3 The technique was originally developed to make specimens for nuclear scattering experiments and foils for X-ray filters. It is also useful for making experimental laminar metallic composite bodies and foils thin enough for direct examination by ultra-high voltage electron microscopy without the need for special thinning techniques. Pack-rolling in the present context means a three-layer pack, with the material to be rolled into foil comprising the center layer. The outer two layers, which constrain the foil during reduction, are ordinarily austenitic stainless steel. Typically, a 130 µm (0.005 in.) metal strip can be reduced to a final thickness of 2 µm or less by this process. This is accomplished at room temperature, without intermediate annealing. It has been observed that foils produced by this process do not exhibit at any stage of their reduction the severe work-hardening found in strip rolled by conventional cold-rolling methods. Neither is the failure characteristic the same."&apos; Conventionally cold-rolled ductile metal strip fails by developing shear cracks on planes whose normals nearly bisect the angle between the rolling direction and normal to the rolling plane; these are planes of maximum shear stress. In pack-rolling this mechanism has not been observed; failure occurs by the formation of pinholes on the foil surface (penetrating the foil). If pack-rolling is continued the hole density increases. These differences in behavior imply the existence of appreciably different substructure in pack-rolled foils compared to substructure in conventionally rolled material, or perhaps that the geometry of pack-rolling has an effect on the foil behavior. This paper describes an investigation of deformation substructure and texture in some specimens of pack-rolled copper and iron, and some considerations of the stress distribution in the foils during rolling that result from the geometry of pack-rolling. EXPERIMENTAL DETAILS Three different materials were used for pack-rolling in the present work: soft copper sheet (99.8 pct Cu, 0.03 pct 0, electrolytic tough pitch) and two types of iron, Ferrovac E* and Armco iron. Each was "Crucible Stccl Co. initially in the form of 130 µm annealed strip with grain size ranges of approximately 10 to 40 µm. The initial texture of the copper (determined as noted below) was the normally observed cube type (001)[100]; there was evidence of a small amount of material in the cube-twin orientation reported by Beck and Hu.4 The initial texture of the Ferrovac E was similar to that reported for recrystallized iron by Kurdjumov and sachs,5 who list the principal orientations as {111}<112>, {001}<110> 15degfrom RD and a weak component {112}(110) 15 deg from RD. The starting texture of the Armco iron was not determined. Pack-Rolling Procedure. A four-high mill was used for all specimens. The work roll and backing roll diameters were 1.625 and 5.25 in., respectively. The peripheral roll speed of the work rolls was about 2.5 in. per sec. All foils were initially reduced from 130 to 100 µm by conventional straight rolling and then inserted into a pack, without any intermediate annealing, for further reduction. The pack consisted of an 0.033 in. (838 µm) thick 3 by 6 in. polished sheet of austenitic stainless steel, folded to make a 3 by 3 in. jacket. After folding, the jacket was given a small reduction to close the fold tightly before insertion of the foil. During pack-rolling a constant change in roll spacing was made every third pass. The roll-spacing change corresponded to a 5 pct reduction in thickness for a new pack. This approached a 10 pct reduction when the pack had decreased to about half its original thickness. At this point the deformed pack was discarded and a new one

