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By B. G. Reisdorf

This paper describes the microstructural changes that occur when quenched ultrahigh-strength steels containing OA pet C and various amounts of nickel, silicon, and cobalt are tempered. The changes that occur in hardness, yield strength, and martensite diffraction-peak widths when these steels are tempered are related to the precipitation of the carbide phases. An unea$ectedly high silicon content (about 30 pct) was found in the E -carbide phase in a steel containing only 1.5 pct Si. TEMPERED martensitic steels have such wide-spread utility that they have been the subject of numerous investigations, and a sizable amount of literature has developed on this subject.M This investigation, which is a part of a larger program to correlate microstructure with mechanical properties at a variety of strength levels, is limited to the microstructural changes that occur when a quenched 0.40 pct carbon steel (USS Airsteel X-200 steel) is tempered, and to the effects of the alloying elements—nickel, cobalt, and silicon—on these microstructures. Used in this investigation were electron microscopy, electron-diffraction identification of the carbide phases, electron-probe micro-analysis of the carbides, X-ray determinations of retained austenite, and measurements of martensite X-ray diffract ion-peak widths. MATERIALS AND METHODS The chemical analyses of the eight heats examined eats No. 30 through 37) are shown in Table L Heat No. 30 has the chemical com~osition of Airsteel X-200, and the remaining seven heats contain various amounts of nickel, chromium, cobalt, and silicon. The heats were air-melted in an induction furnace and cast into 8 by 8 in. ingots that were subsequently heated to 2300 and rolled to 1-in.-thick plate. Oversize 0.505-in.-diam tensile specimens were rough-machined from the plates and austenitized in air at 1700° F for half an hour and oil-quenched. The specimens were then tempered in air at temperatures of 400° to 1000 for tempering times of 1, 4, and 16 hr, and finish-machined to 0.505-in.-diam tensile specimens. Electron micrographs were prepared from Formvar replicas of the midthickness of tensile-specimen shanks that had been electrolytically polished and etched in nital. Electron-diffraction patterns were obtained from carbon-extraction replicas. The replicas were prepared by etching the sample surface in the same manner as for microscopy, evaporating carbon on the etched surface, and re-etching the sample to free the carbon film and the precipitate particles. Electron-probe microanalysis was performed on some of the extraction replicas. To obtain adequate fluorescent X-ray intensities, several thicknesses of replica were exposed to the electron beam so that the results represent an average composition of the extracted particles rather than an analysis of single precipitate particles. The retained austenite contents of the specimens were determined by an empirical X-ray diffraction

Jan 1, 1963

By D. D. Pollock, G. P. Conard II

Equations of the form of the Mott and Jones equations for the absolute thermoelectric powers of metals are derived primarily from a thermodynamic approach. The behaviors of transition thermoelements in common use are then examined and compared with this simple theory. MOTT and ones' derived a general expression for the absolute thermoelectric behavior of metals and alloys using the approach of the solid state physicist. This expression was then applied to specific cases.1,2 The present work develops equations of the same form principally by a thermodynamic approach. These relationships are then employed to gain some insight to the behavior of the transition thermoelements in common use. I) DERIVATION OF AN EXPRESSION FOR ABSOLUTE THERMOELECTRIC POWER First consider a metallic conductor which is maintained in a temperature gradient with no current flowing. At constant pressure, there will be a gradient of the free energy (F,) given by:

Jan 1, 1963

By R. S. Wagner, W. C. Ellis

A new mechanism of crystal growth involving oapor, liquid, crnd solid phases explains many observations of the effect of implurities in crystal growth from the vapor. The role of the impuuitq is to form a liquid Solution with the crystalline tnalerial to be grown from the vapor. Since the solution is n prefevred site for deposition firorti the uapor, the liquid becorrles supersaturated. Crystal growth occurs by precipitatzon from the supersaturated liquid crt tlie solid-liquid zntevfnce. A crystalline defect, such as a screw dislocation, is not essetztial for VLS (vapor -liquid-solid) growth. The concept of the VLS mechanism is discussed in detail with reference to tire controlled growth of silicon crystals using gold, platinum, palladium, nickel, silver, or copper as an implurity agent. RECENTLY a short communication' described a new concept of crystal growth from the vapor, the VLS mechanism. In this paper we present a detailed description of the process and its application to the growth of silicon crystals and we discuss its relevance to existing concepts of .'whisker" crystal growth. Crystal growth from the vapor is usually explained by a theory proposed by Frank2 and developed in detail by Burton, Cabrera, and Frank.3 In this theory a screw dislocation terminating at the growth surface provides a self-perpetuating step. Accommodation of atoms at the step is energetically favorable, and is possible of much lower supersatu-ration than required for two-dimensional nucleation. Crystals of a unique form resulting from aniso-tropic growth from the vapor are "whisker" or filamentary ones. Such crystals have a lengthwise dimension orders of magnitude larger than those of the cross section. For most filamentary crystals both the fast-growth direction and directions of lateral growth have small Miller indices. The special growth form for a whisker crystal implies that the tip surface of the crystal must be a preferred growth site. sears4 proposed that, according to the Frank theory. a whisker contains a screw dislocation emergent at the growing tip. Such an axial defect provides a preferred growth site and accounts for unidirectional growth. The hypothesis was extended by Price. Vermilyea. and Webb," still implying the presence of a dislocation at the whisker tip. They postulated that impurities arriving at the fast-growing tip face become buried while those arriving on the surface of slow-growing lateral faces accumulate and thereby hinder growth. These considerations led to a whisker morphology. There is increasing evidence that most whisker crystals grown from the vapor are dislocation-free. Webb and his coworkers6 searched for an Eshelby twist7 in zinc? cadmium, iron. copper, silver, and palladium whisker crystals. They found unequivocal evidence for an axial screw dislocation in only one element, palladium. However, not every palladium crystal examined contained a dislocation. Observations with the electron microscope have failed to show dislocations in whisker crystals of zinc, silicon.9 and one morphology of AlN.10 Since many whiskers are completely free of dislocations, an axial dislocation does not appear to be required for whisker growth of many substances. A significant advance in understanding whisker growth has been a recognition of the need for impurities. This requirement has been clearly demonstrated for copper,11 iron,13 and silicon9-1 whiskers. For silicon, detailed studies proved conclusively that certain impurities, for example, nickel or gold, are essential. Another pertinent phenomenon which has received little attention is the presence of a liquid layer or droplets on the surface of some crystals growing from the vapor. Crystals in which this has been observed include p-toluidine,14 MoO3,15 ferrites,16 and silicon carbide.'" The liquid layers or globules were considered to be metastable phases, molecular complexes, or intermediate polymers originating from condensation of the vapor phase. The possibility has been suggested that the halide being reduced is condensed at the tip18 or adsorbed on the surface11 of a growing metal whisker, for example copper. The literature on whiskers discloses illustrations of rounded terminations at the tips. These appear. for example, on crystals of A12O3,19,20 sic,21 and BeO.22 For BeO, Edwards and Happel suggested that during growth of the whisker the rounded termination consisted of molten beryllium enclosed in a solid shell of BeO. A recent paper9 on the growth of silicon whiskers contains many observations pertinent to an understanding of the mechanisnl of whisker growth. These observations are summarized as follows. 1) Silicon whiskers are dislocation-free. 2) Certain impurities are essential for whisker growth. Without such impurities the silicon deposit is in the form of a film or consists of discrete polyhedral crystals.

