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By R. Kossowsky

Structural changes in Be-Cu, Be-Ni. Be - Ag, and Be-Fc alloys pressurized in a solid medium were invesligated by resistivity measurements , X-ray diffrac lion in situ and metallogvaphic examination. Some limited tests in liquid medium were also conducted. Good correlation was oblained between diauges of slope of relative resistance us pressure and changes in diffraction pattern. Metallographic examination rez:ealed that the copper, silver, and nickel alloys lwiu heauily due to the applicalion of pressure at room temperature. Using polarized light technique {1012}, {1011}, and possible {1010} twinning planes were identified. At eleuated temperature twinning was moslly confined to the {1012} planes. Although twin-ning could be promoted by application of hydroslutic pvessure (liquid medium), it was strongly enhanced by the pvesence of a nonhydvostatic shear component due to pressurizalion in a solid medium. It was further obserced that a decrease in grain size inlnibiled twinnitzg activily. A great deal of effort has been expended in recent years to render beryllium useful for structural applications. Efforts were concentrated towards a possible phase change and to promoting other than basal deformation modes. Quenching experiments to obtain the high-temperature bcc phase have failed,' nor were alloying additions successful in improving ductility of the brittle hcp phase.2 Herman et a1.3 have reported a new {1011} twinning mode in a Be-4.4 wt pct Cu alloy oriented for a C axis compression sustaining loads to 440,000 psi. A new approach using high-pressure techniques was undertaken at Curtiss-Wright, Wright Aeronautical Division Laboratories. Marder4 reported a 25 pct decrease in relative resistance of commercially pure beryllium at 92 kbar. He proposed that this discontinuity corresponded to the bcc phase found at high temperature; however, X-ray diffraction in silu did not confirm a phase transition.5 contre6 has recently shown that the bcc transition in pure beryllium is lowered to 800°C at 80 kbar accompanied by a 50 pct increase in relative resistance. The purpose of this paper is to report on one phase of an investigation of the effects of high pressures and temperatures in beryllium alloys, namely, twinning behavior in Be-Ni, Be-Cu, Be-Fe, and Be-Ag alloys pressurized to nearly 100 kbar and temperatures up to 200°C. EXPERIMENTAL METHODS Material was obtained from Nuclear Metals, Inc., in the form of a 1.5-mm-diam wire extruded in stainless-steel cladding at 1600° F. Nominal composition of the alloys is listed in Table I, and the major impurities are are given in Table 11. Pressures to 100 kbar* were ob- tained using a National Bureau of Standards type 100/400 ton tetrahedral unit supplied by Barogenics, Inc. This type of apparatus contains a retaining sleeve with a conically tapered internal surface and four pressure-intensifying anvil assemblies with tungsten carbide tips. The 10-mm-long specimen fits into a pyro-

Jan 1, 1968

By E. Miller, K. L. Komarek

Equatiorzs have been derived which related maximum solid solubilities in semicondcting compounds having retvograde solidus curves with 1iqllidus data. Liquidus curves in Lke Pb-Te, Pb-Se, ard PB-S systetris have been defermined by thertrzal aralyses. Fvotrz expevimental maximum solibilities ia CdTe, PbTe, uxd PbS vetvograde tetrperatures hale beep1 calculated. TIze resllts support the concept that under certaiz conditiots pronounced itjlections in the liquidis curves arc indzcatiz:e of retropade solidus curves and that the tenlperatltre of the lmaximum solid solubility will be close to the temperature of the point of inflection in the liquidus curve. The maximum solid solihility within a gvoup of homologous cottrpoods SeetlLs to increase with increasing flatness ol the liquidus curvres. The phenomenon of retrograde solubility in metals, i.e., maximum solubility in a solid terminal phase in equilibrium with a liquid phase, has been theoretically predicted by Van aar' in his calculations of hypothetical binary phase diagrams. It was not until 1926, however, that retrograde solubility was experimentally verified in the Zn-Cd system.' Since then many sys- tems with retrograde solubility have been found, so that at present approximately fifty binary diagrams with a retrograde solidus curve are known.3 Meijering4 has critically appraised the accumulated data and has presented calculations which alloy predictions as to whether or not a solidus line will be retrograde. Interest in retrograde solubility increased when it was found that the solidus curves of germanium and silicon alloyed with a great many doping elements are retrrade. The problem was treated thermody-namically by odkinson,% d all available data on solid solutions in germanium and silicon were summarized by Trumbore.7 Although it is to be expected that intermetallic compounds will also exhibit retrograde solubility, experimental evidence is much more limited. Until now retrograde solidus curves have been reported for the compounds de,' be, Ps:" ne," SnSe," and SnS.13 All these compounds are semiconductors, and the solidus curves were usually obtained by determining the carrier concentration at room temperature of samples equilibrated at elevated temperatures and then quenched. It has been hown,'' however, that it is not always possible to quench in the equilibrium compositions from above a certain temperature. Theoretical discussions have either explicitly excluded intermetallic compounds4 or not treated them with respect to retrograde slubilit.j In the following a thermodynamic treatment of retrograde solu-

Jan 1, 1967

Jan 1, 1967

By G. L. Fisher, R. Maddin

The rate of self-diffusion in silver single crystals during torsional strain was measured over a wide range of tenperatures and strain rates. The torsional strain was applied in a cyclic manner by reversing the divection of twist aftev a certain fraction of the total strain was reached. Surface roughening was substantially reduced in cyclically strained specimens compared with those strained entirely in one direction. Diffusion coefficients were determined using a special sectioning technique whereby slices could be removed parallel to the surface of a strained torsion specimen. The accuracy of the technique was first determined using roughened specinzens statically diffused to various penetration depths. Simultaneous strain-diffusion experiments were then performed over the temperature range 550' to 800 using strain rates of lo-' to 2.2 x 10' sec-'. The increase in silver self-diffusivity during torsional plastic strain was small. In only one case was the enhancement greater than twice the static value of the diffusion coefficzent. The enhancements increased slightly with decreasing tenzperature and increased with increasing strain rate. A dislocation pipe mechanism of enhancement was found to explain the present results satisfactorily. The magnitude of the enhancements and the tenzperatures at which they were observed suggests that a steady-state dislocation density of 10' to 109 dislocations cm-2 existed during the high-tempevature deformation. The diffusion coefficient in an fcc metal can be increased by 1) an excess concentration of point defects and 2) the rapid movement of diffusing atoms along grain boundaries and dislocations. Plastic deformation may be responsible for enhancements by both of these mechanisms. The results of simultaneous strain-diffusion experiments have caused a controversy over the magnitude of the effect of strain upon diffusion. Experiments reporting large enhancements have been criticized for the manner in which the diffusion coefficient was measured. Several of these experiments have been contradicted by other results obtained in a similar manner. No enhancement was reported by two investigators''' who performed their experiments at high temperatures where strain is expected to have little effect upon diffusion. A recent theoretical analysis3 indicates that strain enhancement by a vacancy mechanism will be small and exist only at low temperatures and rapid strain rates. It is doubtful whether any experiment has yet proven that strain enhancements can occur by an excess vacancy mechanism. In the present research, experiments were performed at extremes of temperature and strain rate in an attempt to measure enhancement of diffusion by strain. Self-diffusion of silver during torsional deformation was chosen since two separate investigations4j5 indicate that at least a small enhancement exists under these conditions. An accurate method of determining the diffusion coefficient, mechanical sectioning, was employed after a technique was devised to apply it to the roughened surface of a strained torsion specimen. First, the accuracy of the technique was determined for different penetrations (2fi). Then diffusion experiments were performed at temperatures between 550" and 800°C at strain rates of 10"" to 10"" per sec. I) EXPERIMENTAL PROCEDURE Preparation of Specimens. The experimental procedure detailing the growth of crystals, their treatment, and the annealing techniques during straining are contained in earlier publications.496 The dimensions and orientations of the torsion specimens are shown in Figs. 1 and 2. licatiin of Torsional Strain. The torsion procedure was changed from that used previously. The specimens were strained in cycles to reduce the gross distortion and surface roughening inherent in twisting to high strains in one direction. For all strains above 0.30, the total surface strain was obtained as follows: the specimen was twisted to 0.10 strain in a clockwise direction; the direction was reversed; the backlash in the torsion apparatus was taken up; and the specimen was twisted in a counterclockwise direction through the initial starting point to 0.20 surface shear strain in the opposite direction. The strain reversal took no more than 1 min to accomplish. The total accumulated surface shear strain was arbitrarily taken as the sum of the 0.10 strain in the clockwise direction plus 0.20 in the counterclockwise direction. Although cyclic torsional strain was beneficial, surface roughening and specimen distortion were not entirely eliminated. The variation in the diameter at various points on the specimen was often much greater than the depth of the diffusion zone. Since serious errors might result if specimens were sectioned in the usual manner, a technique of lathe sectioning was devised to allow sections to be taken parallel to planes of equal concentration.

