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By A. G. Metcalfe, A. Siede

The hardening of annealed copper during fatigue testing appears to be independent of the applied stress and to occur largely within the first 4000 cycles. Copper hardened by fatigue is more resistant to annealing than copper hardened by static means, and softens by a multistage process. Creep studies at 300°C show that copper hardened by fatigue also has greater resistance to creep than statically hardened copper. Some theoretical explanations are discussed. RECENT interest in the behavior of metals subjected to fatigue stems from observations of phenomena which could not be explained by current theories of the structure of metals. In 1953 Bullen et al.l showed that the hardening caused by fatigue at low stresses did not cause severe bending of the lattice as did hardening by static methods. This was later confirmed by Wood, 'and Broom and Ham.3 Clarebrough et al4 showed that as the stress level used in fatigue hardening was increased, bending of the lattice was introduced, eventually approaching that of metals deformed by conventional cold-working methods. The type of hardening introduced by fatigue has other interesting characteristics. Kemsley5 showed that copper fractured by fatigue at low stresses resisted annealing as compared to copper hardened an equal amount by static means. The work of Clarebrough etal, shows that the manner of energy release during annealing differs for fatigue-hardened and statically hardened metal in both magnitude and temperature range of release. In addition to hardening of the lattice, fatigue has been shown to cause softening in materials previously hardened by static methods,5 and also in age-hardened alloys.7 The superposition of a small fatigue stress on the static loading of high-temperature alloys has been shown to increase their resistance to creep.' The present work was an attempt to determine the relationship between fatigue hardening, resistance to annealing, and the creep properties of pure copper. EXPERIMENTAL PROGRAM The program described here was designed to answer three questions: 1) Can stress-cycle combinations well below the failure values give significant increases in hardness? 2) Does hardening, under different stress-cycle combinations, give increase resistance to annealing? And if so— 3) Does superior resistance to annealing confer superior creep properties over statically hardened material? Three-quarter hard OFHC copper was annealed in vacuo at 550°C for 1 hr to produce a strain-free material having a fine grain size and uniform hardness. (The standard deviation of the mean hardness of the annealed samples was less than + 1.9 Dpn). Annealing was performed after machining the fatigue specimens so as to avoid work-hardened surfaces. Jigs were used to avoid distortion. The fatigue properties of the annealed copper were determined using an accurately aligned Baldwin-Sonntag SF1-U machine operating at 1800 cycles per min. This limited the minimum number of cycles which could be examined to about 4000 stress reversals. Since failure resulted in specimen damage, hardness increase with number of cycles was measured by testing specimens fatigued to different fractions of the failure values. The results are shown in Fig. 1, and are superimposed on the S-N curve of the copper in Fig. 2. The resistance to annealing of fatigue-hardened material was compared to that of material hardened by uniaxial tensile straining. Specimens hardened to equal values by both methods were progressively annealed for 1 hr at temperature in vacuo. After each annealing treatment the hardness was measured using a Leitz Durimet hardness tester with a 500-g load. At least five tests were made for each hardness determination. The standard deviation for individual specimens varied from 0.26 to 1.48 hardness points. The results are shown in Figs. 3 to 5. The discontinuous nature of the annealing process has been brought out by drawing idealized curves through the data points. This can be justified by the consistency of the results as well as by general agreement with results of Kemsley.5 The creep resistance of fatigue-hardened and

Jan 1, 1960

By W. Vickers

Single-point rotating cantilever fatigue tests have been carried out at 550" to 650°C on beryllium produced by a variety of fabrication routes. All the specimens gave similar plots of stress against number of cycles to failure but failure occurred at a lower stress range in the hot-pressed material than in the extruded material. A discontinuity or "kink" appears to exist in the curves and this is considered. A true endurance limit was not evident up to 10 cycles. When Brush hot-pressed warm-extruded beryllium was tested at 600oC a relationship where Nf = number of cycles to failure, ?ep = plastic strain range, and c = constant, was shown to be applicable for values of ?ep > 6.3 x 10-4. Further for this moterial and temperature and for frequencies between 150 and 4500 cycles per min, the variation of number of cycles to failure with frequency obeyed the expression N = Af0.44 where N =number of cycles to failure, f = frequency, and A = constant. Examination of the fracture surfaces indicated that they were generally intergranular and in all cases the higher the stress the more irregular was the fracture. Microexamination has shown that grain boundary cavities and fine intergranular cracks were associated with the fractures. REVERSING or cyclic stresses set up in fuel elements can lead to failure by fatigue. Fatigue stresses may be developed by instability of the fuel element in the coolant flow leading to rattling against the channel wall or fin vibration. Thermal cycling also sets up reversing stresses due to differential expansion of fuel and can. Fatigue resistance is of some importance therefore in the evaluation of canning materials. At the time the work described in this paper was initiated, beryllium was being considered for the can and endcaps of an advanced gas-cooled reactor fuel element. With this in mind, beryllium obtained from different manufacturing routes was tested on single-point rotating cantilever fatigue machines at temperatures the same as those envisaged in the reactor to obtain appropriate fatigue data. The results obtained indicated a discontinuity in the S-N curves coinciding with the yield stress in the specimens. Although in some cases the data is insufficient to warrant a detailed quantitative analysis, a qualitative analysis of this effect was thought to be justified. 1) EXPERIMENTAL DETAILS The materials used are given in Table I together with the production route and available analyses. The specimen shape is shown in Fig. 1. The fatigue specimens were machined slightly oversize, after which they were given a stress-relieving anneal of 1 hr at '750° C in vacuum. This was followed by an etch in sulfuric-phosphoric-chromic acid mixture down to the finished dimensions given in Fig. 1. Etching served to remove the interference colored oxide film formed on the surface during annealing and very small recrystallized surface grains too. The specimen was mounted in the grips of a cantilever machine and rotated inside a furnace controlled at the testing temperature. The specimen was loaded in increments as the speed was increased until the required load was applied at 5000 cycles per min. A revolution counter was used to record the total number of cycles.