Jan 1, 1965

By W. F. Chiao, R. B. Gordon

Tile sharp-yield point found in magnesium crystals in the solulion-treated and aged condition is studied by dislocation internal-friction experiments. The results show that the sharp yield is not file to the sudden release of pinned dislocations hut is movc likely due to the rapid multiplication of an initially small number of dislocations. Recovery or the dislocation internal friction after deformation is also studied. This yecovery results from the re-pinning of dislocations by a solute, presumably nitrogen, which moves with a relatively small activation energy. SHARP-yield points, when they occur, are a striking feature of the stress-strain curve generated during a tensile test. Although commonly associated with steel, sharp yielding has been found in a variety of metallic and nonmetallic crystalline materials. In particular, sharp-yield points have been found in zinc"' and cadmium3 containing nitrogen. With this background, Geiselman and Guy4 investigated the tensile properties of magnesium single crystals containing nitrogen to see if sharp yielding also occurs in this system. They found that sharp yields did indeed occur in solution-treated and aged specimens tested at elevated temperature but were not able to give conclusive proof that the sharp yield was caused by nitrogen, a yield drop being observed even in their purest crystals. Sharp-yield points have also been found in various polycrystalline magnesium alloys.7'8 In the study of the sharp-yield phenomenon it is desired to observe the behavior of dislocations in the earliest stages of the deformation process. Internal-friction experiments are useful for this purpose because dislocation damping is sensitive to the mobility of free-dislocation segments. At low strain amplitudes the damping, A, due to the the forced vibration of dislocation segments of average length L is ? =KAL4 [1] where A is the dislocation density and K, if the applied frequency is well below the resonant frequency of the dislocation segments? is a constant for the sample under observation.5 Dislocation damping, because of the fourth-power dependence on L, is particularly sensitive to the creation of free-dislocation segments during deformation. Since sharp yielding is associated with the sudden release of pinned-dislocation segments, marked changes in the dislocation damping are expected at the yield point.6 The use of the dislocation-damping observations to help elucidate the incompletely understood mechanism of yielding in magnesium is the primary objective of the experiments reported here. PROCEDURE Many investigations have shown that very marked and rapid changes occur in the dislocation damping of of a deformed material as soon as the straining is stopped.5 It was quite essential, then, for the purpose of this investigation, to make the damping measurements during the deformation of the samples. This can only be accomplished through the use of the ultrasonic-pulse method. In this method traveling sound-wave pulses are used and, in contrast to resonating-bar methods, only the sample ends are set in vibration. Thus, the sample can be gripped along its sides in the tensile-test machine without disturbing the damping measurements. In the pulse method, the decrease in the amplitude of a sound pulse is measured as it travels back and forth through the sample. If A is the amplitude after traversing a distance x and A. is the initial amplitude, A=Aoe-ax [2] and a is called the attenuation. It is commonly measured either in units of cm-I or as db per µ sec. The observed attenuation in a metal sample is due to a number of causes. These include scattering by grain boundaries and impurity particles, thermo-elastic damping, diffraction effects, stress-induced ordering of solute atoms, and dislocation damping. The total observed attenuation in a given sample usually cannot be resolved into these various components, but changes in a due solely to changes in dislocation damping can be accurately determined, provided the experiment is arranged so that all other sources of damping are held constant. It is desired to reduce the extraneous sources of attenuation to a minimum and for this reason the experiments are done on single crystals of high purity. Magnesium crystals offer the further advantage that, when properly oriented, only a single set of slip planes is active during deformation. Crystal Preparation. The method of sample preparation is similar to that of Geiselman and Guy.4 The starting material was high-purity, sublimed magnesium rod supplied by the Dow Chemical Co. Melting under Dow 310 flux was used to reduce the nitrogen content of the starting material: the fluxing was done under an argon atmosphere and the

