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By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By A. W. H. Morris, E. A. Steigerwald

The jatzgue beizazriov oj Mietal matrix co))zpos~tes in tension -lensiom loading has been imestigated as a junction of Dolume fraclion veinfovcelnent using the model systems of a silver matrix reinforced with contlnuous or dzscontztinuous aligned tungsten jilamenls and continuous aligned steel filamenls. Appreciable impvocetnents in fatigue strength were obseved in all syslems inzvesLigated, the degree of sl renglhenng-increasing with increasing volume fraclion of reinforcement. The mode of fatigue failure was found to be a function of colutrre jp-actiotz and was also noted to be controlled by the relative fatigue and strength characlerislics of the matrix and reinforcemenl. THE advantages to be gained by suitably incorporating high-strength filaments or whiskers into metallic matrices are well-recognized.' To date emphasis has been placed on the experimental determination of tensile strengths and elastic moduli of metal matrix composites measured parallel to unidirectionally aligned filaments. Several attempts have been made to relate experimentally measured tensile properties to theoretical values calculated from the properties of the components on the basis of the relatively simple "rule of mixtures" analysis. However, relatively few data have been reported in the literature on the fatigue behavior and mechanism of fatigue failure of metal matrix composites. In a study of fatigue crack propagation in aluminum plus steel wires and aluminum plus tungsten wires, Forsyth et a1.2 found that the incorporation of small numbers of filaments suitably dispersed were capable of substantially reducing the rate of fatigue crack propagation. For this purpose, the strength of the filaments appeared to be more important than the aspect ratio and the authors reported that parallel filaments were not the most favorable orientation for increased strength. In a basic study of the fiber reinforcement of metals, Williams and 0'brien3 report preliminary results which indicate a considerable improvement in fatigue strength in reversed bending fatigue of a steel wire-reinforced aluminum alloy composite. In a study of the influence of interfacial bonding on fatigue behavior, Baker4 has also reported improved fatigue properties in stainless steel-reinforced aluminum composites. In contrast, Ham and place5 report that, although tensile properties are improved greatly by filament reinforcement, the reinforcement of copper with continuous, brittle tungsten wires up to 23 vol pct was comparatively ineffective against fatigue. The authors attribute the poor fatigue properties of the composite to fatigue hardening of the matrix at the tips of cracks which can build up stress concentrations sufficiently large to fracture proximate filaments. Baker and cratchley6 failed to find marked improvements in the reversed-bending fatigue properties of silica-reinforced aluminum. The study was complicated by the complex behavior in a composite during the compres-sive half-cycles imposed in this type of loading. This was manifested in the failure of the composites by de-lamination, a contributing factor being the presence of aluminum oxide at the matrix-filament interface. Prior to the general acceptance of filament-rein-

Jan 1, 1968

By D. A. Woodford

In a constant-load creep test, if the density of nlobile dislocations is assumed constant for strains exceeding that corvesponding to the minimum creep rate, it is shown that the creep rate may be approximated by the equation where E is the nominal strain, o0. is the initial stress, and a' the stress fov unit dislocation velocity. The constant C contains the mean density of mobile dislocations and n is a measure of the stress sensitivity of dislocation celocity. This equation is shoum to be applicable to published data on an alloy steel and on nickel. The degree of plastic instability and hence the creep ductility is dependent on the calue of n for these materials. When instability becomes gross and local macroscopic necking occurs, the assumptions are no longer valid. On the basis of this equation, and the strain-time relation derived from it, a method of predicting the creep behavior at different stresses is suggested. MOst analyses of creep data have been concerned with time-dependent transient creep or time-independ- ent secondary creep in constant-stress tests. The far more widely used constant-load test has been neglected in terms of a mechanistic approach. In general, since the strains involved are usually small, the same laws for transient creep may be applied to both types of tests. However, there is no steady-state creep in a constant-load test since the stress increases continuously. Any apparent steady state observed on a strain-time plot is either fortuitous or illusory, and is generally revealed as a continuously varying creep rate on a carefully constructed strain rate vs time plot.* Transient creep may be understood in terms of a simple differential equation representing the change in mobile dislocation density with time:' where p is the density of mobile dislocations. The first term on the right is related to first-order kinetics of dislocation multiDlication and the second to second-order kinetics of exhaustion. On the basis of this equation, several authors2-4 have found good agreement with experimental transient creep curves for a number of materials. When k1p = k2p2, a steady-state creep

Jan 1, 1968

By D. G. Swarthout, J. W. Savage, R. W. Guard

The Nb-N constitution diagvam has been examined from 1100° to 1450°C at 1 atm N2 pressure. On the basis of- our work plus that of Brauer and coworkers the stable nitvide Phases are: a) a solid solutlion, basic niobium (bcc) with nitrogen contained interstitially; NbN,, x = <0.40; b) ß NhNx,x = 0.39 to 0.45; hexagonal (W2C type) (NbzN); a =3.058A,c = 4.961 + 0.001A c) y NbNx x = 0.75 to 0.80; tetragonal (distorted NaCl type) (Nb4N3); a = 4.386A,c = 4.332 + 0.001A; d) 6 NbN,, x = 0.88 to 0.91; cubic (NaCl type); a = 4.3885 + 0.0007A; e) E NbNx x = 0.92 to 1.00; hexagonal (Tip type); a = 2.958A, c = 11.272 * 0.0015A. In addition, a metastuble transition phase 6&apos; has been observed and occurs only during the transition 6 — E. 6&apos; NbN has these distinguishing parameters: NbNx,x = 0.96; hexagonal (anti-NiAs type); a = 2.94A, c = 5 .46A. The high-temperature phase fields in the system are governed by two reactions: a) 6 + Y + E, a entectoid reaction occurring at 1270" ± 20° C; b) o + N2 = E, a 2 012 1 reaction occurring at 1370" ± 20° C. As part of a study of the electronic low-temperature. properties of transition metal nitrides, a number of specimens of niobium nitride were prepared. Preliminary observations on these specimens showed several points of disagreement with data already in the literature. It was, therefore, decided to determine the constitution diagram for the Nb-N system between 1100" and 1450°C. The objective of this research was to define the temperature and composition regions of stability of the various phases and to explain the differences among previously proposed diagrams. Review of Previous Literature. The research on the Nb-N system to 1964 has been summarized by storms.&apos; Although he does not present a phase diagram, his review covers the research on the system thoroughly. One of the earliest works on NbN is that of Ascher-mann and coworkers2 who studied the superconductivity of the cubic 6 NbN. Subsequent work by Horn and ziegler,3 Cook, Zemansky, and Boorse,1 Rögener:5 Schroder6 and sellmaier7 has qualitatively confirmed the first results on superconductivity, although their methods of preparation differed considerably. The constitution diagrams proposed for the system by Brauer and Esselborn8 and Elliott9 are shown in Fig. l(a)and (b). The diagram in l(a) has been modified by more recent results in Brauer&apos;s laboratory (private communication). Although 6&apos; is shown on this diagram, Brauer has indicated that he now believes 6&apos; to be a metastable phase in the temperature range shown. The diagram of Elliott, Fig. l(b), is based primarily on the results of Elliott and Komjathy10 on ni-trided niobium strip or rod specimens examined by X-ray diffraction and metallography. It will be noted that these proposed diagrams are in conflict with respect to the temperature and composition ranges of

