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By R. W. Cahn, C. D. Graham

Two predictions of the oriented growth theory of recrystallization textures have been tested by measuring the orientation dependence of the rate of growth of a single grain into a strained single crystal of aluminum, and determining the orientations of artificially and spontaneously nucleated grains growing preferentially into strained aluminum single crystals. Growth rates are found to be insensitive to orientation, except that new grains with orientations similar to the matrix or to a twin of the matrix have very low mobilities. Similarly, new grains growing preferentially into a strained crystal have random orientations, except that orientations near that of the matrix or its twins are avoided. The predictions of oriented growth theory are thus not confirmed. BASICALLY, the oriented growth theory of re-crystallization textures1 rests on the assumption that the rate of growth of a recrystallizing grain depends strongly on the orientation of the growing grain relative to the strained matrix into which it grows. In particular, the theory holds that in face-centered-cubic metals the orientation which corresponds to maximum growth rate is one in which the growing grain and the matrix are related by a rotation about a common <111> direction. The amount of rotation, as derived from several kinds of experiments,2-1 has been assigned various values, generally in the range between 20" and 40". (A <111> rotation of 60" is a twin relationship.) The conclusion that boundary migration rates depend strongly on orientation is based almost entirely on indirect evidence; there have been very few direct measurements of boundary migration rates as a function of orientation.* " The present investigation was undertaken to provide such measurements, to help make possible a decision between the oriented growth and oriented nilcleation theories of recrystal-lization textures. The basic experimental program consisted of measuring the rate of growth of a single recrystal-lizing grain consuming a strained single crystal, with the orientations of both grains preselected so that the effect of orientation on growth rate could be determined. A prerequisite for such an experiment is a strained single crystal which will support the growth of a new grain but which will not spontaneously nucleate new grains on heating. That is, the crystal must support the growth of a grain nucleated artificially, but contain no recrystalliza-tion nuclei which will become active at the testing temperature. Beck was apparently the first to note that such a condition could exist," and to make use of the condition for am experiment of the type described here.&apos; The present work was actually suggested, however, by a report of Tiedema". " that an aluminum single crystal strip, oriented with a (111) plane in the plane of the strip and a < 112> direction parallel to the tensile axis, would not recrystallize after 20 pet extension even when heated almost to the melting point, provided that the strip was heavily etched before being heated. This result could not be duplicated in the present work. In fact, it was found that any crystal which deformed in multiple slip (<100>, <112> and <111> orientations) underwent spontaneous nucleation after 15 pet extension, even if etched. However, crystals which deformed in single slip, and which did not develop heavy deformation bands, could be extended 15 pet without showing spontaneous nucleation at temperatures up to 600°C. Crystals oriented within about 10o of <110> which developed heavy deformation bands could be extended 10 pet without showing spontaneous nucleation. In all cases a heavy etch was required to prevent nucleation. Etching was necessary because of the presence of an oxide layer on the crystal surface at the time of straining, which leads to preferential nucleation at the surface.&apos;&apos; Grain Growth Rates Experimental Procedure and Results—Aluminum strips of 99.6 pet purity (principal impurities 0.19 pet Fe and 0.12 pet Si), 1 mm by 1 cm in cross section, were grown into single crystals of controlled orientation by the strain-anneal method of Fuji-wara.&apos;"&apos; " A sharp temperature gradient was maintained in the strips during growth by lowering them into a salt bath controlled at 650°C. Crystal orientations were determined by the etch-pit method of Barrett and Levenson" to an accuracy of ±2O. The crystals were extended by 10 or 15 pet in a simple hand operated tensile machine. Crystal orientations were rechecked after extension, and were found to be in agreement with the orientations predicted by the formula of Schmid and Boas." After extension, the grip ends of the single crystal specimen were cut off with a jeweller&apos;s saw, and the crystal heavily etched (at least 20 pet wt loss) in hot 10 pet Na or KOH solution. A region of severe local deformation was then introduced at one corner of the strip, usually by cutting off the corner with shears. Heating this end of the strip caused a large number of new grains to nucleate at the sheared edge. One of these grains grew to occupy the full width of the strip. The appearance of the strip at

Jan 1, 1957

By W. A. Tiller

The unidirectional freezing of a semiinfinite liquid from one end has been treated by calculating the solute and temperature distributions in the liquid and solid phases with time, when the solid-liquid interface advances at a rate proportional to (time)lt2. The nucleation probability for new grain formation is calculated as a function of the constitutional and thermal properties of the alloy, the pouring conditions and the catalytic efficiency of the nucleating agents. The transition from columnar crystal formation to equiaxed crystal formation is assumed to occur at a critical nucleation frequency for a particular alloy and the quantitative dependence of the ratio (columnar zone length/equiaxed zone length) upon the freezing conditions has been predicted. The effects of (i) fluid flow in the liquid, (ii) heat transfer through a mold wall, and (iii) a finite ingot length, have been explicitly tveated as departures from ideality. These departures from ideality are found to have very important consequences on the ingot stmcture. In Part I&apos; of this series, a qualitative description of the general ingot structure was developed. The factors that determine i) the ratio of the equiaxed zone length to columnar zone length and ii) the grain sizes in these zones, were discussed. In the present paper, topic (i) will be treated quantitatively, and it is intended that topic (ii) will be treated quantitatively in Part 111. The complete treatment has been split in this manner for ease of development and coherency of presentation. The treatments are quite mathematical in nature and, although some of the conclusions to Part 11 depend upon the treatment presented in Part 111, it was felt that the intended audience would find the material more readable and more useful in its present form. To this same end, it seems worthwhile to reiterate some of the qualitative aspects of grain nucleation during ingot solidification before embarking on the mathematical description. QUALITATIVE ANALYSIS In the conventional method of casting, a liquid alloy with a certain degree of superheat is poured into a mold. The outer rim of liquid metal cools rapidly to the liquidus temperature of the alloy and begins to undercool. As the degree of undercooling increases, nuclei of solid begin to form in this chill layer, this nucleation being catalyzed by certain heterogeneous particles in the liquid. The grains in the chill layer which are generally of random orientation, begin to grow inwards because of heat conduction through the mold. The grains usually develop a columnar shape since the frequency of nucleation of new grains in the liquid ahead of the advancing interface is generally insufficient to seriously impede the growth of the original grains. Due to the slow diffusion rate of solute in the liquid, a solute distribution is formed in the liquid adjacent to the interface which is either an excess or a depletion if the partition coefficient, ko, of the solute is < 1 or > 1, respectively. Thus, the liquidus temperature of the liquid adjacent to the interface is a function of position. The actual temperature in the liquid is also a function of position and the temperature gradient at the interface decreases as the interface moves away from the mold wall. Since the rate of advance of the interface decreases with time, the equilibrium temperature distributions and the actual temperature distributions as a function of interface position, X, can be illustrated as in Fig. 1. Thus, a region of liquid may exist in which the actual temperature is below the liquidus temperature. This liquid is contitutionally supercooled and therefore unstable with respect to the nucleation of new grains. Now, since the supercooling in Fig. 1 increases as the interface moves further away from the mold wall, the nucleation rate of new grains will increase. When the nuclea-