Jan 1, 1965

By C. Hays, R. E. Swift, E. G. Kendall

Investigations of the Zr-Pt system, by metallography, incipient melting, and X-ray diffraction, determined the phase relationshifis from 0 to 50 at. pct Pt. Phase fields in the Pt-~ich region were outlined, and three intermetallics (ZrPt, Zr2Pt, and ZrPtd were located. A eutectic between Zr and Zr2Pt, and a eutectoid veaction between Zr and a Zr + Zr2Pt, were established. The maximum solubility of Pt in P Zr was approximately 13.5 wt pct, as opposed to less than 1 wt pct solubility in a Zr. EARLIER work on the Zr-Pt system was limited to an X-ray study on the intermetallic compound, ZrPt3, by H. J. Wallbaum,1 It was reported that ZrPt3 existed at 86.52 wt pct Pt, and had a hexagonal structure, isomorphous with TiNi3. Wallbaum's data revealed the following structural particulars: a = 5.633A, c = 9.21A, and c/a = 1.635A. Other studies allied to Zr-Pt alloys concerned only 1) Pt-rich alloys (0.05 to 5.0 pct Zr) for corrosion resistance,2 2) a Zr-base alloy with 5 pct Pt and 0.124 pct C for oxidation resistance,3 and 3) electroclad-ding of Zr with Pt for in-pile corrosion resistance of Zr to uranyl sulphate. 4 Metallographic, incipient melting, and X-ray diffraction techniques were applied to accurately resolve the phase relationships in the 0 to 50 at. pct (68.2 wt pct) Pt region, and to outline the phase fields in the Pt-rich area. Three intermediate phases: Zr2Pt, ZrPt, and ZrPt3, were also established by the same methods. PROCEDURE Melting stock for this program was of the highest purity obtainable. The Zr was iodide crystal bar with a low hafnium content of about 0.05 wt pct (Westinghouse "Grade 3"). The as-received Zr was treated to remove the surface film of corrosion product that resulted from a standard autoclave grade designation test. Next, the bars were processed to yield material suitable for arc melting and free of contaminants. Sheet platinum metal (Baker and Co. "Grade 2") was used for alloying additions. This material con-

Jan 1, 1962

By David Turnbull

IN isothermal recrystallization processes, new crystals generally grow into the matrix until they impinge upon other new crystals or an external surface, at constant linear rates G. Before impingement the perceptible course of growth can be described by the equation: 1 = G(t-7) C1I where, G = dl/dt, 1 is a crystal dimension measured in a constant direction, t is the time, and 7, the nucleation period, is a positive intercept on the time axis. Fig. 1 is a schematic representation of I as a function of time for a recrystallizing grain. G is dependent upon temperature, driving energy (strain or surface energy), relative grain and boundary orientations, but is generally independent of time. The frequency of nucleation, fi, (time" volume") can be defined by the equation: N = 1/fV [2] where ? is the mean nucleation period and V is the volume of the specimen that has not recrystallized. The kinetics of primary and secondary recrystallization generally can be described satisfactorily in terms of the parameters N and G only.'-" After recrystallization is complete the average grain size 7 increases with time by "normal grain growth;" didt, the average rate of grain growth, is strongly time dependent and has not yet been precisely related to G for the motion of the individual grain boundaries constituting the system. It has been suggested4* " that the elementary act in grain boundary migration is closely related to the elementary act in grain boundary self-diffusion. Although the distance of atom movement in the two processes may be somewhat different, there is reason to expect that the activated states may be very similar, so that the free energy of activation for grain boundary migration should be of the same order of magnitude as for grain boundary self-diffusion. Therefore, it is desirable to develop a satisfactory basis for comparing data on self-diffusion and grain boundary migration and to make such comparisons where possible. Theory The formal theory of grain boundary migration rates is analogous to the theory for the rate of growth of crystals into supercooled liquids reviewed elsewhere 6-8. Boreliuss has shown that the latter theory describes, within the theoretical uncertainty, the growth of selenium crystals into supercooled liquid selenium. Motto and more recently Smolu-chowski" have derived expressions for the rate of boundary migration in recrystallization. The treatment to be presented is similar to Mott's excepting that the formalism of the absolute reaction rate theory will be used. The atomic mobility, M, in grain boundary migration is defined by: G = -M6p/6x where p is the chemical potential per atom and x is the coordinate measured in the direction of grain boundary movement. Let AF be the free energy difference per gram atom on the two sides of the boundary and k the thickness of the boundary. For RT>>AF the potential gradient across the boundary (6p/6x) is essentially linear and it follows that: SF/8x = - aF/N\ [4] where N is Avogadro's number. According to the Nernst-Einstein equation, M is related to a diffusion coefficient, Do, for matter transport in grain boundary migration by the equation: M = Da/kT [5] Substituting eqs 4 and 5 into eq 3 gives the basic relation between Do and G: G = DoaF/\RT [6] Do values may be calculated from experimental values of G from eq 6 and directly compared with the coefficient of self-diffusion within the crystal, DL, or the grain boundary self-diffusion coefficient D,. However, a more convenient, though equivalent, basis for comparing atomic mobility in grain boundary migration and self-diffusion is through the constants of the absolute reaction rate theory. According to this theory diffusion coefficients may be written:" D = k2(kT/h) exp [-AF,/RT] 171 aFa, the free energy of activation, is related to the measured energy of activation, Q, by the equation: AFA = Q - T aSx - RT [8] where aSa is the entropy of activation. Substituting eqs 8 and 7 into eq 6 gives: G = ek(kT/h) (aF/RT) exp [(AS,,)C/R] exp C-Qc/RTI C91 where the subscript G refers to boundary migration. The relationship between the driving free energy and the free energy of activation in boundary migration is indicated schematically in Fig. 2. Experience indicates that the variation of G with temperature can be described by: G= Go exp [- Qc/RT] [10] where Go and Qc are generally temperature independent over wide ranges of temperature. Comparison of eq 9 with eq 10 gives:

