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By R. H. Hiltz

Three titanium alloys, known to provide a mechanically unstable p structure after quenching, were selected as material for a study of the Origin and nature of stress-induced transformation. Data from hardness and tensile tests were used to study the initiation of marten site and the effect of the transfornation and transformation products on the mechanical properties of B titanium, particularly the stress-strain relationships. With the exception that the materials investigated showed a natural aging reaction in the P condition, their behavior is analogous to that of' stress-transforming stainless steels. The transformation starts after initial yielding and is essentially complete just prior to .maximum loading. Once initiated, the martensite itself is capable of propagating the transformation. The deforn-ing materials show low strength, high ductility, and a high strain-hardening exponent. In metallic systems which undergo a diffusionless transformation on cooling, it is possible to produce a similar transformatiorl by plastic deformation under special conditions. Dewez' in delineating Ms temperatures for the titanium-rich end of most titanium binary systems:, established the point of intersection of Ms with room temperature for those particular alloys. Alloy compositions which would quench to mechanically unstable p were established from these data. The first investigation into the possibility of stress-induced transformation occurring in titanium met with little success. It was concluded that such a transformation in titanium was possible only under very special conditions. Continued effort in this direction, however, showed certain Ti-Mo binaries to be highly susceptible to this phenomenon. This fact was utilized by Liu to study the habit planes of martensite and by Machlin and wenig5 to study the effects of stress and plastic deformation on the P to a prime transformation in titanium alloys. The first investigation of the mechanical properties of these alloys was conducted by Holden and his coworkers at Battelle Memorial Institute.' The potentiality of the alloys i3s sheet-forming material was recognized, and the data reappeared in a survey of this type of titanium material.? The initial optimism was tempered by the difficulties in obtaining homogeneous 2i-Mo alloys in commercial-size ingots. The increasing need for good sheet-forming material kept investigation in this direction active, resulting in the development of a commercial alloy of this type.' This study was undertaken to obtain a clearer picture of the mechanism of stress-induced transformation in titanium. MATERIALS AND TEST PROCEDURE Three alloys were selected for this investigation: one a Ti-Mo alloy; another a Ti-Cr-Mo alloy, known to deform martensitically; and the third, a Ti-V alloy with an Ms below room temperature and an Md above room temperature, but known to contain w phase in the quenched condition. The compositions of these alloys are given in Table I. These alloys were cast as 5-lb experimental ingots, employing skull melting. The ingots were hot-forged into 1-in.-round bars. Two 72-in.-thick slices were cut from each bar for hardness testing; the remainder was cut into 0.252-in. tensile blanks. The tensile blanks and one hardness disc from each bar were heated in salt to a temperature 100°F above the 0 transus, held 2/2 hr, and brine quenched. X-ray analysis showed the pieces to be 100 pct 8.* *Omega cannot be distinguished from p by the technique employed. Tensile blanks were machined to size after this treatment. TO prevent transformation due to machining stresses, the shoulders and gage length were ground. True stress-true strain curves were

Jan 1, 1960

By C. J. Guntner, R. P. Reed

A commercial 18Cr-8Ni iron alloy (AISI 304L) was examined in tension at 300°, 76°, 20°, and 4°K. Continuous stress-strain recordings were made, X-ray analyses at periodic stress (strain) intervals were obtained, and the magnetic measurements were taken. From this data the percentage of martensitic products [bcc(a) and hcp (E)] was computed as a function of stress (strain). It was found thatup to 15 pct E phase forms at low temperntures. The amount of E formed increases to a maximum at about 5 pct strain, then decreases. This decrease indicates the additional transformation of E to a'. The total amount of E and a' was suppressed at constant stress (strain) at 4°K as compared to 76°K. It is proposed that the suppression of E and a' is associated with the decreased mobility of extended dislocations at very low temperatures. The yield strength decreased as the temperature was depressed below room temperature and then increased rapidly near 4°K. SOME ferrous alloys which are austenitic (fcc ?) at room temperature appear to be unique in that two martensitic products (hcp e and bcc a') may form on cooling to lower temperatures or on application of mechanical stress. The most common room-temperature austenitic ferrous alloys are 18Cr, 8Ni stainless steels. Most aspects of the spontaneous transformations have been previously described for these steels.' Several previous papers have described special aspects of the stress-induced transformations at low temperatures for the stainless steels, such as the existence of the hcp phase (c) after straining at 76oK,2-7 the morphology after straining using electron microscopy,7 and the decrease in E at higher strains at 76oK.4 However, for a complete representation, one must know the stress-strain characteristics and the dependence of both martensitic products on applied stress and temperature. It is the intention of this paper to provide that documentation. To accomplish this, continuous stress vs strain recordings were made at four temperatures: 300°, 76", 20°, and 4°K for annealed AISI 304L (a commercial 18Cr-8Ni alloy). At periodic stress intervals at each temperature the integrated X-ray line intensity of a selected peak for each phase (y, E, and a') was measured. In addition, photomicrographs of the strained surfaces were taken and magnetic measurements were made. The magnetic readings can be directly converted into percent a'.',e With these measurements the percentage of each phase may be plotted as a function of stress (or strain) and test temperature. It was found that up to 15 pct E phase forms upon stressing the AISI 304L alloy at low temperatures. The E percentage increases abruptly after the alloy yields, but then decreases gradually at higher stresses. The rapid increase in e at 76°K is associated with an "easy-glide" portion of the stress-strain curve. The total amount of a' + .G is suppressed below 76°K at a constant stress or strain. The yield strength decreases down to 76°K but increases rapidly below 20°K. EXPERIMENTAL PROCEDURE Tensile test specimens were cut parallel to the rolling direction from 0.1-in.-thick sheet. Continuous stress vs strain recordings were obtained at each test temperature (300°, 76o, 20°, and 4°K) using equipment and methods described elsewhere.' The specimens which were used in the X-ray analysis were stressed to successive increments of strain at each temperature, analyzed at room temperature, then restressed at the test temperature. This procedure was repeated until approximately ten X-ray analyses had been performed with approximately 1.0 pct strain increments. The specimens had a reduced section 1 in. long, 1.2 in. wide, and 0.1 in. thick. They were electro polished prior to testing and after each strain increment. Table I lists the chemical composition, grain size, and hardness for the alloy which was used. This is the same alloy for which extensive mechanical-property tests3 and morphological studies of the spontaneous transformations' have previously been made. For the low-temperature tests (76o and 4°K) below the Ms temperature the specimens were initially cooled to the test temperature, held for 1/2 hr, then warmed and X-rayed at room temperature. The results are listed in Table 11. From earlier work8 it was known that additional transformation on the second cycle would be considerably less (-0.1 pct