Jan 1, 1962

By K. G. Davis, P. Fryzuk

A study has been made of the effect of undercooling on the grain structure and solute distribution in small ingots of pure bismuth and of a 100 ppm Ag in bismuth alloy. Autoradiographic evidence shows that in undercooled melts a network of dendrites is formed throughout the melt immediately after nu-cleation. At large undercoolings the dendrites are very thin and closely spaced. The origin of the observed grain morphology can be explained on the basis of information about the mode of solidification revealed by the impurity substructure. WHILE a great number of studies of nucleation in undercooled molten metals have been made, comparatively little attention has been given to the mode of solidification from melts with large undercool- ings. Colligan and Bayles1 and Walker2 have measured the rate of advance of the solid-liquid interface in undercooled nickel melts, but the morphology of the solidifying material remained a matter of speculation. Fehling and Scheil3 have described the grain structure in ingots formed from undercooled melts of nickel, palladium, and copper, and a series of Ni-Cu and Ni-Pd alloys. At small undercoolings, equiaxed structures are observed, the grain diameter tending to increase as the temperature of nucleation is lowered. At greater undercoolings, a columnar structure is developed, while with still further undercooling there is a smaller grain size incorporating rather coarse subgrains. All-bright and Colligan4 examined the grain structure shown by ingots solidified from melts of nickel and of Ni-Ag alloy at an undercooling of 105°C, and concluded that considerable grain growth had taken place after solidification. The object of the present work is to correlate the mode of solidification from undercooled melts with both the grain structure and impurity segregation, using tracers to examine the latter.

Jan 1, 1965

By C. W. Beattie, R. L. Solter

ALUMINUM-KILLED, low carbon steel sheets are used extensively for severe deep drawing and other difficult forming operations. They usually, but not always, have a characteristic grain structure in which the grains are elongated both in the lengthwise and in the transverse direction. As described by Burns and McCabe,&apos; a typical grain in the plane of the sheet has its two axes in that plane from 1 Y2 to 4 times as long as the axis normal to the plane of the sheet. Rickett, Kalin, and MacKenzieZ have also reported on the recrystallization behavior of such steel. The contrast in grain structures of fully processed sheets of aluminum-killed and rimmed steel is illustrated by Figs. 1 and 2. The elongated grain structure of the aluminum-killed sheet is not developed on all heats or lots of this metal, and studies of the factors controlling and influencing its formation are reported in this paper. Jeffries and Archerb tate that unstrained grains are normally equiaxed, but exceptions are common. For example, if a metal containing a material mechanically obstructing grain growth is subjected to considerable working followed by thorough annealing, it may exhibit grains consistently elongated in the direction of working. Our experiments demonstrate that aluminum-killed, low carbon steel is such a metal, and that the substance mechanically obstructing grain growth is aluminum nitride. The effectiveness of aluminum nitride in inhibiting grain growth has been found to be influenced by the degree of cold reduction, the rate of heating in annealing, the thermal history of the sample before cold reduction, and the residual aluminum content. A correlation between grain shape and austenitic grain coarsening temperature also was indicated and additional experiments demonstrated that aluminum nitride is also the principal cause for the fine grain characteristic of aluminum-killed steels. Manufacture In conventional practice, aluminum-killed sheet steel is manufactured from a low carbon steel containing approximately 0.02 to 0.07 pct residual (HC1 soluble) Al. With the exception of certain samples containing greater or lesser amounts of aluminum, the steels used in these investigations were within the following composition range: C, 0.03 to 0.06 pct; Mn, 0.28 to 0.38; S, 0.017 to 0.032; Al, 0.03 to 0.06; P, <0.01; and Si, <0.01. Properly heated ingots are rolled to slabs about 4 in. thick. After surface conditioning, the slabs are reheated to about 2300°F and hot rolled continuouslv to strip about 1/10 in. thick. The strip rolling is completed at a temperature of 1550°F or higher, and the strip is coiled, usually at a temperature near the lower critical transformation. After cooling, the strip is pickled to remove oxide, cold reduced 40 to 70 pet to final thickness, then annealed to 1250° to 1350°F in 20 to 80 ton charges, the size of which results in slow heating and cooling rates. Effect of Cold Reduction According to Sachs and Van Horn,&apos; the deformations of the individual grains in rolling are similar to those of the total volume. Thus individual grains would elongate in rolling according to the amount of cold reduction imposed. This is true theoretically, but as cold reduction increases the individual grains tend to fragment, and measured grain elongations become less than theoretical. The amount of grain elongation may be described by a numerical rating based on grain counts made by the intercept method. Specimens are polished normal to the plane of the sheet, with the polished surface extending parallel to the rolling direction. After etching, grain intercepts are counted along a 50 mm line on a micrograph of suitable magnification. In random locations parallel to the plane of the sample 20 counts are made and 20 are made in the thickness direction of the sample the average count in the thickness direction divided by the average count parallel to the plane of the sample gives a numerical rating of the grain shape called grain elongation. For example, a grain elongation of 2.00 means that the average grain is twice as long as it is thick. The average of both counts may be converted to grains per sq mm by a nomograph relating intercept counts and grain count. By the same procedure the grain elongation in the plane of the sheet but transverse to the rolling direction may be determined, using transverse metallographic samples. A comparison of theoretical and measured grain elongation was obtained on an aluminum-killed