Jan 1, 1968

By E. T. Turkdogan, J. H. Swisher

bi the fivst part of the paper results ave given on the rate of decarburization of Fe-C melts ln CO2-CO atmospheres at 1580°C. The rate -controlling step is believed to he that irvlloluing dissociation of curbotz dioxide on the suvfuce of the melt. 4 genevral reaction mechanistm is poslnlated jor gels-t11eta1 veactions oc-curit~g on the surface of iron coutcotamncited with chemi-sovbed osygesL. Oxygen the present work on decavbuvization of liquid iron and previous studies on the kinetics of nitrogen absorption and desorplion are discussed in terms of the postulated mechanism, ManY of the early studies of rate of decarburization of liquid steel were of an exploratory nature and laboratory exppriments carried out pertained to open-hearth or oxygen steelmaking processes. References to previous work on this subject may be found in a literature survey made by Ward. Using more sophisticated experimental techniques, several investigators have recently studied the kinetics of decarburization of molten Fe-C alloys in oxygen-bearing gases. For example, Baker et al2.&apos; reported their findings on the rate of decarburization of liquid iron, levitated by an electromagnetic field, in carbon dioxide-carbon monoxide-helium atmospheres. In these levitation experiments the samples used were small in size, e.g., -0.6-cm-diam spheres weighing -0.7 g, and the rates were measured for decarburization from about 5 to 1 pct C at 1660°C. The rates obtained under their experimental conditions were considered to be controlled primarily by gaseous diffusion through the boundary layer at the surface of the levitated melt. Parlee and coworkers3 measured the rate of absorption of carbon monoxide in liquid iron. The rates were found to follow first-order reaction kinetics, yielding a reaction velocity or a mass transfer coefficient in the range 0.2 to 0.4 cm per min. The coefficient was found to decrease with increasing carbon content of the melt. These investigators attributed the observed rates to the transfer of carbon or oxygen through the diffusion boundary layer adjacent to the surface of the melt. In the work to be reported in this paper, an attempt has been made to study the kinetics of gas-metal surface reactions involved in the decarburization of liquid iron. EXPERIMENTAL The experiments consisted of melting 80-g samples from an Fe-1 pct C master alloy in an induction furnace and decarburizing in controlled CO2-CO mixtures at 1 atm pressure and 1580°C. The master alloy was prepared by adding graphite to electrolytic "Plastiron" melted in racuo. None of the impurities in the master alloy exceeded 0.005 pct. The reacting gases were dried by passage through columns of anhydrone; in addition, CO2 impurity in carbon monoxide was removed by passage through a column of ascarite. A schematic diagram of the apparatus is shown in Fig. 1. A 1.25-in.-diam recrys-tallized alumina crucible containing the sample was placed inside a 3-in.-diam quartz reaction tube, all of which was surrounded by an induction coil. A 450-kcps induction generator was used as the power source. Water-cooled brass flanges, which contained the gas inlet, gas exit, and sight port, were sealed to the top of the reaction tube with epoxy resin. The reacting gases were metered with capillary flowmeters and passed through a platinum wire-wound alumina preheating tube, 0.25 in. ID and 11 in. long. The gases were preheated to about 1300°C. A disappearing-filament optical pyrometer was used to measure the melt temperature. The pyrometer was initially calibrated against a Pt-6 pct Rh/Pt-30 pct Rh thermocouple. The temperature was controlled to within +10°C by manually adjusting the power input to the induction coil. In a typical experiment, an 80-g sample of the master alloy was melted in a CO2-CO atmosphere having pcO2/pco = 0.02 and flowing at 1 liter per min. A negligible amount of carbon was lost and no significant reduction of alumina from the crucible occurred during melting, e.g., 0.005 pct Al in the metal. After reaching the experimental temperature of 1580°C, the gas composition was changed to that desired for a particular series of decarburization experiments. The duration of the transient period for obtaining the desired gas composition at the surface of the melt was about 20 sec . The flow rate of the reacting gas was maintained at 1 liter per min. After a predetermined reaction time, the power to the furnace was turned off. During freezing, which took about 10 sec, the amount of gas evolution was not sufficient to result in a significant loss of carbon. The samples were analyzed for carbon by combustion and in a few cases they were analyzed for oxygen by the vacuum-fusion method. RESULTS A marked increase in the rate of decarburization of iron with increasing pcO2/pco ratio in the gas stream is demonstrated by the experimental results given in Figs. 2 and 3 for pco2/pco ratios from 0.033 to 4.0. In one series of experiments, denoted by filled triangles in Fig. 2, the reacting gas was diluted with argon (48 vol pct) resulting in a slower rate of decarburization. Samples from two series of experiments with pco2/pco = 0.033 and pco2/pco = 0.10 (with argon dilufion) were analyzed for oxygen. In these Samples the oxygen content increased with reaction time

