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By E. T. Hayes, A. H. Roberson, M. H. Davies

R. F. Dornagala and D. J. McPherson (Armour Research Foundation, Chicago)—I should like to compliment the authors for a workmanlike job in determining the partial phase diagram of a system comprised of two rnetals which are certainly not easy to work with. We are completing work at Armour Research Foundation on an Atomic Energy Commission-sponsored project for the determination of eight zirconium binary diagrams. Work on the Zr-Cr system has been completed and should be published within the next year. For our work, Westinghouse Grade 3 iodide crystal bar served as the zirconium melting stock. Johnson-Matthey, electrolytic chromium, specially treated for oxygen removal, was employed. The overall constitution of the system determined at Armour Research Foundation is in very good agreement with the present work. We found a eutectic at 18 pct Cr and 1280 °C, somewhat lower than the value reported. This temperature was confirmed by thermal analysis, incipient melting studies, and regular isothermal anneals. The eutectoid was located close to 1 pct Cr and 835°C by metallographic analysis of annealed specimens. Maximum solubility of chromium in /S zirconium was 4.5 pct at the eutectic temperature. Chromium solubility in a zirconium was less than 0.28 pct at all temperatures. We found the compound at 53 pct to melt around 1700°C, with an open maximum, but determined its crystal structure to be hexagonal close-packed (MgZn, type). The lattice parameters were in excellent agreement with those determined by Wallbaum in 1942. The diagrams are in substantial agreement, and .part of the differences are undoubtedly due to the use of different zirconium melting stock. M. K. McQuillan (Birmingham, England)—I read this paper with a great deal of interest, as it covered the same field as some work of my own.' There are a number of points in the present paper on which I would like to comment. First, I should say that I, too, used zirconium prepared by magnesium reduction of the tetrachloride and electrolytically prepared chromium, and melted the alloys in a Kroll-type arc furnace. The purity of my alloys should, therefore, be comparable with the purity of those of the present authors, and any differences in our observations would not be expected to be attributable to this cause. The differences between my observations and theirs concern the presence of the eutectic, the temperature of the eutectoid, and the melting point of the compound. I would be very much interested in any further evidence the authors may have for the occurrence of the eutectic at 1380°C. During the course of my work I noted that a number of my alloys containing 60 to 90 pct Zr melted at about 1400 °C, and for a time assumed that a eutectic occurred at this temperature as described in the paper. On further investigation, however, I found that the structures of the as-melted alloys could not be made to fit in with this interpretation of the system. If a eutectic exists in this region of the system it would be expected that the as-melted alloys would show the usual type of cast structure, i.e., dendrites of the compound plus eutectic. This, however, does not occur, as may be seen from Fig. 9. The compound seen there is not dendritic in form, and the remaining material is by no means certainly eutectic. It may be argued that a compound such as ZrCrl would not form dendrites but would tend to crystallize in geometric shapes. In this case, however, I have evidence to the contrary, as on the chromium side of the compound, where a eutectic occurs at about 1545"C, the compound formed from the liquid takes on a conventional dendritic form, and the eutectic is observed in the interdendritic spaces in the usual way. There is no reason to suppose that the compound would behave differently in an alloy lying on the zirconium side of the compound composition if a eutectic existed there too.