Jan 1, 1952

By W. W. Stephen, J. P. Walsted, W. J. Kroll

FOR the production of carbides, various furnace types are available, especially those using arc, resistance, and high-frequency heating. Selection of a specific means of heating depends primarily on the material to be treated and the physical properties of the carbide produced. In the present case, zirconium carbide had to be prepared on an industrial scale as a raw material for the production of anhydrous zirconium chloride. Considering that a rather expensive pure oxide was to be used, the arc-furnace treatment recommended for zircon sands in a previous publication&apos; was ruled out because of the considerable volatilization and dust losses caused by the blast of the arc. For this reason, either high-frequency or resistance heating seemed to offer more promise. Since there was not enough capacity of the former available, resistance heating was chosen. It was first thought that the Acheson silicon carbide furnace would be suitable for the present purpose, but the voltage in such a furnace, in which the current passes through the batch, varies from 220 to 75 v from the start to the end of a run. This variation is so great that a special tap transformer would have been required. Trouble was also expected by local melting of the carbide. Pure zirconium carbide melts at about 3527°C, but the melting point is brought down to 2427°C, according to Agte,2 when an excess of 6 pct C is present in the carbide. This we found confirmed by experiments in a high-frequency furnace. Excess carbon is needed in the batch to obtain a complete reduction. Fusion of the charge would cause great difficulties in an Acheson-type furnace because of the good electrical conductivity of the carbide as compared with that of the loose batch. Also, fused carbide is much more difficult to chlorinate than the spongy product that can be made in the radiation furnace described below. It was apparent that, to obtain a good-qual-ity zirconium carbide, the heat input would have to be well-controlled. The hairpin-resistor principle seemed to offer possibilities in this regard, and a furnace of this type was therefore developed. The advantages of the hairpin-resistor radiation principle have been discussed in previous publications, and a split-tube graphite-resistor furnace," now increasingly used in various laboratories, as well as a centrifugal quartz melting furnace4 of this type, has demonstrated the usefulness of this heating method. The hairpin-heater element has the following definite advantages over a straight resistor of the type used, for instance, by Georges:5 Its resistance is four times greater; it can expand freely; it is sturdier because of the larger diameter, and it has a larger radiation surface; there are no hot contacts that might wear out or overheat; only one clamp is used which permits assembling all electrical leads at one side of the furnace, making the other sides easily accessible to the operator. The shorter element and its larger diameter permit greater concentration of heat. The furnace developed is shown in fig. 1. The box (I), made of 2 1/2-in. graphite plates, has inside dimensions of 23x17x16 in. It contains the briquet-ted batch (2). The box is embedded in lampblack (3) up to the cover plate. The cover plate contains an opening for the gas escape (4) and for the observation hole (5), which permits measuring the temperature with an optical pyrometer. The cover plate is embedded in charcoal (6). The lampblack is contained in the insulating brick lining (7), held in the 1/4-in. sheet steel box (8). The graphite box is set on two rows of triangular graphite bars (9). The hairpin-heater element (10), the dimensions of which are given below the main drawing, extends horizontally in the graphite chamber and radiates freely on the batch. A graphite tube (11) keeps the lampblack from falling into the slot. The split electrode, which in reality is turned 90" against the drawing, is so arranged that the slot is vertical. The water-cooled packing gland (12) is insulated by an airgap from the heater element. A thin pipe (13)

Jan 1, 1951

By C. M. Wayman, M. A. Gedwill, C. J. Altstetter

Cobalt Whiskers were grown by the hydrogen reduction of CoBr,. The fcc = hcp martensitic trans-formation in these whiskers was studied using X-ray and metallographic techniques. Present theories of the fee + hcp martensitic transformation were ex-amined in the light of the present findings Experimental evidence for slip as a part of the transformation mechanism is presented. In the bulk form cobalt is known to undergo a martensitic transformation1 from an hcp to an fcc structure upon heating above about 430°C. Upon cooling, the reverse transformation starts at about 400°C, but does not go to completion except in single crystalline or coarse-grained samples, or upon plastic deformation. The transformation may be thought of as the shearing of close-packed atomic planes in such a way as to change the stacking sequence from ABCABC to ABABAB with a contraction normal to the shearing planes and an expansion in the planes,2 producing a c/a ratio slightly less than ideal. This restacking to give {0001) and (112) 11 (1010) can be accomplished by the passage of a shockfey partial dislocation over every other (111)f plane resulting in a theoretical shear of 19.47 deg. To date there has been no completely satisfactory explanation of how the partial dislocations are produced on the close-packed planes or propagated from plane to plane to give the correct stacking sequence. The object of the present research was to study some of the characteristics of the fcc to hcp transformation in geometrically simple single crystals. It was felt that whiskers of cobalt grown by halide reduction would be ideal specimens with which to study the transformation, because whiskers have the following desirable features: 1) are easily grown as fcc single crystals; 2) exhibit relatively simple geometries; 3) have comparatively low dislocation densities;

Jan 1, 1964

By C. G. Dunn, J. L. Walter

A study has been made of the nature of the slow growth or nucleation stage of secondary recrystallization to the cube texture in sheets of high-purity 3 pct SiFe. Cube-oriented nuclei were identified and their growth observed, using surface markings together with micrographic and X-ray techniques to provide information on grain boundary interactions and the driving forces for growth. FACTORS that promote growth of certain grains during the early stages of secondary recrystallization have been considered theoretically1 but have been little explored in a direct experimental way. In certain cases,2&apos;3 it has been reported that the primary recrystallization grains (nuclei), which eventually become secondaries, were found to be larger than the other grains into which they grew-Factors such as grain boundary "mobility" and differences in strain energy may contribute to the