Jan 1, 1967

By J. D. Wood, J. T. Smith

ALLOYS with a dispersed second phase in a metallic matrix are generally much stronger than the matrix itself. Plastic deformation in dispersion-strengthened alloys is usually confined to the matrix phase when recovery processes are active, while in the absence of recovery both phases may yield.' The alloy system studied in the present research was WC-12 wt pct Co and consisted of noncoherent WC particles dispersed in the cobalt matrix. Some particle-to-particle contact existed but not enough to produce a continuous WC skeleton. The microstruc-ture of the WC particles was characterized by very straight edges, forming a trapezoidal shape in any plane of polish. Previous investigations with WC-Co alloys at room temperature have shown that fracture of the WC particles occurs in transverse rupture testing.' Room-temperature slip was reported for WC particles after indentation for hardness measurements.3 Elevated-temperature deformation of WC particles in a WC-12 pct Co alloy was suggested by recent electron microscope studies of specimens deformed at 900' to 1000°C.4 In highly deformed alloys, the WC edges were serrated in contrast to the usual straight or smooth appearance. WC-12 pct Co and WC-15 pct Co alloys have been previously studied under elevated-temperature com-pressive-creep conditions by the present authors. Electron microscope studies of two-stage replicas from deformed specimens showed no evidence of slip or fracture of the WC particles. These specimens were brought to temperature and allowed to equilibrate prior to the application of the creep load. It was believed that the load-application rate, a crosshead speed of 0.005 in. per min on an Instron universal testing machine, was sufficiently low that recovery within the cobalt matrix was sufficient to limit the deformation to this matrix. A series of experiments was performed to evaluate the influence of loading rate on the deformation of WC-Co alloys. A WC-12 pct Co alloy was selected for these determinations. The average WC particle size was 4.45 p with an average linear separation between particles of 0.59 p. The selected temperature was 800°C and was monitored with a Chromel-Alumel thermocouple attached to the specimen. Testing was conducted in an argon-atmosphere chamber to prevent oxidation of the WC-Co specimens. This chamber was mounted on an Instron universal testing machine equipped to apply the load at a fixed rate. Each specimen was loaded to 110,000 psi compression stress at 0.05 and 0.5 in. per min. The loading rate was monitored prior to insertion of the test chamber and was found to be almost precisely the nominal rate selected. The specimens were raised to temperature and held to equilibrate with the surroundings, and then the load was applied and held for 4 hr to duplicate the exposure time utilized for the creep specimens. The time to reach full load at a crosshead speed of 0.005 in. per min was some 500 sec and was reduced to 50 and 5 sec as the loading rate was increased to 0.05 and 0.5 in, per min, respectively. The model developed by Ansell,' when recovery processes do not occur, considers that fracture or deformation of the dispersed particles is necessary to relieve back stresses on dislocation sources and allow dislocations piled up against particles to sweep out in the matrix to cause plastic deformation; he further states that, even at elevated temperatures, the dispersed-particle deformation is necessary for yielding in the absence of recovery. For the case of straight dislocation segments piled up against a straight barrier, such as the straight-sided WC particles, the shear stress, 7 exerted on a particle is: where h is the spacing between particles (0.59 p), a is the applied stress (110,000 psi), p, is the shear modulus of the matrix (6.7 X lo6 psi at 80O°C), and b is the Burgers vector of the matrix dislocation. From Eq. [I], the shear stress, 7, exerted on the WC particles when no recovery occurs is of the order of 6 X lo6 psi at 800°C. The limiting stress, F, that will

Jan 1, 1969

By Lucien F. Trueb

The microstructure of explosion-bonded pairs of similar and dissimilar metals has been investigated by electron microscopy. A review of the specific problems encountered and the methods used for obtaining surface replicas and thin-film transmission specimens of the bond interface is given. The bond area is mainly characterized by continuous and practically diffusionless metallurgical bonding. The very large shear stresses induced along the collision front of the plates being joined causes extreme grain elongation and a symmetrical pattern of subgrains in the bonding direction. The bond zone is also characterized by a very high density of dislocations and pressure-induced twins. Localized heating occurring during the cladding process can result in partial re-crystallization or the formation of thin layers of molten material. The force of precisely controlled explosions causing a high-velocity impact between metal plates has been used for several years to achieve metallurgical bonding between an extremely wide variety of metals. This method essentially consists of accelerating a plate to high velocity toward a stationary plate by a detonating explosive. Since the restrictions to bonding are not those encountered with conventional nethods, it becomes possible to bond pairs of metals having widely different mechanical properties that are immiscible or form brittle intermetallic compounds. Many applications of such composite metals are found in the field of corrosion protection as well as numerous other fields; for example, explosion bonding is being applied for fabricating the materials used by the United States Mint in the new sandwich-type coins. The primary condition for establishing a metallurgical bond is that absolutely clean metal surfaces be brought together. Any metal exposed to the atmosphere is covered with oxides, adsorbed gases, and other contaminants; even a very forceful impact of two such surfaces is not sufficient for bonding. Cowan and Holtz-man,"' who reviewed the dynamics of colliding plates in detail, showed that in order to achieve a good bond the explosion conditions must be chosen in such a way that the plate collision velocity is less than the sonic velocity, in which case no oblique shock waves are attached to the collision front. A pressure wave is then generated ahead of the collision line, and the material forming the colliding surface of each of the plates flows forward and is ejected in the form of a spray, the so-called jet. The dynamic elastic limit of the metals must be exceeded so that there is sufficient plastic deformation. At the point where the jet formed by the junction of the inner surface layers of both plates separates from the combined plates, the material experi- ences a very high shearing strain and the pressure can reach several hundred kilobars. This process strongly influences the microstructure of the bond zone as will be seen later. Behind the collision front, uncontami-nated layers of internal material are brought together under high pressure and are thus metallurgically bonded. I) STRUCTURE OF EXPLOSION BONDS The different types of explosion bonds that can be obtained depend on the explosion conditions, and have been investigated by Cowan and Holtzman,1'2 Holtzman,3 Klein; Bahrani and crossland,' and Buck and Horn-bogen. The preferred kind for practical applications is the so-called wavy bond, typical examples of which are given in Fig. 1 showing light micrographs of various metal-to-metal interfaces. In forming this type-- of bond the collision energy is mainly expended in jetting, the formation of waves, and localized melting. Beyond the crest of the waves, eddy-shaped areas are observed in which the two metals are mixed in a complex pattern of streaks. Cowan and Holtzmanl first proposed that this wavy pattern is analogous to periodic eddy shedding in the flow of a viscous fluid around an obstacle (Von Karman's eddy street). The mass of metal ahead of the stagnation point, which is associated with the jet and has forward momentum, plays the role of an obstacle and the eddies created in the flow of solid metal around the stagnation point are preserved in the final clad specimen. This idea has been reviewed more recently by Klein4 and the variables involved in the wave formation have been discussed in some detail by Bahrani and crosslands and Buck and Hornbogen.6 Several studies of the structure of explosion bonds by light metallography have already been published.1-6 Aside from the waviness and the eddies which were mentioned above, the most striking characteristic of the area in the vicinity of the bond interface is a very considerable longitudinal grain deformation which appears to be strongest at the metal-to-metal boundary and dies out as one moves away from it. Large twins are often observed within the deformed grains, and molten areas are found in the center of the eddy-shaped structures situated beyond the crest of the waves. The large hydrostatic pressures and shear stresses occurring at the interface modify the mechanical and chemical properties of the bond zone. Increases in hardness in this area have been reported by various authors.396 The defects along the interface can also cause a local increase of the chemical reactivity and thus might be expected to boost the etching rate. However, the effects of this preferential etching cannot be observed by light microscopy due to its inherently limited resolution power. The same limitation precludes the observation of morphological features directly along the bond interface as well as the interface itself. Furthermore, no information can be gained by light-

