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By R. L. Moment

The anisotropic elastic behavior of rolled beryllium sheet has been measured, using a pulse echo technique, and compared with X-ray diffraction data. Calculated elastic stiffness constants compared favorably with published values for beryllium single crystals which were attributed to the strong (0002) rolling plane texture. Variations of Young's modulus in the yolling plane could be associated with the velative distribution of (0002) planes out of their ideal position in the rollitzg pkule. WHEN a metal is subjected to cold working such as drawing, forming, or rolling, a crystallographic texture develops which can significantly alter its physical properties. One method for detecting this texture is X-ray diffraction, but Alers and Liu' have recently pointed out how the prediction of anisotropic physical properties from pole figures alone is not always accurate due to differences in interpretation. Variations in Young's modulus with orientation or, more completely, the values of the effective elastic constants of the worked metal, also serve to indicate the presence of a texture. In fact, as Alers and Liu' pointed out, calculated variations in Young's modulus for assumed orientations, when compared with experimental data, can be used to eliminate some of the uncertainty in interpretation of X-ray pole figures. Thus, elasticity measurements can serve not only to clarify any unusual elastic behavior of worked metal, but also to detect and in part determine the nature of its texture. X-ray determination of the texture of rolled beryllium has been reported by Smigelskas and Barrett,2 who found a strong texture of (0002) in the rolling plane with (1070) planes normal to the rolling direction. In the case of metal rolled at room temperature, they reported that [1010] directions also appeared at positions 60 and 120 deg from the rolling direction in the rolling plane, while in more recent work Keeler3 found these directions were also tilted towards the rolling plane. The texture for beryllium rolled at 80O0C, however, only showed (1010) planes normal to the rolling direction and the spread of (0002) planes out of the rolling plane was less. In looking for elastic anisotropy one might consider unidirectional rolling of a metal as introducing an or-thorhombic symmetry through reorientation of the grains, since the three deformations, compression, extension in the rolling direction, and extension in the cross direction, are orthogonal to each other and unequal in magnitude. Thus the rolled sheet could be treated like an orthorhombic single crystal and the nine stiffness constants of the elasticity tensor used to calculate the anisotropy of Young's modulus, the shear modulus and Poisson's ratio. In this case we could write: which is symmetric about its diagonal. Borik and Alers4 have recently used this approach on rolled die steel with very good results. They found, however, that instead of displaying orthorhombic elastic symmetry their specimens could be considered tetragonal in which case Cr1 = c22, c13 = Ca, and c44 =cjj. This conclusion was made solely on the basis of the measured tensor elements, and serves to point out the advantage of this method for studying the anisotropy of rolled metals. Their calculated values for Young's modulus as a function of angle in the rolling plane also checked very well with direct measurements made on different specimens using the resonance technique. In the present study, cross-rolled beryllium was used which had been unidirectionally rolled about 11 pct for the final reduction. This imparted a slight anisotropy in the rolling plane which was detected both by X-ray techniques and elasticity measurements. For purposes of discussion in this paper, the rolling direction is that direction in which the most reduction passes were made and cross direction is the normal to the rolling direction in the rolling plane. It was also decided to consider the rolled sheet as displaying orthorhombic symmetry for the purpose of obtaining elasticity samples with the direction defined as in Table I. Any change in the final symmetry attributed to the sheet would then be made on the basis of the measured elastic stiffnesses. The final data would then be compared with that expected from the X-ray study and that reported for beryllium single crystals. EXPERIMENTAL PROCEDURE Rolling Schedule. The samples used in this study were taken from a large sheet which, because of its size, had to be unidirectionally rolled for the final reduction. The resulting texture was that of cross-rolled metal with a slight unidirectional texture superimposed. A cast beryllium ingot, 9.500 in. sq by 3.325 in. thick, was cross-rolled to 81 pct reduction followed by unidirectional rolling for an additional 11 pct to give a total reduction of 92 pct. The thickness of the final sheet ranged from 0.265 to 0.280 in. Reduction up to 67 pct was done at 980°C and the final 25 pct at 870°C. Analysis for metallic impurities showed aluminum 0.06 pct, iron 0.19 pct, and silicon 0.11 pct, giving a beryllium purity of 99.64 pct.

