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By K. P. Gupta

The Cb-rich boundary of the (Cb,Al) a phase field at 1250OC is near 41 pct Al. The Al atoms tend to occupy the C. N. 12 sites in this structure. A homologous (Ta,Al)a phase was identified. No a phase was found in the Mo-Al system at 1200°C. The first binary o-phase with a non-transition element as a major component was found1,2 in the Cb-Al system. The composition of this phase was reported2 as approximately 34 at. pct Al, based on X-ray diffraction patterns taken of alloys in the as-cast condition. Further study of the composition of this o-phase, therefore, appeared desirable. Since Si was previously found3,4 to occupy preferentially the lowest C.N. sites (I and IV) in the a phase, and preliminary resultsa indicated that Al may show similar ordering, one of the aims of the present work was to obtain more complete information on ordering in (Cb, Al) o. Among the binary systems of Al with Ti-, V-, and Cr-group elements, the Ti-Al, Zr-Al, V-Al, and Cr-Al systems are known to comprise no o-phase. In the present work a Ta-Al and a Mo-Al alloy were studied in an effort to find additional o phases with Al as a major component. EXPERIMENTAL PROCEDURES AND RESULTS An alloy with the intended composition of Ta + 40 at. pct Al was prepared by arc melting in He atmosphere. In both the as-cast condition and after annealing for 10 days at 1250°C and quenching in cold water this alloy consisted of two phases, as seen in the X-ray pattern and the microstructure. One of these phases was identified as the o-phase; the observed and calculated d-spacings are shown in Table I. The lattice parameters of this o-phase are a = 9.972 A, c = 5.214 A and c/a =0.5228, as determined from a Debye-Scherrer pattern using Fe K a radiation. The d-spacings for the unknown second phase are given in Table 11. The alloy contained approximately 25 pct of the unknown phase after annealing, as estimated on the basis of microscopic examination. A Mo-Al alloy was prepared by arc melting, with an intended Al-content of 35 at. pct. The alloy button was annealed for 7 days at 1200°C and water quenched. The X-ray pattern of the alloy in both the as-cast and the annealed state showed the reflections of Mo3Al (Cr30 type structure) and an unknown phase different from a. Six Cb-Al alloys were prepared in the composition range 30 to 50 pct Al. All alloys were arc melted in He atmosphere. After annealing for three days at 1175oC in evacuated silica capsules and quenching in water, the alloys with 30 to 40 pct Al contained three phases, namely the o-phase, Cb3Al (Cr3O-type structure) and an unknown phase. The alloys with more than 40 pct Al contained two phases, namely, what appeared metallographically, the o-phase and the same unknown phase. In the alloys containing less that 38 pct Al, the unknown phase was not present after annealing for 4 days at 1250°c,

Jan 1, 1962

By Joseph B. Darby, Paul A. Beck

IN isothermal sections of several ternary systems, the a-phase was found1 to extend in the form of a relatively narrow elongated field, connecting the U-phases that are present in the adjoining binary systems. This was interpreted in accordance with the conception that the U-phase is an electron compound and the ternary U-phase fields were shown in several systems' to extend approximately in the direction of constant average d-shell electron vacancy number per atom. ' However, in the various isothermal sections of the Fe-Cr-Mo system" the ternary a-phase field was

Jan 1, 1958

By T. L. Chu, G. A. Gruber

Silica films hare been rleposited 011 silicon substmtes at 400° to 600°C by a chemical-transport technique using hydrogen fluoride as the transport agent ill a closed system. This transport takes place from a source materia1 1071: temperature to substrates at higher temperatures, as indicated by the thermochemistry of the transport reaction. The experimental variables of- the transport process, such as the substrate temperature, the pressure pi the transport agent, and so forth, have been studied. The rate -determining step of the transport process appears to he the ),ale of chemical reaction in the source region. The transported films are similar to thermally grown silica films in physical proper-ties with the exception of 'some what higher dissolrrtion rates. SILICA films deposited on suitable substrates serve many purposes in electronic devices. They are used for the fabrication of tunneling devices, the surface passivation of devices, and the shielding of devices from nuclear radiation: and as selective masks against the diffusion of specific impurities into semiconductors. Doped silica films can also be used as sources for the diffusion of impurities into semiconductors. Several oxidation and deposition techniques for the preparation of silica films have been developed to meet the requirements of these applications. The therma1 oxidation of silicon by oxygen or steam at temperatures above 900 C is commonly used in silicon technology. The deposition techniques are perhaps more advantageous since they usually require lower temperatures and are not limited to silicon substrates. Silica films have been deposited on silicon and other substrates by reactive sputtering and chemical reactions. The sputtering of silicon in an oxygen atmosphere is capable of depositing good-quality silica films on silicon' and gallium arenide. Many chemical reactions are known to yield silica at room temperature or higher. These reactions may involve intermediate steps. However, the final step yielding silica should take place predominately on the substrate surface in order to produce adherent films. When silica is formed in the gas phase by volume reactions, no adherent deposit can be obtained. Generally, the experimental conditions of a reaction can be varied so that the surface reaction predominates over the volume reaction. The chemical reactions which have been used successfully for the deposition of silica films are briefly as follows. The pyrolysis of alkoxysilanes in an inert atmosphere or under reduced pressure has been employed to deposit silica films on germanium3 and silicon4 at 650" to 750°C in a flow system. The deposition of silica films from alkoxysilanes has also been achieved at nearly room temperature by a low-pressure plasma. Device quality silica films have been deposited on germanium and gallium arsenide by the deposition of an amorphous thin silicon film followed by oxidation at 600" to 700" . Silica films for high-temperature capacitors have been produced by the hydrolysis of silicon tetrabromide at 950°C in argon and hydrogen atmospheres.7 We have developed a chemical-transport technique for the deposition of silica films on semiconductor substrates at relatively low temperatures. The thermochemistry of the transport reaction, the experimental variables of the transport process, and the properties of the transported silica films are described in this paper. THERMOCHEMICAL CONSDERATIONS The transport of solid substances by chemical reactions in the presence of a temperature gradient has been used for the preparation of films and crystals of many electronic materials. In this technique, a gaseous reagent is chosen so that it reacts reversibly with the solid substance under consideration to form volatile products. Since the equilibrium constants of most reactions are temperature-dependent, the transport of these products to regions of suitable temperature in the reaction system would cause the reverse reaction to take place. depositing the original solid. When the equilibrium is shifted toward the formation of the solid as the temperature is decreased, the solid is transported from a high-temperature zone to a lower-temperature region, and vice versa. This chemical-transport technique can be carried out in a closed or gas-flow system. In a closed system, chemical equilibrium is presumably established in the different temperature regions of the system, and the transport agent regenerated in the deposition region repeats the transport process in a cyclic manner. The local chemical equilibrium may not be approached in a flow system: however, this system offers a greater degree of flexibility. Silica reacts reversibly with hydrogen fluoride and this reaction was chosen for the transport process. The over-all reaction between silica and hydrogen fluoride may be written as: SiO2(s) + 4HF(g-) = SiF4Ur) + 2H2O(^)