Jan 1, 1968

By S. G. Epstein

Using the capillary-reservoir technique, electromi-gvation rates of cadmium and indium in liquid bismuth were measured at several temperatures. The electric mobility of cadmium Jrom 305° to 535°C and indium from 310° to 595°C can be expressed as a function of temperature by the equations UIn = 1.52 x 10-3 exp sq caz per v-sec Migraion of both solutes was cathode-divected at a rate rnore than four tiMes tHAt previously found for siluer in liquid bisnmth. The electric mobilities of cadmium and indiulrz in liquid bismuth at 500° C are nearly identical with their respective mobilities in mercury at room temperature. AS part of a systematic study of the variables which are considered to control electromigration in liquid metals, the electromigration rates of cadmium and indium in liquid bismuth have been measured. Mass transport properties of silver in liquid bismuth have been reported previously,&apos; and measurements of tin and antimony in liquid bismuth are forthcoming. Comparisons will be made with literature values for these same solutes in mercury.2&apos;3 This series of solutes was selected to determine the effect of the solute valence on its electromigration. Silver, cadmium, indium, tin, and antimony have nearly equal atomic masses but have chemical valences ranging from +1 to +5. They are all fairly soluble in bismuth above 300°C and all have radioactive isotopes, which are an aid in making analyses. EXPERIMENTAL TECHNIQUE Electromigration of cadmium and indium in liquid bismuth was measured by the modified capillary-reservoir technique previously described.&apos; In this method irradiated cadmium or indium is added to bismuth to form alloys containing about 1 wt pct solute (<2 at. pct solute). Several quartz or Pyrex capillaries: 1 mm ID and 5 cm long, vertically oriented, are simultaneously filled in the reservoir of the liquid alloy. A direct current is passed through two of the capillaries, which contain tungsten electrodes sealed in the upper end. The other capillaries sample the reservoir during the experiment. After a measured time interval the capillaries are removed from the reservoir and rapidly cooled. The glass is then broken away from the solidi- fied alloy, which is then weighed, dissolved in acid, and analyzed for solute content by chemical and radiochem-ical techniques. An electric mobility (velocity per unit field) can be calculated from the amount of solute entering or leaving each capillary by the simplified expression1 in which Ui is the electric mobility of the solute, ?mi the solute weight change, Ci the solute concentration of the reservoir, I the current, p the alloy resistivity, and l the duration of the experiment. This expression is valid as long as the experiment is terminated before a concentration gradient develops across the capillary orifice. Earlier experiments showed that the concentration gradient formed initially at the electrode changes with time and eventually reaches the orifice, due to back-diffusion. This condition produces a solute exchange between capillary and reservoir by diffusion or convection, opposing the electromigration, which results in a lower measured value for the electric mobility. To determine if the concentration gradient had reached the orifice, the capillaries used in some of the experiments were sectioned at 1-cm intervals and the solute content of the alloy from each section was radiochemically determined. A typical concentration profile for an experiment with indium in bismuth is shown in Fig. 1; cadmium in bismuth showed similar behavior. As illustrated in the graph, very little back-diffusion has occurred in the capillary containing the cathode, since the concentration gradient is confined to the upper 1 cm of the capillary. In the capillary containing the anode, however, the concentration gradient is much broader, extending nearly to the orifice, even though the net change in solute concentration is nearlv the same in both capillaries. Since cadmium and indium probably lower the density of bismuth when alloyed, depletion of the solute from the alloy adjacent to the anode would increase the density of the liquid in the uppermost region of the capillary. This would give rise to convective mixing within the capillary, causing the broadened concentration gradient. Conversely, the alloy adjacent to the cathode should have a reduced density as the solute concentration is increased by migration, explaining the "normal" concentration profiles found in these capillaries. This disparity was not found for electromigration of silver in bismuth. Both metals have similar densities at the operating temperatures, and nearly symmetrical concentration profiles were found in the two capillaries of each exueriment. This density effect was also apparently encountered when an attempt was made to measure diffusion coefficients for indium in liquid bismuth by the same technique which was successfully used to measure diffusion of silver in bismuth.&apos; Capillaries 1 mm ID and 2 cm

Jan 1, 1968

By R. Taggart, D. H. Polonis, J. C. McMillan

Thin foil electron microscopy techniques have been used to study the micros tructure of a Ti- 7.5 wt pct vanadium alloy in the quenched and aged cond_itions. Selected area diffraction has identified a (1011) twinning mode accompanying the martens ite t9.an.sfo?rn~ation. Precipitation of the 0 phase during the aging of quenched alloys has been obsevced to occuv in the form of plates and needles with preferential growth along the (1120) direction in the a&apos; matrix. In the present work, the micro structures of quenched and aged alloys of the 0 isomorphous Ti-V system have been investigated by means of thin-foil electron-microscopy techniques. Most of the previous studies of martensitic phases in titanium-base alloys have utilized optical microscopy and X-ray diffraction techniques. The application of transmission electron microscopy is more recent, and only a few such studies have been reported.1-5 This paper is concerned particularly with the crystallographic nature of substructures formed in the martensitic a&apos; plates. The early stages of aging or tempering have also been examined to determine the modes of precipitation from the martensitic solid solutions. Such information is essential in studying strengthening mechanisms and in determining the feasibility of high-strength rnartensitic alloys based on titanium. Liu and Margolin6 reported several types of substructures within the martensitic plates of quenched Ti-Mn alloys. It was later suggested by Liu7 that the structure of martensitic plates might be very complex and not single crystals as normally assumed. The sub-markings could not be identified with the two possible habit-plane orientations {334}ß and {344}ß, and it was not positively determined whether they are associated with mechanical twinning. The recent studies by Armitage5 on titanium martensites in a variety of commercial alloys have indicated that twinning does not generally accompany the transformation. This observation is in accordance with the Mackenzie and Bowles model for the transformation in pure titanium8 which suggests that twinning is not to be expected. However, a number of other recent investigators have reported twinlike substructures in the martensitic plates of several titanium systems including commercia1 titanium,2,3 Ti-Cu,5,9 Ti-Ta,1 and the commercial alloy Ti-8A1-1Mo-1V. Blackburn* has reported that the structure of quenched Ti-8A1-1Mo-1V depends on the prior solution temperature. He identified two types of martensitic structures, one of which is described as a heavily faulted hcp or twinned fcc structure and the other an hcp structure with a high internal dislocation density. The latter type exhibited some twinning with a (1011) twin plane. EXPERIMENTAL PROCEDURES AND RESULTS The alloy used in the present work was a 7.5 wt pct V alloy that was prepared by conventional arc-melting techniques. This alloy composition was selected

Jan 1, 1968

By R. L. Stegman, M. R. Achter

Nickel, fatigued in vacuum, shows intragranular crack initiation and growth at low temperatures. An increase in temperature initially prolongs fatigue life due to a more homogeneous distribution of slip. With a further temperature increase, the mode of failure undergoes a transitiotz to intergranular crack initiation with concurrent recrystallization which results in a shorter life. The transition temperature varies with bending strain and specimen purity. UNTIL recently, very little work has been done on the effect of temperature on the mechanism of fatigue and the resultant variation in fatigue life. Except for mild steel, where strain aging raises the strength at moderate temperature, fatigue lives had been shown to decrease with an increase in temperature. In their review article, Allen and Forrest&apos; summarized the work of McCammon and Rosenberg and of Forrest and Mann on the fatigue of copper from -269" to 325°C. The fatigue life vs stress curves remained roughly parallel over this temperature range, the fatigue strength decreasing progressively with increasing temperature. When testing was done in vacuum, the present authors&apos; found the results for nickel were different from those quoted above. Initially, the fatigue lives increased with temperature and then decreased as a grain boundary mode of failure was observed. The initial increase was attributed to a more homogeneous distribution of slip, a condition which was not as conducive to crack initiation as the bunching of slip lines observed at 20°C. Ronay, Reimann, and wood3 observed a similar change of slip line distribution in brass, tested in air, with rising temperature. Our previous observations were based on preliminary work with relatively few specimens, fatigued at comparatively low strains. To learn more about the mechanisms, the present investigation was undertaken for the purpose of studying systematically this effect over a wider range of strains and as a function of purity of the nickel. EXPERIMENTAL PROCEDURES The testing equipment, procedures, and specimen geometry have been described elsewhere.&apos; An optical technique to measure bending strains was used as de-