Jan 1, 1968

By Klaus Detert

Fifteen and 18 pct Ni maraging steel and several binavy and ternary alloys of the iron-rich corner of the Fe-Co-Ni system have been studied. After annealing in the austenite range, these alloys were deformed slightly by cold rolling and subsequently aged. Compavison of experimental measurements at various processing stages indicates that small degrees of deforn~ation (5 to 10 pct reduction in thickness) do not influence hardness and strength or the aging kinetics. Electrical resistivity and ductility are somewhat redu]ced and the coercive force is substantially lower when compared to identical samples which were not deformed. The results are explained in terms of retained austenite which transforms into martensite with the small amount of deformation. RECENTLY there has been increasing interest in maraging steel for applications in electric power generators requiring a high ratio of power to weight.' Fifteen pct Ni maraging steel has been investigated to evaluate its properties and performance for application as high-strength magnetic rotor steel,' and a thorough investigation of the precipitation and transformation processes in this alloy has been conducted in this laboratory.3 The influence of deformation, which preceded the aging treatment, was also studied. It was found that a small deformation in the order of 5 pct has a rather striking effect in reducing the coercive force. Other interesting effects on the properties caused by such deformation have led to the more detailed studies reported herein. EXPERIMENTAL METHOD The methods used to produce the samples from 15 pct Ni maraging steel have been described elsewhere.3 The general procedure of hot forging and cold rolling to sheet has been followed. The composition is included in Table I which also contains the composition of the 18 pct Ni maraging steel grade 250 studied. More data about the material and the processing of the 18 pct Ni maraging steel have been recently reported.4 The experimental alloys of binary and ternary Fe-Ni-Co alloys were made by levitation melting in an argon atmosphere and casting into rod-shaped ingots 7 mm thick weighing 20 g. From these ingots 25-mm-long rods were machined to study the phase transformation by a dilatometer. These rods were then cold-rolled to strips, 2.4 mm thick. Annealing for austenitizing was done in tube furnaces in an argon or helium atmosphere followed by cooling in the water-cooled portion of the tube. Aging was done in a salt bath containing a neutral blend of Alkali nitrates and nitrites. Vickers hardness was measured using a load of 50 kg for 15 sec. Tensile tests were carried out on a hard beam tensile tester at a strain rate of 5 X lo-' per sec using flat samples with a gage length of 37.5 mm and a cross section of 1.25 by 6.25 mm. Estimated sensitivity was 5 K x strain and 0.35 kg per sq mm stress. Magnetic saturation was determined on small cylindrical samples, 2.5 mm in length and diameter, by measuring the force exerted by the gradient of a magnetic field of 1000 oe per cm in a mean field of 11,500 oe. The measured values could be reproduced within *1 pct. Coercive force was measured by a precision-type magnetic field probe in a magnetic coil as described by Foerster.5 The magnetizing field was 1300 oe. The samples were 5 cm long, 1 cm wide, and 2.4 mm thick. he coercive force was measured to within +0.1 oe. Electrical resistivity was measured by using a potentiometer on flat strips with a gage length of 100 mm and a cross section of 2.5 by 0.5 mm. The accuracy of the measurement was 0.1 pct but the reproducibility of the measured specific resistivity among different samples was in the order of 1 pct. The method used to prepare the samples for electron transmission has been reported elsewhere.3 RESULTS Fig. 1 shows the influence of deformation after annealing on the resistivity, hardness, and coercivity. The samples were annealed for 30 min at 1000"C,

Jan 1, 1968

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By L. R. Woodyatt, H. J. Beattie, C. T. Sims

Theories correlating the formation of u and related intermetallic compounds to the electron-per-atom density of binary and ternary alloys have appeared regularly in recent technical literature. These same principles can be modified and applied to complex precipitation-strengthened alloys such as the iron-, cobalt-, and nickel-base superalloys and the stainless steels. Since these complex alloys contain carbides and other phases that normally precipitate before the U-type phases, the nature and amount of the precipitated phases must be calculated first. The following general formula is then applied to the residual matrix composition of the alloy: element. The magnitude of the resulting number is indicative of whether the alloy will form a a -type phase. When these calculations (which are computerized) are systematically applied to alloys of knoun phase analysis, a breakoff in average electron-vacancy number is noted between U-free and U-prone alloys. Alloys with an average electron-vacancy number higher than the breakoff form a-type phases, while those with lower ones do not form these phases. This method could then be used to eliminate from consideration all experimental compositions that would precipitate undesirable phases. It also is useful in evaluating analyzed heats of alloys where minor heat-to-heat variations determine whether the alloy is o-free or o-prone. THE highly significant development of strong, ductile superalloys to provide reliable construction materials in the 1000" to 2500° F temperature range has been due principally to unremitting application of Edisonian techniques and logic by the dedicated physical metallurgists who have shouldered this responsibility. Tools such as the electron microscope, phase analysis, and computers to accomplish regression analyses have been used heavily, but the effort has been essentially practice of an art, rather than a science. The objective of this paper is to describe and illustrate application of some relatively fundamental principles to certain of these alloy systems in an attempt to remove some of the empiricism from the technology. Specifically, the work presented here deals with the use of periodic-group relationships to predict the formation of intermetallic phases which can occur in primarily austenitic (fcc) structures. Calculations that have been developed might be applied in the design of new alloys and the evaluation of known alloys, and thus have the potential of eliminating vast areas of unnecessary alloy preparation and evaluation. ALLOYING CONCEPTS AND STRUCTURAL FEATURES OF SUPERALLOYS Strength is produced in austenitic superalloys by three principle mechanisms: 1) precipitation of y'; 2) formation of carbides; 3) solid-solution hardening by soluble refractory metals. The first mechanism requires the addition of aluminum and titanium, the second requires carbon and carbide-forming elements, while the third calls for the addition of molybdenum and/or tungsten. A considerable concentration of chromium is usually maintained to resist oxidation/corrosion, but it is also an important carbide-forming element. Fig. 1 shows a sketch and electron micrograph of the structure of a typical wrought nickel-base super-