Jan 1, 1964

By F. D. Rosi

The plastic properties of extended silver and copper crystals of varying purity were studied as a function of crystal orientation in the early stages of flow. Variations in the gross shape of the shear stress-shear diagram and in the properties of critical Variationsshear stress and shear-hardening coefficient were correlated with changes in slip-band developments. The phenomenon of work hardening is discussed in terms of the existing dislocation theory. IT appears certain from the early studies on the deformation characteristics in metal crystals1-3 that plastic flow takes place in a preferred crystallo-graphic slip system which is determined by the geometry of the crystal (law of maximum shear stress), and that the value of shear stress for this system is independent of crystal orientation (law of critical shear stress). Experimentally, it has been demonstrated further that the law of critical shear stress can be extended to include extensive plastic flow.&apos; Thus, the shear-hardening coefficient, which is defined as the slope of the shear stress-shear curve, also is considered to be independent of orientation. It is noteworthy that deviations from this empirical shear-hardening law have been reported in cubic crystals whose initial orientation favors slip on more than two systems.&apos; Moreover, this law appears to have been derived from stress-strain data relating to relatively high values of shear strain (0.5 to 4), where widespread slip and complex distortions can be expected, regardless of crystal orientation. Since existing data indicate that the strain inhomogeneity in a crystal is manifested particularly in the early stages of flow, it would appear that a more exacting test as to the fundamental nature of the shear-hardening law would be to investigate systematically the shape of the stress-strain curve as a function of crystal orientation in the earlier stages of deformation. With regard to the general form of the shear stress-shear curve for cubic crystals, early studies show a parabolic hardening law, where the shear 1 stress is proportional to the square root of the shear-strain. Since this law was predicted theoretically by Taylor" in his original dislocation model for hard- ening, it has been accepted widely as a fundamental flow characteristic of cubic metals. However, it was recently pointed out by Masing6 hat the parabolic law is not the elementary form of hardening in cubic crystals, but instead is a consequence of complexities in the flow process (e. g., deformation bands and unpredicted secondary slip). Thus, in the very early stages of deformation (< 2 pct extension) where the occurrence of such complexities is unlikely, a different strain-hardening behavior might be anticipated. This view is supported by the recent work of Rosi and Mathewson7 on high purity aluminum where a linear law was obtained for extensions up to 2 pct. A linear hardening over a wider range of deformation also was reported by Rohm and Kochendorfer8 ho deformed aluminum crystals under conditions approximating pure shear. Even more pertinent is the recent evidence of Masing and Raffelsieper9 on high purity aluminum crystals. It was found that for crystals having initial orientations near a <l00> or <1ll> axis, a high hardening was obtained, whereas crystals with a <110> orientation exhibited a low and linear hardening curve followed by a region of more rapid hardening. Since much still remains obscure concerning the details of strain hardening as well as slip-band formation in face-centered-cubic crystals in the early stages of deformation, the present study was undertaken to evaluate the effect of crystal orientation on these two important manifestations of glide. It is important to note here that at the time of this study, Lucke and Lange11 presented information on the orientation-dependence of the shape of the strain-hardening curve in aluminum of various purities. Their work, which essentially represents an extension of that of Masing and Raffelsieper, in many respects is parallel to that of the present study. Experimental Procedure Production of Single Crystals: Single crystals of silver and copper of varying purity were used in

Jan 1, 1955

By N. K. Chen, C. H. Mathewson

Single crystals of high purity aluminum of various orientations were carefully documented after plastic extension. Special attention was given to the formation of slip lines, deformation bands, and asterism. An explanation for the geometry and mechanism of formation of deformation bands is considered. WHILE the general process of plastic extension of face-centered cubic metals is well understood,&apos; the accompanying structural changes due to slip and rotation are far more complex than ordinarily assumed. In the case of stretched single crystals of aluminum, the complicated behavior is especially marked by the formation of deformation bands, as first indicated by Collins and Mathewson." Such bands were believed by them and also by others,".&apos;7 who have discussed banded structure in general, to represent one of the important modes of lattice reorientation and to be intimately connected with the recrystallization process. Yet, despite their fundamental importance to the understanding of the mechanism df both plastic deformation and recrystallization, practically no study of the crystallographic features of these bands in their relationship to the conventional slip process has been attempted. This paper describes part of an extensive investigation on the structural behavior during plastic deformation of aluminum single crystals and is especially concerned with the characteristics of deformation bands. The investigation of the subsequent re-crystallization of deformed aluminum single crystals will be discussed in a later publication. Experimental Procedure Single crystal specimens of 99.996+ pct pure aluminum, Yz in. in diam and 5 to 6 in. in length were made both by the Bridgman method5 nd by a modified temperature gradient method.&apos;* Crystals were selected in which the lineage deviation did not exceed 2"; i.e., as determined from the back-reflection Laue X-ray photograms. These crystals were radiographed to insure that no internal porosity was present. The orientations showed good coverage of the whole area of the Taylor and Elam triangle.&apos; Orientations of the crystals were obtained by the back-reflection Laue technique described by Greninger." Crystals so selected were tapered very carefully in a lathe to obtain a linear decrease in diameter from 0.500 to 0.350 in. along a gage length of 3 in. This is considered desirable because it permits a strain gradient to be introduced in a single specimen at one initial orientation. The advantages of tapered crystals for studying the development of slip lines and recrystallized grains have been pointed out by previous investigators." The cold-worked layer resulting from the machining operation was removed by alternate etching in aqua regia and careful polishing with 2/0 emery paper until undistorted Laue back-reflection spots were obtained. A homogenization treatment at 600 °C for 24 hr was then introduced to insure the removal of residual stress. Two of the crystals so prepared were also checked by use of a glancing angle technique. Using a copper target, at 30 kv and 10 microamperes, a monochromatic beam was positioned at right angles to the axis of the crystal about which it rotated. The time of exposure was 24 hr. From these X-ray photograms, it was concluded that the present method of preparation of single crystals is satisfactory. Following this procedure, the crystals were elec-trolytically polished in a 2:l solution of methyl alcohol and concentrated nitric acid. Intermittent