Jan 1, 1968

By Daniel N. Beshers, Ralph H. Condit

An expression for the diffusion coefficient of inlerstitial atoms in the bcc lattice is derived which takes account of jumps between tetrahedral and octahedral interstices. The results are applied to the case of carbon diffusion in iron to find values for jump frequencies of the types, octahedral-tetrahedral, tetra-hedral-tetrahedral, and tetrahedral-octahedral. ThERE has been renewed discussion1-5 concerning the mechanism of diffusion of interstitial atoms in the bcc lattice. This lattice has both octahedral and tetrahedral interstices, and it has been pointed out that the interstitial atoms may make jumps of the octahedral-octahedral type, hereafter called o-o, octahedral-tetrahedral, o-t, and tetrahedral-tetrahedral, t-t. Doubt has been cast on the applicability of snoek&apos;s8 model for internal friction to some interstitial migrations in bcc lattices wherein he proposed 0-0 jumps as the principal mechanism of migration. Also, the anomalous excess diffusion of carbon in iron at high temperatures4 has been ascribed to t-t jumps,2,3 even though the sites normally occupied are octahedral. In this paper an expression is derived for the diffusion coefficient, taking account of the three types of jump mentioned. The relationship of the coefficient to the corresponding internal friction relaxation time is found for the limiting case corresponding to Snoek&apos;s model. These results are applied to the case of carbon in iron. In Fig. 1, the structure is shown with the locations of the interstices. Each o site has four t site neighbors coplanar with it, and each t site lies halfway between two o sites. There are four t site first neighbors of a t site lying at the vertices of a tetrahedron. Let the average fraction of atoms occupying o sites and t sites be No and Nt, respectively. Since there are six o and twelve t interstices per unit cell having a lattice parameter, a, the concentration of interstitial atoms will It will be assumed that three types of jumps may be distinguished, t — t, t — o, o — t,for which the jump

Jan 1, 1968

By William C. Sleppy

The nmgnetic susceptibility of heat-treatable aluminuin alloys is sensitive to chanyes such as solution or dissolution of solute and the precipitation of mew phases. By measuring the change in the magnetic susceptibility of aluminum alloys caused by various heat treatments, an empirical relation was found from which atomic arrangements in dilute binary alloys of copper, zinc, and magnesiutn in aluminum have been delineated. The relation predicts the ultimate formation of C1LA12 when copper is precipitated from solid solution in aluminum. Euidexce joy silovt- range order is found for copper in solid solution in aluminum in the sense that copper atoms avoid being nearest neighbors to an extent greater than would result from a purely random arrangertzeizt. Hume-Rothery has predicted such short-range order joy solid solution of copper in aluminum The Al-Zn system agrees with evidence obtained from X-ray scattering at small angles and predicts a tendency for zinc atoms to cluster in solid solution in aluminum. In the Al-mg system, the empirical relation indicates an approach to randor distribution of magnesium in solid solution in aluminum with a tendency for magnesium segvegation which increases with incveasing temperature. ThE magnetic properties of metals are complicated by the fact that contributions are made to them both by electrons of a "metallic" type which belong to the crystal as a whole, and by electrons in states localized on particular atoms. An expression1&apos;2 for the bulk magnetic susceptibility of aluminum may be written as the sum of three contributions: where XA1 is the bulk susceptibility of aluminum per gram of material (in the cgs system, the units are those of reciprocal density); Xa1+3 is the diamagnetic contribution of the electrons localized in ion cores; Xa1 is. the paramagnetic spin contribution of conduction electrons often called Pauli paramag-netism: Xa1 is the diamagnetic contribution of the conduction electrons often called Landau diamag-netism. Ion core diamagnetism arises from the precession of the electron orbits which occurs when a magnetic field is applied to a system of electrons moving about a nucleus. Its contribution to the magnetic suscepti- bility is small, temperature-independent, and unaffected by alloying. The conduction electron diamagnetism is also temperature-independent and arises from the translatory motion of the electrons. For perfectly free electrons this contribution should be exactly one-third of the Pauli spin paramagnetism, but this relation is seldom even approximately true. Blythe2 determined the conduction electron diamagnetism in pure aluminum and found it to be extremely small. Any change in the conduction electron diamagnetism caused by alloying is neglected in this work. The Pauli paramagnetic contribution3 to the magnetic susceptibility of aluminum depends upon the number of electrons that occupy excited states and whose spins can be turned parallel to an applied magnetic field. The number of electrons free to turn in the field is proportional to the temperature and each spin contribution to the susceptibility is inversely proportional to the temperature. A slight temperature dependence of Pauli paramagnetism occurs when the number of electrons occupying excited states cannot increase sufficiently to balance the inverse dependence on temperature of each spin contribution. The decrease of the magnetic susceptibility of aluminum with increasing temperature is attributed to a temperature dependence of the Pauli paramagnetism. Estimates of the Pauli paramagnetism of aluminum have been made by several workers.2,4,5 All of the values are in reasonably good agreement with each other. In this work Xal at 17°C is taken as 0.761 X 10-8 cu cm per g. An expression similar to [I] can be written for the magnetic susceptibility of an aluminum base alloy containing a fractional weight percent x of solute:&apos; Xa = (1 -x)XAl+3 +xXsoluteion * XaPauli +Xadia) [2] where X, is the magnetic susceptibility per gram of alloy, Xal&apos;3and Xsolute ion are the ion core diamag-netic contributions, and xpauli and xdia are the Pauli and diamagnetic contributions of conduction electrons in the alloy. If the components of a mixture are not alloyed but simply mixed together in their pure states without producing a new phase, then the magnetic susceptibility of the mixture is given by the Wiedemann additivity law: Xm =x1X1 +x2x2 + ..xnxp [3] where X, is the susceptibility per gram of mixture and xnXp are the weight fractions and susceptibilities, respectively,-. for the pure components. The additivity law is not applicable to alloys because the outer electronic structures of the components are changed by alloying.&apos; Both the Pauli paramagnetism and Landau diamagnetism are affected; hence the magnetic susceptibilitv of an alloy is usually different from that calculated using the additivity law. In this work the difference, X, -X,, is taken as a measure of the change caused by alloying.