Jan 1, 1969

By Robert E. Green, Edmund G. Henneke

The velocities of the three possible modes of elastic wave propagation have been calculated for single-crystal copper at 1-deg intervals throughout the standard stereographic triangle. The results are presented as isospeed contours. The deviations between the direction of maximum energy flux and specimen axes are presented as arrows drawn on stereographic projections. The orientation factors associated with dislocation motion on the primary slip system only and also on all twelve slip systems have been calculated for all three elastic waves. The orientation factors associated with a longitudinal standing wave resonant specimen have also been calculated. The results of these calculatians are compared with earlier calculations on aluminum crystals and the relevance of these results to ultrasonic attenuation measurements is discussed. GREEN and inton' have recently outlined a procedure for determining the orientation factors for dislocation damping in single crystals. The stress field associated with a given mode of elastic wave propagation is resolved on the slip systems in which it is assumed the dislocations are vibrating due to this stress field. Since, at room temperature, slip has been observed on a limited number of systems in fcc and hcp metal crystals, it is assumed that these systems are the appropriate ones to use for the resolving process. This procedure has been applied to aluminum crystals by Hinton and hreen' and to zinc crystals by Henneke and Green.3 In the present paper the modes of elastic wave propagation have been calculated for copper crystals possessing orientations at 1-deg intervals throughout the standard stereographic triangle. The deviation of the energy flux vectors from the specimen axis have been calculated for each mode. The stress field associated with each mode has been resolved on the (111)(110) slip systems in order to determine the orientation factors for dislocation damping. MODES OF ELASTIC WAVE PROPAGATION For any direction in a linear homogeneous aniso-tropic material three elastic modes can be propagated. In general, each of these modes has both longitudinal and transverse particle displacements associated with it and thus are not "pure" modes. However, there is always one component which is greatest in either a longitudinal or transverse direction and hence the mode may be referred to as quasi-longitudinal or quasi-transverse, accordingly. For certain axes of high symmetry pure modes may be propagated. The phenomenon of refraction of the energy flux vector is also exhibited by elastic wave propagation in ani-

Jan 1, 1969

By A. C. D. Chaklader, Ashok K. Kakar

The basic density equation originally dericed ' to predict the increase in density of a compact of spherical particles with the progressive deformation at the points of contact has been further modified to include the yield strength of the material. This has been done by assuming that the contact areas grow to stable sizes under a fixed stress which is equal to three times the yield strength. The final equation has the form: where Do and D me the initial and final bulk densities of the compact, u is the applied pressure, and Y is the yield strength of the material. This equation was tested with the data obtained on spheres of lead, K-Monel, and sapphire. The calculated yield strength t~alues for lead and sapphire are within the range of values reported in the literature. A few of the earliest hot pressing models proposed to explain the mechanism by Murray, Livey, and williams2 and then by McClelland3 are based on a plastic flow mechanism. However, more recent investigations suggest that the overall densification process is a combination of several mechanisms, such as particle rearrangement, fragmentation, plastic flow, and stress-enhanced diffusional creep. While fragmentation and particle rearrangement are considered to be responsible for the densification in the early stages,"475 it has been concluded that the final stages of hot pressing are controlled by stress-enhanced diffusional creep.516 The manner in which the densification takes place, i.e., by fragmentation, particle rearrangement, plastic flow, or stress-enhanced diffusional creep, would depend upon the type of material, the temperature, and the stress level used during the hot-pressing experiments. Metal compacts can be expected to have a much greater contribution from plastic flow than ceramic oxides. Also, plastic flow would be a significant contributing factor to densification at high temperatures and high stresses. Most of these works, directed towards elucidation of densification mechanism, have dealt with kinetics of the process. The results of most of the authors vary from one another and they have proposed either new empirical or semiempirical equations to fit their data. The densification rate was found to vary with the type of the powder, shape and size of the powder, initial packing density of the compact, and a few other factors such as rate of heating, pressure, and so forth. Beyond the initial stages, the densification process has been considered to be as time-dependent flow, controlled by a diffusional process, e.g., Nabarro-Herring creep. Palm our, Bradley, and johnson' have attempted to use modified creep rate equations to interpret the data of densification under hot-pressing conditions. Beyond the initial stages, however, the densification would be controlled by a process depending upon the temperature, pressure, and size of the powders. It is the authors' belief that such densification cannot be exclusively controlled by a single process and so attempts should be made to study some observable phenomenon like microstructure, yield strength, and so forth. The emphasis of this work has been toward studying the densification problem from a more fundamental point of view. Some of the principal variables, like initial packing density, mode of packing, and size of the powders, have been controlled to a great extent. The total strain produced on pressure application (instantaneous) in such a case can be considered to be due to plastic and elastic deformation. The elastic component of the strain can be determined by decreasing the load to the initial value. The strain remaining then can be correlated with the contact areas produced by deformation and the corresponding applied load. In a previous paper,' the possible deformation behavior of spheres in a compact has been theoretically analyzed and experimentally tested. The change in contact area radius a relative to the particle radius R was related to the bulk density and the bulk strain for simple and systematic modes of packing. Tt was found that a density equation relating the above parameters can be represented by: where D and Do are the bulk densities of the compact at any value of a/R and a/R = 0, respectively. This basic equation should hold for any material as it was derived from geometrical considerations alone. An attempt has been made in this work to include the yield strength in the above density equation, so that a knowledge of the properties of any material can be used in predicting the densification behavior during the hot-pressing process. THEORETICAL CONSIDERATTONS The deformation of two spheres in contact under a static load can be compared to the deformation occurring between a hard spherical indentor and the flat face of a softer metal. Tt has been shown theoretically by both ~encky~ and lshlinskyg and experimentally by ~abor" that, for a material incapable of appreciable work hardening, the mean pressure required to produce plastic yielding (for deformation occurring between flat face and a hemispherical indentor) is approximately equal to three times the elastic limit, Y, of the material (in tension or compression experiments). Tabor has further observed that the same relationship is valid in the case of work-hardening materials, if the elastic limit at the edge of the indenta-