Jan 1, 1952

By Robert Bakish, William D. Robertson

AFTER more than fifty years of investigation and continuing failure in service, a satisfactory mechanism to explain stress corrosion cracking in homogeneous alloys is still lacking. The relative chemical activity of grain boundaries and adjacent grains, inferred from the boundary structure, has been used to explain intergranular cracking in a brass.&apos; This concept is probably correct as a general hypothesis, but it requires much more extensive development in order to explain satisfactorily the observed phenomena. For example, the specific function of the solute in an alloy must be considered, because intergranular failure does not occur in pure metals,&apos; which are structurally similar to homogeneous alloys. Also, in this connection, an inter crystalline fracture path in binary copper alloys can be changed to a transcrystalline path by relatively small ternary additions.&apos; The fracture path in ß brass is predominantly transcrystalline,&apos; in contrast with an inter crystalline path in a brass. Whether the two different fracture paths are the result of a difference in composition, crystal structure, or the state of long range order is unknown and cannot be determined with ß brass, because only the ordered state can be obtained at room temperature. The study of chemical activity at structural sites in the Cu-Zn system is restricted by the formation of opaque films in an ammonia environment in which stress corrosion cracking is generally observed. Furthermore, both components of the alloy are chemically active and the interpretation of observations is therefore relatively complicated. The Cu-Au system is a better choice for the purpose of studying structural factors. In particular, CuAu is very susceptible to cracking in ferric chloride and opaque films are not formed in this solution; it may be obtained in different states of long and short range order; and, finally, only copper is oxidized in dilute ferric chloride, which considerably simplifies the chemical problem. To provide information necessary for a more general explanation of stress corrosion cracking in homogeneous solid solutions, the following structural factors have been investigated in a Cu-Au alloy having a composition corresponding to Cu,Au: 1) the effect of long and short range order; 2) the structural sites from which copper is removed from the annealed and cold worked polycrystalline alloy; and 3) the effect of annealing time and temperature on structural reactions in the cold worked alloy. Experimental Procedure A Cu-Au alloy of nominal Cu3Au composition was cast from cathode copper and high purity gold and fabricated into sheet and wire. Chemical analysis for copper and gold indicated 48.92 wt pct Cu and 51.01 pct Au. Quantitative spectrographic analysis indicated 0.01 pct Ag, 0.002 pct Pd, 0.001 pct Pb, and 0.002 pct Fe, with traces of magnesium, silicon, and zinc. Presumably most of the remaining 0.055 pct corresponds to the limits of analytical precision. Heat treatments of wire and sheet were conducted in argon or vacuum. Wire specimens, 0.064 in. diam, were heated for 1 hr at 850 °C to establish a definite

Jan 1, 1957

By Nicholas J. Grant, Italo S. Servi

THE creep and stress rupture properties of three grades of aluminum have been reported in a previous paper.&apos; It was found that the stress coefficient of the creep rate and of the rupture time changes at the transition from low temperature-type to high temperature-type deformation. The transition corresponds to the equicohesion for grains and grain boundaries. In order to support the conclusions obtained from the examination of creep and stress rupture data, the deformed specimens were observed metallographically and a few special tests were conducted. The results of these qualitative observations are given in the present paper. Experimental Procedure and Results Table I gives the types of aluminum specimens.&apos; The creep and stress rupture tests were conducted in simple tension at constant stress. Further details on the experimental techniques have been given.&apos; The test bars were electropolished in a perchloric-acetic mixture before testing and were observed after testing without any further preparation unless otherwise specified. Observations of specimen cross-sections were made after electrolytic polishing and etching. The samples were extended along a direction parallel to the longer side of the micrographs of Figs. 12 through 27. The log-log plots of stress vs. minimum creep rate for the three grades of aluminum appear in Figs. 1 and 2. The reference numbers on each curve help relate the photographs to the conditions of testing, indicating where high temperature-type deformation and failure prevailed and where low temperature behavior prevailed. Deformation of Single Crystals at Very High Temperature: An annealed, high purity aluminum specimen was slightly strained at one end and re-annealed. A large single crystal was formed at the strained end of the specimen during re-annealing; the other end remained polycrystalline (see Fig. 3). A stress of 50 psi was applied to the cold specimen to avoid loading at 1100°F. The temperature was then raised to 1100°F, kept at 1100°F for 3 hr, and lowered again to room temperature. Fig. 4 shows the appearance of the specimen after testing. The single crystal deformed by gliding along parallel planes, while the polycrystalline part deformed mainly by grain boundary flow. Some grain growth occurred in the polycrystalline part. Another high purity specimen, which had two large single crystals at the two ends and a polycrystalline zone in the middle portion, was tested at 1000 °F under a stress of 100 psi. The appearance of the sample after test is shown in Fig. 5. Even though considerable slip occurred in the single crystals, the fracture occurred in the weaker polycrystalline portion. Evidence of Grain Boundary Migration during Creep Testing: A high purity, coarse grained specimen, which had a large crystal in the middle portion (see Fig. 6) was tested at 700°F under a constant stress of 175 psi for 30 hr. The appearance of the specimen after testing (Fig. 7) indicates that the large crystal deformed by gliding along parallel planes, while the rest of the specimen deformed mainly by grain boundary flow. Microscopic examination showed clear evidence of grain boundary flow and grain boundary migration, an example of

Jan 1, 1952

By D. A. Thomas, E. S. Meieran

Tungsten wires were examined by transmission electron microscopy after drawing and after high-temperature annealing. Drawn wire consists of highly elongated grains called fibers, whose long axis is parallel to [110]. Each fiber is ribbon-shaped, with the wide dimension of the ribbon parallel to (001) and the narrow dimension parallel to (110). Furthermore, most fibers are bent about [I10] and twisted along their length. The fibers are divided into cells, which in some cases contain a platelet substructure lying on (110) planes. The misorien-tations of these platelets accumulate to allow the macroscopic twist of the fibers. During annealing, several competing reactions occur, starting at different temperatures and progressing at different rates. Among these processes are fiber-boz~ndary migration, polygonization, dislocation rearrangement, and possibly impurity segregation. The fiber-boundary migration accompanied by the formation of transverse boundaries during polygonization leads to an equiaxed grain structure although recrystal-lization does not occur. There is a relationship between the flow stress of the wires and their average subgrain width in the form sy = s0 + kyd-1/2 . Also, there appears to be a relatio&apos;nship between wire ductility and the formation of transverse boundaries during annealing at about 800°C. THERE have been many investigations of the structures and properties of tungsten wires1-4 due to their commercial importance for use as lamp filaments. The structural studies have so far been limited to optical microscope and replica electron-microscope studies. due to the difficulty of .-me- paring from wires thin foils which can be examined by transmission electron microscopy. However, this difficulty has been recently overcome,5 and it is now possible to examine tungsten wires by transmission electron microscopy as well as by other techniques. In this paper, the structure of drawn tungsten wire is described, as are the changes in the structure during high-temperature annealing. Some discussion of the relationship between structures and properties is also given. EXPERIMENTAL MATERIALS AND PROCEDURES Commercial 0.030-in.-diam doped tungsten wires drawn at progressively decreasing temperatures between about 1400° and about 800°C were examined. The composition, mechanical properties, and optical microstructures are described in detail elsewhere.&apos; All experimental materials were vacuum-annealed for 10 ot 30 min at temperatures at 100°C intervals between 700° and 2000°C. Specimens were thinned for examination in the Siemens Elmiskop I electron microscope by the method of Meieran and Thomas.5 STRUCTURE OF AS-DRAWN WIRE The optical microstructure of as-drawn tungsten wire has been described by Peck and Thomas.7 They observed that wire in longitudinal section consists of highly elongated grains called fibers whose width varies between 1 and 10 µ, while in transverse section the fibers appear to be elliptical in cross section and bent about their common [110] wire axis. They explained this unusual appearance as being due to the drawing of a bcc material with a [110] texture, and predicted that the wide and narrow planes of the fiber cross section would be parallel to (001) and (110), respectively. The fibers apparently bend about the [110] axis during drawing to maintain grain boundary continuity during drawing. Transmission electron microscopy offers a way of checking these predictions as well as providing a more detailed picture of the wire structure. Figs. 1, 2, and 3 are typical electron micrographs of