Jan 1, 1970

By R. K. Iyengar, G. C. Duderstadt

An investigation was carried out to determine the effect of Ca-Si additions on the dissolved oxygen content of liquid steel. An apparent equilibrium was reached after holding the melt for some time when the total oxygen content of the melt was identical with the dissolved oxygen. Results of the investigation show that for deoxidation with silicon and manganese the apparent equilibrium is reached after 8 to 12 min and the oxygen content of the melt is in good agreement with values reported in the literature for similar steel compositions. Ca-Si additions decrease the dissolved oxygen content appreciably below that obtained with Si-Mn deoxidation. It is postulated that some calcium dissolved in liquid steel at the time of its vaporization combines with dissolved oxygen to form CaO which then fluxes the manganese silicate, thereby lowering the activity of the deoxidation products. Slow flotation of calcium silicate inclusions is attributed to their slower growth rate. An addition of aluminum (to yield <0.005 pct Alsol) prior to introduction of Ca-Si improves the kinetics of removal of resulting deoxidation products. WITH the introduction of continuous casting of billets and blooms, application of calcium-containing alloys for deoxidation purposes has gained new interest. More so than in conventional ingot casting, the degree of control of the dissolved and total oxygen contents in steel for continuous casting can determine the success or failure of the operation because these affect both surface (pinholes) and internal quality of the billets. Of the available deoxidizers, only silicon has so far found wide application. However, in the typical range of application (0.20/0.30 pct Si), it is too weak a deoxidizer to suppress pinhole frequency to the level desirable for all but the least demanding appli-cations (approximately 10/50 pinholes per sq ft, de-pending on degree of subsequent reduction). On the other hand, Vincent&apos; has shown that it requires ap-proximately 0.007/0.008 pct A1 soluble in the steel to suppress pinhole formation to <10 pinholes per sq ft. In view of the difficulty of consistently maintaining this aluminum level and the associated problem of tundish nozzle constriction2 when aluminum is added to the ladle, steelmakers have searched for other de-oxidation alloys to circumvent the problem. Calcium-containing alloys offer such a possibility. When employed as a partial substitute for silicon, CaSi (30 pct Ca/60 pct Si) additions are reported to yield adequate pinhole contro1.3 Its use simultaneously preserves the "fluidity" of the steel and ensures good castability.4 Oxygen contents as low as 0.007 to 0.014 pct have been obtained with CaSi additions varying between 3 to 8 lb per ton.5-7 Due to the high degree of vaporization of calcium at the temperature of molten steel and the different methods used to introduce it into the liquid, the reported results show considerable scatter and lack of consistency. According to several investiga- deoxidation tors, the flotation characteristics of CaSi products are not as favorable as those found for alumi-num but are similar to those established for silicates with low alumina content.678 Thus, cleanliness ratings were improved when CaSi was replaced by a com-bination of Si + A1 followed by CaMnSi additions.5,9 In view of the lack of a comprehensive description of the deoxidation potential of CaSi alloys, a study was undertaken of the effect of CaSi additions on oxygen content in comparison to Si + Mn and Si + Mn + Al. The alloy chosen for this study contained 63 pct Si, 32 pct Ca, <3 pct Al, and 2.5 pct Fe. EXPERIMENTAL PROCEDURE The experiments were divided in three groups as shown in Table I. In each group, the CaSi addition was increased successively while maintaining the melt composition constant. The experiments in the third group were designed to determine the effect of prede-oxidation with small amounts of aluminum. Ingot iron, containing 0.02 to 0.03 pct C and 0.03 to 0.05 pct Mn, was melted in a 100-lb magnesia crucible. Pig iron was added to the melt under air in an induction furnace to attain the desired carbon content of 0.05 to 0.15 pct and thereby control the initial oxygen content of the melt between 0.04 and 0.015 pct. After removal of the slag, the furnace was sealed and argon was introduced through an opening in the graphite cover, Fig. 1. When the desired temperature was reached, electrolytic manganese was added to the melt and pin samples were taken (7 mm silica tubing) to establish initial oxygen content. To obtain maximum efficiency, CaSi and metallic silicon were introduced in a sealed steel pipe into the bath. This procedure assured minimum loss of calcium through vaporization as the deoxidants were always released at the bottom of the melt. Samples were taken at regular intervals and quenched in water. Temperature of the bath was measured with a Pt/Pt-10 pct Rh thermocouple. Portions of the pin sample were used for oxygen analysis; five determinations per sample were made to obtain average oxygen content. Oxygen analyses were made by the inert carrier gas fusion method with frequent cross checks with the vacuum fusion method.