Jan 1, 1967

By Y. C. Liu, G. A. Alers

The anisotropy of Young's modules has been measured in a series of Cu-Zn alloys containing from 1 to 28 wt pct Zn and cold-rolled to 97.5 pct reduction in thickness. These modulus data show a transition in texture as a function of zinc content. In alloys containing 3 pct Zn or less, the texture is essentially that of copper. A transition is clearly seen to develop in 5 and 8 pct Zn alloys, and to have been completed in a 12 pct Zn alloy. Increasing the proportion of zinc to 28 pct does not produce any further changes in texture. The ease and clarity with which this texture transition can be seen in the modulus data is in great contrast with the inccertainty in the visual detertiination of the range of texture transition from a series of pole figures. It is also shown that the rolling texture of the high zinc content alloys cannot be a one-COIIIponenl texture, characterized by the (110)(112) ideal orientations, as usually assumed. A second, quite important component must also be present. Furthermore, the present data are inconsistent with matrix orientations on which the "oriented growth" hypothesis of the Formation of recrystallization textures is based. THE rolling textures of binary fcc alloy systems have generally been considered to lie between two terminal textures. One of these terminal textures is the copper type and the other is the 70:30 brass type. Alloys of intermediate solute content exhibit a texture which is said to be a transition between the two terminal textures. On the basis of efforts to correlate rolling and recrystallization textures, two concepts have been advanced in the literature on the nature of these transition textures. One school1 suggests that the addition of alloying elements, e.g., zinc, causes a gradual rotation about one of the (111) poles from the (358)( 523) ideal orientation of the copper-type rolling texture to the terminal {1 10)( 112) ideal orientation used to describe the rolling texture of 70:30 brass. This concept is depicted in Fig. 1 with the angle of rotation corresponding approximately to the zinc content and is designated here as the "rotational concept", since the ideal orientation of the transition textures varies continuously with alloy content. The other concept,' the "mixture concept", suggests that the copper-type rolling texture is a two-component texture. {358) (523) and {110)(112). The addition of alloying elements affects only quantitatively the relative amounts of these two components—a decrease in the amount of material in the {385}(523) orientation and an increase of that in the {110)(112) orientation with increasing solute content. An experimental distinction between these two concepts is essential to a better understanding of both the mechanism of formation of rolling textures and the subsequent formation of recrystailization textures in fcc metals. Because of the lack of resolution inherent in pole figures, it has not been possible to differentiate between the two concepts on the basis of this data. Both concepts, in fact, make use of the same set of pole figures but interpret them in a manner acco-rding to the view held.'" Experimental results obtained from inverse pole figures or selected-area electron diffraction3j4 simply -yield more refined pole figures but do not eliminate the ambiguity of interpretation. Quantitative measurement of an entirely different, orientation-dependent property must thus be considered

Jan 1, 1967

By D. R. Uhlmann, T. P. Seward, O. Chalmers

A magnetic field has been used to damp out liquid convection during the solidification of castings. Ingots of Al-2 pct Cu were poured from various sperheats (10" to 65°C) into a room-temperature graphite mold located between the poles of an electromagnet. The effect on ingot structure of varying the strength and time of application of the magnetic field was investigated, and the results are interpreted in light 01- current theories of ingot structure. In the solidification of alloy systems, thermal gradients in the melt and differences in density of the constituents are expected to produce convective motion in the liquid. The thermal convection caused by temperature gradients should be present during the freezing of both alloys and pure materials, while the solute convection caused by density differences should be of concern only for alloys. The possible influence of this natural convection on the structure of castings has been discussed by Ruddle,' Chalmers, and Tiller. More recently, an experimental investigation of such effects was carried out by Cole and Bolling. These workers took stationary molds containing lead- and tin-based alloys and. using a brine solution. quenched them from various superheats above their respective liquidus temperatures. When grids were placed across the mold diameter to suppress convection, the grid region was later observed to contain a larger percentage of columnar grains than other parts of the casting or than similar castings poured without the grids present. From thermocouple measurements, they found the temperature in the grid region to be higher than that in the region outside the grids throughout the freezing process, and concluded that convection should be an important mode of heat transfer in normal castings. In addition to such convection arising from thermal gradients or differences in density of the constituents, a further source of convective motion, which we shall call "momentum convection", may be particularly important in small (laboratory-size) castings. By this term we refer to the convective motion produced in the initial pouring process, a motion which is damped out as the linear momentum and angular momentum of the liquid are dissipated. Besides these sources of convection, which are present to some extent in all castings. external influences may also be effective in producing convective motion. Examples of such "forced" convection which have been discussed in the literature include stirring the melt, shaking the mold, rotating the mold, and so forth The purpose of the present study was to examine the effect of convection on the structure of castings poured into a cold mold. In this work, a magnetic field was employed to damp out the convective motions within the liquid, and hence control the extent of con- The effect of a magnetic field on convective currents in a conducting liquid is to induce eddy currents which oppose and damp out the convective motion. vection. The technique of magnetic damping was previously used by Utech and F1emings" in their study of convective effects on impurity banding and other substructure in alloy crystals grown unidirectionally from the melt. In their investigation, fields as small as 200 gauss were found to be effective in damping the convection currents which influence the banding. I) EXPERIMENTAL TECHNIQUE In the present study, alloys of A1-2 wt pct Cu were poured into a room-temperature graphite mold. The mold, in the shape of a circular cylinder, 2 in. ID, 2-3/4 in. OD, 5 in. inside height, and 5-1/2 in. outside