Jan 1, 1968

By M. D. Banus, M. B. Bever, A. K. Jena

Measurements of the heat effects on addition of various solid phases of InSb to a solution calorimeter have confirmed the existence of a new high-pressure plzase InSbQII), which was jormed at 37 kbar and 623°K. The heats of formation of InSbQ), InSbfl), and InSb(111) have been measured and the heats of transjormation of InSb(1) to InSb(1l) and InSb(Iii) and of &apos;InSb(ll) to InSb(iiI) at atmospheric pressure and 78°K have been determined independently. Other thermodynamic properties of these phases, the phase boundary InSb(i)/InSb(ll), and the relative positions of the triple points are calculated. The pressure-Dolume term is shown to be more critical than the internal energy difference in making the phase InSbQ) less stable than InSb(II) at high pressures. Observations on partially transformed specimens suggest that the transformation of&apos; metastable InSb (III) takes place in the two steps InSb(lll) — InSbQI) and InSbQI) — InSb(l). The compound InSb can exist as several phases depending on the temperature and pressure. The phase InSb(I), which is a semiconductor having the zinc-blende structure, transforms into the phase InSb(11) at a pressure of about 23 kbar and room temperature.&apos;-3 The phase InSb(II) has the 6 tin structure,4-6 is metallic, and becomes a superconductor below 2.lok7 An orthorhombic phase of InSb has been reported to occur above a pressure of approximately 30 kbar at room temperature.&apos; This phase is also a superconductor below about 3.4k9 The phase InSb(I1) is retained at atmospheric pressure if it is quenched to 78°K under pressure,6,7 but tends to transform at higher temperatures and does so explosively above approximately 210ok,7 A value of the heat of transformation of InSb(1) to InSb(II) at 210°K and atmospheric pressure has been reported.&apos; A concurrent publication&apos;0 reports evidence for a new solid phase InSb(III), which was formed by annealing InSb above 58 1°K at 37 kbar, above 560°K at 52 kbar, and above 473°K at 65 kbar. Specimens of InSb(II1) had a superconducting transition temperature of 4.lo ± 0.1oK. X-ray diffraction patterns also indicated the presence of a new phase. In this communication, thermodynamic properties of the phases InSb(I), InSb(II), and InSb(II1) are reported and discussed. The phase boundary InSb(I)/InSb(II) and the relative positions of the triple points are calculated. 1) EXPERIMENTAL 1.1) Preparation of Specimens. Specimens of the high-pressure phases of InSb were prepared in a belt-type high-pressure chamber by a tichnique described in detail elsewhere.&apos;&apos; Charges of 0.6 to 0.8 g of Cominco semiconductor grade InSb were used. The temperatures were measured with a chromel-alumel thermocouple, the hot junction of which was within 0.5 mm of the specimen. The specimens were heated under a pressure of 37 kbar for 1 hr at 723°K (which is well above the liquidus) and quenched to room temperature. One set was annealed at 523°K and another set at 623°K for 20 to 24 hr. These annealing temperatures were chosen because 523°K was below and 623°K was above the temperature of the transformation of InSb(II) to InSb(1Tl) at 37 kbar.10 The specimens were then cooled to 125°K by passing liquid nitrogen through the jacket of the belt die before the

Jan 1, 1968

By M. J. Blackburn

The ordering reaction and its effect on dislocation awangements in alloys based on Mg3Cd has been studied by transmission electron microscopy. Ordering occurs by the growth of ordered domains until they impinge, thus producing an antiphase domain boundary (APB) network. In the disordered alloy, slip is confined to the basal plane while in the ordered condition slip occurs on the basal, prism, and pyramidal planes. Superdislocations have been identuied on these planes and their origin and expected spacings are discussed and compared with the observations. The APBs between the dislocation pairs have been resolved and have proved useful in the identification of superdislocations. Observed slip structures are related to the changes in mechanical properties produced by ordering. At high temperatures magnesium and cadmium form a continuous series of disordered hexagonal solid solutions. At lower temperatures three ordering reactions occur; two based on the compositions Mg3Cd and MgCd3 are transformations to DO19-type superlattices while alloys based on the composition MgCd transform to a B19 lattice. The ordering process in alloys near the composition Mg3Cd has been studied by several workers&apos;-4 and it has been shown to be a first-order type transformation. The variation of mechanical properties with the degree of order and temperature have been reported in some detail by Stoloff and Davies.5 It was shown that the disordered alloy was stronger and less ductile than the ordered alloy, the differences being attributed to changes in the number of active slip planes and to the presence of short-range order in the disordered alloy. In this investigation the ordering reaction has been qualitatively followed by transmission electron microscopy. The effect of this ordering transformation on the dislocation arrangements in deformed specimens has been studied in some detail. EXPERIMENTAL Alloys were melted in a stainless-steel crucible under a flux and chill cast; both melting and casting were performed in an argon atmosphere. The ingots were hot-rolled and tensile specimens cut from the resultant strips. Some large-grained specimens were grown by the strain-anneal method. Heat treatment was carried out in inert atmosphere furnaces and in oil baths at the lower temperatures. Thin foils for transmission electron microscopy were produced by electropolishing in a cooled solution (temp = -40°C) containing 50 cu cm of nitric acid and 180 cu cm of methanol at a potential of 10 v. The ordering reaction was followed by transmission electron microscopy, X-ray, and electrical resistivity measurements but this paper will be concerned chiefly with the electron-microscopy results. Much of the work described in this paper was performed on an alloy containing 26.10 at. pct Cd although two of the micrographs are taken from work on a 25.55 at. pct Cd alloy. RESULTS i) The Quenched Solid Solution. Specimens which were quenched from above the critical temperature showed diffuse superlattice reflections. sark-field analysis on these reflections failed to reveal the presence of ordered domains and thus the superlattice reflections were assumed to arise from regions of short-range order. Quenching from temperatures of 400" to 450°C results in the formation of dislocation loops and helical dislocations. Such defects have been observed and analyzed in detail in several hexagonal metals6-&apos; and as the crystallography and interactions of such loops appear similar in this alloy they will not be reported in detail. Fig. 1 shows a high density of loops