Jan 1, 1969

By Jaakko Kajamaa

Neutron diffraction was applied to determine sheet textures by the transmission method. Cold-rolled and recrystallized copper sheets were investigated. The amount of cube texture was determined for three compositions, in which the phosphorus content was, respectively, 0, 0.005, and 0.03 wt pct. The heat treatment was in every case 8 sec at 650°C. In the two latter cases the cube texture was prevented. In addition a comparison with the X-ray diffraction transmission method was made with the 96 pct cold-rolled copper sheet. Outer parts of both (111) pole figures can be considered to be rather identical. This is seen from the fact that the intensity ratio ITD/120" was 0.45 for neutron diffraction and 0.40 for X-ray diffraction. Differences between the methods were discussed in detail. Features peculiar to neutron and X-ray diffraction in texture studies were listed and compared. In this work neutron diffraction was applied to determine sheet textures. Specifically, it was desired to ascertain whether this method can be used to reveal differences when compared to other methods. In addition, the amount of the cube texture in copper sheets was determined as a function of phosphorus content. Previous applications of neutron diffraction to texture problems include the following: nickel wires,' wire of some bcc metals,' and uranium bars.3 In the neutron diffraction technique the greatest difference is in the sample—its method of production and its volume. A sample needs no treatment and its volume is roughly 105 times larger than the volume of an X-ray diffraction sample. The cold-rolled sheet was investigated both by neutron diffraction and by X-ray diffraction, because it is expected that, due to large number of defects, possible differences in the results of the two methods would be revealed. It is a well-known fact that X-ray lines show broadening when cold-worked. Analysis has shown that this is based chiefly on small crystalline size, micro-stresses, and/or faults.4'5 Neutrons are sensitive to the above-mentioned disturbing factors as well, but circumstances in diffraction are different from the X-ray case. Because the sample represents a larger volume, the result is an average over that volume. In addition, it can be assumed that the sample has preserved its original structure, because it needs no special preparation. The particular limitation of neutrons is the relatively low neutron intensity available from nuclear reactors. This decreases the resolution as compared to the X-ray diffraction methods. Furthermore, absorption mainly reduces diffracted X-ray intensity, while multiple scattering effects, i.e., secondary extinction, disturb neutron diffraction. SO neutrons and X-rays behave in a different way when interacting with matter. As in other structural investigations, one can utilize this difference in texture studies as well. One cold-rolled and three recrystallization textures in copper sheets were investigated by neutron diffraction. The samples were produced at the Outokumpu copper factory to the specifications shown in Table I. The paper is divided into five parts. The first deals with the theory of the measurement. In the second, experimental procedures are described. Results are presented in the third part. Both cold-rolled and re-crystallized samples are studied. Discussion is in the fourth part, and finally in the fifth part some conclusions are drawn. 1) THEORETICAL CONSIDERATIONS Properties peculiar to neutron diffraction are the following: a) the scattering length varies greatly between one element and another; b) many of the elements do not absorb neutrons appreciably. In this connection it is of primary interest to know the interaction of neutrons with lattice imperfections. As with X-rays this problem leads to diffraction analysis of deformed and recrystallized metals. From the physical point of view the main difference is that neutrons are scattered by nuclei (magnetic scattering is not considered here), whereas X-rays are scattered by electrons. The features peculiar to neutron and X-ray diffraction methods in texture studies are listed in Table 11. Pole figures are an important tool in performing structural analysis of deformed or recrystallized metal. Present texture research technology requires pole figures which are as precise as possible. The choice between these two methods depends on the technical information which is required. The X-ray diffraction transmission technique may give results which are not necessarily representative of the average physical state of the sample. Although foil samples normally contain enough crystallites for diffraction, they may not necessarily represent the whole structure. An example of this problem is the frequently observed difference between the "surface" and the "inside" texture of a sample. The production of foil samples may disturb the original structure of the parent material. The selection and orientation of the foil from the sample is quite arbitrary. Normally, a highly deformed piece of metal has several texture components. Different components are deformed in a slightly different manner. This is a re-

Jan 1, 1969

By O. P. Quist, S. H. Carpenter

The internal friction of single-crystal LiF has been investigated as a function of crystal orientation, while simultaneously applying a static compressive load. Three different crystal orientations were used, these being samples with the (100), (110), and (111) directions along the sample length. Results show the internal friction measured to be similar in appearance but different in magnitude for the (100) and (110) samples. With both orientations, application of a static stress caused an increase in the amplitude-independent damping, which recovered with time. The amplitude-dependent damping was found to first decrease with load up to the yield stress and then increase rapidly. Samples of the (111) orientation were found to have no measurable internal friction even when loaded up to 3.0 kg per sq mm. These results are discussed in terms of current theories of internal friction in ionic crystals. This paper presents the results of an investigation of the dislocation mobility and dislocation motion in high-purity single-crystal LiF at applied stress levels up to the yield stress. Internal friction measurements of the dislocation damping while simultaneously applying a static compressive load was the experimental technique used. LiF crystals much prefer to slip on the (110) set of slip planes. However, with a suitable stress distribution they can be forced to slip on the {100} set of slip planes.' For both sets of slip planes the slip direction is the same, namely (110). The object of this investigation was to try and learn more about the dynamical properties of dislocations on the different slip systems in LiF crystals. EXPERIMENTAL PROCEDURE Dislocation damping was measured, in terms of the log decrement, using a five-component marx2 composite piezoelectric oscillator. The apparatus used allows one to measure the dislocation damping while simultaneously applying a static compressive load on the sample. A schematic of the apparatus used is shown in Fig. 1 and a complete discussion of its construction and operation is given elsewhere.3 All measurements were made at room temperature with a longitudinal resonant frequency of approximately 50 kc per sec. Damping measurements were made using longitudinal vibrations with strain amplitudes from up to 10. Static loads up to 3.0 kg per sq mm were applied to the sample while the damping was being measured. Samples used in this investigation were high-purity single crystals of LiF purchased from the Harshaw Chemical Co. All samples were approximately of an in. square and were hand-ground in length to one-half wavelength to match the resonant frequency of the driver and gage quartz crystals. Samples of three different crystallographic orientations were used, namely, crystals with the (loo), (110), and (111) direction parallel to their length. The magnitude of the damping is a direct measure of the area on the slip planes swept out by dislocations during a complete oscillatory cycle. With a sample of the (100) orientation the maximum applied shear stress, due to longitudinal vibrations, is on the (110) slip planes with zero shear stress on the (100) slip planes. Thus, damping measured from a (100) sample is due entirely to dislocation motion taking place on the (110) set of slip planes. Similarly, for a sample of the (111) orientation there is zero shear stress on the (110) set of slip planes and the damping measured from a sample of this orientation is due entirely to dislocation motion on the (100) set of slip planes. Samples of the (110) orientation will have a component of shear stress on both sets of slip planes and