Jan 1, 1967

By G. R. Love, M. L. Picklesimer

Aboue 950°C the Nb-Zr system consists of a completely miscible bcc solid solution, commonly called the phase. Between 950 and 600°C, and between 20 and 85 pct Nb, the phase deconlposes, after sunciently long times, into two bcc solid solutions. The pct Zr alloys are conveniently descibecl with T-T-T (time-temperature-transformation) curves having a nose at about 2 hr at 700°C. The reaction rate varies only slowly with zirconium content and negligibly with oxygen contanzination; it is speeded up by a factor of 10 to 15 by 90 pct cold ulork and slowed dou by n factor oj 10 to 30 by a two-hundrecljold increase in grain size. Nb-r alloys with compositions between 40 and 85 pct Nb have been the basis for the majority of commercially important superconducting materials. In part because of their commercial promise, more is known about these alloys than about most other high-field superconducting materials. At the same time, there is considerable disputed or incomplete metallurgical information. For example, although Rogers and tkins&apos; indicate a monotectoid reaction at approximately 600°C and a two-phase 01 + 0, field extending between 20 and 85 pct Nb and to a maximum of 95OGC, erhout&apos; has reported that this entire region would be a single homogeneous B were it not for oxygen contamination. Again, although it has been shown that relatively short-time heat treatments in the vicinity of 700CZ significantly improve the ability of short wire samples to carry high currents in high magnetic fields at 4.2K, these observations have never been fully correlated with the structural change or changes occurring during the anneal. We intend to investigate in detail the effect of metallurgical variables, including heat treatment, on the superconducting properties of hard superconductors. To verify that our experimental techniques are valid and to establish a relative standard against which other materials may be measured, we feel it advisable to know the behavior of the Nb-Zr alloys under a variety of processing conditions. As an initial step toward this goal, we have determined in detail the kinetics of the transformations in Nb-Zr alloys. EXPERIMENT A number of problems had to be solved before beginning any fruitful work on the reaction kinetics in this system. While solving some of these problems, either by chance or by design, small amounts of information were obtained about alloys containing 40, 50, 60, 65, 67, 70, and 75 pct Nb, bal. Zr. In addition, a large range of grain sizes and a range of temperatures considerably greater than the range indicated by Rogers and Atkins phase diagram were examined. We will, however, report in detail only the results obtained for the Nb + 33 pct Zr and Nb + 25 pct Zr alloys at three grain sizes, two levels of oxygen contamination, and the temperature range 550 to 950°C. These data are most complete, but the other data are sufficiently complete to indicate the kind and magnitude of the variation of the transformation kinetics outside this range. The first and most difficult problem encountered in this inquiry was one of sample homogeneity. When Nb-Zr alloys are arc- or electron-beam-melted on a cooled copper hearth, solidification is sufficiently slow that there is appreciable coring in the cast structure and a large variation of grain size across the button thickness. Both these factors significantly affect the apparent reaction rate in the system. A two-step solution to the problem was attempted; an arc-melting and drop-casting technique has been developed by conald that greatly reduces the as-cast grain size and virtually eliminates coring segregation. Ingots made in this way exhibited no detectable (3 pct maximum) zirconium segregation. Before it was evident just how good this technique was, we attempted to supplement it with rather long-time, high-temperature annealing of the cast ingots. This annealing was carried out in evacuated and sealed (seal-off pressures < 1.0 x 106 torr) quartz capsules lined with tantalum foil at 1400 to 1450 C for 8 to 72 hr. There were two principal effects of this treatment: the grain size increased to a fairly uniform 150 p, and the surface and all grain boundaries near the surface acquired a film of a second phase, tentatively identified as an oxide (possibly additionally contaminated with silicon). There was no evidence that this 1400 C treatment had affected the zirconium segregation. High-temperature annealing was subsequently used only for grain-size control, but anneals of longer than 4 hr at temperatures greater than 1000°C were performed in dynamic vacuums (pressure no greater than 1.0 x lo torr). Any contamination resulting from these treatments was well below the limits of detection of our techniques. All samples, as cast, were cold-swaged to at least 85 pct reduction in area. The samples called cold-worked were tested as swaged. The minimum re-crystallization anneal for these alloys was about 12 hr at 1050 C; this produced an equiaxed grain diameter of about 4 to 8 P. Annealing for 4 hr at 1450°C produced a grain size of about 80 to 150 p; and annealing for 4 hr at 1650aC, close to the melting point of many of these alloys, produced a grain size of 0.5 to 1.0 mm. At all temperatures, the larger grain size was

Jan 1, 1967

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult&apos;s law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.&apos; This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3&apos;4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner&apos;&apos; and has been used to determine the thermodynamic data for Cu-Ni alloys.&apos; THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday&apos;s constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.&apos; The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By George L. Montgomery

In a recent article Heckler, Elias, and woods1 have described an automatic computer technique for plotting of pole figures. To anyone who has constructed pole figures manually from raw X-ray data, the development of computer plotting techniques has been a very welcome development. The purpose of the present note is to describe an alternative computer plotting method which, if somewhat less precise than the method described by Heckler et al., has the advantages of being faster and of not requiring the availability of a plotter. The plot is made directly by the printer of the terminal system and, by its nature, has a good deal of visual impact. Each character of output symbolizes a level of intensity. For example the numerals 1 to 9 might represent intensities referred to some reference obtained from a randomly oriented sample. Should more levels be required (this is seldom necessary) alphabetic or other characters may be used in addition. When these are arranged in the proper fashion, the result is a pole figure such as is shown in Fig. 1. It is the purpose of the computer program to transform the data and carry out the arrangement in a suitable manner. The computation is carried out on a line by line basis in order to reduce the amount of storage required and thus keep the program "small". It is, thereby, well within the limitations of the time-sharing systems which are becoming increasingly available. The inaccuracies introduced are slight and the plot can easily be made as precise as the technique used to collect the data. Comparison of pole figures produced by this method with those constructed manually shows a high degree of equivalence. To the present, the technique has been applied to reflected X-ray data only. X-ray data are collected in a manner identical to that described by Heckler et al. That is, as the goniometer rotates the specimen, a series of counts, accumulated over a preset time, is recorded. The method by which the proper symbol, representing an intensity level, is assigned to each print position is up to the ingenuity of the programmer. Perhaps the simplest method is to section the stereograph in the fashion of a polar net, and to assign all print positions lying within each segment a symbol representing the level of intensity recorded at the data point nearest to the center of the segment, see Fig. 2. The number and arrangement of the segments are selected to conform more or less with the number of accumulated counts and the geometry of the goniometer path used to collect them. Since the angular distance between accumulated counts is usually not infinitely controllable, it is impossible to locate one reading within each segment and, at the same time, maintain symmetry in the sectioning of the stereograph. This latter requirement is essential to keep the computer program simple and flexible. As an expedient it was found that the number of data points could be increased to conform with the number of segments, with very little loss of