Jan 1, 1964

By Harry M. Bendler, W. A. Wood

Electron metallography has been applied to the study of the torsional fatigue of polycrystalline OFHC* copper. The development of slip bands, fis- sures, and microcracks has been followed as a function of strain amplitude and number of cycles. Those factors that have been found to be relevant to a geometrical theory of the fatigue process are described. From the point of view of this theory it is important to distinguish between the effects of cycling at large amplitudes and at small amplitudes (true fatigue deformation). EARLY investigations showed metal fatigue cracking is caused by continued reversal of a small plastic strain. Fundamental study of fatigue, therefore, has been largely concerned with the cumulative effects of these plastic reversals on the metal structure. In particular, recent work has shown that the plastic reversals produce slip movements that are finer than the slip movements produced by unidirectional increments of plastic strain; individual slip movements in fatigue, for instance, are too fine to see by optical microscopy.2 It has also been shown that the fine slip movements of fatigue tend to concentrate in bands and that in this way they can build up, after enough cycles, a progressive surface disturbance. It is this disturbance which, in effect, makes the slip movement visible. It is also in this disturbance that the first cracks appear to form. From this point of view, therefore, the problem of fatigue becomes one of finding why the fine slip movements should concentrate in bands and why the. bands should finally open into cracks. Thus far, study of the slip bands has been limited to the changes they produce at the surface only. These studies have given interesting results. Ewing and Humfrey3 many years ago showed that the bands in iron could extrude debris. Forsyth found that bands in aluminum alloys could extrude thin tongues of material. Thompson showed that, after lightly dissolving away the surface of copper specimens, some bands persisted as superficial cracks might, and that the life of a specimen under fatigue deformation might be prolonged by dissolving away the surface at intervals. Thus these and related results have suggested that the metal structure in fatigue bands may disintegrate and that this may happen long before obvious cracking. These surface studies, however, have not shown definitely how cracking may begin, for they do not show sufficiently what is happening in depth. However, some advance in this direction has been made recently by a new approach, summarized later, which reveals slip bands and their surface disturbances in section. In the work done thus far, the sections have been studied by optical microscopy only. In the present work they have also been studied by electron microscopy with extended results. This paper also describes some observations on the surface disturbances prior to sectioning. These observations are relevant to a suggested theory of fatigue cracking. REVERSED SLIP MOVEMENTS Slip movements in fatigue deformation must reverse direction in each cycle. The question arises: DO the "backward" and "forward" movements take

Jan 1, 1962

By D. P. Kedzie, R. A. Dodd

The fatigue strength, fatigue hardening, and effect of fatigue deformation on subsequent age hardening of supersaturated Al(Cu) solid solutions have been determined as functions of alloy composition and temperature. The fatigue strength/tensile strength ratios, determined at 150°, 25°, and -195°C, decreased with increase in alloy content for all temperatures, but the F.S./U.T.S. ratios at -195°C decreased much more rapidly than did the ratios for 150" and 25°C. This suggested that strain aging and/or age hardening occurred during tests at higher temperatures. Additionally, the F.S./U.T.S. ratios at 150°C exceeded those at 25°C for all compositions, indicating greater strengthening during fatigue at 150°C. The effect of fatigue or tensile deformation at 150°, 25°, and -195°C on subsequent age hardening showed that the deformatzon increased the rate of precipitation and indicated that mechanically produced vacancies were probably formed during deformation. Fatigue hardening was studied at 150°, 25°, and -195°C, and the effect of room-temperature rests after 10 and 100 cycles was examined. The results confirmed that strain aging occurred at the higher temperatures . DURING the last 15 years various mechanisms of fatigue crack nucleation and growth based on dislocation and vacancy interactions, operating singly or collectively, have been proposed. The probable consensus of present opinion is that the fatigue process in pure metals essentially involves dislocation interactions, and that vacancies formed by such interactions play a minor or inconsequential role. However, there is some evidence that age-hardened alloys tend to overage during fatigue, probably by local vacancy-enhanced diffusion, and strain aging also might be important in selected cases. Furthermore, it has been established that the behavior of quenched-in vacancies in Al(Cu) and other solid solutions is composition-sensitive. Therefore, it seemed worthwhile to investigate various aspects of the fatigue behavior of supersaturated Al(Cu) alloys and to examine the results in terms of vacancy-enhanced effects. EXPERIMENTAL The alloys used in this investigation were prepared from 99.994 wt pet A1 and OFHC copper, the latter containing 0.04 pet 0 as the principal impurity. Six alloys were made, containing, by actual analysis, 0.58, 0.96, 1.96, 2.85, 4.45, and 5.51 wt pet Cu. They were induction-melted in air in graphite crucibles, cast as 7-in. by 7/8-in.-diam rods in graphite molds, and hot-rolled to 5/8 in. diam. The experimental work was a three-part program involving the determination of a) 10' cycle fatigue stresses as a function of alloy composition and temperature; b) the effect of fatigue deformation on subsequent aging of the supersaturated alloys; and c) fatigue hardening as a function of alloy composition and temperature. For determining the 105 cycle fatigue stresses, a portion of the 5/8-in. stock was machined into Krouse rotating cantilever beam fatigue specimens, 2 in. in length by 1/4 in. minimum diameter. These were tested at +150°, 25°, and -195°C (liquid nitrogen) on a Krouse high-speed machine, with special weights to provide lower -than-normal loading ranges, this being necessitated by the small load requirements of those alloys of lower copper content. For the high-temperature tests a small resistance heater was designed to clear the collets and fit in between the chucks, while for the low-temperature tests a hollow nylon cylinder was used, having closed ends drilled to pass a fatigue specimen, and positioned similarly to the heater. A plexiglass container completely enclosed the fatigue machine; rubber gloves fixed to ports in the walls enabled the machine to be operated from outside the box. A tray of magnesium perchlorate dried the air in the container and prevented both atmospheric corrosion fatigue at room and elevated temperatures and troublesome ice build-up at low temperatures. A total of ten to fifteen specimens was used for each combination of alloy composition and temperature. The result of each test was plotted on a standard S-N diagram, and the next stress was selected on the basis of the trends indicated by previous specimens. In this manner a small portion of the S-N diagram was constructed, and the 105 cycle fatigue stress obtained. Small Krouse fatigue specimens were also used to study the effect of cyclic prestrain on subsequent

Jan 1, 1964

By William R. Patterson

ACCORDING to the phase diagram for the Mn-Ni system,' the high-temperature, fcc y-manganese solid solution is stabilized to below room temperature, in the range approximately 22 to 28 wt pct Ni. However, pearson2 cites evidence in the literature showing that for manganese contents greater than about 75 wt pct the quenched phase in Mn-Ni alloys is fct. This is in keeping with zener's3 suggestion that in manganese-rich alloys the fcc high-temperature phase undergoes a diffusionless or martensitic transformation to a fct structure upon quenching. Work by Basinski and christian4 on manganese-rich compositions in the similar alloy system Mn-Cu established that in alloys of greater than about 82 wt pct Mn the y-manganese phase underwent a fee fct martensitic transformation upon quenching to room temperature. Striking evidence for this martensitic transformation was the highly twinned or banded microstructure, an example of which is shown in Fig. 1. Similar microstructures have also been found in quenched Mn-Cr5 and Mn-Au6 alloys. In the present investigation, we attempted to obtain similar evidence of a fcc — fct martensitic transformation in manganese-rich Mn-Ni alloys. Manganese alloys in the range 10 to 30 wt pct Ni were prepared by arc-melting, under argon, at atmospheric pressure. The alloys all were 50 g in size, and negligible weight loss occurred during melting. The starting materials were electrolytic manganese and nickel, both of 99.9+ pct purity. The alloys were subsequently homogenized 48 hr at 1750°F, hot-rolled 50 pct at 1700°F, annealed 2 hr at 1700°F, and water-quenched to room temperature. All heat treatment was done in purified argon. Both X-ray and metallographic techniques were used to examine the structures of the quenched alloys. X-ray diffractometer studies were conducted on powder specimens obtained from filings rean-nealed 2 hr at 1700°F in argon and water-quenched. Identification of the intensity peaks from the diffractometer counter traces showed that below about 10 to 12 pct Ni the y phase decomposed partially upon quenching to give an a- + ?-manganese structure. In the range approximately 12 to 25 pct Ni, the structure was found to be fct ? manganese with a c/a ratio approaching 1.0 at 25 pct Ni. Beyond approximately 25 pct Ni, the structure remained fcc. These results, including lattice-parameter determinations, are given in Table I. Metallographic examination. was carried out on specimens polished and etched after quenching, and also on polished specimens reannealed and quenched. In the first case, the distinctive twinning or banding so prevalent in Mn-Cu alloys was sought, while in the second, the surface relief effect generally regarded as being truly characteristic of a martensitic transformation was sought. The microstructure of representative alloys in the range 12 to 25 pct Ni is shown in Fig. 2. The structure of the Mn-15 pct Ni

