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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 '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' 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.'-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.' 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.' A concurrent publication'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.'' 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'-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-' 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' 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,' 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'' associated with well-known fcc rolling textures were converted, alone or in combination, to martensite according to the Kur-djumov-Sachs (K-s)' 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') and NdCo3 (a0 = 5.067, co = 24.76') 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' 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

By R. K. Ham, M. L. Wayman

TD-Nickel has been broken in tension and in fatigue at voom temperature. Rod specimens failed in tension by necking, with axial cracks attributed to voids elongated in the extrusion direction. Fatigue specimens failed in shear. Thin-film electron microscopy showed that the subgrain structure of TD-Nickel was very stable, and that particle-matrix detachment was very difficult, in tension and fatigue. TD-Nickel softened slightly during fatigue but had a high fatigue ratio (0.5at 10&apos; cycles). Fractography suggested that Stage I fatigue crack propagation is greatly extended in TD-Nickel. Td-NICKEL* is a dispersion of 2 pct by volume of thoria (ThO2) in nickel, produced by powder-metallurgical methods including compaction, sintering, and extrusion. The spherical thoria particles, which may have a mean diameter of a few hundred angstroms, are dispersed with a mean planar spacing of a few thousand angstroms. By a combination of cold working and annealing, a subgrain or cell structure of dislocations intimately associated with the dispersion can be produced.&apos; This gives the material useful tensile properties which are extremely resistant to exposure to high temperatures.&apos;-= At the same time, the material shows considerable ductility.3&apos;4 At the beginning of the present work, it was considered of great interest to investigate the mechanical stability of TD-Nickel under conditions of fatigue. On the one hand, materials which derive strength from a cold-worked structure are unstable in that they are susceptible to fatigue softening: in addition, the presence of discontinuities such as the particle-matrix interfaces might be expected to assist in the initiation and propagation of fatigue cracks, in that they may provide local concentrations of internal stress and sites for the initiation of voids." On the other hand, the substantial ductility of TD-Nickel suggests that if it obeys Coffin&apos;s relation8 (or the more refined form proposed by Manson9) it should have good fatigue resistance. The initial purpose of this investigation was to assess the importance of these factors. Also, relatively little fundamental work has been done on the mechanism of fatigue in dispersion-strengthened materials. Work on overaged A1-4 pct CU10-12 revealed a very large Bauschinger effect indicative of internal stresses at the particles, and very great fatigue hardening1&apos; presumably due to the multiple slip stimulated by these internal stresses, followed by softening which was initially due to softening in the matrix, but later might have arisen from cracking at the particle-matrix interfaces. The study of overaged Al-4 pct Cu could not settle this latter point by the electron microscopy of thin films, since the dispersion is too coarse. A previous study of the fatigue of internally oxidized copper13 was complicated by inter granular failure, attributed to oxide particles at grain bouhdaries; internal oxidation of single crystals, however, improved their fatigue properties.&apos;3 Investigations of SAP (sintered aluminum powder) are complicated by the complex particle shapes, and the possibility of continuous internal oxide films.14 It was hoped to avoid these difficulties with TD-Nickel, which had the further advantages that it was commercially available and suitable for study by the thin-film technique. 1) MATERIALS AND EXPERIMENTAL PROCEDURE TD-Nickel was purchased from the Driver-Harris Co. as 3/9-in.-diam rod which had been extruded, swaged, and "stress-relieved" (normally at 1010°C for 1 hr). Continuous-radius fatigue specimens with a minimum diameter of -0.1 in. were ground to shape and electropolished in 40 pct phosphoric, 35 pct sul-furic, 25 pct water at 25oC, with a stainless-steel cathode, at -6 v. Fatigue tests were carried out at room temperature with a Sonntag SF-1-U machine operating in push-pull at 1800 cycles per min, and in an Instron TT-C-L modified for reversed stressing at 26 cycles per min as described elsewhere.10 Round tensile specimens were ground with 0.85-in. gage lengths of 0.135 in, diam, electropolished, and tested in a Tinius Olsen hydraulic machine. The surfaces of fatigue specimens were examined with a Reichert metallograph. Discs for electron microscopy with a Siemens Elmiskop I were spark-cut 0.01 in. thick with a modified Servomet 11 employing a tool of moving molybdenum wire, cleaned in 50 pct acetic, 30 pct nitric, 10 pct phosphoric, and 10pctsul-furic at 85oC, and thinned by the window method in the electropolishing solution at -20°C and -6 v. Two-stage replicas (parlodion, then Pt-50 pct C self-shadowed at 40 deg) were taken from fatigue fracture surfaces for electron microscopy. Plane sections parallel to the specimen axis and containing the direction of fatigue crack propagation were polished, etched with Carapella&apos;s reagent, and examined optically. Transmission Laue X-ray photographs of as-received material electropolished to a point were used to determine preferred orientation. 2) RESULTS 2.1) The Structure of As-Received Material. Grains -1 µ diam and elongated 20 to 30 u in the direction of the rod axis were observed, With&apos; elongated "intergran-ular" voids (-4 p diam and -90 µ long and identified as such using longitudinal and transverse sections and