Jan 1, 1965

By Kichizo Niwa, Toshio Yokokawa, Mitsuo Shimoji, Yoshihiko Watanabe, Satoshi Kado

A LTHOUGH a systematic research on diffusion in liquid metals has not been carried out, partial studies have been developed by various workers in several systems. A few recent papers among them have shown that this line of approach is quite useful for understanding the structure of the liquid state. Furthermore, it has been found in kinetic

Jan 1, 1958

By J. J. Gilman

Zinc monocrystals, when compressed nearly parallel to their basal planes (within 20), deform in a new way; and certain deformation markings, called "-bands," are typical of this new mode. Characteristics of these bands are described. Mechanical behavior of low angle zinc monocrystals was investigated in some detail. Recrystallization did not occur upon annealing of banded specimens that were free of deformation twins. -Bands do not seem to be the result of nonbasal slip, but rather, a result of a microbuckling mechanism. u-Bands differ qualitatively and quantitatively from ortho kink bands. A dislocation model, consistent with some of the features of u-bands, is described. THE plastic deformation of zinc monocrystals with slip planes (0001) nearly parallel to the stress axis was studied in this investigation. In a previous investigation, it was shown that some low angle zinc crystals (those with slip planes making angles of more than about 2.5+1° with the compression axis), deform by ortho kinking while others (those with slip planes making angles of less than 2.5+1° with the compression axis) deform in a new way.&apos; This new mode of deformation will be described in some detail here. Some of its striking features are: 1—it operates only for compressive stresses, 2—its temperature dependence is anomalous, and 3—it exhibits a new type of "yield-point" behavior. The mode of deformation to be discussed is not new in the sense that no previous evidence of its existence had been reported. The markings that it creates on the cleavage surfaces of zinc crystals have been described by several investigators.&apos;" However, this is the first time that it has been made to operate under controlled conditions so that its response to mechanical variables, temperature, and aging treatments could be investigated and its geometry completely described. Apparently. Jillson&apos; as well as Holden3 and Pratt" believed that the small bands they observed were simply small versions of ortho kink bands. In fact, two of these authors3,6 "alled the markings "micro kink bands." In spite of the precedence, it is felt that this term is not entirely suitable because these bands do not have the same genesis as kink bands, and they are qualitatively different in structure. As will be indicated by later discussion, the bands seem to be related to the tensile deformation bands observed in aluminum. The present author has chosen to call the bands "micro deformation bands," or simply ",ubands," and the deformation process, &apos;&apos;p-banding." Experimental Methods Crystals were grown from 99.999+ pct Zn obtained from the New Jersey Zinc Co. The details of the technique are given elsewhere." It should suffice to say that the crystals were seeded for orientation control, and precision pyrex tubes were used for molding them. About 40 crystals were used, yielding some 130 specimens. Fig. 1 illustrates the typical form of the specimens and shows how the orientation angles are defined. The crystal specimens were usually 1 3/4 in. long and about 150 mil in diameter. The angle between the slip or cleavage plane (0001) and the specimen axis is designated by xo, while a is the angle between the maximum slope of the (0001) plane and the nearest close-packed direction [1210], vary ing from 0°to 30°. The crystals were cut into specimens with a jeweler&apos;s saw and the ends were squared by filing (specimens held in V-block). Crystals of this orientation are stiff toward bending, so this procedure introduced only deformation localized at the ends. Then the specimens were polished either chemically in 50 pct HNO³ or electrolytically in 20 pct chromic acid. The mechanical tests were made with an Instron testing machine. This machine weighs by means of electric strain gages on elastic bars and is quite stiff, since the full-load deflection of its load cells is at most 0.002 in. Most of the testing was done at a

Jan 1, 1956

By David A. Thomas, John F. Peck

Fibrous microstructures and their development have been studied by metallography and by hardness and quantitative metallographic measurements. Thin, curved grains were observed in transverse sections of commercial tungsten wire and were developed in laboratory-drawn iron wire at reductions greater than about 70 pct. The unusual grain shapes are attributed to the nonuniform mode of deformation of the grains associated with the characteristic [I101 preferred orientation that develops in bcc metals during drawing. Transverse sections of heavily swaged iron wire showed a ospiral nebulao structure that appears to result from the elliptical shape of the cross section of the swaging dies and their rotary motion. Hardness and quantitative metallographic results show unusual trends that parallel the changes in microstructure. Other phenomena are considwed in light of the results, including the strength of fine wires of bcc metals, ocylindricalo textures, and the ductility of fibrous tungsten. 1 HE microstructure of tungsten wire in a longitudinal section shows grains highly elongated in the working direction, giving the appearance of a bundle of parallel fibers, Fig. l(a). Wires of tungsten and other bcc metals show a pronounced preferred orientation in which a [I101 direction is parallel to the wire axis.l The microstructure and texture of tungsten develop during warm working (working above room temperature but below the recrystallization temperature) into wire by swaging and drawing. Fibrous tungsten so produced has limited but useful room-temperature ductility, whereas annealed tungsten is brittle at room temperature. During an investigation of the effect of recovery annealing on the substructure of commerical 0.030 in. diam tungsten wire, it was found that transverse sections of the as-received material showed thin, curved grains, Fig. 1(b), instead of the expected equiaxed grains. The fact that Figs. l(a) and (b) show different sections of the same material at the same magnification is at first disconcerting, because the long dimension of the curved grains in the transverse section is several times the average fiber width in the longitudinal section. However, a longitudinal section cuts most of the curved grains across their narrow dimension, giving the appearance of a multitude of narrow fibers. On the other hand, the plane of a longitudinal section occasionally includes a long dimension of a curved grain, resulting in a broad ofibero, such as A in Fig. l(a). EXPERIMENTS AND RESULTS To investigate the origin of fibrous microstructures and particularly the unusual transverse-section structure of tungsten, rods of iron (also bcc) were drawn and swaged in the laboratory. One rod of annealed Ferrovac E was drawn in six steps to a total reduction in area of 87 pct (0.10 to 0.036 in. diam), and a second rod was swaged to the same reduction, using approximately the same reduction steps. Longitudinal and transverse sections of the swaged and drawn iron wires are shown in Fig. 2, for reductions in area of 39, 73, and 87 pct. A fibrous microstructure in longitudinal section is first evident at 73 pct reduction, and it is further developed at 87 pct reduction. The grains in transverse section remain equiaxed until about 73 pct reduction, when they become somewhat elongated and curved. At 87 pct reduction, the drawn wire shows thin, curved grains in the transverse section, similar to those observed in tungsten. The transverse sections of the iron wires swaged 83 and 87 pct reduction in area show the striking ospiral nebulao structure in Fig. 2(d). This struc-