Jan 1, 1969

By G. R. Love

i\ program has been written which allows fully automatic conversion of data for X-ray intensity, as a function of time, to finished conventional pole figures. The program accepts input data in the serial order in which they are taken and is therefore immediately compatible with automatic data-acquisition devices. From these data taped instructions are prepared for the Calcomp plotter to construct ink-on-paper drawings. Because both Siemens and Norelco pole figure goniometers are used in this laboratory, the program was written for pole figure data obtained from one or more interpenetrating spiral scans during which both the polar angle, @, and the equatorial angle, a, are varied simultaneously and continuously. The reference direction for a scan, that is the point @ = 0 deg, may be chosen coincident with either the normal direction (N.D. figures) or the rolling direction (R.D. figures). In either case the plotted figures are drawn with the transverse direction (a = 0 deg) at the right and the rolling direction at the top. The full, circular, pole figure is drawn as two semicircular figures labeled "front side" and "back side". As presently constituted, the program will also accept data from circular scans taken at constant values of @. In every case the angular coordinates of each intensity entry are generated in the computer from a relatively small number of auxiliary data. The X-ray intensity data are corrected for background scattering by direct subtraction of the intensity measured with 28 set appropriately "off" the Bragg angle. It is possible to enter this correction as an additional spiral scan through the a, @ space; because the background correction does not normally vary rapidly enough to warrant this detailed a determination, the background corrections are entered as one or more auxiliary data. All data are normalized to a multiple of random intensity. The data taken in this laboratory for N.D. figures are normally taken in a reflection geometry from from sheet samples and do not extend beyond <p = 75 deg; for these data random intensity must be determined from separate experiments and entered as auxiliary information. When the auxiliary information is not available, a number is chosen to give intensity values normalized to a scale of 1 to 10. In this laboratory, R.D. figures are based upon hemispherical samples for which data are taken out to @ = 90 deg; for these data random intensity is calculated by direct numerical integration of . sin @ d@ using the trapezoidal rule and the background-corrected values of the input data. Points necessary to the construction of the pole figure are identified by simple linear interpolation between adjacent data points to determine the loci of contour lines. Points lying on a given contour are connected to one another with straight-line segments and the search-calculation-drawing sequence is patterned to assure that different contour lines do not cross, that a single line does not branch, and that lines do not end in space. However, so that there be no ambiguity in the data presentation, all contour lines end at the limits of the input data. Since the curves are constructed of straight-line segments, they are not continuous in their derivatives. However,

Jan 1, 1969

By Y. Nakada, E. J. Fasiska, A. S. Keh, L. Zwell

DURING an investigation of solid-solution hardening of nickel by carbon,&apos; we found that there were no reliable data on the dilating effect of dissolved carbon on the unit cell of nickel. Bernier2 reported an increase in lattice parameter of nickel (3.523A) when an unknown amount of carbon was introduced into solid solution (3.536A). Similarly KG, Tsien, and Misek3 found an increase from 3.523 to 3.531A when nickel was carburized. strong4 studied the variation of nickel lattice constant as a function of dissolved carbon. However, in his case carbon was introduced into nickel by solidifying the melt at 65 kbar. Therefore, his carbon concentrations were much above the highest equilibrium solubility limit5 (2.7 at. pct C at 1 atm). Knowledge of the lattice mismatch between solute and solvent is essential in understanding the mechanism of solid-solution hardening. Therefore, we decided to determine the dilation of the nickel lattice by carbon under the more usual conditions of atmospheric pressure. The material used was Inco Electrolytic Nickel of 99.95 pct purity, as specified by the supplier. The impurity contents in wt pct were: Fe, 0.01; Cu, 0.01; Co, 0.03; 0, 0.005; C, Si, S, N, trace. To this base material various amounts of AUC-grade high-purity carbon were added during vacuum induction casting. Ingots, 2 in. in diam, were heated in a muffle furnace at 1000°C for i hr., hot-rolled to 1/2-in. thickness, and quenched into brine. All ingots with carbon concentration greater than 0.98 at. pct were enclosed in a cast iron box during the heating to minimize decar-burization. Small pieces were then either swaged down to 0.028-in.-diam wire or cold-rolled to 0.010-in.-thick sheets. After the final cold reduction in area of 50 pct, the specimens were recrystallized by heating in evacuated capsules at 1100°C for 60 to 80 sec and then quenched into brine. The final grain size was 50 to 100 µ. The carbon contents of the alloys, Table I, were determined by a combustion method

Jan 1, 1969

By Y. Mishima, R. Shiromizu

THE equilibrium y phase in Cu-Be alloys forms by discontinuous precipitation, the new phase nucleating at the grain boundaries and growing into grains on both sides of the boundary. When the alloy is aged above 500°C, however, growth may take place into only one of the grains.1&apos;2 In A1-Ag alloys it is known that the precipitate has the same orientation as the grain in which no growth takes place.3, 4 This was confirmed in the present investigation on a Cu-Be alloy. A Cu-1.79 wt pct Be alloy was solution-treated at 810°C for 2+ hr, quenched into water at O°C, and aged at 600°C for 1 hr in a salt bath. The specimen was thinned by chemical polishing and electropolishing at room temperature in a solution of H3PO4 saturated with CrOs. The foil produced was examined in a JEM 150 electron microscope operating at 150 kv. Fig. 1 shows precipitates growing on only one side of the grain boundary. The black platelike precipitates were identified as the y phase. Electron dif-