Jan 1, 1952

By O. D. Gonzalez, R. A. Oriani

A thermo-osmosis technique has been used to measure the heat of transport, Q* , of hydrogen and of deuterium dissolved in a iron and in nickel, and of hydrogen in Feo.6Nio.4 in the tempevature range 400° to 600°C. For all these systems, Q* is negative and has a large temperature coefficient; an isotope effect can be established for the solutes only in nickel. The magnitude of Q* is considerably larger than the activation energy, E , for migration in the case of these isotopes in a iron, so that all variants of the Wirtz model must be rejected. The phenomenological definition of Q* is developed to show that Q* is related to the mechanisms by which the activation energy is dissipated back into the lattice, and that Q*/E is a function of the ratios of the mean free paths of electrons and of phonons to the distance of jump of the diffusing atom. A correlation is shown to exist between the sign of Q* in thermal diffusion and that of the effective charge in electro migration, and may be understood as due to the large ratio of the mean free path of electrons to that of phonons. THE study of nonisothermal diffusion in the solid state is of interest because certain aspects of the mechanism of diffusion are made manifest which remain concealed though still present in the isothermal case. The thermodynamics of irreversible processes characterizes nonisothermal diffusion, known as thermal diffusion or as the Ludwig-Soret effect, by a quantity, Q*, called the heat of transport, which essentially measures the sign and the magnitude of the steady-state concentration gradient produced by the imposed temperature gradient. The problem then is to understand the quantity Q* at the atomistic level. There does not exist a theory for the atomistic interpretation of the heat of transport. There are, however, two classes of simple models which seem to afford some physical insight into Q*. Wirtz's model1, z and its subsequent generalizations partition the activation energy, E, for the migration of the atom spatially about the region of the migrating atom, so that Q* is the difference between the portion of the activation energy centered about the original site of the jumping atom and that portion about the arrival site. Clearly, the magnitude of Q* cannot on this model be larger than the activation energy for migration. The model of Oriani3 also considers the spatial distribution of E not only before but also after the atomic jump, and Q* is related to the variation of the spatial distribution of E that is produced by the jump. The simplest kind of system with which to compare the consequences of these ideas is the interstitial solid solution, since one may easily choose a temperature at which only the interstitial component moves, the solvent lattice serving as a completely satisfactory frame of reference. Thus, one avoids complications arising when both species in a binary system move. In addition, one avoids the necessity of knowing the energy for the formation of a vacancy, something which is needed for the analysis of thermal-diffusion data on metals which diffuse by the vacancy-exchange mechanism. However, the number of well-measured interstitial systems is extremely small, and, in particular, there are almost no data in the published literature for the temperature dependence of the heat of transport. If one works with solutes which are gases in the pure state at ordinary temperatures, one may use the technique of thermo-osmosis4 which permits thermal diffusion to be measured over a small temperature difference so that the temperature dependence of Q* can be more easily determined. The choice of dissolved hydrogen in iron and nickel was based on these considerations as well as on the desire to look for an isotope effect associated with localized

Jan 1, 1965

By J. F. Butler, H. W. Paxton

The vapor pressures of manganese in equilibrium with several alloys in the iron-manganese-carbon system between 1200° and 1275°K have been measured using the Knudsen effusion technique in conjunction with a vacuum microbalance. The effect of orifice area of the effusion cell upon the measured pressure has been determined. The binary iron-manganese system shows small negative departures from ideality, and the system of mixed carbides, (Fe, Mn)7C3, in equilibrium with graphite behaves ideally. THIS work is a continuation of the investigations in which the Knudsen effusion method has been used to determine thermodynamic activities in systems and at temperatures of interest to metallurgists. In a previous publication,' the free energy of formation of Mn7C3 was determined and some preliminary work on the solution behavior of this carbide with the hypothetical "Fe7C3" was reported. The present work deals with this latter topic and also includes data on the binary ir-on-manganese system. EXPERIMENTAL METHOD The Knudsen effusion method was used to measure the vapor pressure of manganese in both the alloy and carbide sections of this investigation. This dynamic method of vapor pressure measurement presents a problem when studying solid alloy systems in which one of the components has a much larger vapor pressure than the others. Over-all depletion of the alloy in the most volatile component will occur during evaporation so that the pressure of that component will decrease. Even more serious than the over-all concentration change is the surface depletion of volatile component in the alloy brought about by the slow rate of diffusion of this component from the interior to the surface of the solid particle. Since knowledge of this surface composition is necessary in order to relate it to the activity determined through the measurements, changes in surface composition from the analyzed bulk composition are to be avoided in dynamic vapor pressure studies of solid alloys. The system under investigation in this study presents the problem of surface depletion of manganese since its pressure at 1230°K is 105greater than iron and 1020 greater than carbon. Since the existence of a volatile manganese carbide had been ruled out previously,' the high manganese pressure relative to iron and carbon insured that the only species leaving the effusion cell was manganese. Therefore, the effusing species required no analysis so that the manganese pressure was determined directly from the weight loss of the effusion cell. In order to detect small weight losses near the beginning of effusion, a vacuum microbalance was used to weigh the cell continually. These initial weight loss data allowed the rate of manganese effusion to be determined before the surface of the alloy became depleted in manganese. The apparatus used in this investigation is shown in Fig. 1. Temperature was measured using chro-

Jan 1, 1962

By P. A. Farrar, M. D. Silver, K. L. Komarek

Thermodynamic properties of Hf-0 alloys have been determined from 0 to 25 at. pct 0 between 1000" and 1200°K by equilibrating specimens with alkaline metal oxide-metal vapor combinations. Partial molar-free energies, enthalpies, and entropies of oxygen have been obtained and are conzpared with similar results for the Ti-0 and ZY-0 In continuation of a thermodynamic investigation of the Ti-O and Zr-O systems1 activities of oxygen and lattice parameters of Hf-0 alloys have been deter- system. The positional entropy in all three systems corresponds to an ideal random interstitial solution with one interstitial site per one metal atom. The lattice parameters of hafnium and Hf-O solid solutions have been determined in the range 0 to 20 at. pct O from measurements of Debye powder patterns. mined. All three metals dissolve large quantities of oxygen to form interstitial solid solutions. The phase diagram of the Hf-O system is shown in Fig. 1.' The maximum solubility of oxygen in the cph a phase is considerable (up to 25 at. pct O). The solubility in the high-temperature phase is much smaller. The only stable compound in the solid state is HfO2 which may exist with a certain oxygen deficiency. The low partial pressure of oxygen of Hf-0 alloys required the application of an indirect method. As the most suitable procedure a method, first applied by Kubaschewski to the V-O system,3 was combined with a principle developed by Herasymenko for the

Jan 1, 1963

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By B. L. Averbach, Morris Cohen, L. L. Seigle