Jan 1, 1961

By K. R. Janowski, A. B. Chase, E. J. Stofel

Ruby crystals of exceptional optical quality have been grown from fluxes composed of Bi2O3 + PbF2 or Bi2O3 + BiF3. Careful control of growth conditions was required to minimize the number of growth defects consisting primarily of dislocations, occluded flux, and growth twins. Slow growth rates coupled with the addition of small amounts of La2O3 as a flux dopant were helpful in producing nearly perfect crystals. Chromium concentrations up to 1 pet were incorporated into these crystals without adversely affecting their perfection. Crystals up to 10 mm in diameter having as few as one to ten dislocations per crystal were typical of those produced under optimum growth conditions. Under these same conditions the occlusions were eliminated, and growth twins were either eliminated or reduced to one to three twin boundaries per crystal. INTEREST in the nature of lattice imperfections produced during the growth of ruby crystals (Al2O3-corundum structure) has been stimulated recently by the need for ruby lasers of good optical uniformity. As a result, ruby crystals grown by the flame-fusion (Verneuil) process have been studied in detail and have been found to contain high densities of dislocations (106 to 107 dislocations per sq cm) and mosaic structures that impair their optical quality.&apos;-3 Attempts to improve the quality of Verneuil-grown crystals by controlling the growth variables have not been entirely successful. On the other hand, rubies grown by the flux process have received little attention even though their more nearly equilibrium growth conditions suggest that they would have fewer growth defects. Nelson and Remeika have shown recently that small flux-grown rubies can indeed be made into very low-loss lasers. However, they did not report information on crystalline imperfections in these crystals.4 Stephens and Alford have reported briefly on defects found in a flux-grown corundum crystal but they neither described these defects in detail nor related them to the method of growth.5 The present investigation was undertaken to establish the relationship between growth conditions and crystalline perfection of flux-grown rubies, sapphires, and other crystals of the corundum family. EXPERIMENTAL PROCEDURE The corundum crystals used in this study were grown by slowly cooling solutions of A12O3 in molten-salt solvents of PbO + PbF2, Bi2O3 + PbF2 or Bi2O3 + BiF3. The materials employed were Linde A (a Al2O3 powder) with reagent-grade chemicals as solvents. Some of the solutions also contained small additions (1 pet or less) of one or more of the transition metal elements chromium, manganese, iron, and titanium as crystal dopants. La2O3 was added to some of the solutions to alter the growth habit of the crystals. The La2O3 promoted the occurrence of growth facets parallel to (0112) and {1011} planes, where the indexing system is the morphological system described in detail by Kron-berg6 and used throughout this paper. The melts from which the crystals were grown were prepared by mechanically mixing the various constituents and placing them in platinum crucibles. The covered 50- and 100-ml platinum crucibles were heated in muffle furnaces at 1250°C for short periods of time (1 to 4 hr) and then program-cooled at either 2° or 4°C per hr to 1000°C. At this lower

Jan 1, 1965

By S. J. Matas, R. F. Hehemann, R. H. Goodenow

The hot-stage metallographic method has been employed to determine radial growth rates of upper and lower bainite. Lower bainite appears to grow as individual plates that increase in both length and thickness while upper bainite grows as sheaves of closely spaced plates or needles. A discontinuity in the temperature dependence of the growth rate appears to be associated with the transition from upper to lower bainite and stepped quenching experiments suggest that lower bainite will not continue to grow when the temperature is raised to the upper range. Thus, a single process does not appear to control the growth of both upper and lower bainite. A tentative model based on the forces acting on a dislocation interface is proposed to account for the slow growth of bainite. It has been recognized since the early studies of Davenport and Bain that a close relationship exists between the martensite and bainite transformations in steels. However, diffusion of carbon during the transformation has lead to considerable controversy concerning the reaction mechanism.1-7 Many studies4,5,7-9 have emphasized the structura and kinetic aspects of the bainite reaction and, in particular, the difference observed between the two forms of bainite—frequently termed upper and lower bainite. A kinetic difference between the two types of bainite has been revealed in the activation energy determined from the overall reaction;4,5 however, many difficulties arise in an interpretation of these activation energies since a number of temperature dependent factors contribute to the kinetics of the overall reaction. The displacive surface relief10 accompanying the bainite reaction permits a separation of the nuclea-tion and growth contributions to the reaction and allows the kinetics of the growth process to be examined. Several investigations of this type have been conducted; however, they have been restricted to the low temperature range.3&apos;6&apos;11 Here, bainite plates are observed to grow slowly in both length and width. The present investigation extends such studies to include the upper bainite range. MATERIALS AND PROCEDURE Materials. The composition of the steels studied in this investigation are presented in Table I. The range of composition permitted a study of the effect of carbon content on the growth rate of upper bainite in the 9 pct Ni steels and consideration of both upper and lower bainite in the higher carbon steels. These steels were received as hot-rolled rounds and were forged to approximately 1/2 in. thick plates for preparation of metallographic specimens. In order to produce an essentially zero carbon steel, Steel A was decarburized in wet hydrogen at 1550°F for 15 days with the result tabulated as Steel AD. Experimental Procedure. In order to study the slow growth of the displacive transformation product, a commercially available Leitz hot stage was modified to permit heating of the specimen by its own resistance in a manner similar to that employed by other investigators.6 The furnace chamber was maintained at a pressure of 2 to 3 X 10-5 mm Hg prior to austenitizing at 2000° ± 12° F for 5 min. Samples could be cooled from the austenitizing to the transformation temperature in approximately 15 sec and the progress of transformation was recorded with a 9 cm by 12 cm single frame camera or a 16 mm movie camera. RESULTS AND DISCUSSION Growth Characteristics. The general growth characteristics observed in this investigation were analogous to those reported previously.3,6,11 Typical growth sequences for the high temperature and low temperature forms are illustrated in Figs. 1 to 5. In both temperature ranges, bainite plates increase in length at slow, temperature dependent rates until interrupted by a grain boundary, another plate, or