Jan 1, 1962

By J. R. Low, M. B. Reynolds, L. O. Sullivan

The effect of neutron bombardment upon the stability of type 347 austenitic stainless steel has been investigated by a magnetic technique. The relation of the ferrite content of a stainless steel to its magnetic properties is given, and an apparatus suitable for the measurement of the ferromagnetic saturation induction of small specimens is described. Results of measurements on irradiated specimens are tabulated. Exposure to a neutron flux was found to cause a slight increase in the ferrite content of type 347 stainless steel, the change increasing with increasing length of exposure and with increasing initial ferrite content. The similarity of the effect of irradiation to the effect of annealing is pointed out. Possible effect of irradiation upon density of austenitic stainless steel is discussed. COMMERCIAL austenitic stainless steels are alloys of iron, chromium, and nickel, plus small quantities of other elements. Although these alloys are normally used in the austenitic condition, this state is thermodynamically metastable at ordinary temperatures and transformation to a more stable state takes place under favorable conditions. In the austenitic state, these stainless steels have the face-centered-cubic crystal structure characteristic of y iron, but the stable state at room temperature is a mixture of austenite and body-centered-cubic ferrite. The transformation from the pure austenitic condition may be brought about by cold working the alloy at a temperature below that at which the aus- tenite becomes thermodynamically unstable (about 400°C), the completeness of transformation increasing with increasing severity of cold work and decreasing temperature. The behavior of the austenitic stainless steels under ordinary conditions of use is rather well known. However, use of these alloys in a nuclear reactor introduces a new variable: the effect of neutron bombardment upon the transformation from the austenitic to the ferritic state. It was with this in mind that a study of the radiation stability of austenitic type 347 stainless steel was undertaken. Magnetic Technique for Ferrite Determination Commercial austenitic stainless steels such as type 347 undergo little transformation under normal conditions of fabrication and use. In view of this fact, it seemed likely that neutron irradiation would change the ferrite content of the alloy but little. The method chosen for measurement of the effect of neutron irradiation was thus limited to one which would be quite sensitive to small changes in the ferrite content of the alloy. Of the properties of the stainless steel which can be measured, the magnetic characteristics are most sensitive to the quantity of ferrite present.

Jan 1, 1956

By M. von Heimendahl, G. Thomas

The microstructure of TD-Ni has been examined by transmission electron microscopy in the extruded, annealed. and deformed states. The tensile properties hove been correlated with the observed microstructures and the results ore com-pared with those obtained from pure nickel. The important conclusions are that the thorin particles in TD-Ni act as strong burriers to dislocntion motion during both deformation (slip) and annealing (climb). During deformation. the dislocations tangle around the particles and a cell structure is devleloped after 10 pct or more strain. The cell size appears to be determined by the spacing of the largest particles and is about five times smaller than that in pure nickel for the same strain. The higher work-hardening rate in TD-Ni compared to nickel is probably due to the more rapid rate of dislocation multiplication in the alloy as a result of dislocation-particle interactions. The Th0,particles inhibit recrystallization and twin growh so that some strengthening may arise from the high density of small annealing twins. THE strengthening of materials due to the presence of a dispersed second phase has been the subject of considerable experimental and theoretical investigation in recent years. One of the newest dispersion-strengthened alloys to be developed is TD-Ni,1 a system of approximately 2 vol pct thoria (ThO2) dispersed in a matrix of commercially pure nickel. This material is fabricated by powder-metallurgical techniques and offers high-temperature stability and useful mechanical properties virtually to the melting point of the base metal. While the mechanical properties of this system have been investigated,2,3 there have been no reports in the literature concerning the microstruc-ture of TD-Ni and its correlation to mechanical properties. This paper describes a transmission electron microscopy investigation of the micro-structure of TD-Ni together with its mechanical properties. The results are compared with the structure and properties of pure nickel.

Jan 1, 1964

By Craig R. Barrett, Jack L. Lytton, Oleg D. Sherby

The types of substructures developed during high-temperature creep of (110)[001]-oriented polycrys-talline Fe-3.1 pct Si were examined by electroetching of dislocation sites. Edge dislocations were observed to accumulate adjacent to grain boundaries and poly-gonize perpendicular to their glide planes to form a "Pile-up" of nearly parallel tilt boundaries. The dislocation density developed within the grains during steady-state creep was found to increase with increasing stress. The formation of periodically spaced groups of edge dislocations along grain boundaries was observed, and it was proposed that these formed to relive bending stresses at grain boundary shear .faults. Grain boundary serrations developed at these faults, and it was suggested that this was a result of localized grain boundary migration at the polygonized groups. THE authors have conducted a series of high-temperature creep tests on (110)[001]-oriented poly-crystalline Fe-3.1 pct Si sheet. The creep specimens were examined at various stages of creep by means of electrolytic etching of dislocation sites using the chrome-acetic acid solution developed by Morris.&apos; Hibbard and Dunn2 have demonstrated that the etch pits produced with this technique correspond to single dislocations. It is the purpose of this paper to present and discuss the dislocation substructures which were formed during high-temperature creep at constant stress. EXPERIMENTAL PROCEDURES The polycrystalline Fe-3.1 pct Si sheet employed in this study contained a (110)[001] texture. This texture was quite strong, and the elastic properties of the sheet closely approached those of a single crystal of iron.3,4 A typical analysis in weight percent for this material is 3.1 Si, 0.1 Mn, 0.003 C,