Free energies, enthalpies, and entropies of mixing of Ni-Au solid solutions containing 5 to 95 atomic pct Ni have been determined by the electromotive force method at 700° to 900°C. The thermodynamic activities exhibit large positive deviations from Raoult's law, and the entropies of mixing are almost twice those of ideal solutions. The enthalpies of mixing are positive (heat is absorbed) and are attributable to the lattice distortional energy resulting from the size difference between the nickel and gold atoms. This factor appears to be responsible for the miscibility gap at lower temperatures. IN the thermodynamic study of metallic solid solutions, most interest has been directed toward systems with negative deviation from Raoult's law, namely, those exhibiting superlattice or compound formation. The results of previous investigations are summarized in recent publications.'-' Relatively little experimental work has been carried out on solid solutions which manifest a positive deviation, possibly because the range of solubility in such cases is usually quite limited. Nevertheless, the relationship of the thermodynamic properties of these solutions to diffusion, nucleation, and precipitation in the solid state are of considerable importance. The binary Ni-Au alloys are particularly suited to an investigation of these relationships. Despite the presence of a miscibility gap at lower temperatures, Fig. 1, indicating a large positive deviation from Raoult's law, complete solid solubility is found above 840°C. Moreover, the difference in the atomic scattering powers of nickel and gold is sufficiently great to permit X-ray diffraction studies of atomic arrangements and pre-precipitation phenomena. Radioisotopes of both nickel and gold are available for diffusion work, and finally, a large difference in nobility between the two elements facilitates measurement of the thermodynamic properties. The present paper describes the experimental determination of the free energies, enthalpies, and entropies of mixing of solid Ni-Au alloys. Table I gives a list of the symbols used in the paper. Experimental Method The stability of nickel chloride relative to gold chloride" indicated that the galvanic cell method could be used for determining the thermodynamic properties of Ni-Au alloys. An electrolytic cell (Fig. 2) was constructed, similar to that of Weibke and Matthes,7 in which the electrodes were solid nickel and Ni-Au alloys, and the electrolyte was a fused mixture of alkali chlorides containing NiCl,. The cell electrodes were made from fine gold granules and carbonyl nickel shot melted together under argon, chill cast, swaged to 1/16 in. diam rod, and annealed for one week at 850°C. Commercial reagent and chemically pure grade salts, purified by dehydration, were used for the electrolyte. The cell, operating in an atmosphere of purified argon, was heated in a resistance-wound cylindrical furnace whose temperature was controlled to within ±0.5ºC. The potential developed between the pure nickel and the alloy electrodes, which is related to the thermodynamic properties of the alloys by standard equations to be presented later, was measured with a potentiometer and a mirror galvanometer sensitive to 10-7 v. Dehydration of the electrolyte was carried out in the assembled cell by evacuating at 100°C for about

Jan 1, 1953

By A. T. Aldred, K. M. Myles

The vapor pressure of chromium over solid V-Cr alloys has been measured by the torsion-effusion method in the temperature range 1450" to 1650°K. The chemical activities as well as the free energies, entropies, and enthalpies of formation of the alloys have hem computed from the vapor-pressure data. The activities of both chromium and vanadium exhibit fairly small negative deviations from Raoult's law over the entire composition range. The values of the excess entropies and the enthalpies of formation found at 1550°K are considered in terms of the changes in the clzaracteristic properties of vanadium and chromium that occur upon alloying. RECENT interest in the theory and properties of transition-metal alloys has shown the need for relevant thermodynamic data. The present investigation of the V-Cr system was undertaken as part of a more general study of thermodynamic properties of transition-metal alloys. The system was chosen because of the reported complete solid solubility of the components at all temperatures1 and because the difference in magnitude of the vapor pressures of vanadium and chromium allowed a simple effusion technique to be used. The torsion-effusion method was employed to minimize compositional changes in the alloys during the experiments. EXPERIMENTAL Equipment. The torsion-effusion apparatus, shown diagrammatic ally in Fig. 1, consists of a torsion system suspended inside a vertical vacuum chamber whose lower end is surrounded by a high-temperature vacuum furnace. An auxiliary optical lever and screen are used to determine the angle of rotation of the effusion cell. The torsion fiber is an annealed, high-purity, tungsten wire usually between 0.003 and 0.007 cm in diameter and about 43 cm long. The wire supports a concave mirror and a rigid tantalum connector tube. The effusion cell is fastened to the lower end of the connector tube by a dovetailed yoke and har- ness arrangement. The cells, which are 1.27 cm in diameter and 4.4 cm long, were made by electron-beam welding tantalum endcaps onto a 0.025-cm-wall tantalum tube. The two orifices, formed by drilling, have similar areas ranging from 0.011 to 0.031 sq cm. The noninductive sheath-type furnace consists of a single-phase tantalum heating element 6.35 cm in diameter, 15 cm high, and 0.013 cm thick; the element is completely surrounded by radiation shields in an evacuated chamber. The power system includes a 17-kva self-saturating saturable core reactor with an integral magnetic amplifier and a water-cooled, 15-kva, step-down power transformer with a multitap secondary. Temperatures are controlled to within ±1/2o at 1600°K by means of a unit that includes a reference voltage source, a dc electronic null detector, a current-adjusting proportional band relay, and the self - saturating reactor. At 1650°K the temperature variation within the cell, vertically and horizontally, is 3/4oK. Unwanted motions of the torsion system are damped by the movement of an aluminum vane, which is mounted on the connector tube, between the poles of an electromagnet. When not in use the magnet is withdrawn and rotated 90 deg to prevent its interaction with the rotation of the system. Measurements. The vapor pressure, p, is re-