Jan 1, 1965

By J. H. Brophy, J. Wulff, H. W. Hayden

The mickel-activated sintering of tungsten occurs in two stages of densification. A kinetic analysis of the second stage has been based on an appropriate model of the process. As in the first stage, the rate-controlling mechanism for the second stage is also the solution of tungsten in the nickel carrier phase. The transition from the relatively rapid first-stage results from the spherozdization of pores and the initiation of grain growth. Finer grain size due to higher-nickel content leads to more rapid and higher degrees of densification 1 HE sintering of tungsten is accelerated by small additions of nickel, cobalt, and iron.' Experimental evidence in detail has shown that nickel-coated, hydrogen-reduced tungsten powder may be sintered to more than 90 pet of theoretical density at l100o C.2, 3 Simultaneously, a kinetic analysis of the process showed that it took place in two distinct stages. In the first stage, nickel evidently served as a carrier phase through which tungsten atoms could move. This stage was kinetically similar to the "solution-precipitation" step postulated when the carrier phase is a liquid,4 although in the Ni-W case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in microstruc-tures at the temperatures under consideration. It has been shown that this stage corresponds to a process which is rate controlled by a phase boundary reaction.3 More recent evidence has been presented5 showing that after the initial rapid stage of sintering, densification continues in the final stage but at a slower rate, although no mechanism for this stage of densification was defined. An analysis of later stages of densification in solid state sintering has been presented,6 but it is not directly applicable in the present case of activated or carrier phase sintering. It is the purpose of this investigation to study the final stage of nickel activated tungsten sintering in greater detail The effect of varying nickel content has been examined, and a possible kinetic mechanism defined. EXPERIMENTAL PROCEDURE AND RESULTS Commercial hydrogen-reduced tungsten powder from Wah-Chmg Corp., having a nominal particle size of1 µ and a B.E.T. specific surface area of 5500 sq. cm per g was mixed with aqueous solutions of hydrated nickel nitrate in proportions sufficient to produce nominal compositions of 0.25, 1, 3, and 5 wt pet Ni. This solution was then evaporated to dry-ness at approximately 150" C for 15 hr. Following evaporation, the resulting powder cake was broken with a mortar and pestle and reduced in hydrogen at 800oC for 1 hr. Following reduction, the powder

Jan 1, 1962

By G. Krauss, W. Pitsch

The fine structure of the bcc martensite formed in an Fe-33 wt pct ATi single crystal of arrstenite is sho~on by transmission electron microscoPy to consist of combinations of transformation twins, stacking faults, deformation twins, and regular arrays of parallel screw dislocations. These structures constitute evidence for the multiple lattice-invariant deformations which operating during the formation of martensite could produce the real habit-plane scatter measured by a two-surface analysis of the plates formed in the single crystal of this investigation and reported in the literature for other Fe-Ni rnartensites. CRYSTALLOGRAPHIC theories1,2 of martensitic transformation show that the habit plane of martensite in a parent lattice is dependent in part upon an inhomogeneous distortion or lattice-invariant deformation which takes place on a fine scale within a martensite plate during its formation. Several recent theoretical papers3,4 have addressed themselves to an analysis of a wide variety of conceivable lat-tice-invarient deformations and the habit planes which they produce, while experimental investigation have been concerned with either the measurement of habit planes or the description and identification of the martensitic fine structure which reflects the nature of the lattice-invariant deformation operating during transformation. In Fe-Ni alloys with subzero Ms temperatures, the group of alloys with which this paper concerns itself, habit planes have often been found to scatter an amount greater than might be expected from possible experimental errors,5-7 and fine twinning has been identified as a major constituent of the fine structure of martensite.8-11 It has been suggested3,4 that more than one type of invariant shear occurs during martensitic transformation. This possibility has been experimentally supported12,13 by the observation of both dislocation configurations and twinning in a single martensite plate. The purpose of this paper is to report additional evidence for multiple lattice-invariant deformations in martensite and so to account for the real scatter in the habit planes of the martensite plates formed in Fe-Ni alloys. EXPERIMENTAL PROCEDURE The Fe-Ni single crystal was produced by pulling a high-purity iron and nickel charge through a single-crystal vacuum furnace in an alumina crucible. The crystal was double-melted to promote homogeneity and to increase its size by further additions on the second pass. In its final form the crystal was 4 cm in diam and 5 cm long. The nickel and carbon contents were analyzed at 32.9 and 0.006 wt pct, respectively. The austenite of this alloy first transformed to martensite by bursts at about -120°C, and, to preserve as much of the austenite as possible, all transformation was performed just below -120°C. Some observations were made on transformed samples which had been heated for 2 min at 340°C. It is assumed that the features of the martensite of these samples, Figs. 1 and 4, are the same as those of the as-quenched martensite. Orientation of the crystal by X-ray diffraction established 10.735 0.609 0.3161? as the axis of the crystal, an orientation that was checked within 2 deg by neutron diffraction. Further checks by electron diffraction of samples cut normal to the axis confirmed this orientation within the larger limits of error inherent in electron diffraction of thin foils. The X-ray orientation was the one used for the two-surface analysis of the martensite habit planes. A two-surface analysis was performed on the quadrant of the single crystal which had been oriented by both X-ray and neutron-diffraction techniques. Photomicrographs at X50 were made on two surfaces along an edge 2 cm long. Fiducial marks and the fact that many of the plates were almost completely surrounded by retained austenite made good matching of individual plates on two surfaces possible. The habit-plane trace on a surface was taken as the best line parallel to the long axis of a plate. A measure of the accuracy afforded by this criterion was provided by a family of very large plates which appeared at intervals along the entire 2 cm length of the edge. The plates all had habit-plane traces within 2 deg of one another. Many of the plates did not show midribs and, therefore, the use of midribs7 to represent habit-plane traces was not feasible in this investigation. The over-all experimental accuracy is estimated to be better than ±2 deg. Samples for transmission examination in a Siemens Elmiskop I at 100 kv were prepared by cutting 2-mm-thick discs from the single crystal, removing about 0.5 mm by chemical polishing,14 trans-