Jan 1, 1953

By D. F. Atkins, B. A. Rogers

The constitutional diagram presented herein is relatively simple. Complete mutual solid solubility exists for an interval below the solidus line, a continuous curve with a flat minimum near 22 pct Cb and 1740°C. Upon cooling, the solid solution breaks up, except at the columbium-rich side, from two causes: zirconium-rich alloys transform under the influence of the ß-a transformation in zirconium; alloys of intermediate composition decompose into two solid solutions below 1000°C. The combined effect is the formation of a eutectoid at a temperature of 610°C and a composition of 17.5 pct Cb. The eutectoid horizontal extends from 6.5 to 87.0 pct Cb. Some age hardening effects have been observed in the zirconium-rich alloys but the positions of the solvus lines remain uncertain. IN recent years, zirconium has been produced in much larger quantities than were available previously. Correspondingly, the incentive for studying its alloy systems has increased, as the number of recent publications on alloy systems testifies. However, only a partial diagram of the Zr-Cb system has been published and relatively few references have been made to alloys of the two metals. Hodge' investigated the Zr-Cb system up to about 25 pct Cb. His data on melting points were not sufficiently numerous to distinguish with certainty between the alternatives of a narrow eutec-tic horizontal and a wide flat minimum in the solidus curve. Although Hodge considered his results on transformations in the solid state to be only tentative, he suggested that the eutectoid in the zirconium-rich alloys lay at about 625 °C and 10 pct Cb and estimated that the solubility of colum-bium in zirconium at 625 °C was near 6 pct. According to Simcoe and Mudge,2 less than 0.5 pct Cb is soluble in zirconium at 800°C. These authors observed an increased strength in both the 0.5 and I pct Cb alloys made with hafnium-containing zirconium. According to Keeler,3 the strength of zirconium is increased by addition of columbium to a content of at least 3 pct. Keeler' also observed a maximum in hardness at about 10 atomic pct Cb and commented on the brittleness of alloys of this composition. Anderson, Hayes, Rober-son, and Kroll5 investigated the tensile properties of Zr-Cb alloys containing 5.1 and 12.9 pct Cb at room temperature and at 343°C. The 12.9 pct alloy had a high tensile strength at room temperature but also a low percentage of elongation. All alloys had high elongation at 343 °C. Littona measured strength and elongation values of annealed alloys containing up to 27.5 pct Cb and found low elongation values for all of the alloys of high columbium content. Some observations on the resistance of Zr-Cb alloys to corrosion in water at high temperature have been published by Lustman, De Paul, Glatter, and Thomas' who found that additions of columbium up to 1 pct had only a minor effect on the corrosion resistance of zirconium. Preparation of the Alloys Raw Material: Zirconium of a relatively good grade was available for making the alloys. It was obtained as scrap pieces that had been left over from an operation that included production by the iodide process, melting under a protecting atmosphere, and fabrication to plates. The individual pieces had hardness values of 24 to 32 Ra and a typical analysis is shown in Table I. The columbium also was scrap trimmed from sheets. It was furnished by the Fansteel Metallurgical Corp. and had a high ductility but its analysis was known only approximately. The metal probably contained about 0.5 pct Ta, perhaps 0.25 pct C, and a few hundredths percent each of iron, silicon, and titanium. Melting: The alloys were melted in a tungsten-electrode copper-crucible arc furnace similar to units that have been described recently in the metallurgical journals.'.' The crucible of this furnace is provided with a cavity in which a getter charge can be melted before the melting of the alloy charges. Hardness measurements on the ingots indicate that the getter charge takes up a considerable fraction of the oxygen and nitrogen from the helium atmosphere of the furnace. The alloys used in the investigation are given with their intended compositions, hardness, and melting points in Table 11. Fabrication: All alloys of the Zr-Cb system appear to be amenable to fabrication. At least, all of the compositions listed in Table II could be reduced to wires in a rotary swaging machine. The starting material was either slabs cut from ingots and ground by hand to rough cylinders or narrow strips trimmed from sheets made by cold rolling slabs. However, not all of the alloys could be fabricated satisfactorily by the same method. From 0 to 4 pct Cb and from 20 to 30 pct Cb or more, the alloys could be swaged cold from ¼ in. cylinders to 0.80 mm wires with only one intermediate annealing, sometimes with none. From 40 to 90 pct Cb, the alloys were difficult to swage either hot or cold but could