Jan 1, 1964

By J. M. Toguri, K. Grjotheim

It is known 1,2 that the equilibrium between titanium metal, TiCl2 , and TiCl3, in a solvent of molten metal chlorides, is influenced both by the total amount of dissolved titanium and by the type of solvent. Assuming that the trivalent titanium forms the complex ion Ti111 Cl4, the equilibrium reaction may be expressed by the following equation, (Me) TiIII cl4+ 1/2 Ti = 3/2 TiII cl2+ (Me) Cl The ideal ionic equilibrium constant for this reaction is, Where the N's are the molar ionic fractions in the equilibrium melt, and (Me) the different types of cations present in the equilibrium mixture. The following thermodynamic relation is derived between Kand the concentration of cations in the equilibrium melt, mix The N"S are the equivalent ionic fractions, and so forth are constants corresponding to the standard changes in free energy for reactions in melts where only the cation indicated is present, and f (y1) is a function of the activity coefficients in the equilibrium mixture. When this term vanishes, a simplified linear relationship between In Kideal and the concentration is obtained. The simplified relationship has been applied with satisfactory results to the experimental data of Mellgren and pie,' and Kreye and Kellogg.2 MANY existing methods for the production of light metals involve the reduction of their respective metal halides in the presence of salt melts composed of alkali or alkaline earth chlorides. In such a solution phase, the light-metal halide may undergo stepwise reduction from a higher, to a lower valence, and finally to a zero valent state. In this connection, the disproportionation equilibrium is of great interest. In the case where the higher valence is three and the lower valence is two, the disproportionation equilibrium may be written as follows, 3 Me11 = 2 Me111 + Me [I] If this equilibrium occurs in a salt melt containing a large excess of alkali chlorides, a typical ionic melt is obtained. It is then possible to formulate the cation equilibrium: 2 Me+h' + Me = 3 Me++ [II] Reaction [11] is analogous to a cation exchange reaction. It has been shown thermodynamically that the equilibrium constant for such a reaction in 2

Jan 1, 1960

By James C. M. Li

The thermodynamics of the set of functions including the activation enthalpy. the activation free energy, and the activation entropy for the motion of dislocations at low temperatures is formulated without a specific model or a mechanism. The behniiior near absolute zero of all these functions and of other relevant quantities related to dislocation mobility Is examined in the light of the third law of thermodynamics. The velocity measurements of Stein and Low for edge dislocations in Si-Fe are used .for illustrotion. In the plastic deformation of crystalline materials, a fundamental assumption, which is supported by direct measurements using etch-pit techniques,'-4 is that the average velocity of a certain mobile dislocation is a single-valued function of temperature and the effective shear stress exerted on the mobile dislocation: Sometimes under certain assumptions, even without direct dislocation-velocity measurements, an activation volume can be obtained from a change in strain rate in a simple tension test. Similarly an ac tivation enthalpy can be obtained by changing the temperature in a creep test. However, the assumptions involved should be studied carefully before using the results of these tests. Consider, for example, a tensile specimen at some stage of deformation with a distribution of mobile dislocations. Let the total length of dislocations of type i be pi per unit volume. The Burgers vector of these dislocations is hi which makes an angle ?i with the tensile axis. With respect to the same tensile axis, let the normal of the slip plane of these dislocations

Jan 1, 1965

By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963

By Michael Hoch

The phase diagrams of binary systems of some of the transition elements of Groups IV, V, and VI were used to compute the partial free energies of these elements and the free energy of formation of their Laves-type compounds. From these data, isothermal sections of ternary phase diagrams were calculated and compared with experimental results. DURING the investigation of ternary and quaternary high temperature systems formed by the transition elements of Groups IV, V and VI, the binary phase diagrams for these elements available in the literature were studied. In this study, the free energies of formation of the compounds formed in these binary systems were calculated; these values were then used to determine the general shape of the ternary and quaternary phase diagrams. Above 900°C, the transition elements of Groups IV, V, and VI are all bcc and form only Laves-type compounds in binary systems. The investigation was based on the binary phase diagrams published by Hansen.1 The Cr-Nb system was constructed from the data of Elyutin and Funke.' Several unpublished phase diagrams were taken from Schmidt'sLo and English'sl1 compilations. THE BINARY SYSTEMS valuations of the Thermodynamic Functions. Rostokers evaluated the boundaries of the (a + b) field in Ti-base alloys with a two-constant equation. The authors' interest is mainly in the center of the diagrams; therefore the miscibility gaps in the Zr-Nb, W-Cr, Ta-Zr, Ta-Hf, and Ti-W systems were used to evaluate the thermodynamic behavior of the binary systems. Lumsden's4 Equations 29.2, 32.1, and 33.1, page 287, were used for the excess integral free energy FeX, and for the excess partial free energies Fx and replaces b and b replacesP in Lumsden's notation):