Jan 1, 1965

By W. C. Hagel, J. H. Westbrook

THERE has been a recent revival of interest in the intermetallic compound AgMg as an experimental material for study of the physical and chemical properties of simple ordered structures. Studies of mechanical behaviors,1-4 diffusion,5,6 and thermo-dynamic properties7'8 have been reported. In several of these studies, heat treatments have been carried out in argon-filled silica capsules at temperatures as high as 750°C with no apparent adverse effects. The present authors were, therefore, startled to discover in the course of some yet unpublished work, that gross melting of near-stoichio-metric AgMg compositions occurred in such samples more than 100 deg below their melting point of about 800°C. This note is to report a brief series of experiments carried out to establish the reason for this behavior. Gross errors in sample composition and failure of furnace temperature controls were quickly eliminated as causes of melting. The first tangible lead came from chemical analysis of an AgMg sample which had melted during treatment at 750°C. A silicon content of 3.3 wt pct was found. Since satisfactory analyses had been obtained on the original as-cast ingot, contamination by diffusion and/or reaction with the fused silica capsule seemed a distinct possibility. A perplexing fact, however, was the apparently capricious incidence of the effect. Not only was it previously unknown, even in the experience of the present authors; but, in the early part of the present study, melting sometimes occurred and sometimes not with specimens treated under constant conditions. Indeed, one sample successfully survived a 750°C heat treatment and yet melted completely during the course of a subsequent anneal in an identical capsule at a lower temperature. To obtain evidence that silicon contamination could lower the melting point to the extent observed, the following experiment was performed. A series of ternary alloys was made up with a stoichiometric AgMg base and containing 0.1, 0.2, 0.4, 1, 2, and 4 wt pct Si. Melting was done in MgO crucibles under a cover of argon gas. After holding 10 to 20 min in the temperature range 850° to 900°C, the alloys were allowed to solidify in the crucible and the temperature during cooling automatically recorded with a Pt/Pt-10 Rh thermocouple. Results from the cooling curves are shown in Fig. 1. Checks within 2 to 5C° were obtained upon repeated melting, cooling, and freezing. The whole series of cooling curves as well as metallographic examination of the melted alloys established that the AgMg rich portion of the AgMg-Si quasibinary is an eutectic-type system. The melting point of AgMg is lowered from approximately 820°C in the pure stoichiometric binary9 to about 710°C in the saturated intermetallic phase. Since second phase was observed in all samples on cooling to room temperature, the solid solubility of AgMg for silicon evidently falls rapidly with decreasing temperature as indicated schematically by the dashed solvus in Fig. 1. It is thus established that a silicon content

Jan 1, 1963

By W. C. Hagel, J. H. Westbrook

Usittg a sectioning technique with Agl10 as the tracer, the diffusion of silver in silver-excess (45.8 at. pct Mg), near-stoichiometric (49.8 at. pct Mg), and magnesium-excess (52.0 at. pct Mg) cylinders of CsCl-type AgMg was determined from 500" to 700°C. Diffusion coefficients conform to the expression D = Do exp (-q/RT) where the respective Do values are 1.53, 0.280, and 0.134 sq cm sec-I and the Q values are 41.3, 40.6, and 38.0 kcal g-atom-'. Lnttice-parameter and density measurements were performed on a more numerous assortment and wider range of compositions. Substitutional defects were found on both sides of stoichiometry. Activation energies for other rate processes in these alloys show related trends with changing composition, although silver may not be the rate-detemining species. KNOWLEDGE of diffusion coefficients is necessary for a quantitative understanding of the many rate processes (e.g., grain growth, precipitation, sintering, oxidation, or mechanical deformation) occurring in solids. Although these data are available for most metals and common alloys, they are quite limited for intermetallic compounds—a group of materials whose unique physical and mechanical properties are presently attracting great interest. From a fundamental viewpoint, diffusion in intermetallic compounds also offers several engaging aspects owing to: their ordering, the possibility of introducing large, stable concentrations of lattice defects, and the variety of bonding types and crystal structures which can be found. In the case of CsC1-type compounds, some previous work has been directed at examining the role of vacancy defects by changing their concentration compositionally. The diffusion of Co60 was measured in 0 NiAl1- and in P COA., Except for the results of Smoluchowski and Burgess, isothermal diffusion coefficients were found to pass through a minimum at the stoichiometric composi- they decreased sharply on what was reported by Bradley and co-wrkers' to be the vacancy-rich (aluminum excess) side of stoichiometry. This investigation of the diffusion of Agl110 in AgMg was undertaken both as an adjunct to a concurrent study of its deformation behavior and for the purpose of obtaining information on the influence of lattice defects and temperature on diffusion in another CsC1-type intermetallic compound. Bcc AgMg remains ordered up to and melts congruently at 820°C. Solubility limits at 300°C are about 41 at. pct Mg and 53 at. pct Mg. It is one of the Hume-Rothery electron compounds with a 3/2 electron-atom ratio. Previous investigations of its properties include hardress,' tenile,'-' electrical reistivity, and thermodyna-mic1',14 studies. Indications of a high bonding strength may be found in the large heat of mixing1' and in the 6-pct vol contraction on compound formaticp, as calculated using atomic radii of l.40 and l.55a for Ag and Mg. EXPERIMENTAL PROCEDURE Alloys were prepared by the induction melting of selected fine silver (99.95) and low-iron magnesium (99.95) in magnesia crucibles under 1 atm of A. Supplied by the Handy and Harmon and Dow Chemical Cos., respectivelv. Melts were poured under argon into graphite molds providing 1 1/8-in.-diarn. by 4-in.-long ingots. These were homogenized in evacuated and argon-filled fused-silica capsules by heating for 16 hr at 750'. Three 1 in.-diam. by 3/4-in.-long cylinders were machined from the mid-portion of each ingot for diffusion measurements. Three alloys, analyzing 45.8, 49.8, and 52.0 at. pct Mg were taken as representing the extremes of interest, with 49.8 at. pct Mg being very close to the stoichiometric composition of 50.0 at. pct Mg.