Jan 1, 1956

By Horace Pops, J. F. Libsch

THE discovery of SAP alloys (sintered aluminum powders) by lrmannl has stimulated investigations in other alloy systems.23 Not only do such alloys have good room-temperature properties, but they maintain high strength after prolonged service at elevated temperatures. In addition, they show high structural stability, including unusually high recrystallization temperatures. These characteristics are secured by dispersion hardening. For this investigation, Zn-ZnO alloys were selected. Practically, the fact that commercially pure zinc recrystallizes near room temperature prohibits strengthening and hardening by cold deformation and therefore limits the application of zinc where mechanical strength is important. Similarly, the poor

Jan 1, 1961

By R. L. Smith, J. L. Rutherford

ZONE refining, as developed by W. G. Pfann,1 has been used extensively for the purification of semiconductors. This method has made it possible to obtain the extremely high purity material necessary for the transistor industry. It has also been utilized to some extent for the purification of relatively low-melting-point metals. However, very little attention has been given to reactive, high-melting-point materials, with the exception of silicon. For this element, it has been necessary to use the floating zone technique in order to avoid contamination from the crucible containing the melt. The method is one in which a narrow molten zone is formed in a vertical rod by induction heating. The molten zone is supported between the two solid sections of the rod by surface tension. It is then moved longitudinally along the rod in order to effect a redistribution of solute. This technique has an advantage over the horizontal boat method, since crucible contamination is avoided. It has the disadvantage of being a much more difficult technique than zone refining in a crucible. Furthermore, it is necessarily a slow process, since only one zone at a time can be formed. However, the floating zone process offers a means of obtaining high-purity metals that are either not available, or can only be obtained in powder or pellet form as the result of complex chemical or electrochemical methods. It should be emphasized that the process is not effective in removing all impurity elements. Those that cannot be redistributed in an ingot during zone melting must be removed by some other means. Very little is known of the prope~ties of very high purity reactive metals such as iron, titanium, zirconium, beryllium, etc. It is quite likely that trace elements in such metals can affect their properties drastically. Therefore, one of the primary objectives of this work is to study the properties of metals which have been obtained in the purest form available and then zone refined. Trace elements can be introduced in a variety of ways, such as by inserting wafers between solid portions of the ingot to be melted, by placing the

Jan 1, 1958

By D. R. Hay, E. Scala

Electrotransport has been superimposed on the rate-limiling- step in zone refining which is the impurity diffusion through the liquid at the solid/liquid interface. The efficiency of zone refining is increased and relative resistivity ratios (P300°k/P4 2°K) he increased by 50 pel in tungsten for a given number of posses using- the electrotransport field-aided method. The effiect of zotze refining in the presence of an electric field on the relative resistivity ratio is examined as a function of its intensity and polarity. THE effect of electrodiffusion on the effective distribution coefficient of zone refining has been discussed by Pfann and Wagner.' Control of the distribution coefficient in zone refining is of twofold interest. A distribution coefficient of unity can be increased or decreased, making possible the transfer of some previously inseparable solutes. The general efficiency of zone refining can also be increased. In the conventional zone-refining process impurities are removed by their retention in the molten zone and subsequent deposition at the end of the rod after a complete passage of the zone. In higher-melting-point systems a second mechanism may also operate, the volatilization of impurities from the molten zone. It has been suggested by schadler2 that, in refractory metals, vacuum distillation plays the predominant role in purification. In Koo's results,3 the resistivity ratio decreased beyond a zone-refined length of 6 in. from the starting end, indicating that some purification does in fact occur by true zone-refining action. Hay and scala4 showed that the degree of purity as measured by the relative resistivity ratio method depends on the square root of time in the molten zone (number of passes) and thus appears to be limited by diffusion in the boundary layer at the solidifying interface assuming good mixing in the body of the molten zone where a linear rate would prevail. The final concentration of impurities in electron-beam floating-zone purification depends very much on the operating conditions and results obtained by various investigators2,3,5 are difficult to correlate. The diameter of the starting material, operating vacuum, and rate of traverse are among the factors to be considered. There are, nevertheless, some general observations to be obtained from the literature. Lawley5 reviewed the literature up to 1962 and concluded that the major contaminants generally remaining in tungsten after electron-beam zone refining are molybdenum and carbon. Molybdenum due to its high melting point and distribution coefficient of nearly unity would be expected to be difficult to remove by either volatilization or zone refining. Carbon is not only a common contaminant in vacuum systems, but is also very difficult to remove by conventional vacuum melting. even with vacuums of 10-7 mm Hg. For each of those impurities removed by zone refining the equation of Pfann and Wagner may be applied: It relates the effective distribution coefficient k to a superimposed driving force which accelerates the solute away from the interface with a terminal velocity L" and to the more conventional zone-refining parameters; v = rate of traverse, t = thickness of the diffusion layer at the solidifying interface, D = diffusivity of the solute in the molten zone, and ko = equilibrium distribution coefficient of the impurity.