Jan 1, 1965

By J. J. Gilman, T. A. Read

S URFACE effects in the cleavage of brittle crystals have been known for some oftime,1, 2 but our knowledge of surface effects in the plastic deformation of crystals is of relatively recent origin. In 1936, Roscoe9 eported his observations comparing oxidized and clean cadmium crystals. He found that cadmium crystals 1/2 mm in diam when covered by an oxide film less than 1200 atoms thick had critical shear stresses about twice those for clean crystals. This effect is anomalous in that it cannot be caused by the inherent shear strength of a normal oxide film. Either an interaction between the film and the crystal causes the large increase in strength, or the oxide film has an abnormal mechanical strength. Several authors since Roscoe have studied surface effects in crystal plasticity. A complete review of the literature will not be presented, but most of the results may be summarized as follows: 1—The critical shear stress for slip is increased markedly by very thin oxide films on zinc4 and cadmium crystals;" &apos; also, the entire stress-strain curve is raised by an oxide coating;3,4 both effects increase with decreasing specimen radius. 2—Surface active substances such as oleic acid destroy the hardening effect of oxide films.4, 6-8 The time required for the reduction of the hardening effect to begin increases with the viscosity of the solvent4~ 3—There has been dispute in recent years about the effects of surface active substances themselves on plastic deformation. Rehbinder, Lichtmann, and Maslenikov9 state that surface active substances reduce the strength of metal monocrystals markedly and increase the number of slip lines per unit length at a given strain. The effect varies with orientation for tin crystals being smallest for x, = 0, largest for x, = 45", and intermediate as x, + 90°.10 Several workers claim to have disproved the results of Rehbinder&apos;)"." but Rehbinder and Lichtmann9 have defended themselves and Masing with his collaborators" has confirmed some of Rehbinder&apos;s results. 4—Immersion of metal specimens in electrolytes such as sodium chloride reduces their strength12,13&apos; and subsequent cathodic polarization increases the strength reduction. For noble metals, the strength reduction occurs for both anodic and cathodic polarization," increasing with increasing polarizing voltage. 5—Electroplated copper coatings effect the creep rates of zinc monocrystals. Poly crystals are not affected." 6—Immersion in dilute acid destroys the hardening effect of an hydroxide film. When an acid solution is applied to a steadily creeping crystal, the creep rate jumps to a very high value and then drops gradually to a steady value which is higher than the initial steady rate.*&apos; " If the hydroxide film to be removed is very thin (about 100A thick), the creep rate does not change measurably, but a small rapid strain-increment is observed when dilute acid is applied." 7—Crystal plasticity depends on specimen dimensions. This was observed by Lichtmann and Ven-stroml" for monocrystalline tin and by Andrade and Kennedy" for polycrystalline lead. 8—Immerson of copper crystals in mercury has no effect on their stress-strain curves.&apos;" 9—Bombardment of creeping cadmium crystals with a particles which penetrate the surface to only 0.005 mm may increase their creep rates as much as five times.&apos;&apos;&apos; The experiments which will be described in this paper pertain to: (a) the effect of a crystal&apos;s shape on its plastic deformation, and (b) the effect of metallic surface films on plastic deformation. For the work pertaining to (a), crystals of zinc, tin, and lead were grown which had various shapes. These were tested in simple tension. Macroscopic rotations about the tension axis which are unpredicted by the classical theory of slip were observed, and serrated edges were observed in tin crystals. For the work pertaining to (b), the effects of evaporated and electrodeposited films of copper, nickel, gold, and zinc on the mechanical properties of zinc, tin, and lead crystals were determined. The films influenced both slip and twinning of the crystals in creep and tensile tests. Experimental Details Chemically pure zinc, tin, and lead were used in this investigation. The zinc was 99.999t pct pure;

Jan 1, 1953

By F. H. Buttner, H. Udin, J. Wulff

Using a modified Udin, Shaler, and Wulff technique, the surface tension of gold Udin, purified helium was found to be 1400 ± 65 dynes per cm for the temperature range 1017° to 1042°C. IN the original Udin, Shaler, and Wulff technique for measuring the surface tension of copper: variously weighted wires were allowed to extend or contract in a copper cell held at elevated temperatures in vacuum. By plotting stress vs. strain for a wire array in one test, the stress at zero strain is obtained. This is the point where the contractile forces resulting from surface tension are balanced by the applied load, according to the expression: y = e=o r [1] where y is the surface tension in dynes per cm; a,,,, the stress at zero strain in dynes per cm; and T, the radius of the wire in cm. The assumption that the wires deform viscously permits the drawing of a straight line through the points on the stress-strain plot. Justification of the assumption has received further experimental support recently.&apos;-&apos; The presence of grain boundaries in the wires requires a correction to the original expression used." Thus: y = d4=T [l- (dl) (ar)Y1 [2] where, n/l is the number of grain boundaries per unit length, and a, the ratio of grain boundary tension to free surface tension. Alexander, Kuczynski, and Dawson in studying the creep of gold wire in vacuum were unable to obtain reproducible values of the surface tension of gold. In plotting stress vs. strain for progressively longer times, they found that the stress at zero strain drifted with time from positive stress values to negative values. Similarly, for the surface tension of silver, reproducible values were obtained only when a purified helium atmosphere was substituted.&apos; Evidently the evaporation rate of silver in vacuum is too high at the temperatures employed to obtain solid-gas equilibrium even in a similar metal enclosure. Thus reproducibility of results is lost. Experimental Procedure The experimental procedure was much the same as that originally developed by Udin, Shaler, and Wulff with a few modifications and improvements. For greater accuracy in strain measurements, knots gave way to cut gage marks as shown in Fig. 1. These were made with a hand-driven lathe in which razor blades serv&apos;ed as cutting tools. Also a more precise cathetometer with a screw accurate to 0.00015 cm was used. The tests were conducted in an atmosphere of purified .helium rather than in vacuum in order to avoid possible evaporation difficulties. Five mil wire of high purity gold (99.98 pct) was used. After cutting in the gage marks, each wire of a series of about 12 was differently loaded by welding a gold ball to one end. This was done by dipping the end of the wire in a cooling gold droplet, previously melted on a charcoal block with a No. 2 acetylene torch. The other end of the wire was strung through a hole in a gold lid and twisted over the edge to hold the wires fixed and in suspension from the lid. The lid and mounted wires were then dipped in pure ethyl alcohol to dissolve any skin oils and dirt on the surface of the wires due to handling. Finally the lid was put in place on an alundum crucible lined with gold so that the wires hung freely within the gold-lined chamber. This whole assembly was next heated in a quartz nichrome wound tube furnace and heated for a few minutes at 600°C to soften the wires. After this anneal the wires were easily straightened with tweezers. The wire assembly was finally annealed 10" to 25°C above the subsequent test temperature for 2 hr. This treatment allowed the grains to grow to equilibrium size and shape. After the anneal, the lid was mounted in front of the cathetometer. The gage length was measured by sighting the 40 power microscope on the upper lip of the lower gage mark for the first reading, then traveling up to the lower lip of the upper gage mark for the final reading. This procedure was repeated four times to give an average gage length value. In this manner the annealed gage length and the final gage length could be measured to determine the strains. During all measurements, grain counts were made.