Jan 1, 1968

By A. R. Rosenfield, G. T. Hahn

The effects of adding 0.025 volume fraction of uniformly dispersed Tho2, particles (particle size -380A) to iron have been examined. The two-phase alloy is shown to have a lower transition temperature and higher cleavage stress than either the base metal or a solid-solution alloy (Fe-3Si). Enhanced cleavage resistance is thought to be a consequence of particles limiting the effective slip distance of dislocations and thus the ability of Pile-ups to act as stress concentrations. Further calculations predict that the highest cleavage strengths are attained with uniform dispersions, where the particle size is kept small (-250A) and the volume fraction is relatively large (-2 to 3 pct). ALTHOUGH a fine dispersion of second-phase particles is known to impart strength to an alloy, the possibility that it might also impart ductility has only recently been explored. Outstanding progress has been made in the production of ductile tungsten alloys containing Tho21,2or (Hf, Zr)C,= but the contribution of the dispersion to ductility has neither been optimized nor fully analyzed. The basis for such an analysis has now been developed1,5 and is discussed briefly below. Experiments on iron are also described that attempt to isolate one of the possible ductilizing mechanisms and test its effectiveness. In analyzing these experiments, it is important to remember that cleavage obeys a stress criterion, and that either a lower ductile-to-brittle transition temperature or a higher cleavage stress is evidence of enhanced resistance to cleavage. DUCTILIZING MECHANISMS Slip Blockage. Cleavage fracture of polycrystals may be initiated at the intersection of a slip band (or twin) and a neighboring grain or a large (-1 to 5 µ) particle. The slip band generates a stress concentration at its head, and either the grain boundary fractures, the particle fractures, or cleavage is initiated in a neighboring grain. Experimental evidence for this viewpoint is found in metallographic studies8-8 and from the observation that cleavage is usually preceded by yielding.8-11 The potency of a slip band as a stress concentrator

Jan 1, 1968

By R. T. DeHoff

In any structural transfortnation which is driven by surface tension, the geometric variable of fimdamental importance is the local value of the mean surface curvatuve. Acting through the suvface free energy, this quantity determines the magtnitude of both the pressure and the chemical potential that develops in the neighborhood of an arbitrarily curved surface. A metallographic method which would permit the quaniitatiue estinzation of this propevty is of fundarnerztal irztevest to studies of such processes. In the present paper, it is shoun that the average value of the mean surface curvature in a structuve can be estimated from two simple counting measuretnents made upon a vepresentative metallograpIzic section. No simplifyirlg geonzetric assurmptions are necessary to this deviuation. It is further shoum that the result may be applied to parts of interfaces, e.g., interparticle welds in sintering, or the edge of growing platelets in a phase transformation, without loss of validity. In virtually every metallurgical process in which an interface is important, the local value of the mean surface curvature is the key structural property. This is true because the mean curvature determines the chemical potential of material adjacent to the surface, as well as the state of stress of that material. The theoretical description of such broadly different processes as sintering,1,2 grain growth,3 particle redistrib~tion4,5 and growth of Widmanstatten platelets8 all have as a central geometric variable the "local value of the mean surface curvature". The tools of quantitative metallography currently available permit the statistically precise estimation of the total or extensive geometric properties of a structure: the volume fraction of any distinguishable part:-&apos; the total extent of any observable interface,10,11 and the total length of some three-dimensional lineal feature:&apos; and, if some simplifying assumptions about particle shape are allowed, the total number of particles.&apos;2"3 The size of particles in a structure, specified by a distribution or a mean value, can only be estimated if the particles are all the same shape, and if this shape is relatively simple.14-16 The relationships involved in converting measurements made upon a metallographic section to properties of the three dimensional structure of which the section is a sample are now well-established, and their utility amply demonstrated. In the present paper, another fundamental relationship is added to the tools of quantitative metallography. This relationship is fundamental in the sense that its validity depends only upon the observation of an appropriately representative sample of the structure, and not upon the geometric nature of the structure itself. It involves a new sampling procedure, devised by Rhines, called the "area tangent count". It will first be shown that the "area tangent count" is simply related to the average value of the curvature of particle outline in the two-dimensional section upon which the count is performed. The average curvature of such a section will then be shown to be proportional to the average value of the Mean surface curVature of the structure of which the section is a sample. The final result of the development is thus a relationship which permits the evaluation of the average value of the mean surface curvature from relatively simple counting measurements made upon a representative metallographic section. The result is quite independent of the geometric or even topological nature of the interface being studied. QUANTITATNE EVALUATION OF AVERAGE CURVATURE IN TWO DIMENSIONS The Area Tangent Count. Consider a two-dimen-sional structure composed of two different kinds of distinguishable areas (phases), Fig. l(a). If the system is composed of more than two "phases", it is possible to focus attention upon one phase, and consider the remaining structure as the other phase. The reference phase is separated from the rest of the structure by a set of linear boundaries, of arbitrary shapes and sizes. These boundaries may be totally smooth and continuous, or piecewise smooth and continuous. An element of such a boundary, dA, is shown in Fig. l(b). One may define the "angle subtended" by this arbitrarily curved element of arc, dO, as the angle between the normals erected at its ends, Fig. l(c). Now consider the following experiment. Let a line be swept across this two-dimensional structure, and let the number of tangents that this line forms with elements of arc in the structure be counted. This procedure constitutes the Rhines Area Tangent Count. Suppose that this experiment were repeated a large number of times, with the direction of traverse of the sweeping lines distributed uniformly over the semicircle of orientation.&apos; Those test lines which ap- proach from orientations which lie in the range O to O + dO form a tangent with dA; those outside this range do not, see Fig. l(c). Since the lines are presumed to be uniformly distributed in direction of traverse, the fraction of test lines which form a tangent with dA is the fraction of the circumference of a semicircle which is contained in the orientation range, dO; i.e., vdO/nr or dB/n. If the number of test lines is N, the number forming tangents with dA is N(d0/n). Since each test line sweeps the entire area of the sample, the total area traversed by all N test lines is NL2. The number of tangents formed with dA, per unit area of structure sampled, is therefore