Jan 1, 1968

By R. H. Richman, F. Borik

A 0.3 pct C-12 pct Cr-6 pct Ni steel was rolled to 93 pct reduclion in area as austenite at 510°C, and then partially transformed as desired to ~rlartensite by qnenching to - 196°C. Pole figures for the austenitic matrix and for the martensitic product were separately determined by an X-ray transmission method. The deforitration texture of&apos; the warm-worked austenite is characlerized by (110)(225) components, and is thus closely similar to those produced in a brasses. The pole jigure of the martensite in partially transformed material agrees well with that which can be constructed by transfortnation of the {110)(225) orientations according to either the Kuvdjuniov- Sacks or the Nishi-yatuu relatiotship. Howeuer, an important result of this construction is that me-third of the predicted orientations are missing. A graphical analysis can then be used to show that in deformed austenite certain crystallographic variants of martensite (related to the most probable austenite slip systems) are suppressed, resulting in this preferred transformation. The evidence for preferred transformation is corroborated by the measured elastic anisotropy of warm-rolled and fully transformed H-11 steel. EXTENSIVE plastic deformation of a polycrystal-line aggregate in a manner that causes flow predominantly in one direction results in a preferred orientation of the constituent crystallites. The particular orientations that are produced depend upon the crystal structure and composition of the material, as well as upon the temperature, mode, and degree of deformation; in any case, the preferred crystallo-graphic orientations, or textures, are reflected in directionality of mechanical properties. Although such anisotropy may be exploited in certain specialized applications, it is more commonly diminished or eliminated by heat treatment lest it interfere undesirably in subsequent forming operations or in structural design. In the recently developed thermomechanical treatments that significantly enhance the strength of some steels,1,2 considerable deformation of the metastable austenite prior to the martensite transformation is essential to the strengthening process. If the austenite is textured by the deformation, and if the transformation to martensite proceeds according to one of the relationships established for transformation in annealed austenite, then it must be expected that the martensite will also possess a preferred orientation even though the multiplicity of martensite orientations possible in a given austen- ite crystal will tend to restore some degree of randomness. The existence of a residual anisotropy, both mechanical 3-6 and crystallographic,&apos; has been substantiated. In the latter crystallographic investigation, preferred orientations were determined for the martensitic structure of an SAE 4340 steel rolled 72 pct as austenite at 833°C and then quenched. However, the choice of a composition that transformed almost completely to martensite during the quench to room temperature did not permit direct measurement of the prior austenitic texture. In fact, when the "ideal orientations&apos;&apos; associated with well-known fcc rolling textures were converted, alone or in combination, to martensite according to the Kur-djumov-Sachs (K-s)&apos; or Nishiyama8 relations, the agreement obtained with the observed martensite texture was only fair at best. Recently a pertinent aspect of the austenite to martensite transformation was reported by Bokros and parker,10 who found that certain habit-plane variants of martensite were suppressed by tensile deformation of Fe-31.7 Ni single crystals prior to the necessary subzero cooling. It might be anticipated that the consequences of such preferred transformation are sustained during the formation of martensite in warm-worked austenite that has a well-developed deformation texture. The present investigation was undertaken first to establish more firmly the relation between preferred orientations in plastically deformed austenite and in the resulting martensite, and second to examine the textures for evidence of deformation-induced preferred transformation. EXPERIMENTAL PROCEDURES An alloy containing 0.3 pct C, 12 pct Cr, 6 pct Ni, and the balance iron, was selected because the mar-tensite-start temperature (M,) of about -100°C allowed convenient experimental manipulation of either austenite or martensite at room temperature. Furthermore, this composition can be readily deformed as metastable austenite at moderately elevated temperatures without intervention of appreciable isothermal or athermal decomposition products. The alloy was austenitized at 1150°C, aircooled to 510°C, rolled unidirectionally at this temperature to 93 pct reduction of cross-sectional area, and finally oil-quenched to room temperature. Partial transformation to martensite was accomplished by quenching to -196°C as needed. The rolled stock was reduced in thickness from 0.067 to 0.010 in. by etching in a solution of 5 pct HC1, 45 pct HNO3, and 50 pct water, and further thinned by careful mechanical polishing to maintain the two sides of the sheet parallel within 0.0003 in. After mechanical polishing to 0.005 in., electropolishing in 1:9 perchloric-acetic acid solution produced a final thickness of 0.002 in. The preferred orientations were determined from

Jan 1, 1968

By Werner Ostertag

A series of rare earth cobalt compounds of the composition RCoa (r = Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Ev, Tm, Lu) has been prepared. The compounds crystallize in space gvoup R3m and are isomorphous with PuNi3. Except for CeCo3 and PrCo, the series shows decreasing- values of a. and co. The relalively small parameters of CeCo, and PrCo, are explained by valencies of cerium or praseodymium which exceed the usual rare earth valency of three. The structure of the compounds is discussed as in-fillings of kagome nets in direct and staggered superposition. In the course of a systematic investigation of rare earth cobalt compounds"2 and their magnetic properties,, a series of alloys corresponding to the formula Rco3 has been prepared. The investigation of the Rco3 series was stimulated by our investigation of the yttrium cobalt system2 as well as by reports in the literature: Smith and Hansen4 reported the structure of YcO3 and Van vucht5 that of GdCo3; ceco3,6 Gdco3,7 and DyCo3 7 have been found to be single-phase during phase diagram studies. It was the purpose of this work to report crystallographic data on the entire Rco3 series and to interpret the structure of these compounds on the basis of general principles as discussed by Frank and Kasper.8 At the time this work was terminated, it was learned that a similar investigation has been carried out independently by Bertaut, Lemaire, and schweizer.9 Except for CeCo3 (ao = 4.952, co = 24.73&apos;) and NdCo3 (a0 = 5.067, co = 24.76&apos;) data of this work are in satisfactory agreement with their investigation. EXPERIMENTAL TECHNIQUES A series of samples having the composition Rc03 was prepared from stoichiometric amounts of the rare

Jan 1, 1968

By H. E. Cline, T. H. Alden

A study zvas made of rate-sensitive plastic deformation and superplasticity in alloys of lead and tin. These alloys (lead, PO-19 pct Sn, Sn-38 pct Pb, Sn-2 pct Pb, tin) were extruded, aged at room temperature, or melted and resolidified to produce a variety of ~nicrostrnctures. Flow stress us strain rate data were obtained frorn tension tests for strain rates between 10-6 and 1 min-1. The curve log o .us log £ was S-shaped jor fine-grained materials and approxinzately linear for coarse-grained nzaterials. At constant grain size, the behavior was relatively insensitive to conposition. High rate sensitivity (d log o/d log k) and superplasticity occurred at intermediate strain rates in fine-grained materials and are believed to be associated with a transition with strain rate in the mode of plastic flow. This transition was shifted to higher strain rates with increasing temperataire or decrensing grain size. The high rate rneclzanisrn is presunzed to be slip, while rnetallographic evidence sug-gests that the low rate lnechanism is pain boundary sliding. PEARSON&apos; discovered that extruded eutectic alloys of Pb-Sn and Bi-Sn could be elongated as much as 2000 pct in tension. The ability for stretching decreased with aging time or annealing to increase the grain size. At high strain rates, or if the material was in the cast condition, normal ductility was observed. Following deformation of the extruded Pb-Sn eutectic at low rates, Pearson observed an equiaxed granular structure on an initially flat surface, while rapid straining produced elongated grains. He attributed the large deformation in the extruded alloys to the persistence of extremely small grains to a temperature sufficiently high for inter granular flow. Avery and backofen2 measured the strain rate sensitivity of the flow stress, m = d In old In 6, in the Pb-Sn eutectic and established a correlation between m and the tensile elongation. In the extruded eutectic alloy the strain rate sensitivity was 0.1 to 0.2 at rapid rates and the elongation was small, while at low rates m increased to 0.4 to 0.6 and superplastic elongation was observed. They also noted a grain size effect. In the case of the cast Pb-Sn eutectic the strain rate sensitivity remained at 0.1 over the range of strain rates of their experiment (3 x 10"3 to 2 min-I). These authors suggested that diffusional (Nabarro-Herring) creep was the mechanism by which deformation occurred at low strain rates, while climb-controlled creep occurred at high rates. Two predictions of this model are that, at low strain rates, the strain rate sensitivity approaches 1, i.e., Newtonian viscosity, and that the strain rate at constant stress varies as D/L2, where D is the coefficient of self-diffusion and L the grain size. More recently, a mechanical and microstructural investigation of the dilute superplastic alloy, Sn-5 pct Bi, has been done.3 The results show that the high strain rate sensitivity is associated with a transition with strain rate of the mechanism of plastic flow. At low strain rates, grain boundary sliding and its associated accommodation processes were evident, while at high strain rates quasi-uniform slip was concluded to be the dominant deformation process. The following experiments were performed to extend our knowledge of the phenomena of superplasticity to a larger range of strain rates, compositions, temperatures, and microstructures in the Pb-Sn alloy system. The question of why a cast structure does not exhibit viscous behavior although it appears to have a fine microstructure2 was investigated.