Jan 1, 1970

By D. O. Hobson, P. L. Rittenhouse

We have recently found that many lots of Zircaloy-2 and -4 tubing tested in tension deform to cross section shapes that are "polyhedral" rather than circular. The noncircular cross sections seem to result from a circumferential variation in plastic proper -ties and, therefore, in texture. We examined the diffracted X-ray intensity from (OOOl), {1010), {ll20}, and {1011} planes parallel to the tubing surface around the entire circumference. Tubing that deformed to a circular cross section showed <5 pct variation in diffraction intensity around the circumference from any of these planes. Greater intensity variations were found for all the tubing materials that developed non-circular cross sections during deformation. In each instance the number of intensity maxima and minima was consistent with the number of sides of the &apos;polyhedral" cross section. THE effects of crystallographic texture on the mechanical properties of zirconium, zirconium alloys, and other anisotropic hexagonal materials such as titanium and hafnium have been intensively studied. If the natural crystallographic anisotropy of these materials could be controlled by selected fabrication operations, a material could be produced with a texture, or preferred orientation, in which the maximum strength directions are in the stress directions of the structure. The permissible stress levels of the structure could then be increased. Rittenhouse and Pickle-simerl have shown that highly textured Zircaloy-2 plate can vary from 52,000 to 70,000 psi in tensile yield and from 62,700 to 122,000 psi in compressive yield strengths as a function of specimen orientation. Similar texture effects have been observed in Zircaloy tubing, whose mechanical properties differ depending upon whether the tubing has basal poles predominantly radial or tangential and upon the mode of testing. These same texture effects might be troublesome if the texture in the tubing is not uniform around the tube walls. This paper is concerned with the effects of nonuniform texture on the strain behavior of commercial Zircaloy tubing. BACKGROUND Previously, various lots of commercial Zircaloy tubing were tested under selected stress conditions as part of a program to determine the four quadrants of the yield locus. One of the testing procedures was uniaxial tension and it is the influence of texture variations on the tensile deformation behavior of the tubing that is of interest here. The effect of texture on the strain behavior in tubing is very apparent from a uni-axial tensile test.2 This behavior is illustrated schematically in Fig. 1 for three different tubing textures: 1) basal poles predominantly in the radial direction; 2) basal poles predominantly in the tangential direction, and 3) basal poles equally distributed between the radial and tangential directions. In the first example most of the grains are oriented for prism slip to operate to allow axial lengthening and diametral reduction of the tube. Reduction in wall thickness requires {1122} twinning, a more difficult operation than slip.* In the second example, the texture is such that *The singleCrystal analogy will be used quite often in this paper when strong texturesare being discussed. The textured material is assumed to react as if it were a single crystal aligned in the same orientation and under the same stress system as the predominant texture._____________________________________________ prism slip operates to give axial lengthening and wall thinning. Diametral reduction requires twinning and again should be more difficult to accomplish. A specimen with basal poles equally distributed between the radial and tangential directions should exhibit about equal diametral and wall strains.* Table I shows the *Diametral strain is accomplished by a combination of circumferential and longitudinal strains. But, for the purposes of this paper, it will be considered as a strain causing a change in the length of a specified diameter.__________ strain behavior of two lots of tubing with different textures. The first tube has a texture with basal poles equally distributed between the radial and the tangential directions. The ratio of true thickness strain to true diametral strain is almost unity. The second tube has a predominantly radial basal pole texture and it is apparent that most of the total strain has occurred by diameter reduction, just as one would predict. There is over three times as much diametral strain as thickness strain. RESULTS We found that specimens from certain lots of commercially fabricated tubing did not retain round cross sections during uniaxial testing. Instead, the speci-

Jan 1, 1970

By J. Szekely, G. P. Martins

A formulation is given for describing the rate of expansion of spherical bubbles rising in liquids the freeboard of which is evacuated. The computer solution of the resultant differential equations has shown that, for low freeboard pressures (less than about 5 mm Hg), on approaching the free surface the bubbles expand much less rapidly than predictable from equilibrium considerations. In other words, in this region the pressure inside the bubbles will be significantly larger than the static pressure in the liquid corresponding to the position of the bubble. These theoretical predictions were confirmed by experimental work, using two-dimensional air bubbles rising in mercury. The important consequence of these findings is that the expansion of gas bubbles in vacuum degassing operations will be a great deal less than expected from hydrostatic considerations. This would lead to a significant reduction in the available interfacial area and may explain the apparent poor efficiency of many vacuum degassing units. VACUUM degassing as a treatment for liquid steel has gained widespread popularity in recent years; the number of known installations exceeds several hundred at the present time.&apos; Although much information is available on both the thermodynamics of the system and the overall performance of various industrial units, much less is known about the fundamental aspects of the process kinetics.2-4 The basic physical situation common to virtually all vacuum degassing operations is the interaction between gas bubbles (swarms of bubbles) and the surrounding molten metal, held in a container, the freeborad of which is at a low absolute pressure. Once formed (or introduced from an external source) the bubbles will ascend, due to the buoyancy forces, and, during this ascent, a significant increase in their volume will occur. This progressive increase in the bubble volume is due to two factors: a) the continuous reduction in the static pressure acting on the bubble during its rise; and b) mass transfer into the bubble from the surrounding molten steel. In a recent paper Richardson and Bradshaw developed equations5 for describing mass transfer into gas bubbles from molten metals at reduced pressures. However, in deriving these expressions it was assumed that the pressure inside the bubble was identical to the static pressure in the adjacent liquid. In other words, the volume of the bubble was considered to be in equilibrium with the pressure of the fluid adjacent to it. This assumption, thus their analysis presented, was thought to be reasonably accurate for most of the bubble&apos;s ascent; however, it was unlikely to be valid in the immediate vicinity of the free surface, held at a low pressure. It was pointed out in the discussion6 that the region close to the surface may be of considerable importance as both the driving force and the interfacial area available for mass transfer are at their highest value here. The &apos; &apos;anomalous" behavior of gas bubbles when approaching a free surface at low pressures was recently confirmed in a preliminary investigation by Szekely and Martins. ?1 Here high-speed motion photography was used to study air bubbles rising in a column of n-tetradecane with a freeboard pressure of 0.1 mm Hg. It was found that significant distortion of the bubbles occurred on approaching the free surface; furthermore, the expansion observed was much less than what one could expect from hydrostatic considerations, i.e., factor a previously discussed. It follows from the foregoing that a detailed study of these phenomena would be justified both from fundamental considerations and because of their potential relevance to technology. The purpose of the paper is to present a more realistic formulation for the expansion of a gas bubble approaching a low-pressure region, together with a comparison of the theoretical prediction with experimental measurement. An inert bubble will be considered in the first instance; it is thought that the understanding of the fluid mechanics is an essential first step toward the realistic formulation of the mass transfer process. This latter problem will be the subject of a subsequent publication. FORMULATION The Physical Model. Consider a spherical bubble, of initial radius Ro, rising in a fluid, having a density pL. Initially let the bubble be at a distance H from the free surface, and at a pressure Pgo, as illustrated in Fig. 1. Pgo, the initial pressure in the bubble, is given by the following equation: pgo = Po = Ptp +pLgH [ la] where Po is the pressure in the liquid corresponding to the initial position of the bubble and Ptp is the pressure at the free surface. The fluid pressure at