Jan 1, 1965

By Rollin E. Hook, Attwell M. Adair

The response of CrzO3 and C~304 to various heat treatments was studied in are-melted iodide chromizim over the temperature range 1000" to 1750°C. These oxides, which are present as impurity phases in this material, were identified by X-ray diffraction teclzniques which were supplemented by optical metallop-aphy. As a function of increasing temperature, Crs04 is first observable in samples annealed at 1300°C and coexists with Cr2O3 (the low-temperature oxide) over a temperature range exceeding 200°C. As the temperature decreases, Cr3O4 dissolves with the concomitant precipttation of Cr2Y2. Both oxides precipitate predominantly at pain boundaries. The reactions which occur are involved with at least ternary equilibria, possibly due to iron which is present as an impurity in arc-melted iodide chromium. HILTY, Forgeng, and Folkman' reported in their investigation of the Fe-Cr-0 system that Cr3O4 (with about 8 pct Fe substituted for chromium) is a primary phase found in alloys with 9 or more pct Cr. They reported that this phase is stable only at high temperatures and that below the liquidus Cr3O4 is disproportionated into Cr2O3 and chromium-rich metal for both Fe-Cr-O alloys and in oxygen saturated pure chromium. Further, they proposed that CrsO4 forms by a peritectic reaction between Cr2O3 and the liquid. On the other hand, Hook, Garrett, and Adair2 found in their investigation of impurity phases formed in "pure" chromium (material consolidated from iodide chromium crystals) that Cr3O4 forms intergranularly and is stable as low as 1500°C which is 375OC below the melting point of chromium. The purpose of the research described herein is to determine the temperature range of stability of Cr3O4, and to show the nature of its decomposition. This further investigation indicates that Cr3O4 undoubtedly occurs in this material as low as 1300°C. The chromium studied was consolidated and fabricated from iodide chromium crystals (ICr-5) and contained Fe r 135 ppm, Si = 20 to 100 ppm, and 0 = 35 to 137 ppm. A complete chemical analysis is given elsewhere.' Annealing was conducted in 1 atm of purified helium and all samples were rapidly cooled (-200°C per sec) by withdrawing them from the furnace hot zone under a high flow rate of helium. The details of the electrolytic-etching technique and electrolytic-digestion techniques for preparation of insoluble residues for X-ray examination are given elsewhere also.' EXPERIMENTAL RESULTS The Starting Material. The as-swaged rod (final swaging done at 900°C) had a wrought grain structure and contained a dispersion of CrzO3 inclusions of maximum particle size of about 2 or 3 p, Fig. 1. The microstructure also contained a dispersed

Jan 1, 1964

By J. E. Burke

THE origin of so-called annealing or recrystalli-zation twins in face-centered-cubic metals continues to be a matter for speculation, and in the present report an attempt is made to explain their origin and to account for at least a majority of the observations concerning their behavior. The fact that annealing twins are prominent only The speelmen was deformed 8 pet in compression and then indented over the lower left-hand corner in a Rockwell in-denter, and then annealed to cause partial recrystallization. Note intense twinning in heavily deformed part and slight twinning in less deformed part. The upper right-hand corner is unrecrystalized. Area reduced approximately 25 pot for reproduction. after recrystallization suggests that deformation may be necessary for their formation. In 1926, Mathewson1 reported the observation by Phillips that annealing twins are frequently parallel to strain markings which delineate octahedral planes in the deformed (and partially recrystallized) matrix, and suggested that strain markings are mechanical twins which grow into annealing twins during recrystallization. Later work by Burke and Barrett' has shown that strain markings are traces of planes upon which slip has occurred, and that there is no evidence for the formation of mechanical twins of microscopically resolvable width in face-centered-cubic metals. Mathewson3 has pointed out, however, that slip may produce twin faults, and later modifications of this hypothesis have assumed that twin faults rather than true mechanical twins serve as the nuclei for annealing twins. Carpenter and Tamura5 suggested, also in 1926, that annealing twins might form by accidents of growth. A close-packed layer of atoms can be added to the octahedral plane of a face-centered-cubic metal in two possible positions, the right position

Jan 1, 1951

By C. H. Li, R. J. Stokes, T. L. Johnson

The effect of alumina particles on the nucleation and growth of cracks through a silver- chloride matrzx has been investigated. It has been found possible to promote fibrous cracking in dispersion-strengthened silver, chloride under notch-impact conditions at temperatures at which silver chloride alone cleaves brittlely The modification) of fracture beIzavzor is thought to be due to the relaxation of hydrostatrc stress beneath a notch by the nucleation of cavities near alumina particles. In recent years, composite or dispersion-strengthened materials have been studied primarily to understand their high resistance to plastic flow particularly at elevated temperatures. Dislocation models have been developed with which it is possible to deduce with fair success the effects of interparticle distance, particle size, temperature, upon yielding and creep behavior.l-4 Much less attention has been paid to the fracture behavior of these materials (with the notable exception of common structural steels) and little is known experimentally about the manner in which inclusions affect the nucleation and growth of cracks through a matrix. Nevertheless a beginning has been made in connection with fibrous cracking in ductile matrices where inclusions appear to play an essential ro1e.5-7 During the severe localized plastic deformation which accompanies necking in a tensile test, cavities are believed to develop at inclusions; these cavities subsequently grow and coalesce by plastic flow until separation is complete. It is of interest to consider whether inclusions can affect fracture behavior under loading conditions which restrict the plasticity of the matrix itself (for example, cleavage under conditions of a high imposed strain rate at low temperatures). It is particularly interesting to study these effects in a solid which shows a spectrum of behavior ranging from fully ductile to semi-brittle behavior. Such a solid is silver chloride whose mechanical behavior depends sensitively upon temperature and strain rate.'," The present paper is concerned with a study of the influence of inclusions (in the form of alumina particles) on the fracture behavior of silver chloride loaded uniaxially at low strain rates at room temper- ature and also under notch impact conditions over a wide range of temperature. In particular, it will be shown that the alumina particles can exert a startling effect on the ductile-brittle transition temperature of notched silver chloride and that the magnitude and nature of the effect depends upon both the quantity of alumina and the shape of the alumina particles. 1. EXPERIMENTAL PROCEDURE 1.1 Materials Used. Silver chloride powder of analytical reagent (AR) quality having an average particle size 6 was supplied by the Mallinckrodt Chemical Works (st. Louis, MO.). Acid washed 900 mesh alumina powder, designated A38-900, was supplied by the Norton Co. (Cambridge, Mass.). This powder was added to silver chloride in two forms: a) the as-received condition in which the individual particles were of random irregular shape; their statistical average size was 7; b) in a condition in which each particle was spherically shaped by a fusion technique. In this case, the statistical average particle size determined with the optical microscope was approximately the same (about 5p) but electron micrographic evidence indicated that many ultra fine particles were present in the spheroidized powder. 1.2 Preparation of Composite Materials. Silver chloride-alumina composites containing 2.5, 5, and 15 pct by volume of alumina were produced by the extrusion of mechanically mixed powders blended in a ball mill for 24 hr at room temperature. The mixtures were compacted at 50,000 psi at room temperature in the form of billets 3/4 in. in diameter and 1 in. long which were then extruded with a 16:l reduction ratio at 370°C through a radius-type steel die having a 5 deg lead-in angle. An extrusion temperature of 370°C was selected to ensure that all composites had sufficient plasticity to be extruded. Apart from this general requirement, the choice was arbitrary. 1.3 Microstructure of Composites. Attempts were made to check the distribution of alumina metallo-graphically by polishing transverse and longitudinal sections of the extruded rod. Specimens were wet-ground to 600 emery paper and lapped successively with 5 and 0.25-p grades of diamond paste. They were etched for 10 sec in 10 pct sodium thiosulfate solution and lightly polished in concentrated ammonium hydroxide. The most effective way to render the alumina particles and grain boundaries visible was to radiate the surface with intense white light to decorate the grain boundaries and the particle-matrix interfaces photolytically.