Jan 1, 1962

By Charles F. Hickey, Eric B. Kula

Thermomechanical treatments applied to the maraging steels include a) cold working in the austenitic condition at 650°F, followed by transformation to martensite and aging, b) cold working in the murtensitic condition and aging, and c) cold working in the aged condition with and without subsequent reaging. The strength increases in these steels are very small compared to the increases observed in conventional carbon and alloy steels. The changes that are observed are compatible with the strengthening mechanisms operative during thermomechanical treatment of conventional steels, however. Differences are caused by the absence of a carbide precipitate and the low work-hardening rate in both the solution-treated and the aged conditions. ThE 18 pct Ni maraging steels represent a class of steels which are finding great interest for high-strength applications.1~2 They are essentially carbon-free, and contain 7 to 9 pct Co, 3 to 5 pct Mo, and 0.2 to 0.8 pct Ti. Although austenitic at elevated temperatures, they can be air-cooled to room temperature to form a martensite, which because of the absence of carbon is relatively soft. On subsequent reheating age hardening occurs and strength levels of 250 to 300 ksi yield strength can be attained. These steels appear to be particularly suitable for studying the response to various thermome-chanical treatments for additional reasons other than the obvious one of attempting to improve their already attractive properties. Thermomechanical treatments can be defined as treatments whereby plastic deformation, generally below the recrystal-lization temperature, is introduced into the heat-treatment cycle of a steel in order to improve the properties. With an absence of intermediate transformation products on air cooling the maraging steels have good hardenability and hence can readily be cold-worked in the austenitic condition prior to transformation to martensite. Further, they can be worked in the martensitic condition prior to aging, and even can be deformed in the fully aged condition. Finally, it is of interest to compare their re- sponse to that of the more conventional alloy and carbon steels, where the role of carbides is important in the strength increase by thermomechani-cal treatments. The thermomechanical treatment of conventional steels has been the subject of a recent review.' I) MATERIALS AND PROCEDURE The steel used in this investigation was a commercially produced vacuum-melt heat, which had been rolled to 0.090 in. and mill-annealed. The composition of the alloy was as follows: 0.02 C, 0.08 Mn, 0.10 Si, 0.009 P, 0.009 S, 18.96 Ni, 7.34 Co, 5.04 Mo, 0.29 Ti, 0.05 Al, 0.004 B, 0.01 Zr, and 0.05 Ca. Unless otherwise stated the heat treatments used were the standai-d solution treatment at 1500°F for 1 hr, air cool, followed by a 900°F, 3 hr age. In this condition, the material exhibited 232 ksi yield strength and 239 ksi tensile strength. Mechanical properties were determined by Vicker's hardness measurement (20 kg) and by tensile tests on standard 1/2-in.-wide, 2-in.-gage-length sheet tensile specimens. Notch tensile tests were run using the 1-in.-wide NASA type, edge-notched specimen.4 Fracture-toughness determinations were made on 3-in.-wide, center-notched, fatigue-cracked specimens, following the recommendations of the ASTM Committee on Fracture-Toughness Testing.4 An electric-potential technique was used for measuring the crack size at the onset of rapid crack propagation5 which is necessary for calculations of Kc, the critical stress-intensity factor under plane-stress conditions. The critical stress-intensity factor under plane-strain conditions KI, was also calculated, using the stress at which the first observable crack growth occurred. 11) RESULTS A) Cold-Worked in the Austenitic Condition. The reported M, temperature for the 18 pct Ni maraging steel is about 310°F.1 Therefore, a temperature of 650°F was selected as suitable for rolling in the austenitic condition. Specimens were solution-treated at 1500°F for 1 hr, air-cooled to 650°F, and rolled varying percentages from 0 to 60 pct, at 20 pct reduction per pass. Tensile and hardness properties after aging at 900°F for 3 hr are shown in Fig. 1. The tensile strength increases from 253 to 271 ksi and the yield strength from 247 to 265 ksi as a result of a reduc-

Jan 1, 1964

By O. W. Simmons, L. W. Eastwood, C. M. Craighead

H. Schwartzbart and W. F. Brown, Jr.—The authors have divided the effects of recovery on the true stress-true strain curve into two types; metarecovery, which effects only the first part of the curve or the yield strength, and orthorecovery, which effects the flow stress at any strain. Both of these are said to be true recovery effects, involve no recrystallization, and are explained by the removal of two different types of imperfections caused by work hardening. However, there seems to be some question as to whether the data are sufficiently conclusive to exclude, as an explanation of the authors' results, a mechanism based on the relief of residual stresses between the grains or slip bands and recrystallization. It appears that metarecovery could be interpreted in the same fashion as a customary interpretation of the Bausch-inger effect. The balanced system of internal stresses which exists between grains in a strained specimen due to varying orientation and, hence, yield strengths, of the different grains is responsible for a reduced yield strength in compression following pre-tension, and, similarly, for an elevated yield strength in tension following pre-tension. If the specimen is now heated so that the internal stresses are relieved by creep, then the yield strength in tension following tension will have been reduced and in compression following tension will have been raised. There seems to be a very strong case for the lack of recrystallization in the aluminum investigated by the authors, if one defines recrystallization as the presence of visually detectable new grains or accepts the X-ray evidence as conclusive. One must remember, however, that the appearance of spots on the back-reflection X-ray patterns cannot be taken as the time when recrystallization first started. The areas of recrystallized strain-free material must first have grown to a size large enough to give distinct spots on the patterns and this may take some time. Averbachl7 in an investigation of brass has shown that recrystallization can be detected by extinction measurements at temperatures lower than those based on hardness or X-ray line width determinations. It can be seen from fig. 10 that the rate of recrystallization is extremely low over a considerable time period at the onset of the process. Observations on the rate at which small amounts of recrystallization effect the flow stress would have given further insight as to whether undetectably small amounts of recrystallization might have been responsible for orthorecovery. Also, the question arises as to whether the effects observed in fig. 6 for various times and temperatures could not have been obtained if the time at 212°F were sufficiently long. In addition, the argument that the curve in fig. 10 is not sigmoidal seems weak in view of the scattering of the points. It is conceivable that an accurate determination of the curve for the first 100 hr would exhibit a relationship other than the one drawn. There is one point we would like to raise about the condition of the starting material. The authors annealed their material at 750°F for 15 min to remove the effects of any previous work hardening or machining strains. Reference to the work by Anderson and Mehl shows that this treatment may not have completely recrystallized the aluminum, so that the starting material may have had some strained areas. Higher temperatures or longer times may have been required to remove the effects of any small strains. We would like to mention some results of tests being conducted at the Lewis laboratory of the National Advisory Committee for Aeronautics in an investigation of the Bauschinger effect in relation to fatigue. Tests were performed on annealed electrolytic copper and several annealed brasses. Specimens were pre-strained 1 pct in tension and then tested in compression or tension with and without intermediate stress-relieving annealing treatments at 500°F for various times. Specimens heated at 500°F for 10 1/2 hr showed an elevation of the flow curve in compression and an approximately equal lowering of the flow curve in tension when compared with the curves for the un-heat treated specimens. After approximately 0.8 pct strain, all flow stresses coincided and were equal to the flow stress of the virgin material at this strain. This behavior is consistent with the metarecovery observed for aluminum by the authors and for which a residual stress model can be used. On the other hand, increas-