Jan 1, 1962

By G. R. Speich, D. J. Mack

The transformation of was studied by isothermal methods. At all temperatures, the ß transforms quickly to fine grained ß" which develops silver-rich striations. At higher temperatures the striations disappear, the final structure being Widmanstatten a in ß'. At lower temperatures, the striated ß" is consumed by pearlite nodules of a + ß' which in turn form the Widmanstatten a in ß'. The transformation is unlike any previously reported for a eutectoid. AS part of a general program of study on the eutectoid reaction, the Ag-Cd eutectoid seemed particularly attractive because the ß phase which undergoes the reaction is another of the typical "electron compounds," AgCd, having the disordered body-centered cubic structure. This work deals with the eutectoid which occurs at 50.5 wt pct Ag, and not with the eutectoid which has been reported at 42.9 pct Ag.' There has been no work reported specifically on the Ag-Cd eutectoid which was studied. The only information available on this eutectoid is that work done in the determination of the phase diagram. For the most part, the terminal portions of the diagram, Fig. 1, are well established; however, the region from 40 to 60 pct Cd is still somewhat in doubt. The X-ray evidence'..' in this region is in conflict with the results of thermal analysis. X-ray analysis3 does not show a polymorphic transformation at about 240°C as indicated by thermal analysis.1,5 Even the X-ray evidence, within itself, is confusing in this region of the diagram. One investigator2 reports the ß phase as hexagonal close-packed and has found three phases in the one-phase ß field. Other X-ray investigators"' ' report the ß phase as body-centered cubic. The authors believe that much of the confusion resulted from incomplete homogenization of the alloys. It was found that it takes almost a week to produce a completely homogeneous two-phase structure at 370°C. Another possible source of error is the volatilization of cadmium from the surface and cracks of the specimen during annealing with the possible formation of a cadmium-poor phase. The only metallographic data available on this eutectoid alloy are those of Durrant1 and Fraenkel and Wolff.5 his information is very limited. The phase diagram chosen as most nearly correct is that in the Metals Handbook," which is almost identical with the phase diagram suggested by Durrant.1 Materials and Procedure The alloy was prepared from high purity silver (999.5 plus fine) and high purity cadmium (0.02 Pb, 0.005 Cu, trace Fe). The metals were melted in carbon under a nitrogen atmosphere. Some cadmium was lost by volatilization but by remelting several times and adding cadmium a 200 g ingot of approximately eutectoid composition was obtained. Because the CdO fumes are quite toxic, the exit gas from the furnace was led through a water trap to condense the CdO. The ingot was homogenized at 650°C for 24 hr, no attempt was made to prevent decadmiumization. This resulted in a narrow decadmiumized rim on the ingot which was removed. Filings for analysis were obtained from cross sections of the ingot. Silver was determined by the Volhard thiocyanate method,? cadmium by difference. The ingot analyzed 50.8 pct Ag at the top of the ingot and 50.7 pct at the middle and at the bottom of the ingot. This alloy was only slightly hypo-eutectoid compared to the accepted value of 50.5 pct Ag and was used for the isothermal studies. It was felt that further attempts to adjust the composition might be futile because of the volatility of the cadmium. The ingot was sectioned to specimens approximately 3/4 x 3/4 x 1/8 in. These specimens were "austeni-tized" for 3 hr in air at 650°C to yield homogeneous ß and then quenched into a salt bath held at constant subeutectoid temperatures where the transformation

Jan 1, 1954

By R. S. Wagner, W. G. Pfann

METHODS that have been used to measure stress relaxation in metals and plastics have been reviewed recently by G. R. Gohn and A. FOX.' The ideal stress relaxation test comprises placing a sample under a constant strain (usually considered

Jan 1, 1962

By C. G. Dunn, P. K. Koh

TWO recent review papers have considered the origin of primary and secondary recrystalliza-tion textures from the point of view of oriented nucleation and oriented growth theories."' Both theories require nuclei for primary recrystallization but provide no unequivocal answer to the question of what nuclei are. The answer to the same question regarding secondary recrystallization, however, often is that nuclei are certain primary recrystallization grains or primaries. The two theories differ, however, in specifying what the certain primaries are. In support of the oriented growth theory Beck and Hua originally stated "It may be assumed that in a re-crystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as nuclei for the coarse grains, provided that conditions are favorable for their growth." In commenting on this statement one would say that there are two restricting conditions: namely, that 1) the certain primaries (nuclei) are large enough to grow, and 2) their boundaries have high mobility. More recently Beck2 has con-

