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By C. H. Li, R. J. Stokes

This paper compares the fracture behavior of tungsten rods in three conditions: recrystallized. recovered, and wrought. Notched specimens suhjected to a 50 in.-lb impact load showed ductile-brittle transitions at 700, 4.90°, and 440°C, respectinely. The recrystallized material had an equiaxed pain structure and jracbred by simple cleavage from a grain boundary source at all temperatures up to 700°C. The wrought and recovered material had an elongated fibrous structure and at low temperatures fractured by cleavage originating from the notch. As the transition temperature was approached cleavage was preceeded by more and more intergvanular splitting which deflected the crack front into planes parallel to the tensile axis. The enhanced toughness of wrought and recovered tungsten was attributed both to its inability to initiate cleavage because no pain boundaries were suitably oriented perpendicular to the tensile stress and to its inability to maintain cleavage because of intergranular splitting ahead of the crack. It has been appreciated for a long time in a qualitative manner that the room-temperature brittleness of fully recrystallized tungsten may be alleviated by working the material at relatively low temperatures.' More recently this difference in mechanical behavior between wrought and recrystallized tungsten has been examined quantitatively by measurement of the tensile properties as a function of temperature. In these experiments brittleness has been expressed in terms of ductility or reduction in cross-sectional area upon tensile fracture or in terms of the bend radius before fracture under bending.' This work has shown the existence of a fairly sharp transition from brittle to ductile behavior with an increase in temperature. The ductile-brittle transition temperature for recrystallized material is approximately 200°C higher than for wrought material. An increase in strain rate, small additions of impurity,' or an increase in grain size4 shift the respective transition temperatures to higher values, but the difference between them remains approximately the same at 200°C. A number of explanations for this embrittlement by recrystallization have been given. It has been blamed either on the concentration of impurity at the grain boundaries, the increase in grain size, or the change in texture which occurs upon recrystallization. The present paper examines the effect of different heat treatments on the notch-impact behavior of commercial powder-metallurgy tungsten rods. The change in the ductile-brittle transition temperature for this method of loading and the fracture mode has been related to the different mi-crostructures produced by heat treatment. EXPERIMENTAL PROCEDURE Commercial swaged powder-metallurgy tungsten rods 1-3/8 in. in length and 1/8 in. in diameter were machined to introduce a sharp V notch 0.030 in. deep. To change the microstructure from that of the as-received wrought material some of the specimens were subjected to an anneal in nitrogen either at 1300° or 1400°C for 8 hr or at 1600° or 2000°C for 1/2 hr. The notched rods were then placed in a miniature Charpy-type impact machine and struck at their midpoint (opposite the notch) with a hammer designed to deliver 50 in.-lbs of energy. The strain rate at the base of the notch was estimated to be approximately 100 sec-1 at the instant of impact. The specimens were heated in situ to the desired impact temperature. The microstructures produced by the various anneals were studied by both X-ray diffraction and metallographic techniques. Fig. 1 reproduces the microstructures observed metallographically following a 10-sec electroetch in a 10 pct KOH solution. Fig. l(a) shows the elongated fibrous grain structure of the as-received material. Following the anneal at 1300" or 1400°C the grain structure was still elongated as shown in Fig. l(b) but the etch pits delineated dense polygonized dislocation arrays within many of the grains. Occasionally a relatively dislocation-free recrystallized grain was found growing into the matrix. The anneals at 1600° and 2000°C resulted in complete recrystallization and some grain growth. The grains produced at 1600°C were still slightly elongated as shown in Fig. l(c) whereas the anneal at 2000°C produced equiaxed grains. The changes in grain size produced the expected changes in the X-ray back-reflection patterns; there was no indication either in the as-received material or the annealed material of any preferred orientation. RESULTS a) Impact Behavior. Fig. 2 reproduces the ductile-brittle transition curves measured in the manner described in the previous section. It can be seen that under these testing conditions the as-received