Jan 1, 1970

By H. E. Exner

This article is a critical review of the influence of surface preparation on crack formation at Vickers indentations in the test used by Palmqvist3-7 to evaluate the toughness of cemented carbides. Experimental results are presented which clearly show that grinding introduces compressive surface stresses into the cobalt phase and thus reduces the crack length. The deformed surface layer is removed by polishing and a stress pattern is approached corresponding to that in the bulk material. Cracks of maximum length are characteristic of this stress state. Deformation stresses can be removed by annealing above 800°C. On the basis of these results , sample preparation for the crack length test can be simplified, the accuracy of measurement is improved, and a simple and significani parameter is found to describe crack resistance of cemented carbides. FOLLOWING suggestions by Ammann and Hinniiber,1&apos;2 Palmqvist3-7 developed a method for testing the toughness of cemented carbides using as a measure the sum of crack lengths at the four corners of a Vickers hardness indentation. This method has several advantages over the bend test commonly used in carbide technology: a) specially formed samples are unnecessary; b) sufficient information can be obtained from one sample; c) the scatter is relatively small; d) the range of actual values for commercial cutting alloys is wide. Thus, this test is both cheaper and more precise than the bend test. Nevertheless, Palmqvist&apos;s method is not widely used, mainly for two reasons: a) The relationship between crack length and the technological properties of the material (wear and shock resistance) is not clear. b) The crack length is strongly dependent on surface treatment. It is necessary, therefore, that surface preparation be very precise and reproducible, conditions usually hard to obtain. While any other simple mechanical test has this first drawback, the second became crucial in the application of the crack length method as a practical test. The reasons that this drawback could not be eliminated are, in our opinion, misleading and inconsistent interpretations of the influence of surface preparation on the crack length given in literature. In the following, after a short review of previous experimental results the interpretations given by different authors,4?&apos;-11 cf. Table I, are discussed critically and a consistent explanation is presented on the basis of which improvements of the method of crack length testing are proposed. 1) PREVIOUS EXPERIMENTAL RESULTS In his first attempt to use the cracks at Vickers impressions as a quantitative measure of the toughness of cemented carbides, palmqvist3 calculated the work necessary to initiate cracks by the formula: Sk =k.Pk. [I] where k = numerical constant = 6.49, Sk = critical work to initiate cracks (gf cm), Pk = critical load (load necessary to initiate cracks) HV = Vickers hardness (kp per sq mm). The difficulties involved in experimental determination of the critical load were overcome by the observation that a linear relation holds between the applied load and the sum of the crack lengths at the four corners of the indentation. This linear function, given by Eq. [2] below, was confirmed by Dawihl and Alt-meyer9and by our experiments, see Fig. 1: I = a1.P +a2 [2] where 1 = sum of the crack lengths at a Vickers indentation, P = applied load, al, a2 = parameters dependent on the toughness of the alloy and the surface preparation. The critical load, Pk, is now given by a2, which can be obtained by extrapolating the load vs crack length line to zero crack length, see Fig. 1. This simple relationship, Eq. [2], led Palmqvist1,7 to a parameter which was more reproducible and easier to obtain experimentally than the critical work: the work, S300, put into the sample to produce an average crack length of 300 µm per indentation. This parameter is calculated using the formula: where the load, P3oo, giving a crack length of 300 µm, can be taken from the load-crack length plot, Fig. 1,

Jan 1, 1970

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick&apos;s law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert&apos;s law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick&apos;s Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By G. S. Cole, G. F. Bolling