Jan 1, 1968

By John W. Cahn

Tile avevage value of the mean curvature of surfaces in a specimen can be precisely delermined by sitrlple measurements performed on random sections or on 1 vojectiotzs of these surfaces. For surjaces enclosing particles, the quanlity is sllown to be velated to the probable tlurrrhev ot particles intevcepted by a random platne and, under certain conditions, to the perimeter of their Projected image and to the increuse in surjace area when the particles grow. Many of the velalionsl~ips are valid for any shape or size of the particles. THE recent growth of the field of stereology or quantitative microscopy is largely the result of the discovery of a limited number of rigorously defined geometrical parameters that can be precisely measured on random sections or projections of a structure without assumption about particle shape.&apos; Such parameters have been the volume fraction and surface area and line length in a unit volume. The present paper introduces the average of the mean curvature of surfaces in a volume, and shows that it can be rigorously measured by counting methods alone. AVERAGE CURVATURE ON A PLANE Consider a curve y = v (x) on the xy plane. The curvature Kp in the plane at any point is given by Kp = (dZy/dx2)/[1 + (dy/dx)2]3/2. The average curvature along the curve may be defined as Kp = (1/L) fKpdl |1] where dl = [(dx)&apos; + {dy)2]1/2 is the length of an element of the curve and .(dl = L is the total length of the curve. The integral on the right-hand side of Eq. [l] will be called the total curvature, It is dimensionless and readily evaluated by substituting d = arctan (dy/dx) to give ah which is the change in direction of the tangents to the ends of the curve, Fig. 1. Hence, Kp = (1/L)(?h) [2] It can also be seen that Eq. [2] is applicable in the limit of sharp corners. Even though the curvature is infinite at a corner, f Kpdl remains integrable and equal to the change of angle. The signs of the quantities Kp and dl are arbitrary and, if the areas adjoining the curve are equivalent, there seems to be no compelling reason to fix the signs. For a closed curve, however, it becomes worthwhile to use the signs to distinguish among different types of areas or phases enclosed. For such a closed curve AO = t2r and As a convention, we shall take the direction of the integration along the curve in such a way that the area or phase under consideration (henceforth called a) is kept to the left side of the curve, Fig. 1. Then Kp is positive where the curve is concave and negative where the curve is convex. For a closed curve Ad - +2n if the curve encloses a, and Ad = —2n if the curve is surrounded by a. PLANAR SECTIONS OF THREE-DIMENSIONAL STRUCTURE OF ISOLATED a PARTICLES Consider next a planar section of a microstructure containing particles of a in a matrix. We place no restriction on shape of connectedness of these particles, and begin by considering the curvature of only the boundary between a particles and matrix&apos; Clumps of contiguous a particles are then treated as a single a particle. The two-dimensional section will show in a unit area na simple closed curves enclosing a particles and nh closed curves of holes, in-