Jan 1, 1969

By R. E. Reed-Hill, W. H. Hartt

High-purity magnesium single crystals, oriented with basal plane parallel to stress axis, were deformed in tension at room temperature so as to form second-order (1011)- (1012) twins. Investigation by optical and replica electron microscopy revealed that these twins can support very large internal strains approaching 1000 pct and that fracture follows as a direct consequence of these strains. At low strains the basal plane within (10i1)- (10i2) twins rotates with increasing deformation until it becomes approximately parallel to the twin boundaries. This rotation is not consistent with deformation by basal slip in the double twin, but may be rationalized in terms of nonbasal slip. Observations also indicate that basal slip in the primary (1011) twin, prior to second-order twinning, may contribute to this rotation. Deformation markings that are difficult to interpret in terms of slip on previously observed systems were noted in the twin bands. A possible means of rationalizing these markings is to relate them to grain boundary shear. The fracture associated with these twins is thought to initiate by formation of voids at the twin boundaries. These grow into microcracks, with ultimate fracture occurring by tearing of the interconnecting regions. THE significance of deformation and fracture along second-order (10i1)-(10i2) twins in polycrystalline magnesium1-' and many magnesium alloys4 was discussed in a previous paper.5 It was noted that this double twinning mode effectively controls the room-temperature deformation and fracture of magnesium single crystals, oriented with the basal plane parallel to the tensile axis. Reed-Hill and Robertson6 observed that, although these crystals may fracture at a macroscopic strain of less than 1 pct, shear strains up to 1000 pct could occur within (1011)- (10i2) twin bands. They concluded that the fracture was "ductile" and resulted from concentrating the deformation into a very small volume. The present research was undertaken to obtain a better understanding of the deformation and fracture associated with these twins. EXPERIMENTAL TECHNIQUES The experimental procedure involved straining high-purity magnesium single crystals in tension at room temperature. Specimens were oriented so that the applied stress direction was within 2 deg of the [1010] crystal axis. The specimen cross section was rectangular with faces closely parallel to (1210) and (0002). The specimen preparation and testing procedures have been described in detail elsewhere.5 Second-order (1011)- (1072) twins nucleated during straining were studied using optical and replica electron microscopy techniques. For the latter, cellulose acetate-carbon double replicas were employed. Observations were made on the (1210) crystal surface, which is the plane of shear for twins of this type. In addition to the single crystals, some investigations were carried out on longitudinal polycrystalline specimens. These were obtained from high-purity magnesium plate with a texture in which the basal planes of the grains tended to be nearly parallel to the specimen axis. All. polycrystalline specimens were annealed prior to testing in order to produce a coarse grain structure, permitting Laue back-reflection X-ray photographs to be obtained from grains of interest. EXPERIMENTAL RESULTS a) Deformation Within ( 101 l )-( 1072) Twins. Fig. 1 is an optical micrograph demonstrating the extent of the plastic deformation that can occur in (1011)-(10i2) twin bands. Notice at the lower left corner of the photograph the large displacement of the dark band (a polishing step) where it crosses the twins. The shear strain in the twin band at this position was computed to be 700 pct, using the ratio of step width to twin thickness. It was previously shown5 that (1011)- (1012) twin bands are often composed of small, separate twins aligned close to the macroscopic habit plane. Fig. 2 is an electron micrograph from near the upper end of the twin band in Fig. 1. This illustrates that the twin habit often does not coincide exactly with the macroscopic band habit, but may be inclined at a slightly smaller angle to the matrix basal plane. Figs. 3 through 6 are electron micrographs of the twin band in Fig. 2 illustrating successive steps in the development of deformation inside the band. A twin band such

Jan 1, 1969

By H. Conrad, V. V. Damiano, G. J. London

The slip mode activated during the c axis compression of single crystals of commercial-purity ingot SR beryllium, high-purity (twelve-zone-pass) beryllium, and Be-4.4 wt pct Cu and Be-5.2 wt pct Ni alloys in the temperature range of 25° to 364°C was determined using two-surface slip trace analysis, slip-step height analysis, and electron transmission microscopy. All three techniques indicated the occurrence of copious pyramidal {1 122) (1123) slip in the alloys over the entire temperature range, the amount increasing with temperature. Pyramidal slip was also indicated in the high-purity beryllium by slip trace analysis and electron transmission microscopy, but the amount was somewhat less than in the alloys. For the commercial-purity ingot crystals, only a very small number of pyramidal slip lines were observed, and these were in the immediate vicinity of the fracture surface. No pyramidal dislocations could be detected by electron transmission microscopy in this material. Dislocatransmissiontions with Burgers vectors [0001] and +(ll20) were identified by electron transmission microscopy inthe (1122) slip bands, as well as those with the j (1123) vector. This was interpreted to indicate that the edge components of the 3(1123) vector dislocations activated during c axis compression dissociate upon unloading according to the reaction i (1123) — [0001] + 3(1120) THE microstrain c axis compression of single crystals of commercial-purity ingot SR beryllium (99.6 pct), high-purity twelve-zone-pass beryllium (99.98 pct), Be-5.24 pct Ni and Be-4.37 pct Cu alloys was described in a previous paper.1 This paper covers in detail the analysis of slip traces observed on two mutually perpendicular lateral surfaces of these specimens, and a detailed description of transmission electron microscopy studies performed on foils cut from the bulk crystals after they had been deformed to fracture in the c axis compression. Observation of slip traces on single surfaces of deformed single crystals are generally insufficient to positively identify slip or twinning modes. The use of two carefully cut and oriented perpendicular surfaces can greatly aid in the positive identification and index- ing of slip traces, although even this technique may be quite inadequate if more than one type of slip system operates and if an insufficient number of traces are observed on the surfaces. The problem is greatly simplified for symmetric cases like that for c axis compression of an hep crystal such as beryllium, in which the operating slip systems are all equally inclined to the direction of the applied stress, and each slip system of a given slip mode has an equal chance of operating. For such cases, the traces of any given slip mode observed on the surfaces cut parallel to the c axis are symmetrically tilted about the c axis. It is therefore possible to quickly determine whether one or more slip modes are operating. Confirmatory evidence in support of the observations made on the external surfaces can be obtained from foils cut from the deformed crystals and examined by transmission electron microscopy. This latter technique serves to identify not only the operating slip plane but also the Burgers vector of the dislocations which participate in the slip. For this purpose, a simplified technique based upon a double tetrahedron notation is used in the present paper. The planes and directions in the hep lattice are all designated by letters rather than indices and extinction conditions are easily determined if the Burgers vector lies in the plane contributing to the diffraction. RESULTS 1) Slip Trace Analysis. The standard (0001) stereo-graphic projection of beryllium is shown in Fig. 1. The two mutually perpendicular, lateral surfaces of the compression specimen are represented by the diametrical planes AA' and BB', also referred to as surface A and surface B. For the specific case represented (a Be-5.24 pct Ni specimen deformed by c axis compression at room temperature), the A surface is tilted 5 deg to the (10i0') plane and the B surface is tilted 5 deg to the (1120) plane. Two surface trace analyses may be facilitated by examining in turn the intersection of various great circle traces of specific pyramidal planes with two surfaces and comparing the angles made with the (0001) plane with those actually observed on the two surfaces. One then identifies the slip traces by trial and error on a best-fit basis. The (1122) type planes (it was found that slip occurred on these planes) are shown plotted on the stereographic projection in Fig. 1. One obtains directly the angles between the (0001) plane and the {1122) traces by measuring the angle from the periphery to the point of intersection along the lines