Jan 1, 1958

By J. D. Lubahn

The influence of precipitation from solid solution on the subsequent deformation resistance of alloys is well known. However, the influence of precipitation or aging that occurs simultaneously with deformation may be entirely different and of considerable importance. It is thought1 that the presence or absence of a yield point jog in impure iron at room temperature and the presence or absence of discontinuous flow at higher temperatures may be directly related to aging phenomena, particularly since the yield point jog is absent when the carbon and nitrogen are sufficiently removed.2 As a preliminary attack on the problem of simultaneous aging and deformation, three kinds of tests—constant strain rate tensile tests, constant load creep tests, and variable strain rate tensile tests—were carried out on an age hardenahle aluminum alloy. Constant Strain Rate Tensile Tests Stress-strain curves at a strain rale of about 0.001 min-1 were obtained for specimens of 61S that had been quenched into liquid nitrogen after a one-hour solution treatment at 521°C, then aged at room temperature 10 min., 20 min., 4 hr, and 26.5 hr before testing. Strain-time curves were obtained on the same chart with the stress-strain curve by means of an auxiliary pen, driven parallel to the axis of the chart drum at constant speed by a synchronous motor and gear chain. The angle of rotation of the chart drum was proportional to strain. The strain rates reported are the measured slopes of the strain time curves. Constant strain rate was approximated (within a factor of 2) by manual adjustment of the oil inlet valve of the hydraulic testing machine in such a way that the course of the recorder pen was parallel to pre-drawn strain-time lines of the desired slope. The specimens were machined from 9/16 in. rod. The cylindrical portion was 0.357 in. in diam by 13/4 in. long and

Jan 1, 1950

By F. W. Glaser, W. Ivanick

A pressure-sintering method was used to produce binder-free and very dense TiC specimens. Some physical properties of these TIC bodies were determined and found to compare favorably with those of certain cemented Tic grades. It was also observed that the hot transverse rupture strength of TiC bodies remained substantially the same regardless of the amount or type of binder material used. STUDIES of the structure and physical properties of refractory materials have been intensified recently because of the urgent need for nonstrategic materials that retain their strength at high temperatures. Research aimed at determining and improving the physical properties of cemented carbides and borides has been accelerated with a view toward possible use of such materials in connection with turbine blades, rocket nozzles, and other high temperature applications. On the hypothesis that the strength requirements in connection with some of the above applications could be met only by proper choice of cementing agents for such refractory materials, the literature describing the physical properties of borides or carbides was reviewed. However, with a few exceptions,'-" references were found only to compositions containing at least one or more auxiliary binder metals. Cobalt and nickel are among the most frequently employed cementing agents. The melting point of Tic (approximately 3250°C) and therefore the sintering temperature, at which notable densification of a cold pressed Tic powder compact could be expected in the absence of a liquid binder phase, is relatively high. The present study makes use of a high temperature, pressure-sintering procedure, recently described by one of the authors in connection with the sintering of binder-free ZrB,," to produce dense bodies of sintered Tic—free of any cementing agent. During the course of this sintering study, some physical properties of dense Tic bodies produced by this method will be discussed. Materials, Preparation of Samples, Testing Methods The procedure for the forming of Tic powder consisted of mixing graphite and TiH, powders in stoi-chiometric proportions, and heating this mixture in a H, atmosphere and carbon crucible by high frequency, to temperatures ranging between 1900° and 2100°C (3452" and 3812°F). The powdered carbide was then comminuted and screened to the desired particle size. Table I shows the chemical analysis of the two grades that were employed for the production of samples during this work. Bodies of Tic, approximately 2.5xlx0.5 cm were produced in graphite molds that were heated by direct conduction. Sintering was carried out at temperatures for time intervals ranging from approximately 0 to 30 sec under a constant pressure of about 1.3 tons per sq in. An alternate method for the production of samples consisted in cold pressing the individual Tic grades at pressures ranging from 4 to 10 tons per sq in. and sintering in a hydrogen atmosphere in graphite crucibles heated by high frequency induction. Sintering temperatures ranged from 2600° to 2900°C (4715° to 5255°F). Electrical testing was done by measuring potentiometrically the voltage drop over a length of 1.5 cm for a current of 10 amp at room temperature. Cross-sectional areas as well as densi-

Jan 1, 1953

By J. H. Brophy

Experimental evidence in recent years shows that nickel coated hydrogen reduced tungsten powder can be sintered to 98 pct of theoretical density at 1100°C. New data indicate that the sintering rate is the same for nickel contents ranging from 0.125 wt pct (mon-atomic layer) to 5.0 wt pct Ni coated on 0.561. tungsten powder. Nickel tungsten made by coreduction from oxides sinters in a kinetically similar way, but the rate tends to increase with higher nickel contents. The activation of sintering can be accomplished with a minimum amount of nickel if coated powder is used. Transverse rmpture strength was found to increase in specimens containing 0.25 pct Ni as density increased during the initial stage of the carrier-phase sintering process. Upon the onset of grain growth in the final stage, strength was found to decrease. With increasing nickel contents up to 4 pct, strength increased. Maximum strengths in three-point loading were observed at 73,000 psi for 0.25 pct Ni and 93,000 psi for 5 pct Ni. These were comparable to that of massive tungsten recrystal-lized in the presence of nickel and tested in the same way. The results were sensitive to the mode of powder treatment and ductility was negligible in all cases. The study and application of sintered bodies of nickel and tungsten is not new; however, the analysis of the mechanism by which small additions of nickel increase the sintering rate of tungsten promises to Contribute new information regarding sintering theory in general. Initial experimental evidence was presented by the authors showing that nickel-coated hydrogen-reduced tungsten powder may be sintered to 98 pct of theoretical density at 1100°C in 16 hr.' 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-precipitationo step postulated when the carrier phase is liquid3 although in the nickel tungsten case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in mi-crostructures at the temperatures under consideration. In the present work, new data for nickel-coated tungsten powder are offered in support of the proposed mechanism, and a more explicit study of the second stage of densification is presented. Concurrently, the sintering kinetics of these coated powders are compared to Ni-W powder made by coreduction of oxides. In this way the present work can be compared to earlier results in nickel activated sintering of tungsten in which the coreduction process was emplyed. The ultimate utility of such an activated sintering process will be determined to some extent by the mechanical and physical properties of the final prod-