Jan 1, 1963

By L. S. Castleman, H. A. Froot

A study was made of the growth kinetics of B-brass layers in a-brass us y-brass diffusion couples in which both phases were saturated in the 6 phase. It was found that useful estimates can be made of the difhsion coefficients at the ß-phase interfaces from interface displacement data, which are relatively easy to measure experimentally; also, a useful estimate can be made of the mean heat of activation for diffusion from layer growth data. The effects of pressure on layer growth kinetics were explored and found to be consistent with a vacancy model for diffusion in 6 brass in both the disordered and ordered temperature range. 1 HE study of multiphase diffusion receives relatively little attention in comparison with that devoted to diffusion in homogeneous materials. Of the hundred or so papers on diffusion written each year,&apos; only a few are devoted to the subject, and it is the rare review article2,3 that devotes any space to multiphase diffusional phenomena. This is unfortunate, since the metallurgist frequently encounters practical situations involving cementation processes such as cladding, protective coating of metals, and so forth in which he needs guidance of a fundamental nature. The investigation of multiphase diffusion phenomena is complicated by the fact that one must consider reactions at phase interfaces as well as the migration of atoms within the individual phases; these reactions cause the interfaces to be displaced within the diffusion zone. The relative displacement of two adjacent interfaces corresponds to the growth of an intermetallic layer, and it is not difficult to determine experimentally the kinetics of layer growth. In the past few years it has been pointed out4,5 that valuable fundamental information may be gained about diffusion coefficients and the concentrations at interfaces through a study of their motion. Accordingly, it is the purpose of this paper to report the results of an investigation of interface motion in a simple multiphase binary system. In the work reported herein, attention was focussed on the growth of a 6 -brass layer in a diffusion couple prepared from a- and y-brass compositions saturated with respect to the 6 phase. This particular system was chosen for a number of reasons. First, the bcc ß-brass phase is disordered for all compositions at temperatures above 468°C and becomes increasingly long-range ordered for all compositions at temperatures below 454° C;6,7 thus, the effects of a variation in order on interface displacement could be determined. Second, diffusion coefficients have already been obtained as a function of temperature in the ß phase both in the ordered and disordered Re- and a theoretical picture of the mechanism of diffusion in this and other ordered solutions is emerging.11&apos;12 Third, some thermodynamic data are available for the a-, ß-, and ?-brass phases,13,4 and these data could be used to gain insight into questions of phase equilibria and concentrations at phase interfaces.

Jan 1, 1963

By C. G. Dunn, J. L. Walter

Secondary recrystallization to the (110) [001] texture in high-purity silicon iron occurs if low-oxygen material is annealed in a nonoxidizing atmosphere. Any departure from these conditions results in a growth of (100) oriented grains. The nature of the matrix and secondary recrystallization structures and textures and the nature of grain boundary interactions during growth show that the low gas-metal interfacial energy of the (110) surfaces provides the driving force for growth of these grains. A type of grain growth, characterized by a driving force which derives from energy differences of {hkl} surfaces at the gas-metal interface, has been treated in recent papers.&apos;-7 Secondary recrystallization to the cube text!:: in high-purity silicon iron provides one example. The present paper also deals with a surface energy driving force but the texture that results by secondary recrystallization is not the cube texture; it is a texture in which the (110) plane is in the plane of rolling and the [001] direction is in the direction of rolling. The phenomenon described in this paper is different from the impurity (dispersed phase)-controlled secondary recrystallization process in which the (110) [001] oriented grains grow under the action of grain boundary driving forces.8-12 It is also different from tertiary recrystallization,2 which also produces the (110) [001] texture in high-purity silicon iron, since the matrix textures and grain sizes are different. Finally, it is unlike any other form of secondary recrystallization reported in the literature. The possibility of obtaining the (110) [001] texture in high-purity silicon iron became clear in a study of the effect of impurity atoms on the energy relationships of (100) and (110) surfaces. In this study Walter and Dunn6 observed the migration of (100)/(110) boundaries, i.e., boundaries between two grains, one of which has a (100) plane and the other a (110) plane, respectively, parallel to the plane of the sheet specimen. At 1200°C the (100)/(110) boundaries advanced into (100) grains in a vacuum anneal, then reversed their direction and migrated into (110) grains in a subsequent anneal in impure argon. Finally, the direction of migration reversed once again with (110) grains growing into (100) grains in a second vacuum anneal. These results were explained in terms of a change in concentration of oxygen atoms at the gas-metal interface during the anneals. Thus, oxygen atoms were added to the surface during the anneals in impure argon to the point where ?100, the specific surface energy of the (100) oriented grains, was lower than ?110, the surface energy of (110) oriented grains. In vacuum, however, the oxygen concentration at the surface was lowered to the point where ?110 < ?100. Concerning the possibility of secondary recrystallization in high-purity silicon iron with a low initial oxygen concentration, the observed effect of adsorbed oxygen atoms has indicated6 that a good vacuum anneal would favor the rapid growth of matrix grains with the (110) plane in the plane of the sheet much more than grains in the (100) orientation. The growth of only (110) oriented grains of course would depend upon y110 being less than ?hkl, where hkl refers to any plane different from (110). The present paper is concerned with the application of the above ideas to secondary recrystallization to the (110) [001] texture in high-purity silicon iron. The matrix and secondary recrystallization textures and structures are defined and discussed. Observations of growth of nuclei for secondary recrystallization and of boundary interactions are included to provide direct information on the surface energy relationships between (110) and other (hkl) surfaces. EXPERIMENTAL PROCEDURE As before, 2,4-6 high-purity iron and silicon were melted and cast in vacuum to provide an alloy containing 3 pct Si with less than 0.005 wt pct impurities. The oxygen content of the ingot was lower than in previous ingots, being approximately 3 ppm (by weight). The carbon content of this ingot may have been slightly higher than was found for previous ingots. The same rolling and annealing schedule used previously2 was followed in this study to obtain samples 0.012 in. (0.3 mm) thick. These samples were electropolished prior to annealing. After rolling and polishing, the oxygen content of the material was approximately 6 ppm; material used in the previous studies contained about twice this amount of oxygen.