Jan 1, 1969

By H. Conrad, V. V. Damiano, G. J. London

A method is described for producing single crystals of high-purity beryllium, Be-4.37pct Cu, and Be-5.24 pct Ni. These crystals were prepared for testing in compression parallel to the [0001] by orienting and lapping to within ±3' of arc of the (0001). Microstrain testing apparatus is described along with c axis compression results for ingot purity beryllium, twelve-zone-pass material, and the above-mentioned alloys. Results show no measurable plasticity for the ingot purity material from -196" to 400°C, although some surface traces of (1122) slip was observed at 200°C and above. The twelve-zone-pass material shows substantial microstrain plasticity at 220°C with slip on (1122). Both alloys show significant plasticity at room temperature and above with slip also on (1122) planes. THE two slip systems which normally operate during the plastic deformation of beryllium in the vicinity of room temperature are:' basal slip (0001)(1120) and prism slip . Pyramidal slip with a vector inclined to the basal plane has been reported for elevated temperatures,'-a but occurs near room temperature only at very high stresses.~ A summary of the available data on the effect of temperature on the critical resolved shear stress for slip on these systems has been compiled by Conrad and Perlmutter.~ It has been postulated6'7 that one of the principal factors contributing to the brittleness of poly crystalline beryllium at temperatures below about 200°C is the difficulty of operating pyramidal slip with a vector inclined to the basal plane. Hence, detailed information on the operation of such a slip system is important to understanding the brittleness of beryllium. The operation of pyramidal slip with a vector inclined to the basal plane is best accomplished in beryllium by compressing single crystals in a direction parallel to the c axis. In such a test the resolved macroscopic shear strzss on the basal and prism planes is zero and (1012) twinning which is favored by tension along the c axis does not occur. Hence, in c axis compression of beryllium the normal deformation modes are inhibited and the operation of pyramidal slip with a vector inclined to the basal plane is favored. In the present investigation, c axis compression tests were performed on beryllium single crystal as a function of temperature (77" to 700°K), purity (commercial and twelve zone pass), and alloy content (4.37 wt pct Cu and 5.24 wt pct Ni). Presented here is a description of the test techniques employed and the gross mechanical behavior observed. A detailed analysis of the slip traces developed on the surfaces of the deformed specimens during these tests and the results of electron transmission studies of the deformed crystals are given in a separate paper.B PROCEDURE 1) Materials and Preparation. Single crystals about 1 in. diam were prepared of the following materials: commercial-purity beryllium, high-purity beryllium, and two beryllium alloys, one with 4.37 wt pct Cu and the other with 5.24 wt pct Ni. The commercial-purity single crystals were obtained by cutting specimens from large-grained ingot of Pechiney SR material, which is approximately 99.98 pct pure. The high-purity crystals were prepared by floating-zone refining (twelve passes) a rod (7 in. by 1 in, diam) of Pechiney SR grade cast and extruded beryllium. Although an absolute chemical analysis of the zone-refined material was not established, mass spectro-graphic analysis, emission spectrographic analysis, and y activation analysis indicated that it contained in atomic fractions about 5 to 10 ppm each of carbon and oxygen, 1 to 5 ppm each of nickel and iron, and about 1 to 2 ppm of copper, with the remaining residual impurities being less than 1 ppm. Further indication of the purity of this material is provided by the critical resolved shear stress for basal slip, which was approximately 300 psi. The starting material for the alloy single crystals was 1-in.-diam floating-zone-refined (six passes) rod of Pechiney SR grade beryllium. Two such rods were wrapped respectively with sufficient weight of wire of high-purity copper (99.999 pct) or nickel (99.999 pct) to yield a 5 wt pct alloy. A seventh floating-zone pass was then applied to each of the rods to accomplish the initial alloying and an eighth pass for homogenization. Analytical samples were taken from regions of the rod immediately adjacent to where the mechanical test specimens were cut; these indicated 4.37 wt pct Cu and 5.24 wt pct Ni. 2) Crystal Orientation. To avoid the occurrence of basal slip during c axis compression testing, it is necessary to load the crystals as nearly parallel to the c axis as possible. Preliminary c axis compression tests indicated that plastic flow and/or fracture occurred at stresses of the order of 300,000 psi; hence on the basis of a critical resolved shear stress for basal slip of 300 to 400 psi, the maximum crystal misorientation permitted is about 4 to 5' of arc. Since this accuracy cannot be obtained using the usual back-

Jan 1, 1969

By G. W. Healy, L. F. Sander

was investigated by reacting thin discs of calcium oxide with gas mixtures of CO2, CO, and Son. Its value was 19,300 * 300 cal independent of temperature in this range. No solid solubility of sulfur in calcium oxide was detected within the limits of the experimental method and it is estimated to be below 0.025 pct by weight. The importance of lime in desulfurization is well-established but complete information on the pure phase equilibrium: CaO + 1/2 s2 = CaS + +02 [11 is not yet available. The goal of this work was to evaluate solid solubility of CaS in CaO and to determine the free-energy change associated with Reaction [I] at temperatures of 1400" to 1650°C. The equilibrium constant for Reaction [1] can be written: It is convenient to rewrite Eq. [2] in the form: where A = {Ps /PqJ1'2 has been referred to' as the "sulfurizing power' of a gas mixture. In this work, thin discs of CaO were suspended in a vertical tube furnace and exposed to CO + CO2 + SOz gas mixtures having known values of A. The samples were then analyzed for sulfur. As expected, X-ray diffraction confirmed that CaS was the only sulfur-bearing phase formed at the relatively low oxygen pressures used. EXPERIMENTAL PROCEDURE Reagent-grade CaCO3 was pressed in a 3/8-in.-diam pill die and prefired in air to produce CaO discs weighing between 0.004 and 0.01 g. Several discs were used to provide a suitable weight for chemical analysis while maintaining a large surface area to react with gas mixtures. These were placed in a platinum mesh basket and suspended in the gas stream in the hot zone of a vertical tube furnace. Desired gas mixtures were prepared from cp grade CO and CO2 and anhydrous grade SO2. The method of soap bubble displacement was used to calibrate capillary flow meters. While this gave excellent results with CO and Con, some problems with bubble insta- bility and soap film "drag" arose with the use of SO2 at low flow rates. Hence, frequent sampling and analysis of gas mixtures was carried out to insure proper control of the ingoing SOZ. The furnace used for gas:solid equilibration was a vertical mullite tube externally wound with 60 pct Pt-40 pct Rh wire having a diameter of 0.028 in. An inner tube of $ in. ID served as the reaction chamber having Pyrex ground joints sealed to the mullite to provide gas-tight connections at top and bottom. A Pt-Pt 10 pct Rh thermocouple was inserted into a protection tube adjacent to the sample basket to measure sample temperature during a run. Constant-temperature control to 2C was observed at any desired set point within the range of this investigation. This was accomplished by a control thermocouple imbedded in the furnace windings which served to actuate an electronic controller wired for high-low operation. The sulfur analyses of the solid samples were carried out using a stoichiometric combustion technique based on the method of Fincham and Richardson. Some analyses were done using a modified evolution method3 but these were used primarily to check the results of the combustion method. The results were in good agreement but the combustion technique of-ferred an advantage in economy of time and material. CALCULATION OF GAS EQUILIBRIA Heating a given mixture of CO + CO + SO2 to high temperatures gives rise to a large number of product species. The details of calculating the partial pressures of these products of interaction and dissociation can be found in several references4,5 and need not be repeated here. The thermodynamic data selected for the major species in the gas mixtures are shown in Table I. Equilibrium constants from these reactions were combined with oxygen, carbon, and sulfur balances and a computer program written to facilitate the calculations. Some early difficulties in reproducing experimental results were finally traced to the effect of atmospheric pressure changes. No reference to consideration of this question had been found in the

Jan 1, 1969

By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.' udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4'5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A'-B' develops at the other intersection. The angles A + B and A' + B' are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