Jan 1, 1962

By E. J. Westerman

Prealloyed powders of nickel-base superalloys were sintered to almost theoretical density in short sinterilzg times. It was ascertained that the rapid densification was caused by a small amount of liquid phase at the grain boundaries, which apparently ovriginated by incipient melting at temperatures considerably below those at which macroscopic melting of the compacts occurred. An increase in the quantity of liquid phase present during sintering-, caused by an increase in the sintering temperature, increased the densification rate, but resulted in a decrease in the room temperature tensile propevties. NICKEL-base superalloys, which presently comprise an important group of high temperature alloys, are difficult to fabricate by the forging, casting, and machining operations presently used. As it was felt that fabrication by powder metallurgical techniques might offer advantages in the production of super-alloy parts, a basic investigation of the most important process in the sequence of powder metallurgical operations, the sintering process, was undertaken on Rene 41, Udirnet 500, and Nimonic 90 and 100 powders. These alloys age harden by the precipitation of the ? Ni, rA1,Ti) phase. Nickel-base superalloys of the Nimonic type have been fabricated by powder metallurgical methods, and their mechanical properties reported in detail.' Other alloys for high temperature service which have been fabricated by powder metallurgical methods include a Co-base alloy of the Vitallium type;2,3 alloys with a Co-Ni-Fe-Cr base;4 stainless steels;5'6 Cr-W-Co alloys;" and a Co-base alloy, X-40.8 METAL POWDERS The superalloy powders investigated were: a) a prealloyed at.omized Rene 41 powder; b) a prealloyed atomized Udirnet 500 powder; c) a prealloyed atom-

Jan 1, 1962

By W. L. Finlay

Size effects in quenching steel are particularly prominent and well recognized because of the existence of a critical cooling rate separating nuclea-tion and growth transformations, as exemplified by the formation of pearl-ite, from the shear type of transformation characterizing the martensite reaction. The absence of a similar, sharply demarcating cooling rate is characteristic of precipitation hardening systems and size effects in these are correspondingly less prominent. This paper is concerned with a size effect in high-purity, precipitation-hardenable alloys which appears not to have been recognized previously. This effect is believed to result from the thermal fluctuations which inevitably occur in quenching a specimen of finite size into a cooling liquid rather than from the existence of a critical cooling rate. QUENCHING "ANOMALIES" The precipitation hardening literature contains many references to so-called anomalous quenching and aging results. By "anomalous", investigators usually meant that their alloys did not consistently harden on aging after quenching according to some anticipated pnttern: not infrequently virtually no age hardening occurred with compositions known to be precipitation-hardenable. Perhaps the most prominent series of anomalies was reported over a 15-year period by Gayler and coworkers on aluminum-copper.l,2,3,4 Working with silver-rich copper alloy, Cohen5 secured some very interesting Rockwell F hardness changes of from 1-5 Rockwell points between the first peak and valley. Fink and Smith borrowed one of Cohen's specimens and, following his heat treatment and quenching practice to the letter, secured6 very different results in which only one peak was obtained and in which the hardness level at the aging lime of Cohen's first peak was 20 Rockwell F points higher. Fink and Van Horn7 encountered serious deviations in age-hardening high purity aluminum-zinc alloys. They stated that "the discrepancies were larger than might be expected from possible experimental errors in the Brinell readings." Geisler, Barrett and Mehl8 likewise encountered anomalous hardening results in aluminum-silver alloys, securing quite different age-hardening curves from two identical specimens. They stated that "the treatments of these samples had been the same, so that the different behaviors could be attributed only to accidental variations in the quenching practice."