Jan 1, 1961

By R. S. Wagner, H. Brown

Criteria for nucleation with the aid of twin planes during crystal growth from the melt are discussed. It is shown experimentally that bismuth crystals can grow from a subercooled melt in a twinned bismdtic form. A mechanism of growth based on the presence of at least me twin plane is proposed. It is well known that faceted growth can be observed in crystals grown from the vapor phase, dilute solutions, or from the melt. Faceted growth, in which the crystal is bounded by its slowest growing faces, will occur if the growth rate is strongly orientation dependent. The addition of atom layers on a facet plane can only occur by two-dimensional surface nucleation or with the aid of an imperfection. Nucleation with the aid of dislocations was proposed by rank&apos; and observed to be of particular importance in crystal growth from the vapor phase. Nucleation with the aid of two-dimensional imperfections, notably twin planes, was suggested by stranski2,3 and Frank.4 A twin plane, terminating at the growth interface, can form a reentrant step at which nucleation can occur at a much smaller super-saturation (or supercooling) than required for two-dimensional surface nucleation. Nucleation by a twin plane usually results in a fast growth rate along a crystallographic direction parallel to the twin plane. Such a nucleation mechanism, based on the presence of a twin plane, has been used by Dawson5 to explain the growth and morphology of sheet-like crystals of paraffin n-hectane. In recent years more evidence was found that nucleation by twin planes occurs frequently in crystal growth from the vapor phase and from dilute solutions, for example, in cadmium,&apos; barium titanate,7 silver,8 silicon9 and gallium arsenide.10 In crystal growth from a supercooled melt, however, nucleation by twin planes has so far only been observed in materials with the diamond or zinc blende structure. Bennett and Longini11 were the first to recognize the important role a single twin plane plays in the growth of germanium dendrites. Subsequently, it was found that a prerequisite for continued propagation of germanium dendrites is the presence of two parallel twin planes which form a self-perpetuating system of nucleation sites.12 Sili- con and some III-V compounds such as InSb also grow dendritically by twin plane nucleation. It appears that the following criteria must be satisfied in order that nucleation with the aid of twin planes can occur: A) The growth form of the material must be faceted." B) The formation of twin boundaries, by a fault in layer sequence during growth, by plastic deformation, or by an accidental meeting of properly oriented crystals, must be possible. C) Twinning must form a reentrant step where the twin boundary terminates at the faceted growth interface. D) These three conditions are necessary, but in certain cases not sufficient for continued crystal growth with the aid of a twin plane. Depending on interface morphology, a combination of more twin planes is sometimes required to form a self-perpetuating system of nucleation sites. This investigation was carried out with the idea in mind that nucleation with the aid of twin planes is a more general phenomenon and should occur in those materials, grown from a supercooled melt, which satisfy the criteria outlined above. It has been found that crystals of high-purity bismuth grown from a supercooled melt can grow by the aid of a twin plane. In the first two sections the faceted growth form and the twinning elements of bismuth are discussed. In the last section prismatic crystals of bismuth, which appear to grow with the aid of a deformation twin are discussed.

Jan 1, 1962

By E. Teghtsoonian, K. G. Davis

THE preparation of cobalt crystals offers problems: on cooling through 400°C a phase transformation takes place whereby the structure changes from face-centered cubic to the low temperature close-packed hexagonal form. There are a few references in the literature which describe the preparation of cobalt crystals for magnetic work1,&apos; where melt-solidification methods were used. Reasons will be given why such methods were found unsuitable for our purposes. The following techniques were tried: 1) Solid state methods. Any mechanical shaping of tensile specimens would lead to uncertainty with regard to residual strains. With this in mind, following Kaa, strain-anneal and grain growth techniques were extensively investigated. In no Case were useful single crystals obtained. The transformation boundaries, which are crystallographically similar to twin boundaries, are probably extremely stable and inhibit the grain growth. 2) Growth from the melt. Normal melt-solidification methods were tried, using recrystallised alumina crucibles, and also a osoft moldo technique in which cobalt rod was packed in alumina powder. Trouble was encountered with gas evolution on solidification of the melt, giving porosity. Some adhesion of cobalt to the alumina also took place. Only a small proportion of the runs gave single crystals. 3) Zone-refining. Much the best results have been obtained using an electron-beam floating zone refiner. The refiner, based on a design by Calverly et Al .5 had a single-turn tungsten filament. It was operated at 600 v with an emission current around 45 ma. Commercial cobalt rod 1/8 in. in diam was given one pass at a rate of zone travel normally 25 cm per hr, under a vacuum approximately 10-5mm of Hg. Over 50 pct of the runs gave long sections of single crystal. Crystals up to 2o Cm long with good uniformity of cross section and straightness have been grown in this way. Increase in the length of the molten zone resulted in higher single-crystal yields, but control of zone stability was reduced. Sub-boundaries in the zoned crystals were few, and Laue X-ray spots were sharp. The success of the method is believed to lie in two factors, namely i) the absence of crucible restraints during the transformation, and ii) extreme axiality of heat flow during cooling. The axes of the zoned crystals were clustered around the [ 1010] pole, the pole of the basal plane being at least 60 deg from the specimen axis. Crystals grown at lower rates of zone travel showed the same orientation range, Fig. 1. This orientation is similar to that for other hexagonal metals grown from the melt, which is a little surprising when the mode of formation of the hexagonal phase is considered. The preferred orientation is probably caused by anisotropy of heat conduction, i.e., that crystal which can most effectively conduct heat away from the transformation interface will be favored. Fig. 2 shows the area on a standard cubic stereo-gram in which there are no poles more than 60 deg from one of the four < 111> directions. This area

Jan 1, 1962

By D. L. Wood

INTERNAL oxidation of alloys has been investigated by Rhinesl,2 and by Meijering and Druy-vesteyn. Rhines showed that dilute Cu-A1 alloys can be internally oxidized without forming an external scale by annealing in an oxygen partial pressure equal to the decomposition pressure of Cu2O. The oxygen is supplied at the outside surface at a rate sufficient to maintain saturation of the surface with respect to oxygen. Oxygen diffuses inward and, at the interface between the subscale and the alloy, oxygen meets the solute and reacts to precipitate its