Jan 1, 1968

By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu&apos; of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith&apos; deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-&apos; make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.&apos; It has received confirmation in the recent work of Dench and Kubaschewski,&apos; and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968

By H. I. Aaronson, H. A. Domian

ELectvon-probe analgsis has been used to in7:estigatr the partition ot alloying- elements between aus-tenite and proeutectoid ferrite (or the Jerritic component of bainite) in high-purity Fe-C-X alloys, lsuully at tzco levels of carbon content fca 0.1 and 0.4 pct in ntost steels) at temperatures between the M, and the Ae3 in Si, mn, Ni, mo, Co, Al, Cr, Cu, and PI steels. No partition ous found during the early stages of transformation at any temperature studied in the Si, ,mo. Co, Al, Cr, and Cu steels. Partition did take place, Jrowel&apos;er, in Ihe Mn, ATi, and Pt steels, occurring in lewtperature. regions below the Ae3 of ca 130°, 65", UNDERSTANDING the mechanisms through which alloying elements influence the kinetics of austenite decomposition reactions which proceed by nucleation and 35c respectively. A break was discovered in the TTT curve for the initiation oj the proeutectoid ferrite reaction in the latter steels at the temperature at which partition began. The alloy content in ferrite at the a:y bondavy remained at constart lecels, shown experimentally to be significantly above those corresponding to eqiilib+iu??l, e&apos;en at the longest reaction times investigated (ca 1o6sec). The partition and the TTT curve observations foere rationalized on the basis of the thermodynamic treatment developed in an accompany ing paper. and diffusional growth has been a major research objective of physical metallurgy since the latter part of the 19th century. The measurements made on the dif-fusivities of carbon and of substitutional alloying elements in austenite during the 1930&apos;s and 1940&apos;s seemed to provide a useful clue as to the nature of these mechanisms. These measurements showed that the diffu-sivity of carbon is several orders of magnitude higher than that of the alloying elements at a given tempera-

Jan 1, 1967

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400&apos; to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,&apos; in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886&apos;C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By S. R. Goodman, Hsun Hu