Jan 1, 1950

By Robert E. Green, P. W. Kingman

Application of a constant geometry compression test to single crystals of aluminum of selected diameters from 1/4 to 1/64 in. showed the presence of a diameter-dependmt size effect. The most pronounced effects were found in those crystals oriented for single slip, while for specimens possessing orientations in the comers of the standard stereographic triangle virtually no size effect was exhibited. The yield stress of the crystals oriented for single slip was found to increase with decrease in specimen diameter, while the strain-hardening rate was found to be lower for the smaller specimens. The experimental results are in general agreement with those of other investigators obtained from lensile tests on copper and aluminum crystals. THE earliest systematic investigation of a possible size effect on the plasticity of metals was that of no,' who in 1926 performed tensile tests on cylindrical aluminum single crystals with diameters of 3 to 8 mm. Ono concluded that the gross stress-strain curve did not show a diameter dependence, but that the resistance to slip for strains of 0.1 pet and less appeared higher for 3-mm-diam crystals than for larger sizes. Later studies of aluminum by Maddin et al2 tentatively concluded that a size effect exists, but the conclusions were again open to question because of inconsistencies in the experimental data. Wu and Smoluchowski3 had previously shown that the slip system activated in a single-crystal sheet specimen of aluminum is a function of the specimen cross section in the slip direction, but no stress-strain data were obtained. Subsequently Fleischer and Chalmers4 studied the effect of the length of the slip direction of the primary-slip system on the stress-strain curve by testing aluminum crystals with geometrically dissimilar cross sections. In the course of this investigation a size effect was indicated in rather large crystals; however, the number of these tests was small. Other investigators have indicated that a size effect in aluminum is appreciable only for diameters of 0.5 mm or less.5, 6 Size-effect studies have also been carried out on copper crystals, the most detailed being that of Suzuki et a1.7 who performed tensile tests on specimens of many diameters ranging from 2 to 0.12 mm. Suzuki found a strong size dependence in the easy-glide region, both the extent of the easy glide and the hardening rate in easy glide were size-dependent, and the size effect was found to be orientation-dependent. Suzuki's results are in agreement with the less extensive observations of Pater-sonB and those of Garstone et al.9 A size effect was found by Rebstock using tubular copper crystals.'0 Size effects have also been noted in a brass,6, 11 in cadmium,12'19 and in hexagonal crystals.14 All the previously cited works have been entirely concerned with the variation of specimen cross section. The effects of specimen length and the change of specimen geometry which results from using progressively thinner specimens while maintaining the same specimen length have been largely ignored. A theoretical discussion of the effects of specimen length and geometry has been given by Hauser and Jackson,15 who predict a grip effect on easy glide as a function of specimen geometry provided that the specimen dimensions are large compared with the spacing between the slip bands, and by Fleischer and Chalmers,18 whose analysis of grip effects resulting from lattice rotation predicts an increase in easy glide with an increase in specimen length. A study of size and geometry effects in aluminum crystals by Kitajima and shimba17 indicated increasing amounts of easy glide in specimens of increasing length and identical cross section, and nearly identical stress-strain curves for specimens of different sizes having constant length-to-diameter ratios. Since the present study is primarily concerned with diameter dependence, the following factors were taken into account: specimen material, specimen geometry, testing method, range of sizes to be tested, and possible influence of surface and volume effects. Aluminum was chosen because of the present lack of conclusive results and the seeming possibility of size effects at relatively large diameters, the

Jan 1, 1964

By James R. Holden, Frederick E. Wang

Through both single-crystal and powder X-ray diffraction methods, ten A6B23-type compounds have been confirmed to exist between lanthanides (A) (plus scandium and yttrium) and manganese (B); A = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. The formation of a compound of this type is shown to he extremely atomic size-sensitive; hence it can be classified as a "size-factorH compound. The "enveloping effect", a geometrical consideration observed in its crystal structure, is proposed as the reason for the A6B23-type compound being size-sensitive. The approximate ideal geometrical ratio of the radii R/r is 1.31 while experimentally A6B23-type compounds have a radius ratio lying within the range 1.2 to 1.4. FLORIO t al.' characterized the structure of Th6MnZ3 as fcc, space group Fm3m, with 116 atoms in the unit cell. Since then, a number of isotypic binary compounds, and recently Gd n,,' have been confirmed to exist. The fact that strontium and barium form A6Bz3-type compounds with magnesium strongly suggested the possible existence of Ba6Liz3. However, investigation3 showed the compound Ba6LiZ3 to be absent. Since both strontium and barium are group 11-a elements and are therefore "open metals",6 the nonexistence of Ba6LiZ3 can hardly be explained satisfactorily by valence-electron considerations. On the other hand, the consistent atomic-radius ratio, (R/r),* observed for the known A6Bz3-type compounds,3 strongly suggests that the formation of compounds of this type is atomic size-sensitive. Therefore, one is tempted to explain the nonexistence of Ba6LiZ3 entirely on the basis of the atomic-size difference between strontium and barium. However, this approach is not entirely without objection. Atoms are not rigid spheres and are known to vary in size within certain limits.7 Since the atomic-radius difference between strontium and barium (0.07 to 0.09A) is within these limits, it is reasonable to assume that the size difference would have a negligible effect on the formation of Ba6LiZ3. This view is further supported by the fact that the radius ratio, R/r, in other known "size-factor" compounds is observed to range widely—for example, from 1.08 to 1.45 for ABz-type compounds (C15, MgCuz type)' and from 1.37 to 1.58 for AB5-type compounds (D2d, CaZn5 type).g The present investigation was undertaken in order to find a more satisfactory explanation for the non-existence of Ba6LiZ3 and, consequently, a better understanding of the nature of the A6Bz3-type compound. The primary objectives are to confirm the previous conclusion3 that the A6B23-type compound is indeed a "size-factor" compound and subsequently to determine the atomic-radius ratio range in which the A6Bz3-type compound can exist. In order to achieve these objectives, stoichiometric A6Bz3 alloys, where manganese (B) was alloyed with various lanthanide elements (A), were selected for investigation. The atomic-radius ratios of lanthanide elements with manganese range from 1.26 for Lu/~n to 1.46 for Eu/Mn. This radius ratio range includes and exceeds the range of all previously reported A6Bz3-type compounds—1.32 for Th/Mn' through 1.38 for Sr/Li. Furthermore, the atomic-size difference between successive elements of the lanthanide series in order of atomic number) is of the order of 0.01A (europium and ytterbium are exceptions). The series of lanthanon-manganese alloy systems is ideally suited to a precise determination of the limits of allowable atomic-radius ratio for A6Bz3-type compound formation. EXPERIMENTAL PROCEDURE The lanthanide metals, in ingot form, supplied by Michigan Chemical Corp. (St. Louis, Mich.) and Nuclear Corp. of America (Burbank, Calif.), were guaranteed by the suppliers to be at least 99.9 wt pct pure (traces of silicon, calcium, and other minor constituents present on occasion, not to be more than 0.05 wt pct) as shown by spectrographic analysis. Manganese metal, in polycrystalline form, was redistilled from the commercial, chemically pure grade and was analyzed to be at least 99.95 wt pct pure. In all cases, the atom ratio between the two elements in each charge was A (rare-earth meta1):B (manganese) = 6:23 and a constant weight, 3 g, of