Jan 1, 1969

By H. I. Aaronson, W. L. Winterbottom, G. M. Pound

On the basis of a statistical thermodynamic treatment of the data of smithz2 on the activity of carbon in austenite, a Darken and smith23 deduced that the interaction energy, wy, between carbon atoms occupying nearest-neighboring interstitial sites is repulsive. Aaronson, Domian, and pound 24 (ADP) have applied two different statistical thermodynamic analyses to the same data. One analysis, a composite of the treatments of Darken and Smith,23 Speiser and Spret-nak," and Kaufman, Radcliffe, and Cohen,26 primarily takes account of the positional entropic effects of wy in dilute solutions. The other, due to Lacher 27 and Fowler and Guggenheim," is also applicable to more concentrated solid solutions. The equations which both analyses produce for a,, can be rearranged so that, when In a,, is plotted against the appropriate function of the carbon content of the austenite, the plot will have a slope of unity when the correct value of wy is employed. Since no other constant need be simultaneously evaluated in order to make this determination, ascertaining the most probable value of wy from Smith&apos;s data on the bases of these analyses was an elementary problem in least-squares statistics. ADP demonstrated that the wy&apos;s obtained from both analyses vary with temperature in a statistically significant manner. McLellan, Gerrard, Horowitz, and sprague 29 (MGHS), on the other hand, have recently made a new statistical thermodynamic study of a,, and have concluded from this study that wy is independent of temperature. The equation which they derived for a,, is: where 0 = ratio of the mole fraction of carbon atoms to that of iron atoms, z = number of sites from which occupancy is excluded by the presence of a carbon atom and the repulsive character of its interaction with nearest-neighboring carbon atoms (z = zb in Ref. 24), and x = a geometric parameter taking account of overlapping of the exclusion shells of nearby carbon atoms. z is 1 when wy = 0 and 13 when wy = Q. For a given value of z there is a definite value of X . In the absence of an equation connecting z and X, MGHS computed geometrically the value of x at several integral values of z; x increases from 0.47 to 8.67 as z is increased from 2 to 5. MGHS fitted Eq. [I] to the a,, data of Ellis, Davidson, and Bodsworth30 at 925° and 1050°C and to the data of smithz2 at 1000°C. Confining z to integral values in the range 4 to 6, and also somewhat restricting AG, the values of z, X, and AG were sought which would minimize the average root mean square percent deviation, D, of the calculated a,, values from those obtained experimentally. Finding that D was almost always smallest when z = 5, they concluded that z is independent of temperature. Since:23, 26 where R = gas constant and T = absolute temperature, and w,, was considered to be similarly invariant, this statement cannot be strictly true. The temperature range employed, however, was small and the interval between the values of z tested was sufficiently large so that the results could still be consistent with a constant The statistical treatment of the a,, data applied by MGHS is clearly quite approximate. Since more than three values of a,, are available at each temperature, z, and X, and AG have actually been over deter mined, rather than underdetermined as their treatment implies. In order to make more complete and exact use of the a,, data, we shall employ the Legendre Method of Least Squares, as described by Whittaker and Robinson. This technique permits conversion of the overdetermined system of equations produced by the substitution into Eq. [I] of the available pairs of a,, and 0 data at a given temperature into an even determined system. Solution of the latter system yields the most probable value of each of the three constants. This procedure will allow a statistically rigorous test to be made of the conclusion drawn by MGHS in respect of the temperature dependence of In order to obtain linear iiequations of conditions" from Eq. [I], the exact values of the three unknown constants are replaced by G/RT = =/RT + y, where z, i, and aG are estimated values of the constants. This allows the conditional equations to be written in the form:&apos;l where fi -f6, i, =/RT) = the right-hand side of Eq. [I] for a given pair of ayi and values. When applied to Eq. [I], these relationships become: The i equations of condition are reduced to three "normal equations" in the manner discussed by Whittaker and Robinson. The normal equations are then solved for a, ß, and y. Both of these operations are most conveniently performed by means of the computer technique of Winterbottom and Gjostein.32 This technique was used iteratively until the value of 0 (the most sensitive of the three correction factors) became 10.01. (Until they became small, a, 8, and y

Jan 1, 1969

By J. R. Cahoon, W. V. Youdelis

In a recent publication by Flemings and Nereo, equations for the calculation of the solute distribution in castings were developed, and the solute distributions for unidirectionally solidified A1-4.5 pct Cu ingots cast under various thermal conditions were calculated. The equations derived by Flemings and Nereo for the dendrite "expansion" and "steady-state" zones are essentially equivalent to those previously published by Kirkaldy and Youdelis, 16 for, although the flow velocity cooling rate, and temperature gradients appear in the fundamental differential equations, calculation of the solute distribution requires that the above be explicitly related to the assumed or measured solid-liquid mass distributions during solidification. In the treatment of Kirkaldy and Y-oudelis the mass distributions are simply assumed or measured without any prior and explicit association of the mass distributions to a velocity parameter. The treatment of Flemings and Nereo permits solidification conditions more complicated than the simple unidirectional case to be considered (although in principle the treatment of Kirkaldy and Youdelis could also be extended to include the more general solidification case); however, we note some limitations in the treatment of Flemings and Nereo, and the purpose of this discussion is to point these out and also to indicate those points of similarity in the mass distribution models used which make the two treatments equivalent. Both the Kirkaldy-Youdelis and Flemings-Nereo treatments consider a zone of dendrite "expansion" followed by a "steady-state" zone. However, Flemings and Nereo have failed to consider a zone of "collapse" which begins at the base of the first dendrites to reach the top of the ingot. The omission of this zone of "collapse" results in too high a value for the solute concentration in the latter portion of the ingot to solidify and the conservation of total solute is not possible. In the zone of "collapse" the solute concentration rapidly decreases, which may be accounted for as follows: consider a mushy zone of length X,, shown schematically in Fig. 11 (a), which develops at the chill face and then moves as a steady-state configuration along the length of a solidifying ingot. The solute distribution in this zone, when it first attains the steady state, is shown qualitatively in Fig. 11(b). The segregation is positive (above Co) in the region ab because this region contains primary dendritic solid, ranging from kco to kcE in composition (where k is the partition coefficient and CE is the composition of the eutectic liquid), and liquid metal near eutectic composition. The segregation is negative (below Co) in the region bc because it contains primary dendritic solid only slightly above kco in average composition and liquid metal only slightly above Co in composition. As the zone X, moves as a steady state