Jan 1, 1957

By H. W. Mead, C. E. Birchenall

The rates of growth of graphite nodules in cast irons are calculated for a model of a growing graphite sphere surrounded by a shell of austenite through which carbon and iron are diffusing. The carbon is supplied by a cementite-austenite mixture at the outer edge of the shell. The calculated rates from carbon diffusion agree fairly well with the measured values, but the rates based on iron self-diffusion are much too low. Because the iron must be removed for the process to continue, o plastic deformation mechanism is suggested. THERE has been an unfortunate tendency in the literature of growth and dissolution reactions to identify the slope of a plot of the logarithm of the growth or dissolution rate vs reciprocal of temperature with the activation energies determined by diffusion measurements in chemically similar systems. If the solubility limits at the growing or dissolving phase interfaces change appreciably with temperature, such procedures may lead to serious errors in specifying the mechanisms controlling the rates of these processes. A reaction involving the simultaneous growth of graphite from and dissolution of cementite in austenite will be discussed here to show that substantial oversimplifications have been made in earlier studies of this process. From a dilatometric study of the overall y-range graphitization process, Bunin and Danil&apos;chenko&apos; found an apparent activation energy of 90 kcal per g-atom. They concluded that, since this value was much nearer the approximately 68 kcal per g-atom observed for self-diffusion in pure iron than it was to 32 kcal per g-atom for diffusion of carbon in iron, the rate-controlling process must be the diffusion of iron away from the growth interface to provide space for graphite to grow. Bunin and Salli&apos; bolstered this agreement with the observation that graphite forms preferentially at surfaces, cracks, and pores where free volume is present initially. Ziegler, Meinhart, and DeaconQ ad found an apparent activation energy for graphitization of 98 kcal per g-atom. This value, like that of Bunin and Danil&apos;chenko, applies to nucleation and growth occurring simultaneously. It is not generally assumed that nucleation is entirely diffusion-controlled. Treatments such as prior cold-working and prequenching, which strongly affect the rate of graphitization, would be expected to have little effect on diffusion processes occurring at the graphitization temperature. In any case 90 kcal per g-atom is not particularly close to the 54 kcal or lower to be expected for diffusion of iron which is carbon-saturated.&apos; The presence of silicon in iron is said to reduce the activation energy for diffusion,&apos; so its presence in cast irons would be expected to have a similar effect. The growth rates of nearly spherical graphite nodules have been studied by Brown and Hawkes." The initial rate of growth before impingement of adjacent carbon-depleted areas was found to be parabolic, and rate constants were measured at several temperatures. Their apparent activation energy for the growth process only was roughly 45 kcal per mol. Burke and Owen&apos; made growth-rate measurements on several alloys, recording appreciable induction periods, initial nucleation rates, and average radial growth rates based on an assumed linear rate of radial growth. They found that increased silicon content increases the ovel-all reaction rate and the initial rate of nucleation, and decreases the induction period. Assuming 1) spherical nodules. 2) constant volume rate of nucleation, 3) austenite in equilibrium with cementite at positions where the cementite is not depleted, and 4) a constant diffusion distance during the growth of a nodule, they calculated an apparent overall activation energy of 68 kcal per mol, which was related to an activation energy for nucleation of 79 kcal per mol and activation energy

Jan 1, 1957

By J. M. Lommel

DURING an investigation into the effect of heat-treatment on the creep properties of the magnesium alloy ZW1, (1 pct Zn, 0.6 pct Zr), the previously published methods of final polishing were found to be unsatisfactory. A new diamond-polishing technique has been developed to facilitate the study of fine precipitates in this and other magnesium alloys, and is described in this note. The sectioning and coarse grinding techniques are those of Fox and Hall,&apos; and Hess and Cieorge.&apos; Pre- liminary mechanical polishing is done with 6-µ, and 1-µ( grades of diamond compound on &apos;Microcloth&apos; using a lubricant of &apos;Hyprez&apos; oil. When the conventional technique is used with a 1/4- µ diamond wheel for the final polishing of magnesium alloys, scratching is likely to result from the abrasive action of the &apos;Microcloth&apos; nap on the soft metal surface. This problem has been overcome by the use of a cream on the wheel in order to separate the specimen surface from the polishing cloth. To prepare this cream, a solution of 6-ml tri-ethanolamine in 75-ml water is stirred into 12.5 g stearic acid at a constant temperature of 80o to 90°C. The cream is allowed to cool, and is then &apos;whipped&apos; to a smooth consistency with 100-ml &apos;Hyprez&apos; oil. Before polishing, the diamond loaded &apos;Microcloth&apos; is moistened with a few drops of &apos;Hyprez&apos; oil, then a small amount of cream is worked into the nap. For the best results a wheel speed of 500 rpm should be used for polishing, and the specimen should be held by hand with a light pressure while being rotated in the opposite direction to the wheel. After polishing it is necessary to swab the specimen thoroughly in methylated spirits to remove residual cream and oil from the surface in order to avoid uneven etching and drying stains. Fig. 1 shows the surface finish obtained on a specimen by polishing on a 1/4- µ diamond wheel using the cream, and Figs. 2 and 3 the precipitate observed in ZW1 after polishing, and etching for two seconds in nitric acid 15 pct in ethylene glycol. This new diamond-polishing technique has made a valuable contribution to the programme of metal-lographic research on ZW1 and has become a routine laboratory practice for other low alloy content magnesium alloys.

Jan 1, 1961

By N. K. Chen, R. Maddin, R. B. Pond

A METHOD has been described by Andrade&apos; for obtaining very rapid grain growth so that single crystals of high melting point metals could be made with comparative ease. The furnace construction was essentially a very thin wire through which was passed an electrical current so that "a high uniform temperature" was maintained. The wire was surrounded by a fused quartz tube from which the air had been evacuated. Andrade applied this method to the growth of single-crystal wires of alpha iron, and Tsien and Chow2 prepared single crystals of molybdenum 0.25 mm diam in this way. In the present report a method is described in which the basic idea of the Andrade furnace is utilized. However, modifications are employed so that large single crystals of molybdenum or of any refractory metals can be grown. Furnace The modified Andrade furnace is shown in Fig. 1, and the detailed drawing of its construction can be seen in Fig. 2. The furnace proper consists of a 2&apos;/2-in. diam fused silica tube, 20 in. long, which is evacuated continuously at the bottom. Two water-cooled copper electrodes hold the specimen by means of collets held in place in the electrodes by set screws. These electrodes serve also to transmit power to the specimen. The lower electrodes can be clamped to the stand, while the upper electrode is fastened in place to the bellows which in turn is further connected to one side of the lever arm, flexibly supported at the top. After the specimen is mo;nted- and the vacuum is secured, the lever arm is adjusted by means of the counter weight so