A series of Al-Cu alloys has been cast from constant superheat to solidify either with a hot top or with a free liquid/air interface. All the other variables which affect relative fluid motions were kept constant except the imposition of slow rotations m oscillations of the mold. Depending upon the exact circumstances, evi-dence could be found for the nucleation of equiaxed grains from dendrite bits detached from the columnar zone, or from the free surface, or from solid bits induced at pouring; a special experiment showed the solute buildup during ingot solidification and by inference the reality of constitutional supercooling. All methods of grain nucleation are thus supported. When solidification is arranged in a static mold the columnar- to-equiaxed transition occurs by one of these nucleation paths, subject to the natural decay of temperature gradients which promotes nucleation or the survival of nuclei. But when solidification is forced under special fluid flows it may display odd transitions. In one of these the equiaxed zone is synihesized from. dendrite bits detached from the solid/liquid interface. These survive under the concurrent lowering of temperature gradients and eventually cause transition by impeding columnar growth. GRAIN structure control is desired because real experience shows that specific properties are associated with specific cast grain structures. But since control is thus a matter of need and does not require understanding, much of casting remains art. For example, the manipulation of relative fluid motions in simple ingots provides a control of grain structure development,1-4 but theoretical insight is not required in order to broaden its potential applicability. Fortunately, however, once a variable like fluid flow is recognized it can also provide paths toward new insight. New observations using this variable have provided an insight which is curious. All the theories or descriptions of the columnar-to-equiaxed transition (CET) seem to be supported as long as the appropriate experiment is carried out. In order to develop this idea, let us ignore segregation, the chill zone (until a later section of this paper), and the origin and development of the columnar zone.= The details of questioning how equiaxed material forms in a casting may be divided in two. The first part is simply a questioning of the origin for equi-axed grains: are there fresh nuclei from heterogeneous nucleation, or dendrite bits broken off or melted from the columnar zone or elsewhere,6 or other solid bits surviving from the outset of freezing? The second is more complex, a questioning of the CET: does columnar growth slow down and allow the dominance of equiaxed grains, however they are formed, or do equi-axed grains take over and force columnar growth to stop? This "chicken-or-the-egg" second question can be quite useful, especially because it allows us to delineate the ordinary or NATURAL EQUIAXED ZONE and the induced or SYNTHETIC EQUIAXED ZONE. A natural equiaxed zone occurs if solidification proceeds in the absence of disturbances or extraneous forces such as ultrasonics, stirrings, and so forth. Both the CET theory proposed by Winegard and Chal-mers, 7requiring constitutional supercooling, and the CET theory suggested by Chalmers,8 requiring nuclea-tion only on pouring, pertain to the natural equiaxed zone. The best collating evidence to date for both these theories is contained in the work by Biloni and Chal-mers;9,10 the former theory7 is supported by special versions of the unidirectional growth experiment performed by Plaskett and winegardl1 and the latter theory&apos; is supported in detail for the solidification of small ingots. An equiaxed zone can be synthesized when disturbances caused by forced fluid flows2-4 or other artificial means9,10 break off or melt off dendrite tips from an advancing solid/liquid interface,* if (and only if) temperature gradients in the melt are (forcibly) reduced enough to ensure the survival of these bits of dendrites, 2&apos;3 Willful disturbances even so trivial as those produced by rapping a mold might be included here; as will be shown for example, this follows Southin&apos;s suggestion that the free liquid/air interface

Jan 1, 1970

By J. S. Pascover, J. K. Abraham

The influence of the early stages of precipitation on the kinetics and structure of martensite formation in Fe-27Ni and Fe-29.5Ni alloys containing from 0 to 10 pct Ti was examined with X-ray and electron microscopy techniques. The formation of a coherent, ordered preprecipitate had a profound stabilizing effect on the austenite. The Ms was decreased by increased titanium content and aging time up to a critical time. When the critical aging time was exceeded, the Ms was observed to increase markedly. The formation of the clusters was insuppressible and the volume fraction of clusters formed during the quench was a function of the titanium content. Martensite resulting from transformation of the clustered austenite is tetragonal with the c/a ratio increasing with titanium content. A model for the tetragonality is suggested. The morphology and substructure of the m artensite is inter-preted in terms of the above information and the cur-rent models of twinned martensite. ThE ramifications of precipitation in austenite to the properties of austenite have been the subject of numerous investigations. The current research is concerned with the influence of precipitation in austenite on the kinetics and structure of subsequent marten-site formation. In a previous investigation, Abraham et al.1 followed the aging reaction in an Fe-29.5Ni-4.2Ti* (at. pct) alloy using an X-ray diffraction technique. This technique, employing a Guinier camera, provided kinetic measurements through observation of the side band position as a function of aging time. The salient results of this work were: 1) The initiation of precipitation was not suppressed by quenching, i.e., there was a finite cluster zone size at zero aging time; and 2) The hardness of the aged austenite correlated extremely well with the zone size. During the previous work it was noted that the mar-tensite formed after aging was tetragonal, substanti-ating an earlier observation.2 Systematic investiga-tion revealed that the martensite was tetragonal in both the solution-treated then quenched, and the solu-tion-treated, aged, and quenched condition, and, furthermore, that a marked stabilization of the austenite occurred as a function of aging time. The present work is concerned with documenting the tetragonality and the stabilization phenomena as well as the ob- served microstruction with a suggested rationale for the behavior noted. EXPERIMENTAL PROCEDURE The compositions of the alloys are listed in Table I. The analyses were performed after the solution treatment of the strip material. Nickel was determined using the standard dimethy1-glyoxime procedure whereas titanium was determined colorimetrically with hydrogen peroxide and volumetrically by titrating with ferric iron. The materials were melted in a 5-lb vacuum induction furnace, cast into 2-in.-diam ingots, and forged in a temperature range of 950. to 1200°C to 1/2-in. slabs. The three higher titanium containing materials cracked during forging; therefore, to get the alloys into strip form, slices 1/8 in. thick were cut from the slab, homogenized 4 hr at 1150°C, then cold-rolled to a 0.04-in. thickness. The remaining slabs were hot-rolled, homogenized 4 hr at 1065"C, then cold-rolled to a final thickness of 0.03 in. All of the heat treatments were performed under a protective atmosphere of argon. The Ms temperature for most of the alloys is below room temperature; therefore, it was possible to solution treat, quench to room temperature, polish, and then observe the transformation optically on a cold-stage microscope. To determine the effect of aus-tenitizing temperature on Ms, eight of the alloys were treated at two temperatures, 1025" and 1120°C. No measurable variations in Ms were noticed. The remaining alloys were treated at 1025°C. The specimens, : by 5/16 by 0.03 in., were austeni-tized in a vertical tube furnace under a dynamic argon atmosphere. The bottom of the tube was submerged in water for quenching purposes. The question of stabilization that may be operating at room temperature was investigated and found to be negligible. Many of the specimens were held at room