By R. L. Pober, L. Kaufman, E. V. Clougherty

Composite structure of hafnium, zirconium, and titanium diboride with additions of metals and/or compound phases were prepared by reactive high-pressure hot pvessing and evaluated in air and in mixtures of oxygen and helium at temperatures up to 2400°K and at linear flow rates of 0.1 to 0.2 ft per sec stp. Oxidation characteristics, principally depth of conversion of diboride to dioxide, were determined by a gas analysis method and by postoxidation metallo-graphic analyses. The best oxidation resistance was observed for hafnium diboride-silicon carbide composite which exhibited a 6-mil conversion to dioxide for a 1-hv oxidation in air at 2200°K compared to a 20-mil recession for hafnium diboride with no additive. Analogous improvements in oxidation resistance were observed for the addition of silicon carbide to zirconium. EARLIER investigationof the oxidation behavior of the diborides of the transition elements of Groups IVA and VA in flowing gas mixtures have produced a ranking of these compounds according to which HfB2 is the most oxidation-resistant followed in turn by ZrB2 > TiB2 > TaBz > NbB2. Other ~tudies~-~ have examined the physical, thermal, and thermodynamic properties of these diborides to provide a sound basis for the more detailed and specialized investigations which are required to generate the information needed to assess the usefulness of such materials in high-temperature oxidizing environments. Recent oxidation studies7 have examined the effect of variations of metal and boron content on the oxidation characteristics of zirconium and hafnium diboride in flowing gas mixtures including air and helium plus oxygen. Results obtained in the latter investigation confirmed the superior oxidation resistance of HfB2 over ZrB2. Moreover, metal-rich compositions of hafnium diboride showed improved oxidation resistance over boron-rich compositions at temperatures up to 2000°K; at higher temperatures the differences are not distinguishable. In particular HfBI.7 exhibited a diboride to dioxide conversion depth of 4 mils in 1 hr at 2000°K; HfB2. 2 exhibited a conversion depth of 16 mils for the same exposure.~ Specimens for the study of metal and boron stoichiometry on the oxidation characteristics of HfB2 and ZrB2 were prepared by high-pressure hot pressing, a specialized type of fabrication which produced dense crack-free bodies of the desired compositions with no significant impurity introductions. The purpose of the present investigation was to explore the possibility of further improving the oxidation resistance of the metal-rich ZrB, and HfB2. The plan to accomplish this objective was based in the formulation of several diboride compositions containing other compounds and phases which are generally known to have good oxidation resistance in one or more types of test environment. Ideally, such additives would also enhance or at least not diminish other boride property values principally mechanical strength and those parameters related to thermal stress resistance. The additions selected for HfBz included zirconium, aluminum, and (Ta + TaB2) designed to produce ternary metal diborides, hafnium to form a discrete HfB phase, chromium to provide a metal skeletal phase, (Hf + Si) to form a discrete hafnium silicide phase, and Sic to provide a discrete second phase. Additions to ZrB2 included A1 + B designed to produce a ternary metal diboride, Zr + Si to form a discrete zirconium silicide phase, and Sic to provide a discrete second phase. All the specimens were prepared by high-pressure hot pressing which was used to advantage to fabricate billets of the variety of compositions desired and suitable for oxidation testing. The present investigation also included the evaluation of high-pressure hot-pressed TiB2and TiB2-20 vol pct Sic, conventionally hot-pressed Boride 2,' and KT silicon carbide. Boride

Jan 1, 1969

By D. O. Hobson

Zirconium single crystals of various specific orientations were fabricated by rolling or drawing. The resulting textures were determined and are discussed with respect to the deformation modes that produced them. The crystals deformed in a predictable manner by combinations of up to third-order twinning with three twinning modes and by slip. Twinning was found to play a major role in initial texture formation. Texture changes produced by slip occurred only at the higher reductions. The twinning sequences that produced each intensity peak during the initial reductions could be identified. Schmid factor criteria were found useful in predicting which deformation modes to expect for each crystal orientation and fabrication procedure. The possible application of these data to poly-crystalline material is discussed. PREFERRED orientation or texture has a significant effect on the properties of most materials, causing anisotropy in fabricated cubic metals and enhancing the natural anisotropy of noncubic metals. This study evaluates the effects of several fabrication methods on the textures formed from specific starting orientations of zirconium single crystals and, it is hoped, gives an insight into the effects of the same operations on poly-crystalline material. BACKGROUND In fcc and bcc metals, texture changes take place by gradual lattice rotations caused by the operation of one or more slip systems. Deformation twinning plays an insignificant role in the deformation of such metals. In zirconium and its alloys, however, and in many other hep metals the ability to twin allows very rapid texture changes to be made with very small amounts of deformation. The deformation systems found in zirconium and its alloys are prism slip and three twinning modes.1 Slip occurs on the {1010}< 1120) system. There is little or no appreciable basal slip in zirconium. The twinning planes, illustrated in Fig. 1, are {1012}, {ll2l}, and {1122}. Two twinning modes, the {1012} and the {ll2l} operate for a tensile stress along the basal pole. A compressive stress parallel to the basal pole is required for {ll22} twinning. These twinning operations cause a 35- to 85-deg reorientation of the basal pole. The {1012} twin is the predominant tensile twin at room temperature. The twinning shears, S, are shown in the figure. A criterion for predicting which deformation system will operate when a grain is subjected to a known stress state is the Schmid (orientation) factor. This factor gives the fraction of the applied stress that computer program was written2 to calculate the Schmid factors for the four deformation modes in zirconium. It assumed three orthogonal stress axes and considered ninety-one different orientations of the basal pole in one octant of this stress space. At each basal pole position the Schmid factors were calculated for seven positions of rotation at 10-deg increments of the unit cell about the basal pole. Schmid factors were determined for a total of 637 orientations and for twenty-four deformation systems in each orientation. The program listed the Schmid factors for uniaxial stress parallel to each axis and, to approximate rolling, or-thonormal biaxial stress was also considered. Fig. 2 shows the range of orientations over which the various types of deformation would tend to predominate in biaxial plane strain with the stresses, equal magnitude. The exact boundary position between regions of different deformation modes depends, however, on the relative values of the critical shear stress for each deformation mode. Fig. 2 is drawn on the assumption that they are equal and it therefore may be only approximately correct. It is also recognized that the biaxial stress analysis may not be applicable in certain crystal orientations. EXPERIMENTAL PROCEDURE Single crystals of zone-refined zirconium, produced by Wilson of this Laboratory,3 were electrical-discharge-machined to form specimens for rolling, tube-drawing, and rod-drawing studies. Specimens were rolled at room temperature on 2-|--in.-diam hand-powered rolls from three different starting orientations: 1) the basal plane parallel to the rolling plane and the [1120] in the rolling direction, (0001)[ll20]; 2) the (1120) plane parallel to the rolling plane and the basal pole in the rolling direction, (1120)[0001]; and 3)_the (1120) plane parallel to the rolling plane and the [1100] in the rolling direction, (1120)[ll00]. Drawing specimens were cut with the [0001] direction as the drawing direction in the tube blank and [1120] as the drawing direction in the rod specimen. The drawing