Jan 1, 1969

By F. A. Crossley

The key to disagreements between Blackburn&apos;s findings and mine is the word equilibrium". My work attempted to define the equilibrium diagram of the titanium-rich end of the Ti-A1 system. It can readily be shown that Blackburn&apos;s conclusions are based primarily on the examination of structures substantially removed from equilibrium. The diagram presented in Fig. 16 is properly labeled a "phase diagram". However, it appears that Blackburn either does not understand or does not accept the difference between "phase diagram" and "equilibrium diagram" as defined in the Metals Handbook.17 The conflict lies not in Blackburn&apos;s data but in his interpretation of it, and his use of "transformation", "phase diagram", and "equilibrium diagram" as synonymous terms. I share his view that the light microscope is much inferior to the transmission electron microscope for the study of transformations; but this fact does not render the light microscope useless or untrustworthy. The difficulties experienced with the Ti-A1 system have not been due to the limitations of the light microscope, but rather to the extreme sluggishness in achieving equilibrium at temperatures below 1000° C. Were it not for the light microscope employed with polarized light, the twin phase syndrome&apos; might still be unrecognized and, as a consequence, still adding to the confusion of Ti-A1 investigations. (Ref. 1 should read ... Contract No. N161-25952 ... vol. 236.) Other, more sophisticated techniques, including electron transmission, simply confirm the erroneous tentative conclusions drawn from observations of structures due to the twin-phase syndrome. By the standards of most of the investigations of the Ti-A1 systems, seven of the fifteen compositions investigated by Blackburn were seriously contaminated with oxygen. The writer has found that 0.1 wt pct 0 shifts the a + Ti3A1 boundary to 1 at. pct lower A1 content at 700°C. At constant aluminum content, this corresponds to a temperature shift of the boundary of +25°c.18 Blackburn advises that the first group of alloys contained 0.1 to 0.15 wt pct 0, bur he does say whether the analyses were performed on as-received material or on specimens in their final state of heat treatment. This is especially important considering the 20-mil-thick starting materials. If specimens had been annealed in the two-phase a + 6 region it would have provided an indication of the final degree of oxygen contamination since up to about 12 at. pct A1 the boundaries of this region are well-defined for low-oxygen alloys. Blackburn questions the capability of light microscopy in determining phase boundaries in the Ti-A1 system. I submit that the a/a + Ti3A1 boundary in Fig. 1 of Ref. 1 over the composition range from 10 to 18 at. pct A1 was determined by dilatometry and supported by electron diffraction. Specimens of alloys containing 8, 10, 12, and 14 at. pct A1 were aged at 550°C for 1000 hr (under stress of 5000 psi to accelerate the tendency to equilibrium) and then fractured in tension at room temperature. Collodion was applied to the as-fractured (unetched) surface and, when stripped, carried away particles identified by electron diffraction as Ti3A1. Perhaps Blackburn will explain why these electron diffraction data were ignored. At this time, a technique for revealing or indicating

Jan 1, 1969

By J. J. Frawley, W. J. Childs

PREVIOUS studies have shown that if a supercooled liquid metal was perturbed by vibration the probability of nucleation is is During a recent investi- gation to determine quantitatively the amount of energy needed to cause nucleation in a given supercooled liquid specimen, it was found that at low-energy values in the megacycle range, below the threshold energy value for cavitation, the amount of dynamic supercooling was greater than the amount of static supercooling. That is, if a specimen had a given amount of thermal supercooling under static conditions, its thermal supercooling could be increased by the addition of low-energy sound waves. The material used in this investigation was high-purity bismuth. This material was chosen because of its low melting point and the high degree of supercooling which could be easily obtained. The sound gener- ator employed in this work was a commercially built Sperry ultrasonic testing unit. This unit was equipped with a barium titanate crystal as a piezoelectric transducer. These sound waves were transmitted to the supercooled melt by a Pyrex rod, as shown in Fig. 1. The transducer was coupled to this Pyrex rod wave carrier by motor oil. The Pyrex wave carrier was approximately 1.5 ft long to prevent damage to the transducer by heat. The diameter of the Pyrex wave carrier appears to be critical. In the initial tests a wave carrier of 0.5 in. in diam was employed. However, the sound waves had no effect on the amount of dynamic supercooling. When the diameter of the wave carrier was increased to approximately the inside diameter of the Pyrex crucible, the sound waves were more effective. Approximately 200 g of metal was melted under a stannous chloride flux in a 30-ml beaker by induction heating. The temperature was recorded by a Pyrex-encapsulated chromel-alumel thermocoule which was placed in the beaker after the bismuth melted. The Pyrex wave carrier was immersed slightly below the surface of the liquid bismuth and the specimen was reheated to about 500°C. It was observed that the amount of supercooling depends on the amount of superheating the specimen receives; therefore, for meaningful results the amount of superheating was the same for all heating cycles. The specimen was allowed to cool in air and the change in temperature was continuously monitored with a potentiometric strip-chart recorder.