Jan 1, 1970

By Richard H. Siller, Rex B. McLellan

A model for interstitial solid solutions has been considered in which a repulsive Potential exists between interstitial atoms in the solvent lattice. It has been shown that this model is consistent with the thermodynamic Properties of certain interstitial solid solutions. The model is then applied to the calculation of the variation of the diffusivity of carbon in au-tenite with composition. Although the energy levels at the saddle point, and thus the absolute values of dif-fusivity, cannot be calculated, it is shown that by taking the repulsive interactions between the diffusing atoms into account the functional form of the dependence of diffusivity on solute concentration can be derived. ThE composition dependence of the diffusivity, D, of carbon in austenite at a given temperature is well-known.&apos;-3 smith3 tried to reconcile the observed composition dependence of D at 1000°C with the previously observed4 composition dependence of carbon activity using equations for D derived by arken5 and Fisher, Hollomon, and Turnbull,6 but was unsuccessful. In this paper we shall modify the approach of Fisher et al. by considering the "blocking" model7 for interstitial solid solutions, based on concept due to Speiser and Spretnak,&apos; in which a repulsive potential exists between interstitial solute atoms in the solvent lattice, causing a certain number of interstitial sites to be "blocked" from occupancy by further solute atoms. We shall thus be able to describe the intimate relationship between the composition dependence of carbon diffusivity, a kinetic phenomenon, and the composition dependence of carbon activity in austenite. THEORY Consider for convenience one-dimensional interstitial diffusion in an fcc lattice in the [loo] direction. Fig. 1. Assume that solute atoms occupy octahedral sites only.7,9&apos;10 These octahedral sites are located on {lOO} planes a/2Å apart. A solute atom, A, occupying an octahedral site on a {100 } plane denoted by 2, has twelve nearest-neighbor octahedral sites: four on plane 1, four on plane 2, and four on plane 3. Diffusion occurs when there is a net flux of solute atoms, through an imaginary plane shown with dashed lines, from plane 2 to plane 3. Fisher et al6. use the concept of activated complexes, as given in the theory of absolute reaction rates." They show that the number of solute atoms per cubic centimeter per second which pc — Fig. 1-Diagram showing the arrangement of octahedral sites (x) in the fcc lattice. pass in the direction of diffusion from activated to new interstitial position is: ?where C is the concentration of the solute in atoms per cubic centimeter, l/m + is the fraction of new interstitial positions corresponding to motion in the forward diffusion direction (transmission coefficient), ?F* is the free-energy difference between the activated complex and the reactants when each is in its standard state at the temperature of the reaction (independent of temperature and composition in the case of carbon in austenite), y is the activity coefficient of the solute species, and, finally, ym is the activity coefficient of the activated complex (assumed constant). The flux of atoms moving in the forward direction through an area of 1 sq cm perpendicular to the direction of diffusion is therefore: m+ Ym l &apos; atoms per second where is the distance between planes. The blocking model states that a nearest-neighbor octahedral site of a given solute atom has a probability, f, of being inaccessible to other solute atoms. The number of available sites for diffusion on a given plane will, therefore, depend on f, which is constant, and Nu, the number of solute atoms on that plane. The effect is to have more available sites in the diffusion direction, thereby increasing the net flux of solute atoms. This is reflected in the transmission coefficient, l/m. To calculate the transmission coefficient for solute