Jan 1, 1952

By R. W. Guard, M. E. Fine

By treating the dislocation like a surface and ap-plying the usual thermodynamic treatment to the adsorption process a Gibbs adsorption equation for dislocations was derived. For extended dislocations in binary solutions the adsorbed concentration on the fault, X2a, may be computed from (jo/da2b) where a2b is the activity of the solute in the bulk material and s is the stacking-fault energy. Using the data of Howie and Swann for s the adsorption concentration goes through a maximum at 2 at. pct Al in Ag-Al, 10 at. pct Zn in Cu-Zn, and 8 at. pct A1 in Cu-Al. The pinning stress calculated from this concentration difference goes Ihrough a maximum at the same concentration us the peak in X2 a. The computed pinning stress thus does not vary with composition in the manner predicted by Suzuki, as was also pointed out by Hendrickson. The results are compared with the stress increment which can be attributed to Suzuki locking in Cu-Zn and Cu-Al stress-strain curves. They both agree in magnitude and in the location of the maximum. The predicted and observed maximum values for the Cu-Zn system (where activity data are available) are 700 g per sq mm (predicted) and 1000 g per sq mm (measured, laking into account the orientation factor of 2.2 to convert poly-crystalline to single-crystal data). CERTAIN simple internal surfaces may be regarded as dislocation grids. This fact suggested that it might be profitable to consider certain phenomena related to segregation of solute atoms at dislocations from the point of view of the thermodynamics of surfaces and surface adsorption. A general treatment of this type is given and then the results are applied to Suzuki segregation and pinning. Confirmation of the results is obtained from comparison of stress-strain behavior for copper and copper-base alloys. Two kinds of dislocations need be treated: perfect and extended dislocations. In either case the line tension of a dislocation, ?. the work which must be done to increase the length of dislocation by a unit length, is analogous to the surface tension. For an undissociated dislocation ? is the self-energy of a unit length of dislocation; for an extended dislocation where is the self-energy per unit length of a pair of partials far enough apart so that there is no interaction energy, is the interaction energy per unit length, is the stacking fault energy per unit area, and w is the equilibrium separation of the paired partials. In the absence of an applied stress the force pushing the dislocation partials apart in a close-packed structure is Gb2/12p where G is the shear modulus, b is the Burgers&apos; vector of the complete dislocation, and is the separation of the partials. At the equilibrium separation, w this force equals s. Thus

Jan 1, 1965

By J. J. Pye, J. B. Drew

The surface-diffusion coefficients of Ni63 diffusing on low-index planes of nickel single crystals have been measured over the temperature range from 400° to 1000°C using a precision autoradio-gvaphic technique. The activation energy for sur -face diffusion appears to he the same on the {111}, {110), and (100) planes and amounts to -0.60 ev. This is in good agreement with the value (-0.62 ev) reported for (111) planes obtained by mass-transport techniques. In an earlier paper, the authors have reported self surface-diffusion coefficients on silver.&apos; In that work, a deviation of the diffusion coefficients from linearity in the Arrhenius plot was observed at high temperatures. This effect was attributed to a loss of tracer atoms into the bulk by volume diffusion. The purpose of the present work was to extend the technique developed to the nickel surface-diffusion system up to the point where volume diffusion would come into play. The nickel system especially lends itself to this technique due to the high efficiency of the isotope in darkening the film and the large absorption of the weak radiation (0.063 mev /3- particle of the trapped tracer atoms. The diffusion coefficients and ictivation energy for different orientations on nickel can also be compared with a report published by Blakely and Mykura 2 where a mass-transfer technique was used. This paper reports the self surface diffusion of nickel on the low-index planes over a wide temperature range using a precision autoradiographic technique. EXPERIMENTAL PROCEDURE The experiment is similar to that described in the earlier publication consisting of a radioactive needle as a source resting on a flat, smooth, chemically polished surface annealed in a dynamic dry-hydrogen atmosphere. The needle is held snugly on the surface by a holder fabricated from commercially pure nickel. The point source is made by grinding down a small-diameter nickel rod until a tip of approximately 0.1 mm radius is formed. It is then etched and the needle tip plated with the radioactive isotope Ni63. Nickel single crystals were used whose main impurities were spectrographically determined as Co 0.05, Fe 0.007, C 0.005, and S 0.003 pct. The surfaces, oriented to within 1/2 deg of the low-index planes, were carefully mechanically polished and etched in a 50-30-10-10 hot solution of acetic, nitric, sulfuric, and phosphoric acids giving a smooth polished surface. The crystals were then washed in distilled water and alcohol. Annealing temperatures ranged from 400° to 1000°C with a furnace arrangement in which the crystals could be brought up to temperature in times short compared to diffusing times. The temperature was maintained constant to ±10°C. In the temperature range investigated, the ratio of the surface-diffusion coefficient to the volume-diffusion coefficient (Ds/Du) was 105 or more and the mean bulk-penetration values, calculated from literature values of volume-diffusion coefficients,3 were on the order of 10-5 cm. After the diffusion anneal, the sintered needle is removed, and both the radius of the needle point and spot left on the crystal face are measured. The crystal is then placed on photographic film. Diffusion profiles are obtained by scanning the film with a recording microdensitometer which has a slit width of 10µ. DISCUSSION AND RESULTS The experimental conditions are such that the source strength and needle radius are essentially constant and the time is adjusted such that the mean bulk penetration is small. An exactly analogous heat-flow problem has been considered by Carslaw and Jaeger4 and the solution can be written in integral form as:

Jan 1, 1964

By David Moskowitz, Ira Binder, Robert Steinitz

THE hard refractory borides of the transition elements of the 4th, 5th, and 6th groups of the Periodic System have been the subject of a number of recent investigations.&apos;-&apos; It is well known now that most of these elements form several different borides, and Kiessling8 has summarized the rules which govern to some extent the arrangements of the boron atoms in the various structures. Melting points of a few borides have been published." The systems Fe-B, Ni-B, and Co-B have been reported," but, as these borides are rather low melting, they are outside of the groups of boron compounds considered here. Brewer&apos; has tested the stability of various borides and estimated a number of eutectic temperatures between different borides, but in no case was the complete system of a transition metal and boron investigated. The phase diagram becomes of special importance if the preparation of the borides from the elements in powdered form is considered; the lowest eutectic temperature will determine the first appearance of a liquid phase. Also, the knowledge of high temperature phases, if they exist, is important for the preparation of bodies from these borides by hot pressing or sintering. During the investigation of various metal borides,7 it was found that there were more boride phases existing in the Mo-B system than reported by Kiessling." They occur, however, only at temperatures above 1500°C and were, therefore, not found by him. This led to a study of the equilibrium diagram of the Mo-B system. ranging from 0 to 25 pct B and from room temperature to the liquidus. Part of this investigation was reported during the "Research in Progress" session at the 1952 Annual Meeting of the AIME.11 Raw Materials and Preparation of the Borides The raw materials used were commercial molybdenum and boron powder, both supplied by the Molybdenum Corp. of America. The molybdenum powder was 99+ pct pure? while the boron powder contained about 83 to 85 pct B. A large percentage of the impurities in this powder was oxygen, with the rest formed by iron, calcium, and unknown substances. The low purity of the boron used was, however, not considered detrimental to the final product, as most of the impurities evaporated at the high temperatures at which the borides were formed. The final product always had a minimum purity of 96 to 98 pct (figured as molybdenum and boron), with carbon, iron, and probably oxygen being the remaining products. Carbon is usually present as graphite. The chemical analyses always confirmed the compositions which corresponded to the crystallographic structures as determined by X-ray diffraction, and the boron content of the finished product agreed closely with that of the starting mixture; no boron was lost during the boride preparation. The chemical analysis methods employed for molybdenum and boron were previously described by Blumenthal.12,13 The powders were mixed by hand in the desired proportions, compressed at room temperature under low pressure, and then heated under hydrogen to about 1500" to 1700°C in a graphite crucible to form the borides. Usually, the three well-known borides Mo,B, MOB, and Mo,B,, which are stable at room temperatures, were prepared in this way, and all other compositions were made by mixing these borides in various ratios or by the addition of molybdenum or boron powders for the very low or very high boron contents. Preparation of two-phase compositions directly from the elemental powders was tried only occasionally to check whether equilibrium could be reached in this way. Experimental Procedures The stable borides were mixed in the desired ratios and heated under hydrogen in graphite crucibles to various temperatures. The well insulated crucibles were heated in a high frequency induction furnace. Special care was taken to obtain exact temperature measurement, which proved much more difficult than originally anticipated. It is believed that individual temperature measurements have an error of less than ±25ºC, while melting or transformation temperatures are accurate within ±50°C. The temperatures were measured with an optical pyrometer which was aimed at the closed end of a graphite tube extending down into the crucible. close to the samples. Attempts to measure directly through the hydrogen exit stack failed. The crucible arrangement is shown in Fig. 1. Heating was done at a slow rate to be sure that the temperature inside the crucible was uniform. The specimens were kept at the final temperature for about 30 min. For the investigation of high temperature phases, some samples were quenched. They were heated, without atmosphere protection, in a very small graphite crucible which could be rapidly removed from the high frequency coil, and dropped into water. These quenched samples were afterwards annealed to establish the equilibrium at lower temperatures. The melting points or the positions of the solidus and liquidus lines were determined by heating the specimens to various temperatures and examining them at room temperature for evidence of a liquid phase. These results were checked later on by thermal arrest curves, especially to determine the exact position of the eutectic temperature line. For this purpose about 200 g of the boride were melted in a graphite crucible, in an arrangement similar to Fig. 1. Slow cooling was assured by very good

Jan 1, 1953

By W. Rostoker, R. P. Elliott, B. W. Levincer

Phase equilibria in the Ti-Cr-Mo system have been investigated for alloys containing 100 to 40 pct Ti in the temperature range 550° to 1300°C. Five experimental isothermal sections and a surface of incipient melting are presented in addition to a summary projection of the space. Seven vertical sections have been constructed from the isothermal sections. A STUDY of the system Ti-Cr-Mo was undertaken as part of a program sponsored by Watertown Arsenal toward the development of titanium-base phase equilibrium diagrams of potential technical importance to alloy development. The scope of the investigation included the composition range contained by the titanium corner and the line of 64 pct Ti (all compositions are by weight) and the temperature range 550" to 1100°C. A surface of incipient melting was constructed from measurements on a large number of alloys. The system Ti-Cr has been established.&apos;-? The phase diagram is characterized by a wide miscibility field of the solid solution at elevated temperatures and a eutectoid reaction of the type: (15 pct Cr) + TiCr, (685C). The a solid solution has a very limited capacity for solution of chromium (< 0.5 pct Cr). The intermediate phase TiCr2 has at best a very narrow composition range. It has been shown that two allotropic modifications of this phase exist. However, this behavior does not appear to be perceptibly reflected in the form of phase boundaries of the type + TiCr,. In the system Ti-Mo,9-10 the phase is stabilized to successively lower temperatures with increasing molybdenum content. There are no known intermediate phases. The a solid solution is limited to less than 0.5 pct Mo. Because of the very extensive range of the phase, the ternary system was ideally suited to the determination of the phase boundaries by the parametric method of Andersen and Jette." A parametric surface was constructed to provide the necessary basis for the application of this method. Preparation and Treatment of Alloys More than 60 alloy compositions were prepared for the study of this system. Alloy buttons of 10 grams were arc-melted in a nonconsumable electrode furnace using inert atmosphere protection and a water-cooled copper crucible. The construction and operation of this type of melting unit have been adequately described elsewhere.&apos;&apos; To insure complete solution of alloy additions, the buttons were remelted alternately on top or bottom as many as five times. This was accomplished by a suitable mechanism for "flipping" over the ingots. Iodide titanium (99.97 pct Ti) was used as the alloy base. An especially high quality chromium (99.9 pct Cr) was obtained from the National Research Corp. Molybdenum sheet (0.005 in.) of 99.9 pct purity was used.

Jan 1, 1954

By B. Post, F. W. Glaser

Three borides of zirconium have been reported: ZrB,l ZrB2,2,3 and ZrB12, 4 The phase relationships, ranges of stability, and some physical properties of these compounds are described. THE zirconium borides differ considerably from one another, particularly with respect to their relative stabilities at high temperatures in the presence of carbon.4,5 ZrB2 is extremelv stable at all temperatures (to the melting point) in contact with carbon. Both ZrB and ZrB12 tend to decompose at elevated temperatures when carbon is present in excess of about 0.5 pct. ZrB forms ZrB2 and ZrC, and ZrB12 decomposes to form ZrB2 and a boron-carbide phase. In the ZrB12 preparation, boron present in excess of that needed to form ZrB2 reacts with carbon, if present, to form carbides, in preference to forming the higher boride. Similar instability of borides, other than diborides of the transition metals of the 4th and 5th groups of the periodic table, has been reported.5,6 special precautions had, therefore, to be taken to minimize carbon contamination in the preparation of ZrB and ZrB12. Reactions below 1400°C were carried out by heating powdered mixtures of zirconium hydride and boron in quartz tubes in a hydrogen atmosphere. For temperatures above 1400°C, reactions were carried out in graphite molds. Carbon contamination from the molds was minimized by employing extremely rapid heating rates to reduce carbon diffusion into the body of the specimen, and by subsequent "shaving" of sample surfaces that had been in contact with the graphite dies. A heating rate of about 2000°C per min was obtained by heating the dies (by direct conduction), using a current of 40,000 amp. Although this type of heating cycle apparently allowed little time for "homogenization," close approximations to equilibrium conditions were usually obtained as a result of the very strongly exothermic reactions between zirconium hydride and boron at elevated temperatures. Reproducibility of results in repeated runs under varying conditions was taken as a reasonable indication that equilibrium conditions had been effectively achieved. Quenching was accomplished by rapidly immersing the entire die, containing the reaction products, in water. Specimens could also be cooled at controlled rates by adjustment of the rate of flow of water through the water-cooled copper electrodes in contact with the graphite dies.

Jan 1, 1954