Jan 1, 1962

By J. Gurland

The strength variation ofWC-Co alloys with composition and particle spacing falls into two ranges. 1) Above a critical value of the mean free path, the strength follows a dispersion hardening relation; it is proportional to the volume fraction of WC and in-versely proportional to the particle size. 2) Below a critical value of the mean free path, the strength variation is based upon the Griffith criterion of fracture and is controlled by the case of crack propagation. The maximum strength is attained when the structure and load just satisfy the critical conditions for spontaneous crack propagation. THE relation between the strength and the structure of cemented carbides is of interest not only for its own sake but also for its contribution to the understanding of composite materials in general. The cemented carbides are essentially aggregates of a brittle carbide constituent and a ductile binder phase and, at certain structures of intermediate composition, the composite alloys attain strengths far higher than those of the separate constituents in bulk. It is this variation of strength with structure which will be discussed. The experimental procedures of sample preparation, mechanical testing, and quantitative metallo-graphic analysis have been described in Ref. 1. The reported strengths are the maximum fiber-stresses in bending calculated on the basis of completely elastic behavior. The plastic contribution to the over-all deformation is small and was neglected in the calculations (the elongation at fracture of the most ductile alloy, 50 pct WC-50 pct Co, is less than 0.5 pct).2 The pertinent structural parameters are: f, the volume fraction of tungsten carbide; p, the mean free path through the binder phase; the contiguity C, defined as the average fraction of surface area shared by a particle of wc with all neighboring particles of the same phase; and d, the average equivalent spherical diameter of the WC particles. The strength variation of WC-Co alloys with composition and particle spacing is shown in Fig. 1 and Table I, which are based partly on previously published data' and partly on new experimental work which extends the range to higher values of the mean free path. Each data point represents the average of five samples. For a given composition, the transverse rupture strength reaches a maximum

Jan 1, 1963

By J. C. Fisher

Martensite transformations in steels and other alloys are characterized in part by the absence of composition changes during the growth of a new phase. Transformation occurs rapidly, and there is insufficient time for long range diffusion or partition of alloying elements to take place; martensite reactions in alloys thus are similar to phase transformations in single component systems. A fundamental understanding of martensite transformations in steels is impossible without knowledge of the free energy change upon transforming austenite (face centered cubic iron containing alloying elements) to ferrite (body centered cubic iron containing alloying elements) of the same chemical composition. The present paper assembles the best information available concerning the influence of temperature and composition on this free energy change. Most of the material has been taken from the work of Johansson,' Mehl and Wells,2 Zener3,4 and Smith;5 and indirectly, through these authors, from the work of Austin.6 In agreement with the generally accepted viewpoint, martensite is assumed to be an ordered solution of carbon in ferrite of the same composition as the parent austenite; only at high temperatures and low carbon concentrations is the carbon in ferrite distributed at random. The properties of the disordered solution are estimated by extrapolating the known properties of iron-carbon solid solutions into the range of supersaturation, and the free energy change associated with ordering is estimated from the theory developed by Zener. By incorporating Smith's recent thermodynamic measurements and Zener's theory of ordering, the present analysis modifies previous estimates of the free energy change associ- ated with martensite transformations. Consider a two component system consisting of a solvent A and a solute B. Let Na and Nb represent mol fractions of A and B respectively, let aa = raNa and ab = YbNb represent activities, and let superscripts 1 and 2 refer to phases 1 and 2. The partial molal free energies of A and B in phases 1 and 2 can be summarized as follows: free energy standard state Fa' - Fao1 = RT In an1 pure A' Fa2 - Fa2 = RT In aa2 pure A2 Fb1 - Fbo = RT In ab1 pure B Fs2 - FB2 = RT In aB2 pure B. The free energy of a gram atom of phase 1 is* AF1 = Na'Fa1 + Nb'Fb1 and that of phase 2 is AF2 = NA2FA2 + NB2Fb2. A martensite transformation from phase 1 to phase 2 requires Na1 = Na2 = Na and NB1 = NB2 = Nb, and the free energy change per gram atom accompanying transformation is AFi-2 = NA(Fa2 - Fa1) + Nb(Fb2 - Fb1) = NA[RT In (aA2/aA1) + AFa1?2] + Nb RT In (aB2/aB1) = Na[RT In (ra2/ra1) + AFa1?2] + Nb RT In (TaVTB1). [1] where yn2, yn1, yB2, yB1 are activity coefficients, and where Ma'+* is the free energy change upon transforming a gram atom of pure A from phase 1 to phase 2 at the temperature in question. For martensite transformations in plain carbon steels, A = iron (Fe), B = carbon (C), 1 = austenite (7). 2 = ferrite (a), and Eq 1 is AFr ?a= NFe[RT In (rf.a/rfer) + AFF.r?a] + TVc RT In (eca/rc1)- L2] Nothing is known concerning the values of yFea and yca for carbon concen- , trations in excess of 0.025 pct. However, the approximation rf.7 = 7f." = 1 cannot be appreciably in error for small carbon concentrations, and Eq 2 reduces to Afr-a = NfeFfer?a1 + NC RT In (rca/rcr)- [3] Johanssonl and Zenera have calculated MFfr?a from the specific heat measurements compiled by Austin.6* Their calculated values agree closely, and are summarized in Table 1. The activity coefficients relative to graphite for carbon dissolved in iron vary with temperature according to the relationships d In rcr/d(1/T) = AHcr-R dlnyca/d(l/T) = AHCa/R where AHc? and AHca are the heats of solution of graphite in y and a iron. Assuming the values of AH to be independent of carbon concentration and temperature, In rCr = AHcr/RT + I1 In rca = AHCa/RT + 12