Jan 1, 1951

By C. F. Floe, N. J. Grant, A. Joukainen

A CCORDING to Guertler,¹ Smith and Hamilton were the first to study the Cu-Ti alloy system, but because of the presence of large amounts of impurities their data are inconclusive. Hensel and Larsen² in 1930 and Kroll³ in 1931 determined the high copper end of the diagram. In 1939 Laves and Wallbaum,4 in a short summary of compound determinations in titanium binary alloys, mentioned the existence of a face-centered cubic compound, Ti2Cu, with 96 atoms per unit cell, and also a compound, TiCu3, which was said to have a deformed hexagonal close-packed structure in which ordering had been observed. The existence of a compound, TiCu, was also found but the crystal structure was not determined. Craighead, Simmons, and Eastwood determined the effect of copper on the allotropic transformation in titanium. The investigation was limited to alloys containing from 0 to 5 pct Cu, using titanium of fairly high impurity content. Experimental Procedure The methods used for determination of the diagram included metallographic examination and X-ray and thermal analyses. The system was first worked out using the higher purity "Process A" sponge titanium and oxygen-free copper. The high titanium region was next determined more accurately using iodide titanium and vacuum-melted, oxygen-free copper. Preparation of Alloys: The alloys were prepared by arc melting under prepurified helium atmos- pheres in water-cooled copper crucibles. The high purity iodide titanium alloys were prepared by melting three compositions along with a specimen of unalloyed titanium in a single charge. A multiple crucible was used which consisted of a copper plate with four cup-like depressions. The unalloyed titanium was melted first and acted as a getter for any oxygen and nitrogen in the melting chamber. Since these elements harden titanium, the hardness of the standard specimen was an index of the highest probable contamination of the alloy melts. The sponge titanium alloy melts weighed from 100 to 200 g each and the iodide titanium melts from 20 to 25 g. In order to insure greater homogeneity most of the alloys were melted, turned, and remelted twice. The larger buttons made from sponge titanium were sectioned or crushed before remelting. These alloys up to 30 pct Cu were further homogenized by forging at 925°C. They forged readily up to 20 pct Cu but numerous cracks were formed in the alloys containing from 20 to 30 pct. Above 30 pct Cu the sponge titanium alloys were homogenized by heating for 200 hr at 850°C under prepurified helium. Similarly, the iodide-grade titanium alloys containing up to 3 pct Cu were homogenized at 1000°C for 24 hr and all others at 880°C for 200 hr.

Jan 1, 1953

By J. P. Nielsen, H. Margolin, E. Ence

The Ti-Ni phase diagram has been investigated up to 68 pct Ni with iodide titanium base alloys by metallographic, X-ray, and melting point methods, and from 68 to 90 pct Ni by examination of as-cast structures of sponge titanium base alloys. NVESTIGATION of the nickel-rich portion of the I Ti-Ni phase diagram was first reported by Vogel and Wallbaum in 1938.' This work was subsequently extended to lower nickel contents by Wallbaum' who indicated the possibility of a eutectic reaction for nickel contents below 38 pct. Long et al.3 studied the titanium-rich portion of the phase diagram and found eutectic and eutectoid reactions below 38 pct Ni. However, the temperature of the eutectic indicated by Long et al. was considerably lower than that suggested by Wallbaum. Long and his coworkers synthesized their alloys by powder metallurgical techniques and encountered oxygen and/or nitrogen contamination. Thus the diagram which was obtained did not represent binary alloying conditions. However from these results the features of the binary diagram were predicted. At Battelle Memorial Institute4 the Ti-Ni diagram was investigated up to approximately 11.5 pct Ni with sponge titanium alloys. The range of temperatures used was not sufficient to define the eutectoid temperature or composition. The data of Wallbaum2 and Long et al.8 were of particular interest for the present study, and although the work was originally concerned with the region below 40 pct Ni, the investigation was extended to higher nickel contents in an attempt to resolve the differences between these workers. Experimental Procedure Preliminary work on the Ti-Ni system was carried out with duPont Process A sponge titanium alloys to reduce the amount of subsequent work to be done with iodide titanium base alloys. The sponge titanium used contained 99.71 to 99.77 pct Ti, 0.1 pct Fe and 0.005 to 0.009 pct Ni. The iodide titanium obtained from the New Jersey Zinc Co. contained 99.9 to 99.95 pct Ti. Nickel used with sponge titanium was 98.9 pct pure. The high-purity nickel alloyed with iodide titanium was cobalt-free with approximately 0.05 pct C and was obtained through the courtesy of the International Nickel Co. The 15 g sponge titanium charges for melting were prepared by compacting in a die or by placing the weighed portions of nickel and titanium directly into the furnace. Iodide titanium charges were made by drilling holes in the as-received rod and inserting the nickel or by wrapping the nickel in sheet. Sponge titanium alloys containing from 0.2 to 90 pct Ni and iodide titanium alloys containing 0.2 to 68 pct Ni were prepared by these methods. In addition to these alloys several 1/2 1b sponge titanium alloys were supplied by the Allegheny Ludlum Co. The charges were melted in an arc furnace under an argon atmosphere. The procedures used were similar to those reported in the literature5,' and the furnace has been described.' Except for iodide titanium alloys with 40 to 68 pct Ni (see section on copper contamination), each alloy was melted for 1 min, then either turned over or broken before re-melting for an additional minute. Currents of 200 to 400 amp were used depending on the melting point of the alloy. Prior to heat treatment, alloys containing less than 14.5 pct Ni were hot-forged at 750°C. With the exception of alloys in the homogeneity range of the compound TiNi, alloys of higher nickel contents could not be hot-forged. Heat treatment of iodide titanium base alloys was carried out in argon-filled quartz capsules which were broken under water at the conclusion of heat treatment to quench the specimens. Temperatures were controlled to ±5oC and annealing times up to 48 hr were used. For melting point determination, specimens were placed in carbon crucibles which were in turn en-capsuled in argon-filled quartz capsules. The start of melting was determined by rounding of corners and by metallographic examination. Complete melting was considered to have occurred at that temperature at which the specimen assumed the shape of the crucible. Specimens were prepared for metallographic examination by mechanical polishing or by an electrolytic procedure." For alloys containing up to 80 pct Ni Remington A etch7 50 pct glycerine, 25 pct HNO,, 25 8 HF) was used. For higher nickel alloys aqua regia and Carapella's etch (5 g FeCl,, 2 ml HNO,, and 99 ml methyl alcohol) were employed. Specimens to be exposed for powder patterns were prepared by filing, by breaking specimens in a

Jan 1, 1954