Jan 1, 1968

By R. B. Adamson

The fatigue behauior of irradiated copper single crystals is compared to that of unirradiated crystals. Proton or electron irradiation did not substantially change the fatigue-lzj.e, fatigue-hardening-, or slip-line characteristics, while neutron irradiation did appear to alter these parameters. Postfatigue transrrzission electron microscopy did not reveal any marked structural differazces between irradiated and unirradiated specimens. Possible dislocatio~a mechanisnzs to explain the observed behavior are discussed. A LTHOUGH considerable work has been done to ascertain the effects of radiation on the tensile properties of metals (e.g., Refs. 1 and 2), little work of a basic nature has been reported on the effect of radiation on fatigue properties. Since it is known that fatigue properties are sensitive to conditions at the surface of the metal, it was felt that charged particle irradiation, whose penetration into metals is very small, might influence the fatigue behavior. To investigate this surface effect, irradiations with 10 mev protons and 1.5 mev electrons were conducted. The range of 10 mev protons in copper is about 0.236 mm; which is very small compared with the thickness of the specimens used (1.53 mm). The range of 1.5 mev electrons is somewhat larger, on the order of 0.665 mm.4 On the other hand, irradiation with reactor neutrons produces damage throughout the entire specimen, so neutron irradiation can be used to study the effects of bulk damage. The damage introduced by proton and neutron irradiation is expected to con!ist of large interstitial dislocation loops,5 tiny (<25A) vacancy loops," and/or various vacancy-rich regions called depleted zones.&apos; In the case of electron irradiation at about -173°C the damage is expected to consist of isolated Frenkel pairs.&apos; The effect of radiation damage on the fatigue properties of some engineering materials has been reported,g,10 but the results are not clear-cut or consistent. SPECIMEN PREPARATION Zone-refined copper was used to grow single crystals by a modified Bridgeman technique in an inert helium atmosphere. Using a seeding method, single crystals were obtained as bars about 6 in. long with a cross section of 3 by $ in. Immediately upon removal from the split-mold graphite boat in which they were grown, the very soft bars were embedded in a room-temperature setting plastic. They could then be cut into specimen lengths without introducing any long-range damage. Generally, four or five specimens plus one seed were obtained from each bar. The plastic material was dissolved away in acetone and the orientation of each sample was checked by the standard Laue X-ray

Jan 1, 1968

By Forrest V. Williams

The dislocatiorl and stacking-fault structuve of epitaxial GaAs1-,PX lms been examined by chemical etching. The layers were groun in the (100) direction and etch Pils were developed on (111} planes which nad been lapped and polished on the epiLaxia1 layevs. Tile effecL of the jollolcing cariables on the quality of the epilaxial layers has been examined: doping leuel, grouth rate, and composition. High stacking-faullL densilies weve found in the GuAsi_xpx layers. These are not observed in heavily dolled epitaxial layers tzar in layers with low phosphorus compositions. The dislocatiorz density in GuAsi-x px was highest at the sub-stvate- epilaxia1 layer interface. Composilion changes introduced dislocations in the epitaxial layers. ManY semiconductor p-n junction lasers of Group TIT-Group V compounds and their alloys have been reported in the past several years. Laser action at visible wavelengths in GaAsl-x,Px was first reported by Holonyak and Bevacqua. GaAs, a direct transition semiconductor which lases, and Gap, an indirect transition semiconductor which does not lase, form a continuous series of solid solutions.2 Laser junctions can be fabricated in GaAsl-xPx crystals with phosphorus compositions up to about 40 mol pct. In addition to the production of coherent radiation in these crystals, the efficient recombination radiation of p-n junctions in this material has equally important potential in the development of low-power semiconductor lamps. To achieve a high conversion efficiency of electrical to optical energy in p-n junctions in this material, the relation of physical properties of the crystal to luminescence efficiency must be better understood. Although the electrical, optical, and device properties of GaAsl -xPx junction lasers are understandably of considerable interest, the work to date indicates that the more serious problems are the chemical and metallurgical difficulties encountered in the growth of this material.3 In addition to the problems of chemical purity, crystal imperfections, such as dislocations and stacking faults, can be expected to affect both the efficiency of the radiative recombination process and the perfection of the p-n junction.3 The last requirement, i.c., that of the perfection of the p-n junction, is a particularly troublesome one in the fabrication of laser diodes. To obtain good laser diodes, the p-n junction must be flat, which permits the radiation to be reflected from the resonant cavity boundaries. Junction planarity is extremely sensitive to the crystal perfection of the semiconductor material. Also, it is known that at high dislocation densities (-105 per sq cm) it has not been possible to build laser junctions in GaAsl-xPx . Few studies have been reported on the crystal defect structure of GaAsl-,P,. The first serious study seems to be that of Wolfe, Nuese, and Holonyak,3 who examined the dislocation structure of monocrystalline bulk (nonepitaxial) material grown by halogen vapor transport. In this paper are reported some observations on the dislocation and stacking-fault structure of GaAsl_,P, crystals grown by a vapor transport process on substrates of GaAs. EXPERIMENTAL Crystal Growth. The GaAsl-xPx crystals were grown in an open-tube flow system, using two sets of reagents. GaAs, Pr(red), and HC1 were employed in one method. The transport reaction is =950JC GaAs+HC1 = GaCl +1/4As4 +1/2H2 and the deposition reaction is 2GaAs1-xPx +GaCl3 Composition control is obtained by the flow rate of the HC1 and the vapor pressure of the P4, which is maintained in a separately controlled furnace. The second method has been described by Ruehr-wein4 and utilizes gallium, AsH3, PH3, and HC1. The same transport and deposition reactions as above are involved. Composition control is obtained solely by the flow rates of the three gases involved. All of the crystals were grown on chemically polished GaAs substrates oriented on the (100) plane. The thicknesses of the epitaxial layers were typically 100 to 300p. Revealing of Dislocations. Dislocations were re-vealed on both the( 111 ) and { l l l }b faces by chemical etching. The specimen to be examined was mounted at 54.7 deg, lapped on glass with 3-p alumina, polished on cloth with 3-p diamond paste, and, to remove work damage, chemically polished at room temperature for

Jan 1, 1968

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"&apos; the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,&apos; and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,&apos; or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By J. D. Verhoeven