Jan 1, 1970

By Carl Altstetter, Emmanuel deLamotte

The influence of an external stress and plastic deformation on the allotropic transformation of single crystals of a Co-30.5 pct Ni alloy was investigated. Experimental results were obtained from dilatometry, X-ray diffraction, and optical and electron microscopy. The effects of stresses could be conveniently divided into three stress ranges. In range I, from 0 to about 400 g per sq mm, the specimens exhibited a multi-variant phase change on cooling and a considerable amount of retained cubic phase. In range II, from 400 g per sq mm to the elastic limit, hexagonal regions of a given orientation grew in size and the cubic phase disappeared with increasing stress level. In range III, just above the elastic limit, specimens transformed into hexagonal single crystals. It was found that plastic deformation, not applied stress, was the factor which determined whether a single-crystal product was formed. The observed macroscopic shear directions were mainly (112) on cooling, but the behavior was more complicated on heating under stress. To explain these properties of the phase change, a model based on the nucleation of partial dislocations is proposed. IT is well-known1 that, on heating, hcp cobalt transforms into an fcc arrangement by shearing on close-packed planes. The crystallographic orientation relationship of the phases is as follows: the habit plane is (OOO1)hcp ?{lll}fcc and a (1010)hcp direction is parallel to a (112)fcc direction. The temperature at which the transformation occurs in pure cobalt is around 420.C 1,2This temperature decreases with increasing nickel concentration: and at about 30 pct Ni it reaches room temperature. However, many of the transformation characteristics remain essentially the same, particularly the crystallographic features.495 A convenient way of studying the transformation is to alloy cobalt with nickel, thus avoiding the difficulties of doing experiments at the high temperatures needed to transform pure cobalt. Due to the hysteresis of the transformation it is possible to choose a Co-Ni alloy with an Ms temperature below room temperature and an A, temperature above room temperature. Either structure of such an alloy could then be studied at room temperature, depending on whether it had just been heated or cooled to room temperature. The choice of nickel is further favored by the small difference in lattice parameters between cubic cobalt and nickel and the similarity of their physical, chemical, and electronic properties. Co-Ni alloys are reported to have neither long- nor short-range order.6 The main purpose of this work was to investigate the influence of an external stress on the transformation characteristics of Co-Ni single crystals. It may be expected that slip, twinning, and transformation should have many features in common in cobalt, because the (111) planes of the cubic phase operate as slip planes when plastic deformation by slip occurs, they are the twinning planes, and they are the habit planes for the transformation. Many previous investigators7-&apos;6 have concluded that dislocations must play an important role in the nucleation and propagation of the transformation, just as they do for slip and twinning propagation. An external stress will affect their motion, and a study of its influence should yield further information about the atomic mechanism of transformation. The present work extends that of Gaunt and christian17 and Nelson and Altstette18 in both qualitative and quantitative effects of stress. The basic concept underlying all the present theories of the transformation of cobalt and Co-Ni alloys is the motion of a/6<112> partial dislocations over {1ll} planes of the cubic lattice. The ABCABC... stacking of the close-packed planes of the cubic phase can be changed into the hexagonal ABABAB... stacking by the sweeping of an a/6 <112> partial on every second plane. Twinning, on the other hand, requires a shear of a/6 <112> on each close-packed plane. The reverse transformation can be effected in a similar way by a/3 (1010) dislocations moving over every other basal plane of the hexagonal phase. Transformation theories2, 7- 12,14 differ in the details of the nucleation of the transformation and the propagation of the partial dislocations from plane to plane. EXPERIMENTAL PROCEDURE Nickel and cobalt rods supplied as 99.999 pct pure were induct ion-melted together under a vacuum of about 10-5 torr in a 97 pct alumina crucible. An alloy containing 30.5 pct Ni was found to have the desired transformation range, with an Ms near -10°C and an j4s in the vicinity of +10O°C. The ingots were swaged to &--in. rod and electron beam zone-leveled in a 10-6 torr vacuum. This procedure resulted in 12-in.-long single fcc crystal rods (designated I to VII) from each of which several tensile specimens of identical orientation were made. Chemical analysis of the bar ends indicated no contamination or gross segregation and no micro segregation was seen in electron micro-probe scans. Tensile specimens with a 9/32-in.-sq by 1-in.-long gage section were spark-machined from the rods and then electropolished or chemically polished to remove the machining damage and to provide a flat surface