Jan 1, 1965

By R. L. Fullman

Relationships are derived between average dimensions measured on a polished cross section and the spatial dimensions of particles dispersed as uniform cylinders. The equations are applicable to the measurement of rods or plates without the stipulation that they be extremely thin. QUANTITATIVE analysis of the elements of mi-crostructures has been limited by a lack of knowledge concerning the relationships between observations on plane surfaces and the spatial nature of the structure. This paper is an extension of previous efforts to establish equations suitable for the quantitative investigation of microstructures. The equations derived fill two gaps in the range of particle shapes for which measurements may be required, namely those shapes lying between extremely thin plates and equiaxed particles (approximately spherical), and those intermediate between equiaxed particles and extremely thin rods or needles. In a previous paper' equations were developed relating dimensions measured on a polished cross section to the average spatial dimensions of particles in the form of spheres, extremely thin plates, and extremely thin rods. For extremely thin rods the dimensions measured on a polished cross section were found to depend on the radius only, so that no information concerning the rod lengths or number of rods per unit volume could be obtained from observations on a cross section. In this paper equations are derived relating dimensions measured on a polished cross section to the spatial dimensions of particles in the form of identical cylinders. These equations may be used to evaluate the dimensions of rods, as well as the dimensions of plates, without the stipulation that the plates or rods be extremely thin. The impossibility of evaluating the length of extremely thin rods from planar measurements appears as an increase in the amount of data required for a given precision, as the length-radius ratio increases. Consider a sample containing particles of a phase in the form of cylinders of uniform radius T and height t. If the cylinders are randomly oriented, as in a sufficiently large sample of a fine grained poly-crystalline material, area and lineal analysis may be carried out with parallel cross-sectional planes and lineal traverses. If the cylinders are not randomly oriented, it is necessary to randomize the orientations of the cross-sectional planes and traverse lines. Let a unit cube be cut from the sample, and a cross-section plane be passed through the cube parallel to one of the cube faces. The number of particles N, cut by the cross-sectional plane per unit area is equal to the number of particles N, per unit volume times the probability p1 of a plane intersecting a single randomly positioned and randomly oriented cylinder in the cube. Let J be the maximum cylinder dimension in the direction normal to the cross-section planes, as shown in Fig. 1. Since, of the various possible positions for the cross-sectional plane over the unit length from top to bottom of the cube, only those positions existing over the length J

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Jan 1, 1932

By C. H. Mathewson

EXCEPTING the joint sessions on gases in metals held during the day on Tuesday, the Institute of .Metals opened its activities with a division dinner at the Commodore on Tuesday evening, with Sam Tour, retiring chairman, presiding. W. M. Corse, secretary-treasurer, outlined the financial status of the division and stated the investment fund is becoming large enough so that in the near future it will be possible to pay all expenses of a foreign lecturer once in two years and not rely on an extended speaking tour to cover expenses. W. B. Price reported on his attendance at the Zurich, Switzerland, meeting of the International Society of Testing Materials and gave a graphic account of his visit to the Grand Salon, his meeting with Mussolini, and his audience with the Pope. Buffalo was announced as the place of the fall meeting, to be held during the week of Oct. 3.

Jan 1, 1932