Jan 1, 1950

By L. Kaufman

An equation is derived relating AF a", the difference in free energy between austenite and martensite, to temperature and composition in the iron-chrmnium and iron-chromium -nickel systems. This equation is used to calculate at M,for low-carbon stainless steels. A method for utilizing the energetic equations to calculate M, in stainless steels is suggested. In addition, an explanation is given for the anomalous effect of chromium in forming a y loop concurrent with the lowering of M, in iron-base alloys. It has been demonstrated that the effect of alloying elements on the Ms temperature is strongly dependent upon the influence of the alloying element on the thermodynamic properties of the y and a phases. Notwithstanding the fact that alloying elements affect the Ms temperature by changing the lattice parameters, elastic constants, and inter-facial energies of the a and y phases, their primary role is a thermodynamic one. Thermodynamic analyses have been presented for the iron-carbon'-4 and iron-nickele systems in which equations are derived for Fa and FY, the free energies of the b.c.c. (or b.c.t.) and f.c.c. phases. These equations, which can be obtained with the aid of the equilibrium diagrams, can be used to help predict the Ms vs composition curves. This paper deals with a calculation of the thermodynamic properties necessary to compute AFffLY for iron-chromium alloys. In view of the lack of direct information concerning the activity of chromium in the a and y phases of iron, the regular solution approximationa,g was utilized to bridge the gap. After the necessary equations were derived for the iron-chromium system they were used to calculate AFff— Y for stainless steels by combining them with the previous results obtained for iron-nickel alloys. The results of these calculations offer a means of rationalizing the anomalous behavior of chromium in iron-base alloys. The latter depends on the regular solution approximation in contrast to the explanation offered by zener , which is based upon the "magnetic specific heat effect." THERMODYNAMICS OF THE IRON-CHROMIUM SYSTEM If y represents the atomic fraction of chromium in an iron-chromium alloy, then the free energy of the b.c.c. phase Fa, the f.c.c. phase FY, and the difference in free energy between the f.c.c. and b.c.c. phases of the same composition are given through [3] and Fmy represent the free energies of mixing of the a and y phases; while @era -' and uFea 4Y represent the difference in free energy between f.c.c. and b.c.c. chromium and iron respectively. The values of AEFe0ff4Y in the temperature range between 0" and 900K ( .

Jan 1, 1960

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram for the gadolinium-cobalt system has been determined. Seven intermetallic compounds have been found at compositions corresponding to the follwing gadolinium-cobalt ratios: 3:1, 1:1, 2:3, 1:2, 1:3, 1:4, 1:5. The GdCor compound has a congruent melting point above 1600°C. whereas the remaining compounds melt incongruently. Eutectics exist at 16 wt pct Co and 84 wt pct Co, with melting points of 620° and 1260°C, respectively. PREVIOUS papers'" have recorded constitutional data for systems of gadolinium with iron and nickel. This paper presents data obtained on alloys of gadolinium with the remaining 3d transition element-cobalt. voge13 found that cerium forms, with cobalt, the intermetallic compounds; Ce3Co, CeCo, CeCo2, CeCo3, CeCo4, and CeCo5 Other workers4-' found the 1:2 compound in this series to exist in a C-15 (face-centered cubic) structure and the 1:5 compound to exist in a hexagonal crystal system. Comparison of earlier data with that now reported will be made subsequently. EXPERIMENTAL Methods of alloy preparation, annealing procedures, and experimental techniques have been previously reported.' The cobalt content of alloy specimens was determined volumetrically. RESULTS Microstructure—The alloy containing 10.5 wt pct Co corresponds closely to the composition of the first intermetallic compound Gd3CO. In Fig. 1 the microstructure is essentially single phase composed of Gd3Co which formed peritectically. The globular areas are remnants of the peritectic reaction which did not quite go to completion. A eutectic occurs between Gd3Co and the next higher compound GdCO, which is followed by a series of peritectic compounds. Fig. 2, an arc-cast alloy containing 20.2 wt pct Co, shows large primary crystals of GdCo etching either white or black (depending on crystallographic orientation), embedded in the eutectic. Similarly, in Fig. 3 at 31.2 wt pct Co, a compound, probably GdCo3, has separated from the melt. Subsequent peritectic reactions were almost completely by-passed as the alloy cooled, the residual liquid freezing as a fine eutectic. In the 47.5 wt pct Co alloy, Fig. 4, the high melting point compound, GdCO4, has solidified as massive, white-etching grains, which reacted with the liquid to form GdCo3 as the second phase. The microstructure of an arc-melted alloy containing 60.5 pct Co is complex, Fig. 5, and presents some difficulty in interpretation. The grey etching matrix is probably primary GdCO4. The dappled phase represents grains of GdCO5 which have separated from the melt on cooling. The discrete spots in this phase are eutectic liquid. Small light etching crystallites are probably GdCO5 formed by the incomplete high-temperature peritectic reaction. GdCO4 is retained in arc-melted specimens containing 70.5 wt pct Co, Fig. 6. White areas of this compound are held in a matrix of GdCO5 the appearance of which is mottled slightly by inclusions of the second eutectic in this system. The development of the spheroidized eutectic at high cobalt contents is depicted in Fig. 7 (80.3 wt pct Co) in which the white massive crystals are GdCO5 compound. Further development of this eutectic is seen in Fig. 8, the primary white phase here being pure cobalt. Thermal Studies—Differential thermal analyses and melting point determinations have yielded the data shown in Fig. 10. The high gadolinium eutectic, indicated by microscopy, was confirmed at about 16 wt pct Co, melting at 620°C . A eutectic also occurs at about 84 wt pct Co melting at about 1260°C. The thermal arrests at 8803 960°, 1060; and 1210°C,