Jan 1, 1965

By R. L. Fleischer

IN 1925 a criterion for localized deformation in a single crystal was derived by Taylor and Elam.' They noted that for a single active slip plane the slip plane area is constant, but the direction of the stress with respect to the slip direction changes during deformation so that, when the increase in stress due to this rotation is large enough relative to the work hardening, instability occurs. (By instability is meant continued slip on the active slip plane.) The instability criterion may be written t>dt/d?/m tan2? [1] where t and ? are resolved shear stress and strain, m the Schmid factor for resolving shear stress, and ? is the angle between the slip direction and the axis of tension. The formula points out that regardless of the atomic mechanism involved, for large flow stresses and low work hardening rates, slip on a single plane—once started—should continue. The case of alloying provides a direct possibility of adjusting the parameters in Eq. [I]: As an alloying element is added to a pure metal, the flow stress is raised and the work hardening in easy glide may be either decreased2 or unaltered.3 Since flow stresses in easy glide may rise to the kg/mm2 range for alloy crystals while easy glide slopes may be less than % kg/mm2, 2 it is possible for the inequality to be satisfied. Indeed Garstone and Honeycombe3 report that slip becomes coarser with increasing stress in the easy glide range, where the flow stress would be increasing and the slope would be essentially constant. Another case where high flow stresses and low hardening rates accompany coarse slip is that of quench hardening.4 Maddin and Cottrell report that quenched aluminum crystals display slip markings resembling those of a brass. A similar effect has been observed after irradiation.'

Jan 1, 1960

By E. Hein, R. A. Dodd

The fatigue softening of prior strain-hardened poly crystalline copper has been determined by measuring changes inflow stress resulting from fatigue treatments. Tensile fatigue does not soften the metal, while the softening due to reversed stress fatigue depends on the extent to which fully reversed stressing is approached. True tensile fatigue is shown to be possible only in the case of long wire specimens. Annealing following fatiguing of strain-hardened metal shows that tensile fatigue is very effective in modifying normal recovery and recrys-tallization. OBSERVATIONS by Ludwik and Scheu,' Kenyon,' Polakowski and Palchoudhuri, Kemsley, and Broom and Ham,596 have shown beyond doubt that strain-hardened metals are softened by reversed-stress fatigue. To some extent the softening might be associated with a rearrangement of dislocations, but the results of Broom and Ham5 on the temperature dependency of the fatigue hardening of annealed copper, and those of McCammon and Rosenberg7 on the partial recovery at 100'C of fatigue-hardened copper suggest that point defects may be involved. Since lattice vacancies are the only species of point defect present in appreciable quantities in thermody-namic equilibrium, most attention has been accorded them in the various theories advanced to explain hardening and softening effects resulting from fatigue. Precise mechanisms remain uncertain, and while some effects may be due to single vacancies, defects arising from vacancy clusters may also contribute to the changes in properties. All types of plastic deformation result in point-defect formation, one frequently invoked formation mechanism involving the nonconservative motion of jogs formed by the intersection of, for example, mixed dislocations. But since fatigue deformation is thought to be a particularly effective way of forming point defects, additional mechanisms peculiar to fatigue must be sought. One possibility is that jogged loops contract during the unloading cycle to give rows of vacancies. A local high-vacancy concentration could conceivably promote polygonization and recovery by climb, and, therefore, could explain the fatigue softening of strain-hardened metals under appropriate conditions of temperature. Conversely, the experiments by Broom and Ham6 on the fatigue hardening of copper single crystals involving subsequent tensile testing of previously fatigued specimens, resulted in the observation of distinctly lowered yield points. This could be due to vacancy atmospheres associated with dislocations, possibly augmented by jogs on dislocations. In addition to the yield-point phenomenon, a post-yield hardening was observed, with a temperature-dependence resembling the friction-hardening of irradiated metals,9 this again suggesting a point-defect mechanism. An important development in this field has been the observation,10 by transmission electron microscopy, of high concentrations of prismatic loops in fatigued aluminum. By analogy with quenched aluminum filmso11 it seems certain that these loops originate in the collapse of vacancy clusters formed during deformation. Metals, such as copper, having a relatively low-stacking fault energy would tend to produce Frank sessile loops (in practice tetrahedral defects with stacking faults on all (111) planes) rather than the glissile prismatic loops observed in aluminum. The manner in which these various defects affect the different aspects of fatigue behavior has not yet been fully investigated. The present work was designed principally to indicate whether tensile fatigue gives rise to hardening and softening effects similar to those associated with reversed stress fatigue, and with the hope of providing additional information on the contribution of point defects to fatigue deformation. Despite the uncertain ty often associated with the interpretation of resistivity data, i.e., the relative contribution of stacking faults and other defects, such measurements are conveniently employed to study point defect pheno-