Jan 1, 1969

By A. U. Seybolt

DURING the course of an investigation of hot corrosion of nickel-base superalloys (combination oxidation-sulfidation attack at high temperature), it was considered possible that sulfur might gain entrance to the alloy in part, at least, by diffusion through the scale. Cr203 is nearly always observed as a prominent component of the oxide scale, and hence some experiments were carried out to examine the tracer diffusion of sulfur through Cr203 at 1000° C in the upper temperature range experienced by jet engine blades and vanes. Some hot-pressed Cr203 discs of quite high density were available from an earlier investigation1 on the rate of crf3 migration through Cr203. The Cr203 was 99.3 pct pure and contained -0.06 pct Fe as the largest metallic impurity. Additional data is given in Ref. 1. In this earlier work it was found that the rate of cation diffusion was independent of the atmosphere of thermal equilibration when using nitrogen, argon, or air, and also that the electrical conductivity of the hot-pressed Cr203 compacts was likewise independent of atmosphere in this range, thus indicating that the de-

Jan 1, 1969

By J. A. Goebel, S. Rosen

IN the NiAl phase diagram the NiAl (CsC1-type) phase field extends over a large composition range. At elevated temperatures the nickel-rich phase boundary extends to a composition of about 70 at. pct Ni, a value which is within 5 at. pct of the Ni3A1 (Cu 3 Au-type) phase boundary.&apos; At room temperature, however, the maximum nickel content is only about 60 at. pct. Experiments have shown that alloys containing greater than 63 at. pct Ni when quenched from temperatures below 1000°C contain the equilibrium phases NiAl and Ni3A1. On the other hand, when these same alloys are quenched from temperatures above 1000°C and examined microscopically, a typically martensitic decomposition product appears in the microstructure as shown in the micrograph of Fig. 1. The structure of the martensitic phase has been determined by employing powder X-ray diffraction techniques to be an "ordered" AuCu type (Strukturbericht Llo, space group P/4 mmm - DL). The diffraction pattern of this phase differs from that of AuCu in the appearance of superlattice lines. The structure is shown in Fig. 2. The open circles represent nickel atoms and the half-shaded circles represent nickel and aluminum atoms which are randomly distributed. The sites represented by half-shaded circles would be occupied solely by nickel atoms at a stoichiometry of Ni3A1. The alloys used in this investigation were prepared from 99.99 wt pct Al and 99.99 wt pct Ni by arc melting charges of varying compositions in a water-cooled copper hearth using a tungsten electrode in a gettered argon atmosphere. In all cases chemical analysis agreed within $ at. pct with the nominal compositions of the alloys. Annealing treatments were carried out in a vertical resistance furnace through which a stream of argon gas was flowing. Specimens, which were wrapped in tantalum foil, were quenched by allowing the specimens to drop into a bucket containing iced brine. X-ray diffraction patterns were obtained from -325 mesh powder specimens by using a 114.8-mm

Jan 1, 1969

By J. Pinto, F. Galasso

THE current emphasis in preparing boron fibers by reduction of gaseous boron compounds on a resistively heated metal wire substrate has renewed interest in the borides of those metals which have relatively high melting points and are available as fine wires. A knowledge of the structures and properties of the borides, which are formed when boron diffuses into the metal core during boron deposition, can be of assistance in the understanding of the boron fiber formation process and the fiber properties. Many of these borides are well-known and their properties have been measured. However, when an unidentified boride is found in the core, it may be difficult to establish its composition because of the small amount of material available, the preferred orientation effects on the reflections in its X-ray pattern, and the possible overlap of X-ray reflections if several borides are present in the core. For example. the proper indexing of the X-ray pattern of WB4, which was formed in the tungsten substrate core during boron fiber formation, was accomplished only after small single crystals of this boride were grown and X-ray precession investigations were conducted.&apos; This note presents the results of a study of the phases formed in the core when tungsten, tantalum, and molybdenum metal wires were used as substrates in the boron fiber preparation process with particular emphasis on the identification and characterization of a higher boride of molybdenum analogous to WB,. Boron was deposited on resistively heated stationary 0.0012-in.-diam tantalum, tungsten, and molybdenum wires at 1050°C for various times up to 60 sec using boron trichloride and hydrogen as the reactant gases. After 60 sec of boron deposition the fibers were approximately 0.006 in. in diam. Examination of photomicrographs of fiber cross sections showed that the boron had diffused nearly to the center of the tungsten and molybdenum cores in 15 and 30 sec, respectively, and only halfway to the center of the tantalum core in 60 sec. X-ray diffraction photographs of the fibers indicated that it was also after 15 and 30 sec deposition times that the tungsten and molybdenum metal reflections, respectively, had disappeared from the X-ray patterns of the fibers. The patterns of the boron fibers produced using tantalum wire as a substrate showed that amorphous boron, TaB2, and tantalum metal were present after a few seconds deposition time and remained even after deposition times of 60 sec. Until a deposition time of 15 sec was reached, the tungsten substrate fibers contained amorphous boron,273 6WB, W2B5, and WB4 as well as tungsten metal, while the molybdenum substrate fibers contained amorphous boron, MoBa, Mo2B5, and molybdenum metal for deposition times up to 30 sec. Just before the molybdenum metal pattern disappeared, a pattern similar to that of WB, appeared, suggesting that a phase, MOB,, isomorphous with WB,, was present in the fiber. This same pattern was obtained from the product formed by heating a mixture of molybdenum metal and excess boron powder in a boron nitride crucible at 1960°C in an argon atmosphere. As was the case with the WBn pattern, this pattern could best be indexed on the basis of a hexagonal unit cell rather than the tetragonal unit cell Chrktien and Helgorsky reported for ~0~4,~ see Table I. The unit cell parameters for MoB4 were calculated to be a, = 5.214A, co = 6.358A. Assuming the space group P63/mmc and positions5 2M01 in 2b and 2MoII in 2c found for tungsten in WB~,&apos; a logical structure for MOB, was determined using geometrical considerations to place the boron

Jan 1, 1969

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."&apos; By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.&apos; However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969