The formation of secondary - recrystallization tex-tlires in cube-textured 18-8 stain less steel (Type 304) Ilas been studied at three temperatures. Prolonged annealing at 100°&apos;C protluces a PredoninanGly (520) [OOZJ-type texture, which is related to the cube te.ture of the primary lnatrix by a rotation of approxivzately 22 deg around the [001] axis in the rolling direction. Annealing at 1200 or 1300°C facers the formation of the (123)[272/-type texture, which is related to the matrix texture by a [111] rotation of app.voxiniately 40 deg. These observations suggest that in the secondary recrystallization of cube-texlut-ed stainless steel an apparent actilation energy for growth is higher for grains related to the tncrtuix Og [111] rotations thun those reloted by [100] rotations. THE formation of secondary-recrystallization textures in cube-textured primary matrices of fcc metals has been studied widely by various investigators. For Fe-40 pct Ni alloys, Pawlek&apos; and wassermann2 reported that the orientations of secondary grains were related to the cube texture by rotations of 30 and 38 deg around [001] in the rolling direction. However, Rathenau and custers3 found that, while in one Fe-48 pct Ni alloy, most of the secondary grains were oriented with respect to the cube-textured matrix by rotations around [001] of 26.5 deg, in another alloy of a different origin, the orientations of secondary grains were related to the cube texture by rotations of approximately 35 deg around a [lll] axis. Similar orientation relationships were also observed between the secondary grains and the cube-textured primary matrices of copper.4"a No attempt was made to differentiate these two types of orientation relationships; reorientation by either a [111] or a [100] rotation was considered to be equally favored. The present investigation consisted of a study of the secondary recrystallization textures in cube-textured stainless steel. It was noted that the secondary grains formed in stainless steel were considerably smaller than those of Fe-Ni alloys or copper. This offered the advantage that the secondary recrystallization texture could be determined by the texture-goniometer technique, and a more detailed study of the textural development during the course of secondary recrystallization could be made. The effect of annealing temperature on the formation of secondary-recrystallization textures was also investigated. MATERLAL AND METHOD It was shown earlier"-" that a strong cube texture can be obtained in 18-8 stainless steels by rolling at 800°C to produce the copper-type deformation texture, followed by annealing at 800" to 1000°C for recrystallization. To improve the cube texture for the present study, a commercial-grade 18-8 stainless steel (Type 304) was rolled at 800°C first to 5 mm (0.2 in.) thick plates. Three of these plates were then stacked and welded together along the edges into a sandwich assembly. After annealing at 900°C for 20 min: the assembly was finally rolled at 800&apos;C to 90 pct reduction in thickness with reheats and end-for-end reversals after each pass. Only the central strip, which was reduced from 5.0 to 0.50 mm (0.7 in. to 0.020 in.) thick, was used. The chemical composition of the steel in weight percent was as follows: C, 0.06; Mn, 0.38: Cr, 18.71; Ni, 9.56: P, 0.011; S, 0.009; and Si, 0.39. The purpose of rolling the strip in a sandwich assembly was to prevent direct contact between the central strip and the rolls. It was observed earlier" that, when the strip was rolled at 800°C without being enclosed in a sandwich assembly, the cube texture obtained by subsequent annealing at 900" or 1000° C for recrystallization was largely confined to the central section of the strip, while most of the recrystallized grains formed in the surface section of the strip were not cube-textured. This was obviously due to the fact that the actual temperature at the strip surface during rolling, as a result of direct contact between the strip and the cold and massive rolls, was considerably lower than 800°C. By using a sandwich assembly for hot rolling, the cube texture obtained upon subsequent annealing for recrystallization was found to extend through the entire thickness of the strip. After rolling, the central strip was taken from the sandwich assembly. and cut into specimens. Prior to annealing. the specimens were etched to 0.25 mm (0.010 in.) thick. A tube furnace provided with a purified, dry argon atmosphere was used for annealing. Textures were determined by the reflection technique. using a Siemens automatic texture-goniometer and ZrOz-filtered MoKa radiation. With a time constant of 4 sec. the preferred orientation of the secondary grains could be measured satisfactorily by the integrated intensities. Both (111) and (200) reflections were measured, and corresponding pole figures were constructed according to the techniques described previously.10 The agreement between results deduced from these two reflections was excellent. RESULTS AND DISCUSSION Secondary-Recrystallization Texture due to Prolonged Annealing at 1000°C. Fig. 1 shows the primary-recrystallization texture of a specimen annealed at 1000°C for 30 min. A substantial improvement in both sharpness and intensity of the cube texture, owing to the present processing method, can be noted readily by comparing Fig. 1 with similar pole figures shown earlier in Refs. 9 and 11. Secondary recrystallization

Jan 1, 1967

By Merton C. Flemings, Harold D. Brody

Analyses that include diffusion of solute in the solid phase are formulated to describe solute redistribution in dendritic solidification of metallic alloys. The analyses are based on conditions that include negligible undercooling before nucleation of solid phases, negligible increase of solute in advance of the tips of growing dendrites, complete diffusion within the liquid over distances the order of dendrite spacings, and a plate-like dendrite morphology. The classical nonequilibrium freezing equation, Cs = kCo(I - fS)k-l accurately describes solute redistribution between dendrite arms for the solidification processes considered, provided diffusion in the solid is negligible. To account for the effect of diffusion in the solid, an analytic expression is given which is similar inform to the classical expression. 172 addition, a numerical-analysis procedure is etnployed to examine in more detail the effect of diffusion both during and after solidification. The analyses are intended for application to solidification of castings and ingots to describe a) final solute distribution after solidification and cooling to room temperature (microsegregation) and b) local fraction solid as a function of ternperatcre within the solidifying casting or ingol. SOLUTE redistribution in cellular and dendritic solidification has been discussed quantitatively in recent papers&apos;-3 and in a series of earlier work.4-6 However, none of the analyses developed have permitted close correlation of theory with final solute distribution (microsegregation) observed in castings and ingots. In this paper, discussion is given of approximations which may reasonably be made in mathematical treatment of microsegregation, and analyses are presented based on these approximations. Numerical results are given for Al-Cu alloys. In a second paper the analyses will be compared with exeriment.7 CLASSICAL ANALYSIS The classical quantitative treatment of solute redistribution within a closed "volume element" has been derived repeatedly, for example by Gulliver,4 Scheil,&apos; and Pfann.&apos; This "classical nonequilibrium solidification equation" is written for constant partition ratio: where Cs = interface composition of the solid when the weight-fraction solid within the "volume element" is fs (weight fraction, wt pct); k = equilibrium partition ratio; Co = initial alloy composition within the volume element (weight fraction, wt pct). Assumptions of Eq. [11 are: 1) There is negligible undercooling before nuclea-tion, or from curvature or kinetic effects. 2) There is no mass flow in or out of the volume

Jan 1, 1967

Jan 1, 1967