Jan 1, 1969

By M. J. Duggin

Structural similarities between the E, X, and iron carbides are illustrated. Experimental evidence regarding phase transformations occurring during ternpering reactions in finely divided carbides, thin-film carbides, and carbides which occur in steels is considered and possible mechanisms for the E — x and x — 9 transformations proposed. HOFER1 has shown that within the appropriate temperature ranges carbon monoxide will react with finely divided a iron to form either iron carbide or x iron carbide. He has shown that at an elevated temperature the E iron carbide will transform to the x iron carbide (Hagg carbide) which, upon further elevation of temperature, will transform to 9 iron carbide (cementite). Jack,2,3 using X-ray diffraction methods, has observed that during the tempering reactions occurring in steel the E iron carbide formed in the first stage of tempering passes into two-dimensional platelets of 0 iron carbide during the second stage of tempering. The three-dimensional form of the 0 carbide is formed during the third stage of tempering. Jack suggested2 that the two-dimensional platelets of 0 carbide could be related to the faulted x iron carbide. Okada and Arata4 investigated a Swedish steel containing 1.05 wt pct C and approximately 1.0 wt pct Mn using permeability measurements at low field strength. A Curie point of 360°C was observed in the quenched steel, which indicated the presence of E iron carbide. On tempering at 400°C the specimen developed a Curie point at 230°C, indicating the presence of x iron carbide, and on tempering at 700°C the specimen developed a Curie point at 190°C which was assigned to 0 iron carbide. The carbides were extracted electro-lytically and the use of X-ray diffraction techniques4r5 indicated the carbide with a Curie point of 230°C to be x iron carbide. The Curie points of the carbides are 10 to 22°C lower than the accepted values which is probably due to the presence of manganese in the carbides, since it has often been observed (e.g., Ref, 6) that a partial substitution of manganese for iron in cementite will lower the Curie point of this carbide. Hofer&apos; summarizes additional evidence of the tempering reactions in steel in which E iron carbide, formed during the first stage of tempering, transforms to x iron carbide during the second stage of tempering. During the third stage of tempering, the x carbide disappears as the 0 carbide is formed. By carburizing thin iron films in a CO gas stream, ~a~akura&apos; has been able to produce the E, X, and 0 iron carbides. He found that below 250°C the E iron carbide was formed; between 250" and 350°C the x iron carbide was formed and above 350°C the 0 iron carbide was formed. He has shown that the E iron carbide transforms to form x iron carbide at 380" to 400°C and that the x ir°n carbide transforms to form the 0 iron carbide at approximately 550" C; both of these phase transformations are irreversible. Hofer&apos; presents a review of evidence to show that the sequence of reactions occurring during tempering processes subsequent to the formation of E iron carbide formed by the direct carburization of finely divided a iron is the same as the sequence of reactions which occur during the tempering processes subsequent to the formation of E iron carbide in steel during the first stage of tempering. It is evident from Nagakura&apos;s work that identical tempering reactions are found in thin films of iron which have been carburized to form iron carbide. The purpose of this paper is to discuss the structural similarities between the E, X, and 0 carbides and to suggest a possible mechanism by which regions of the E carbide, formed during the first stage of tempering, may transform to the x carbide during the second stage of tempering. For the finely divided or thin film carbides a mechanism will be proposed for the transformation of the x carbide to the 0 carbide during the third stage of tempering, although it will be suggested that there is evidence that such a transformation may not occur in steels. STRUCTURAL DATA OF THE E, X, AND 0 IRON CARBIDES € Iron Carbide. It is evident from X-ray diffractions and electron diffraction&apos;, investigations that the metal atoms in the E iron carbide form an hcp structure with lattice constants ah = 2.752A, ch = 4.3534, using electron diffraction, reports the lattice paramet$rs of the superlattice cell to be a = 4.767A, c = 4.354, c/a = 0.9134. He finds that the carbon atoms occupy the octahedral voids in the metal atom structure so as to form a hexagonal stacking sequence with its basal plane parallel to that of the metal atoms. Considerable long-range disorder occurs in the positioning of the carbon atoms, however, which is in agreement with the possible range of composition Fe2C-Fe3C discussed by Hofer.&apos; Barton and ale" have made X-ray diffraction measurements on a sample of E iron carbide extracted from a catalyst in an organic process. Although there were few reflections recorded on the obtained X-ray powder diffraction pattern, they have proposed that the structure could belong to one of the three possible space groups p3m1, P63/mmc, or Pbcn if one assumed the composition to be Fe2C. Nagakura, using electron diffraction data, suggests a space group of P 6322 for a specimen of c iron carbide of apparent composition Fez.&. x Iron Carbide. The x iron carbide has been studied by Duggin and Hofer" and by Jack and wild,&apos; who

Jan 1, 1969

By M. H. Richman, W. D. Sproul

THE indexing of a field-ion micrograph is in many cases similar to the indexing of the poles of a stereo-graphic projection.* If one has a standard projection as a guide, the task of indexing is relatively simple. In this way, field-ion micrographs of bcc and fcc wires have been oriented from projections available in most any text on X-ray diffraction. These books always illustrate the projections for the bcc and fcc structures and even for a particular hcp structure. There is no "standard" hcp projection because the angles between planes depend on the c/o ratio of the unit cell. In order to index field-ion micrographs of hcp metals, one must compute the angles between various planes—a rather laborious task. In recent work,, we have had to identify the structure and index the orientation of field-ion micrographs of the compounds WC and W,C. To overcome the problem of computing angles by hand or calculator, a program was written in Fortran lV for use on the IBM 360, Model 50 which will compute all angles between planeswith indices (hlklll) and (17,k,l2) in the range from (447) to (444) for any given c/o ratio. The program, which is more specific than that of Camp and clum, was so written as to take advantage of the multiplicity of the hexagonal system, and, for the limits defined above, only 26,649 values out of a possible 265,721 values had to be computed. This is a 90 pct saving in time (and cost) and was accomplished in the following way. Because the lattice parameters of the hexagonal crystal system are defined such that: a = b * c [1] the I index does not enter into the multiplicity (i.e., it cannot be transposed with the h or k indices), and all possible values of h and I, from 4 to 4 must be used—a total of eighty-one combinations. The index h2 varies the most—it must assume values from - Ill,: to 3Ihl. The indices kl and k2 are always equal and vary

Jan 1, 1969

By W. A. Backofen, N. E. Paton

DEFORMATION twinning contributes to the plasticity of titanium and has been reported on {10i2}, {1121},{11221}, {1123}, and {1124} planes.&apos; Twinning on {1011} has also been reported in commercially pure titanium as a result of quenching from 1000&apos;, but no reports of such twins occurring as a result of deformation alone are known to the authors. In this study single crystals grown from iodide titanium were compressed parallel to the c axis over the temperature range 25 to 800°C. From it has come evidence that (10il) deformation twins are the most common type between 400" and 800°C. Crystals about 6 mm high with a rectangular cross section measuring about 3 by 4 mm were used in the tests. Chemical analyses showed them to contain 220 to 250 ppm 0 arid 10 to 15 ppm N. The long axes of the crystals were made parallel to the c axis while the sides were parallel to (i100) and (1120), as shown in Fig. 1. The crystals were compressed between polished alumina platens with no lubrication, in a vacuum of 2 x lom5 torr. Between 25&apos; and 300°C the predominant twinning mode was (11221, which is to be expected for this stress state. There was an abrupt change at 400°C, however, and from that temperature up to 800°C twinning took place almost entirely on (10i1 ). Twin planes were determined by the two-surface rnethd. Measurement of the crystal orientation within several (10i1) twins by means of polarized-light4 and transmission electron microscopy showed that the lattice reorientations were the same as those previously reported for the (10i l ) twinning in magnesium.&apos; This reorientation is consistent with The calculated (10il ) twinning shear for titanium is 0.10, while that measured from surface offsets on a (1150) face, which is parallel to the shear direction, was about 0.15. Slip within the twins, or in the matrix adjacent to the twins, probably accounts for the larger measurement. Slip in both locations was judged to have occurred from observations on foils in the electron microscope.

Jan 1, 1970