The effectiue distriblltion coefficient has been Measured in a series of vertical, normal freezing experirtzents with large current densities passing through the solid-liquid interface. The results indicate that the effect of the current on solute redistribution is due to electvotransport in the liquid. The high currents produced extensive mixing in the liquid which was considerably reduced by solidifying in small lubing. Analysis of the convection indicates that it probably vesulls from a horizontal temperature gradient produced by the Joule heating- of the electvic crirver~t. Due to the strong dependence of this convection upon the specimen radius, it is conclnded that only for specit~ens with radii of less than somewhere between 1 and 2 mm wilt electric field freezing be getlerally effec-tire at enhancing the purification of zone-melting experittierats in loe-melting alloys. Experiments on 0.8-mm lubes illustrate some interesting potential applications of this techniqne as a means of solute control on smcrll specimens. In a number of papers published within the last few years&apos;-4 it has been found that passage of large dc currents through the solid-liquid interface of a freezing alloy produces a change in the solute redistribution accompanying the solidification. It had been predicted theoretically by Hucke et al.s and by Pfann and Wagner that such an effect would occur as the result of electrotransport within the liquid boundary layer at the solid-liquid interface. These authors independently derived the following relation between the effective distribution coefficient and the variables of the process: Where k0 is the equilibrium distribution coefficient, V is the mobility of the solute relative to the solvent, E is the electric field intensity, D is the solute diffusion coefficient, R is the rate of interface motion, and 6 is the boundary layer thickness. Both groups of authors show that this equation predicts the possibility of extending the purification ability of zone-melting experiments by the addition of an electric current. However, there are other effects in addition to electro-transport which could be produced by the high dc current and might, perhaps, invalidate the applicability of Eq. [I]. For example, high electric current might affect the interface reaction or perhaps the equilibrium distribution which was assumed to exist at the interface. It was the purpose of this work to determine the applicability of Eq. [I] by systematically investigating a simple system for which all of the necessary parameters were known. It was of particular interest for speculating on the potential usefulness of this technique to determine the maximum practical field intensities obtainable, and the effect of these high fields upon convective mixing in the liquid. The initial work in this study was published in a previous paper3 which will be referred to as I. In that work, a current density of 2000 amps per sq cm was used with specimen diameters of 5 mm. The results gave a qualitative confirmation of Eq. [I.], and also showed that a large amount of convective mixing was produced in the liquid by the current. The present study is an extension of that work to smaller specimen diameters and higher current densities. Two points were overlooked in I and will be emphasized here: a) the value of ko has not been well-established in the Sn-Bi system and b) the observed convection could be due to thermal convection produced from the Joule heating. EVALUATION OF k0 To evaluate Eq. [ I.] it is necessary to know the value of the equilibrium distribution coefficient, k,. Tn I the value of k, was taken as 0.3 from a published phase diagram.7 According to ansen&apos; the best data on the phase boundaries of the Sn-Bi system are those of Davidson.5 The data of Davidson give a k, value ranging from 0.21 to 0.25 for the compositions studied in this work, or an average value of around 0.23. In a recent publication, Rigaud and Tougas&apos;10 determined ko by means of a solidification technique. For an alloy of approximately the same composition as that used in this work they obtained a ko value of 0.39. Hence, there is considerable uncertainty in the value of ko and, consequently, a series of experiments were made to determine k, more accurately.

Jan 1, 1968

By R. Grierson, L. J. Bonis

The high-temperature Strength oF TD nickel has been observed to be dependent upon the previons thermal and mechanical history of the material. Variations in both the level and the anisotropy of strength have been observed. 01 this paper- these variations are correlated with the storing of annealing resistant elastic strain energy in the matrix of the TD nickel. An x-vay line -broadening tecknique is used to measure the maLrTis elastie strain. THE inclusion of a finely dispersed second phase into a ductile matrix has long been recognized as an extremely effective method of strengthening the matrix both at high and at low homologous temperatures. It has been found, however, that the factors which determine the high-temperature strength are not the same as those which are important at low temperatures. Below 0.5 Tm the size and distribution of the second phase particles are of prime importance in determining the strength,&apos;)&apos; while above this temperature the strength is mainly dependent upon the previous thermal and mechanical history of the alloy,3-7 This paper is primarily concerned with explaining the response of the high-temperature mechanical strength of one of these alloys (DuPont&apos;s TD nickel) to various thermo-mechanical treatments. It will be shown that this response is not associated with the occurrence of any form of dislocation substructure within the matrix of the alloy. It has been found, however, that a correlation does exist between the elastic strain level in the matrix and the previous thermomechanical history of the alloy and that the observed changes in elastic strain level parallel the measured changes in high-temperature strength. It therefore must be concluded that variations in high-temperature strength are a direct result of the variations in elastic strain level. MATERIAL TD nickel contains approximately 2 vol pct of Tho2 in an unalloyed nickel matrix. It is formed, as a powder, by a chemical technique and this powder is compacted to form ingots which are then extruded to give 21/2-in.-diam rod. Rod of smaller diameter is prepared from the as-extruded rod by swaging. In the studies reported in this paper, 1/2-in.-diam rod was used. This rod received an anneal of 1 hr at 1100°C prior to being used in any of these studies. EXPERIMENTAL TECHNIQUES Two methods were used to examine the structure of the nickel matrix of the TD nickel. These were: 1) transmission electron microscopy; 2) the analysis of the position and profile of X-ray diffraction lines obtained using the nickel matrix as the diffracting media. To prepare thin foils for electron-microscopical examination, slices of TD nickel approximately 0.050 in. thick were cut from the as-received 1/2-in.-diam rod. These were then chemically polished down to 0.045 in., rolled to 0.009 in., given a predetermined heat treatment, and thinned, using a modified Bollman technique, to provide the foils for observation. All observations were carried out at 100 kv, using a Hitachi HU-11 electron microscope. Specimens of the undeformed rod were prepared by grinding down the 0.050-in.-thick slices to approximately 0.015 in. and then thinning chemically and electrolytically to give the thin foils. The X-ray specimens were prepared by rolling 0.375-in.-thick rectangular blocks down to 0.075 in. The surfaces of the rolled material were ground flat, chemically polished to remove the layer disturbed by the grinding, and given a predetermined anneal in an inert atmosphere. They were then ground lightly to check their flatness and given a final chemical polish prior to being examined. The X-ray diffraction line profiles were measured using an automated Picker biplane diffractometer. A special specimen holder was built to allow a more accurate and reproducible positioning of the specimen. The line profiles were determined by carrying out intensity measurements at intervals of either 1/30 deg or 1/60 deg over a range of 3 deg on either side of the nickel peaks of interest. A piece of pure nickel which had been recrystallized to give a large grain size was used as a standard to give the X-ray line profile generated by a strain-free matrix. The analysis of the X-ray diffraction line profiles is a modification of that due initially to Warren and Aver-bach8and has been described elsewhere.3 This analysis gives a measurement of two parameters associated with the structure of the nickel matrix. These parameters are: 1) the size of the coherently diffracting domains within the nickel matrix; 2) the magnitude of the elastic strains in these domains. Both of these parameters are first determined in terms of a Fourier series. These series are obtained from other Fourier series which describe the measured profile of the X-ray diffraction lines. Thus, for both the coherently diffracting domain size and the elastic strain level, it is possible to plot Ft (the Fourier coefficient) against t (the term in the Fourier series), where t can be expressed in terms of a distance L and the Fourier coefficient Ft(S) (associated with elastic strain level) can be expressed in terms of the root mean square strain (e2)1/2. Thus a plot of (F 2)1/2 vs L can be obtained. Plots of this type are shown graphically in Figs. 6 and 8. Interpretation

Jan 1, 1968