Jan 1, 1952

By J. J. Kramer, G. W. Wiener, K. Foster

The effects of the primary grain size and sheet thickness on the secondary growth rates of grains with (100) surface planes were studied in 3 pct Si-Fe sheets. This secondary grain growth was carried out under conditions in which the {100} plane had the lowest surface free energy. The value of the surface energy difference, between the (100) plane and the random matrix planes was found to he only about 3 pct of the grain boundary energy, indicating that most of the driving force for secondary growth is supplzed by grain boundary energy. A method for obtaining cube texture in 3 pct Si-Fe sheets by a secondary recrystallization process has been reported.&apos; It has been demonstrated that a difference in surface free energy between the (100) plane and other planes is responsible for this growth, where the (100) plane has the lowest surface energy. A semiquantitative relation has been derived for secondary grain growth in sheets where primary grain growth has proceeded until the grains have grown through the sheet and the average grain diameter in the plane of the sheet is from one to two times the sheet thickness. Then, the linear growth rate, G, for the secondary grains can be given by where M is the grain boundary mobility, is the grain boundary free energy, is the average primary grain radius, A is the average difference in surface free energy between the (100) plane and planes of other orientations, t is the sheet thickness, and C is a term first proposed by zener6 which acts as a negative driving force, the effect of inclusions in holding up grain boundary motion. Since the problem of grain growth being discussed is under conditions where the matrix grain size is at least equal to the sheet thickness, the radius r is, of course, a function of the sheet thickness. The term B/r is the grain boundary driving force normally associated with inclusion inhibited or texture inhibited secondary recrystallization. Here, however, the term is modified to account for the fact that growth occurs in thin sheets. The term is the additional driving force available because of the difference in surface free energy. The purpose of the present work has been to evaluate the driving force terms of the growth equation by studying growth rates of (100) secondary grains as a function of sheet thickness and primary grain size. From these data it has been possible to determine the relative values of grain boundary energy, surface energy difference, and the inclusion term, C. EXPERIMENTAL PROCEDURE A 3 pct Si-Fe alloy was melted and cast under a helium atmosphere using electrolytic iron and a pure commercial grade of silicon as raw materials. The alloy was hot and cold rolled to a thickness of 0.6 mm, and samples approximately 5 in. long by 1 1/4 in. wide were cut from the cold-rolled sheets. Four different primary grain sizes were obtained

Jan 1, 1963

By F. Weinberg

WHEN impure Zn (< 99.99 pct)&apos;&apos;Z or Zn-Cd alloys3 are progressively solidified, a cell or "corrugation" substructure4 is produced in the solid, with a high impurity or solute concentration along the cell walls. When these materials are polished and suitably etched, etch pits are often observed along the cell walls. For the Zn-Cd alloys these etch pits have been associated with decorated dislocations, present in the corrugation boundaries to accommodate the lattice strain. In the course of an investigation of Zn-2 pct Au alloy, molten metal of this alloy was poured into cold water and the resultant solid pieces were sectioned, polished and etched with a Cr0 ethant. An extremely regular cell pattern was observed on the etched surface, similar in general to the corrugation structure previously reported for impure zinc and Zn-Cd alloys. At higher magnification, regularly spaced pits were observed along the cell boundaries. An example of the regular cell pattern at the center of a specimen is shown in the center and lower portions of Fig. 1; the top of the figure shows the pattern near the specimen surface. Typical etch pits in the cell walls are shown in Fig. 2. It was surprising that a cell pattern as regular as that shown in the center of Fig. 1 was produced at the very rapid solidification rates used (estimated as > 1 cm per sec). In addition, the distribution coefficient for the Zn-Au system is greater than 1. Accordingly, the center of the cells should be rich in solute and should etch

Jan 1, 1963

By E. S. Machlin, Morris Cohen

GRENINGER and Troiano&apos; were the first to establish the fact that the habit planes of mar-tensitic products are usually planes of high indices. In steels containing 0.55 to 1.4 pct C, the habit plane indices are {225}A.* In steels with more than 1.5 pct C and in Fe-Ni alloys, the indices are {259In. The presence of both habits in certain alloy steels has been reported recently." Several investigators"-" have subsequently attempted to provide an understanding of these complex habit relations. Bowles&apos;6 work is the most recent and the most successful. Like Greninger and Troiano, Bowles concluded that the transformation occurs in two steps, the first, a strain (or displacement) that is homogeneous throughout the volume of the martensitic plate, while the second is a strain that is homogeneous only within relatively small portions of the martensitic plate. The first strain yields the measured tilt of the specimen surface, but does not produce the final martensitic structure. This and the correct lattice orientations are achieved by the second strain. Bowles also reasoned that each strain could be described by the motion of a plane of no rotation and no distortion (hereinafter called the invariant plane) in a direction not necessarily contained in the plane.** In applying these considerations to steels with {225}a habits, Bowles found that the habit plane coincided with the invariant plane of the first strain, a result which signified that the atoms move along certain paths during the transformation. Whether this correlation results from the existence of some sort of a plate nucleus6 lying along the invariant plane of the first strain, or whether the invariant plane primarily defines the preferred directions of propagation of the first strain, will be discussed in a later section. There are two obstacles to the general acceptance of Bowles&apos; treatment: 1—it has not been shown that elements of his double-strain analysis are unique, and 2—it is not known whether his treatment applies to transformations yielding the {2591A habit. Unless these two questions are resolved, the correlation between the habit and invariant planes in the {225}A systems might be regarded as coincidental. Experimental Procedure Using a 70 pct Fe-30 pct Ni alloy as an example of a {2591A habit system, preliminary attempts were made to obtain a double-strain solution based on a Nishiyamax** set of orientation relations and on a Greninger-Troianot set, adopting the stereographic technique described by Bowles" who used the Kurd-jumow-Sachstt set in connection with the {225}A habit. These attempts were unsuccessful because the method is essentially one of trial and error and requires either exceedingly good luck or a prior knowledge of the results being sought. Consequently it was decided to measure independently the strain associated with the formation of a martensitic plate as well as the habit-plane indices of the particular plate. By means of matrix algebra, the measured strain was applied to the austenite lattice, whose orientation with respect to the strain was determined, in order to ascertain whether the resultant structure would have the lattice of martensite. This was not found to be the case, and hence it was assumed that the measured strain was the first of two Bowles-type strains, characterized by the motion of an invariant plane. A solution of this displacement was obtained in terms of the invariant-plane indices and the direction of motion of the atoms. Then the second strain

Jan 1, 1952