Jan 1, 1962

By W. H. Smith

IN connection with some recent work on the effect of impurities on the ductility of chromium, it appeared desirable to know the solid solubility of carbon in chromium. A literature survey indicated that this information was not available. Although considerable work has been done on the Cr-C phase diagram,&apos;.&apos; previous investigators have been more concerned with the structure and phase boundaries of the carbide phases than with the terminal solid solution. The phase diagram shown in Fig. 1 is taken from the work of Bloom and Grant&apos; and represents the most recent determination. As indicated by the dashed line, the a solid-solubility limit was not determined. Experimental Procedure Alloys of chromium were prepared from hydrogen-treated and vacuum-degassed electrolytic chromium plus spectrographic grade carbon. The oxygen and nitrogen content of the alloys was <0.002 pct. After melting, analysis of the alloys showed them to contain 0.02, 0.08, 0.15, and 0.55 pct C. Pieces of the alloys were heated in a protective atmosphere to various temperatures and then quenched after holding for a time sufficient to insure equilibrium. Microscopic examination of the as-quenched alloys for the presence of a second phase was used as a measure of the solubility limit. The heats were made in a multiple hearth arc-furnace using a zirconium-gettered static argon atmosphere. A zirconium melt was made before each Cr-C heat. Triple melting was used to insure ingot homogeneity as shown by microscopic examination. The alloys were prepared by adding portions of a 4.5 pct C-Cr master alloy to high purity chromium. The carbon contents listed previously were those obtained by analysis. The nitrogen and oxygen contents after arc melting were both <0.002 pct. Sections 1/8X1/4X1/2 in. were cut from the 100-g ingots and a hole drilled in one end in order to suspend the sample from a molybdenum wire. After the surface was carefully cleaned, a sample of each melt was hung in a mullite tube heated externally by a platinum resistance furnace connected to a vacuum system. The lower portion of the mullite tube was sealed to Pyrex and closed off several inches below the furnace. This was filled with sili-cone oil kept cold by circulating cold water around the outside of the Pyrex. Quenching into the oil bath was achieved by melting a fuse wire supporting the sample. It required about 4 sec for the sample to cool from 1400" to 600°C. This severity of quench was considered satisfactory to freeze-in the high temperature equilibrium. For tests made at temperatures of 900" to 1200°C, heating was done in vacuum; for tests above 1200°C, an argon atmosphere was used. The holding time employed ranged from 12 hr at 900°C to 6 hr at 1400°C. Experiments were performed at temperatures of 900°, 1000°, 1100°, 1200°, 1300°, and 1400°C. Microscopic examination for evidence of a second phase was done at X1500. Experimental Result The microstructures of a 0.08 pct C-Cr alloy as-cast and after quenching from 1300°C are shown in Figs. 2 and 3. A 0.15 pct C-Cr alloy quenched from 1300°C is shown in Fig. 4. The data obtained from the quenching experiments is shown graphically in Fig. 5. If the Van&apos;t Hoff equation is obeyed, a plot on a logarithmic scale of the mol fraction of solute vs the reciprocal of the absolute temperature should give a straight line. For dilute solutions the weight percentage can be substituted for the mol fraction without introducing any appreciable error. The Van&apos;t Hoff equation can then be written as where H is the heat of solution in calories per mol. The slope of the straight line on the log pct C vs 1/T plot gives the value of AH. Assuming that the Van&apos;t Hoff equation is obeyed, which is probably justified for the dilute solution of carbon in chromium, the heavy straight line shown on Fig. 5 represents the best fit of the data. This line was obtained as follows. On Fig. 5 the results of the microscopic examination of all alloys following quenching were plotted and designated as to whether one or two phases were seen. Below 1100°C all alloys showed a second phase on quenching. The heavy vertical lines shown in Fig. 5 therefore represent the possible range of the ter-

Jan 1, 1958

By C. A. Wert

THE solid solubility of cementite in a-iron has been investigated a number of times and there is now general agreement on the solubility of about 0.018 wt pct at the eutectoid temperature, 720°C. With decreasing temperature, the solubility falls off so rapidly and to such a low value that no data obtained by standard metallurgical methods are available below 500°C. Using a new technique, however, Dijkstral has obtained apparently accurate solubilities down to 400°C; which data agree well with previously measured solubilities in the 600" to 700°C temperature range.&apos; The present paper has in part the purpose of extending his work to still lower temperatures. Earlier work of Low and Gensamer3 on iron has established that the presence of a relatively small amount of carbon can play a tremendous role in affecting the mechanical properties. In particular they found that the yield point remained high as they reduced the amount of carbon in the iron; the yield point dropped only after the carbon content had fallen to something less than 0.003 wt pct, the point where their carbon analysis failed. It seemed desirable to the present author to see if some means could not be found to extend this part of their work. This investigation has then the additional purpose to determine the range of carbon concentration in which the major change occurs. Solubility The method used in the present work to measure small percentages of carbon in a-iron utilizes internal friction. Since this method may not be fa-miliar to the reader, the following explanation will be given (a part of this procedure is from unpublished results of Dijkstra): It is known that the internal friction associated with the diffusion of

Jan 1, 1951

By S. K. Nowak

The lithium solubility limit in solid aluminum was determined by the use of micro-graphic techniques. The solubility limit thus established was shown to be a true equilibrium by checking the reversibility of AlLi phase precipitation and dissolution around the equilibrium temperature. The experimental results fit a straight line by plotting log N(LI) against 1/T. The metallurgical reasons explaining the lack of agreement among previous investigations are discussed. THE solubility limit of lithium in solid aluminum was determined by Shamray and Saldau1 by micrography and by Grube et al.&apos; and also Voss-Kiihler- by measurement of electrical resistivity. Since the addition of lithium induces extremely small changes in the aluminum lattice, X-ray techniques could not be employed for this purpose; in fact, the addition of lithium does not cause an expansion of the lattice as might be expected from a consideration of atomic radii, but causes a small contraction from 4.040 to 4.037A3, 4 when the solvent aluminum is saturated with this element. An analysis of the results from previous investiga-tions&apos;" shows that with improvement of investigation techniques the solubility limit tends toward a lower lithium content. Again, some of the author&apos;s own experimental results on the action of atomic hydrogen on A1-Li alloys seemed to indicate that the solubility of lithium should be much lower, i.e., about 0.3 pet at 300°C: instead of 1.15 pet, the lowest published value.4 For the foregoing reasons it was decided to investigate this problem. The aluminum and the lithium used for this purpose were of the highest purity. The lithium solubility limit was determined by metallographic techniques, in particular by the use of a reagent especially developed for the purpose of revealing the AlLi phase. The solubility limit thus determined was shown to be a true equilibrium by checking the reversibility of AlLi phase dissolution and precipitation around the equilibrium temperature. All of the experimental work was carried out in 1951 at the Centre d&apos;Etudes de Chimie Metallur-gique at Vitry, France, under the direction of Georges Chaudron.

Jan 1, 1957