Jan 1, 1970

By R. Priestner, R. F. Krause

Solid, cylindrical crystals of a iron have been fractured at 10°K by the simultaneous application of tension and torsion stresses. Thus, a complex distribution of normal (sN) and shear (ss) stresses existed in a cleavage plane at fracture. In every crystal the clearage-plane normal was inclined to the specimen axis, so that a unique point, M*, in the operative cleavage plane was defined where the quantities sn and s2 N + s2 S) were maximized. It is shown that the maxirrzum resolved normal stress on the cleavage plane at fracture decreased as the resolved shear stress in the cleavage plane at M* increased. Thus, a normal stress la?*! for fracture was not satisfied. A fracture law which takes shear stress into account. and which predicts that (s2 N +s2S) should be constant, is to be preferred. However, the data is best represented by a linear dependence of sN on sS, sS which 110 physical significance can be attached. It is suggested that the fracture-nucleating -mechanism is a short-range one. A critical stress law has not yet been unequivocally established for the propagation of cracks in metals. Measurements of the tensile fracture stresses of variously oriented zinc single crystals1 failed to establish the normal stress law expressed by In Eq. [1], sN is the fracture stress, P, resolved normal to the fracture plane, and 0 is the angle between the fracture -plane normal and the stress axis. Similarly, a comprehensive investigation failed to verify the normal stress law for the tensile fracture of a-iron single crystals.&apos; However, a subsequent investigation,3 using iron from the same ingot, presented fracture data which obeyed the normal stress law. It has been shown previously4,5 that the Griffith criterion for fracture6 does not predict such a normal stress law. This result is of particular significance in considering the fracture of metals, such as zinc and iron, which may fail by cleavage. In these metals fracture propagates in a well-defined "cleavage" plane, whether or not an applied stress is normal to it. When the cleavage-plane normal deviates from the direction of application of a uniaxial stress, for example, the crack propagates under the combined action of normal (sN) and shear (ss) stresses. When the presence of a resolved shear stress in the crack plane is taken into account, the Griffith criterion is expressed by4

Jan 1, 1967

By G. S. Cole, G. F. Bolling

ThE exact type of fluid flow which occurs in a solidifying ingot is important in determining subsequent grain structure. This has been shown in studies of natural Convection" and of forced stirring or other disturbances of the melt."16 We shall explicitly argue that a complement to the existing natural flow in an ingot should be more effective than other types of flow in promoting the columnar-to-equiaxed transition. The ultimate effects of fluid flow upon structure is one of the topics of solidification that we have investigated in the alloy system Pb-Sb, under conditions simulating casting. In Fig. 1, the essential features of a bidirectional growth apparatus are shown; horizontal freezing from water-cooled faces within a low-thermal-conductivity lavite boat is a reasonable simulation of an ingot section. Details such as the furnace and thermocouples are omitted in order to show the location of four permanent. magnets, each with a pole separation of 21 in. providing a central field of about 1000 Gauss. When coupled with a dc current imposed through appropriate connections made at the cooled faces, a flow of fluid is produced as shown schematically. This technique described by Pfann and ~orsi" is ideal for our purpose since the flow indicated is the same as that we observe to occur naturally in this system. Components of 99.999 pct purity were used for study and all due precautions were taken in alloy preparation to avoid contaminants. Sections of the specimens were taken to ensure results representative of the interior as well as the surface of specimens. All proportions of equiaxed and columnar regions were measured by tracing the etched grain structures onto graph paper and simply counting squares. Four alloys were examined at superheats of 40" * 5°C and 100" * 9°C. Preliminary tests had shown that no appreciable enhancement of structure was obtained with magnetic field alone, so that this condition is not reported; it should nevertheless be noted that other configurations of magnetic field will reduce convection and thus enhance columnar growth.&apos;8 For the tests reported the magnetic field was applied to a specimen by bringing the four preassembled magnets to a position 2 mm from an outer tube immediately after the ingot was poured. The dc current of 30 amps passed through the sample throughout the entire solidification cycle, resulting in a power dissipation of 9 w per sq cm of interface. This may be compared to the evolution of latent heat of approximately 18 w per sq cm. Table I contains the results of this experiment in terms of the total area ratio, equiaxed/columnar grains, as a function of the field interactions, solute concentrations, and superheats employed. The total structure of the ingot is seen to be most influenced when both the field and current are applied simultaneously; when current acts separately, little effect may be noted in spite of the heat supplied. In addition, the change in structure from the no field-no current case to the field-current condition is more pronounced at the higher superheat, and the higher the concentration of antimony. An example of the grain refinement, as well as the increased equiaxed zone, is shown in Fig. 2. It is now important to prove that there is indeed an increase in fluid flow due to the presence of the field-current interaction; this is done by temperature measurements in the liquid metal. Let us consider a bidirectional casting in which heat is applied to and removed from the system, in such a way that rate of solidification is zero.* When a sensitive thermocouple

Jan 1, 1967