Jan 1, 1962

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined in part for the sgstem Gd-Fe. Seven intermetallic compounds have been found at compositions corresponding to the following Gd-Fe ratios; 2:3, 1.2, 1:3, 2:7, 1:4, 1:5, and 2:17. The GdFe, com-pound has a congruent melting point above 18000C, whereas all of the remaining compounds melt incongruently, A eutectic exists at 13 wt pct Fe at a temperature of 860°C. ALTHOUGH an increasing amount of information is becoming available on the metallurgy of pure rare earth metals, relatively few studies have been made on alloy systems of the rare earths with the transition metals; iron, nickel, and cobalt. Even less data are extant on gadolinium alloys although it could be expected that such alloys might possess interesting structural and magnetic properties. In this paper, we report investigation of the gadolinium-iron alloy system. Studies on systems containing nickel and cobalt will be presented in subsequent papers. Previous data on gadolinium-iron compounds have been reported by Endter and Klemm1 and Jep-son and Duwez.2 Both reports agree on the existence of the GdFe2 phase, which crystallizes with the C-15type structure (face-centered cubic). This is in accord with results of the present work. EXPERIMENTAL The gadolinium metal used was prepared by met-allothermic reduction of high purity gadolinium fluoride. A typical analysis of the metal thus produced indicated the principal impurities to be oxygen, 0.24 pct, and tantalum, 0.2 pct. The iron metal used for alloying was a reagent grade material. Alloys were prepared by arc melting mixtures of the respective metals. Appropriate quantities of the two component metals were carefully weighed, blended and compacted. The compacts were then melted in an arc furnace consisting of a water-cooled copper hearth plate and a water-cooled tungsten-tipped counter electrode contained in a brass vacuum chamber. The furnace was evacuated to an absolute pressure of less than 1 with the leak rate established as being less than 20 per min. The furnace was then back-filled to a pressure of 25 mm of Hg, with a 75 pct He-25 pct Ar mixture. Arc melting at 25 v and 300 amp was maintained for about 30 to 60 sec until the entire visible area of the sample became molten, by which time surface tension had drawn the molten metal pool into a large bead. After allowing the furnace to cool, the alloy button was inverted and the melting process repeated. A series of melts was made covering entire composition ranges from 100 pct Gd to 100 pct Fe. All samples were examined metallographically in the as-melted condition. As the phase diagram became rationalized, and differential thermal analysis had given indications of temperature arrests, annealing was carried out in vacuo or in argon. Generally, compositions containing more than about 60 pct Gd were heat treated at 750°C and alloys containing less than this quantity of gadolinium were annealed at 1000°C. Prolonged annealing times were of the order of 100 to 200 hr. Metallographic examination was repeated on the annealed materials. Although little material loss was noted during alloy preparation, chemical analyses were made on all specimens prepared. The following standard, analytical techniques were used. Samples were dissolved in hydrochloric acid; insoluble material was filtered off, ignited and fused with potassium pyro-sulfate. The cold melt was leached with dilute acid and the solution thus obtained added to the main sample solution. Gadolinium was always determined gravimetri-callv as oxide from oxalate ignition. Iron was removed from an aliquot sample by electrolysis on a mercury cathode at approximately six volts. Gadolinium in the iron-free electrolyte was then precipitated as oxalate which was subsequently ignited to oxide. Iron was determined volumetrically in an aliquot solution by reduction with stannous chloride fol-

Jan 1, 1962

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined for the system gadolinium-nickel. Nine intermetallic compounds have been found at compositions corresponding to the following gadolinium-nickel ratios: 3:1, 3:2, 1:1, 1:2, 1:3, 2:7, 1:4, 1:5, 2:17. The GdNi and GdNi5 compounds have congruent melting points of 1300' and 1500°C, respectively while the remaining compounds melt in-congruently. Eutectics exist at 15 wt pct Ni, 31 1/2 wt pct Ni and 87 wt pct Ni with melting points of 6703 8803 and 1220°C, respectively. IN a continuing investigation of the properties of rare earth alloys, a study has been made of the gadolinium-nickel system. Previous work encompassed the iron containing alloys and a subsequent paper will deal with the constitution of the gadolinium-cobalt system. Vogel,1 examined alloys of nickel with lanthanum and cerium. R3Ni, RNi, RNi2, RNi3, RNi4, and RNi5 compounds were found. Endter and Klemm,2 Fulling et al.3 Heumann,4 and Nowotny5 found the 1:2 compositions of this series to exist in a C-15 (face-centered cubic) structure, and the 1:5 compositions in a hexagonal system. Jepson and Duwez6 more recently examined these 1:2 and 1:5 compositions and generally confirmed earlier data while Wernick and Geller7 most recently have given additional data on the GdNi5 compound. Comparisons with our results will be made in the appropriate section of this report. EXPERIMENTAL Methods of alloy preparation, annealing procedures, and experimental techniques have been given in our earlier paper.8 Chemical analyses of the alloy samples were made by dissolving the specimen in nitric acid, precipitating the gadolinium as hydroxide and the nickel with dimethylglyoxime. Both precipitates were ignited to oxide and weighed. RESULTS Microstructure— Metallography of alloy specimens in this series has been conducted on both arc-melted and annealed materials. Etchants used have been 5 pct nital with approximately 10 pct distilled water added, for high gadolinium samples; Carapella's ferric chloride solution for intermediate compositions; and Marble's (copper sulfate) reagent for high nickel content alloys. Because of difficulties encountered in the grinding and polishing of specimens containing 40 to 75 wt pct Ni, no photomicrographs were made of such specimens. The microstructure of an arc-melted 5.3 wt pct Ni alloy is shown in Fig. 1. Light etching primary grains of gadolinium are embedded in an eutectic matrix. The microstructure of an alloy of 9.55 wt pct Ni alloy, Fig. 2, annealed 50 hr at 700°C, consists almost entirely of the intermetallic compound Gd3Ni. The structure of an arc metal alloy of approximately 19 pct Ni, Fig. 3, consists of grains of the compound GdNi embedded in the Gd3Ni2-Gd3Ni eutectic. The arc-cast structure of the 38.7 wt pct Ni alloy is shown in Fig. 4. Large primary grains of a compound rest in a matrix structure of coarse GdNi-GdNiz eutectic. Because of the occurrence of several peritectic compounds in the central region of the diagram, identification of the primary structure in this alloy is not certain. As has been indicated above, microstructures of alloy specimens containing between ca 40 and 75 wt pct Ni have not been photographed. These specimens were highly brittle, and macro- and micro-cracking were impossible to control in the grinding and polishing procedures. Prolonged annealing did not alleviate this condition. Visual observations in small specimens did, however, provide evidence for a multiplicity of phases and peritectic dissociations of compounds although rationalization of structures was not possible.

Jan 1, 1962

By A. A. Bauer

The ?-to-? transformation has been studied in zirconium alloys containing 22 to 70 wt pct U. In this range of compositions the ? phase can be retained by quenching. Transformation to ? occurs by a nucleation-and-growth process. The diffusion of atoms to preferred lattice sites to yield a partially ordered structure apparently controls the rate of reaction. Alpha uranium and a zirconium precipitate from the supersaturated E phase initially formed in alloys outside the equilibrium E phase composition limits. ZIRCONIUM-Uranium alloys have long been of interest for reactor-fuel applications because of the low thermal-neutron cross section of zirconium. Considerable information is available on the various properties and behavior of these alloys1 although there had been a number of areas where information was incomplete. As part of a program to provide more detailed knowledge in these areas, the presently reported investigation was undertaken. The constitutional diagram of the zirconium-uranium system is shown in Fig. 1.' The system is distinguished by a region of complete solid solubility between the body-centered cubic ß-zirconium and ? uranium phases and the existence of an intermediate phase in the vicinity of 50 wt pct U. This intermediate phase, designated as E, is reported3 to have a primitive hexagonal structure with a = 5.03 and c = 3.08A. The structure is partially ordered with zirconium atoms at the 0, 0, 0 position and zirconium and uranium atoms located randomly at the 1/3, 2/3, 1/2, and 2/3, 1/3, 1/2 positions. While the E phase may be nominally designated as of UZr2 stoichio-metry, the random distribution of uranium and zirconium atoms permit a considerable range in composition. Of interest in the research performed were alloys in the range from 20 wt pct (10 at. pct) to 70 wt pct (47 at. pct) U. In this range of compositions the body-centered-cubic ? phase can be retained either completely or partially on quenching. The nature and kinetics of transformation of the ? phase were the subject of study. Proceeding concurrently with the presently reported work was an investigation by Kearns4 which has since been reported. Kearns studied alloys containing 50 to 60 wt pct U prepared from sponge zirconium. While the work reported here is for alloys prepared from crystal-bar zirconium and the techniques of study are to some extent dissimilar to those employed by Kearns, general agreement so far as results and interpretation can be reported. Experimental Techniques—Alloys were prepared and the transformation of the ? phase studied during interrupted-quench and quench-and-temper isothermal heat treatments by means of hardness measurements and X-ray diffraction and metallographic techniques. The isothermal transformation of the ? phase on quenching and tempering was investigated further employing dynamic-modulus measurements. Electrical resistivity and limited Hall coefficient measurements were also obtained as part of the study. Alloy Preparation and Heat Treatment— Alloys containing 15, 20, 22, 30, 40, 45, 50, 55, 60, and 70 wt pct U were prepared from as-reduced uranium and crystal-bar zirconium. The alloys were double arc melted by consumable-electrode are-melting techniques. The final ingots were forged and rolled at temperatures between 790" and 840oC to 1/4-in. rod and 1/8-in. sheet. Chemical analyses of the fabricated alloys were

Jan 1, 1961

By W. A. Tiller, J. P. McHugh

THE phase diagram of the Ge-Te system was first investigated by Klemm and Frischmuth.' They arrived at the phase diagram shown in Fig. 1 indicating the presence of a peritectic phase boundary at the 50 at. pct Ge composition. Later, Schubert and Fricke2 obtained data which suggested to them the possible existence of a eutectic at about 55 at. pct Ge. In order to resolve these differences, we have carefully studied this system in the region 40 to 60 at. pct Ge using both the conventional thermal analysis technique and a new solidification technique.3y4 The alloys were prepared from semiconductor grade germanium and 99.999+ Te by reacting the elements in evacuated, graphite coated, vycor tubes. The samples were placed in a thermal analysis apparatus described elsewhere4 and cooling curves were taken of each alloy to determine the liquidus surface. The cooling curve for a 50 at. pct alloy shows two distinct arrests about 1°C apart which

Jan 1, 1961

By S. Weinig, J. Winter

The grain boundary adsorption of solutes as a function of bulk concentration and solution temperature was studied using internal-frictimz techniques. From the variation of the cor-responding energy of activation for the Phenomenon, the inter-actior2 energy between a solute atom and a high-angle boundary was calculated. Interaction energies in the range of 0.3 ev were obtained, and were used to obtain the actual concentration of solute at the grain boundary. In corroboralory creel, studies the direct grain boundary contribution to the total creep strain was measured. It was found that the interface creep varied with the type and magnitude of the solute adsorbed. Subscribing to the theory of their being energetically favorable sites at the grain boundary for solutes of both Positive and negative size deviations, ternaries were investigated in Which solutes of both types were present. A marked increase in the resistance to grain boundary creep was manifested. THE major difficulty which has been encountered in investigations of the grain boundary segregation of solutes has been the lack of a sufficiently sensitive method of measuring the amount of adsorbed solute at the boundary. For the general case of a high-angle boundary, no direct method of measuring the adsorption at the boundary has been found to date. Internal friction has been used in several studies of grain boundary adsorption1-3 and although it is somewhat indirect, it was demonstrated to have the necessary sensitivity. In this investigation the authors have used internal-friction techniques in conjunction with a study of the grain boundary contribution to the total creep strain. As both parts of the investigation were performed on the same specimens it was possible to combine a highly sensitive technique with a somewhat more direct method in order to obtain information about the adsorption phenomenon. From internal-friction studies the rate of increase of the activation energy was observed to be a function of the difference in size between the solute and solvent atoms. It was proposed that if Gibbs' adsorption isotherm is considered, i.e., where r is the excess solute at the boundary, c is the bulk concentration, and ay/ac is the change in grain boundary energy with bulk concentration, then AH b/ac must vary in the same way as ay/ac and therefore In this way a relative measure of the grain boundary adsorption of solutes is directly obtainable from in-ternal-friction studies. If the previous work in the field of grain boundary adsorption of solutes is examined, certain apparent information is desirable if the phenomenon is to be understood. The most important questions that must be asked are as follows: 1) Is the adsorption of solutes at the grain boundary an equilibrium process? 2) Can the Mott model of the grain boundary be used as a basis of setting up an elastic interaction between the grain boundary and solute atoms? 3) Is it possible to obtain an exact measure of the excess solute at the grain boundary as a function of temperature and bulk concentration rather than merely a relative measure of the adsorption 4) Are the conclusions obtained from an indirect method such as internal-friction studies meaningful in considering gross grain boundary effects such as creep? EXPERIMENTAL PROCEDURE The material used in this investigation was Bureau of Mines "superpurity" titanium (79 Bhn—1500 kg

Jan 1, 1960

By C. J. Osborn

The temperature dependence of the free energies of formation of metallurgically important oxides, sulphides, chlorides, carbonates and sulphates is presented graphically, whereby the task of deriving practical metallurgical information is greatly simplified. The diagrams have been revised according to the latest available thermodynamic data. WHILE it is true that much careful investiga-tional work remains to be done, there are already available in the literature sufficient thermo-dynamic data to enable the metallurgist to predict with reasonable confidence the equilibrium conditions to be expected in most important, and potentially important, metallurgical reactions. In this connection, the careful, critical compilations of K. K. Kelley and his collaborators in numerous U. S. Bureau of Mines Bulletins are particularly valuable. However, the translation of reliable thermo-dynamic data into metallurgical language unfortunately involves lengthy manipulations of the cumbersome formulas which can be set up from heat of formation, entropy, and heat capacity data. Many years ago, Kelley20 predicted that thermo-dynamic calculations would be made in the future "with the aid of free energy, heat content, and entropy tables, rather than by means of the algebraic methods employed at present", and where such tables are available they greatly simplify the task of deriving practical metallurgical information. However, in addition to these tables, there are also available one or two reliable graphical presentations, particularly of free energy data, which may be used in the same way as the tables, but which have the added advantages that interpolation is never necessary, and that the behavior of different metals or compounds may be compared at a glance. Some years ago Professor Robert Lepsoe, Head of the Department of Metallurgy at Norways Institute of Technology (N.T.H.), began a compilation of curves showing the temperature dependence of the heat contents of the elements, and the heat contents and heats and free energies of formation of the common metallurgical compounds. With such a compilation, the thermal and free energy requirements of a reaction may be read from curves in a matter of seconds; and this statement applies not only to the formation of compounds from their elements, and to the reverse dissociation, but to any reaction involving substances whose thermodynamic properties are available. This follows from the fact that heats and free energies of formation are completely additive. For example, the free energy change associated with the chlorination of a metallic oxide at any temperature, T, is given by the free energy of formation of the chloride at temperature T minus that of the oxide also at T; both of these quantities may be read directly from curves of the type suggested above. Since this early, unpublished work of Lepsoe, both Ellingham7 and Richardson and Jeffes46 have

Jan 1, 1951