Jan 1, 1964

By A. S. Koster, G. D. Rieck

X-ray experiments were carried out to show the occurrence of cylindrical texture in drawn tungsten wire. Only a small amount of (110) (110) cylindrical texture could he found in wires of intermediate thickness, i.e., of about 1.5 mm diameter. DRAWN wires of tungsten and other bcc metals like iron and molybdenum show a well-established (110) fiber texture. Now it might be conceivable that in drawing radial stresses remove the randomness of the crystallites around the [110} axis, thus giving a fiber texture of higher symmetry. In the resulting so-called cylindrical textures a specified plane normal coincides with the radius of the wire. Several authors discuss the occurrence of cylindrical textures in bcc metals. ~ieck' found no cylindrical texture in drawn tungsten wires of 165 n diameter. Leber~ states that in tungsten wires of 3 mm diameter a cylindrical {100)(110) texture is developed, which is gradually converted to a normal fiber texture by subsequent drawing. He also reported a definite cylindrical texture at the surface of iron wires. Peck and Thomas3 observed a nonuniform mode of deformation of the grains in transverse sections of heavily drawn tungsten and iron wires. According to Bhandary and cullity4 a swaged iron wire has neither a perfect (110) fiber texture nor a perfect {100}(110) cylindrical texture. It is clear that the concept of cylindrical texture in bcc metals still lacks a firm experimental basis. Leber's eviden~e,~ which seems to be the strongest, rests upon qualitative interpretation of photographs. The appearance of the 110 and 200 lines on the photograph of 3-mm wire, however, can be very well attributed5 to a normal ( 110) fiber texture superimposed on random background; our Fig. 1, giving a Debye-Scherrer diagram of etched tungsten wire of 180 p, is free of cylindrical texture according to all authors, but is quite similar to Leber's diagram. It was therefore decided to use a different method of X-ray texture determination on tungsten wires of diameters where cylindrical textures may be expected.

Jan 1, 1965

By J. J. Kramer, K. Foster

The orientation distribution of surface-energy -induced secondary recrystallized grains was determined. This work was conducted on thin sheets of a 3 pct Si-Fe alloy annealed under environmental conditions that furor grouth of grains with a (100) plane in the surface of the sheet. The texture was found to be extremely sharp and almost independent of sheet thickness. The distribution varied exponentially with the angular deviation from the {100} plane. It was possible to relate the distribution to the nu-cleation rate of the secondary rains as influenced by the surface-energy difference. THE role of surface energy in the secondary grain growth of cube-oriented grains (grains with a (100) plane in the plane of the sheet) in thin Si-Fe sheets has been previously discussed.1-4 In high-purity sheet material normal grain growth usually occurs until the grains have extended through the sheet. Further grain growth is inhibited by the thermal grooving of the boundaries at the sheet surface. However, additional growth of cube grains can occur by a secondary grain growth process under conditions where the (100) plane has a lower surface energy than other orientations. Apparently for these alloys, cusps exist in the polar plot5 of surface free energy with the lowest cusp energy occurring at the (100) orientations. This has been reported to be the result of preferential adsorption of sulfur on the (100) planes.6 As a result of this process, a distribution of orientations could arise from two possible mechanisms. First, when a cusp is present in the polar plot of surface free energy, there are orientations inside the cusp that have a lower surface energy than elsewhere on the polar plot. Also, at sufficiently high temperatures, flat surfaces whose orientations are inside or just outside the cusp (depending on its shape) can often thermally etch, yielding a microscopically stepped surface of even lower surface energy. As a result, grains oriented close to cube would also have a lower surface free energy, either because of the cusp shape or by thermal etching, and could possibly grow as secondary grains by the surface-energy phenomenon. One should thus observe a distribution in the surface orientation of the cube grains comprising the secondary structure. It is the purpose of this paper to investigate this orientation distribution experimentally and to discuss the factors involved in its formation. For this purpose, the surface orientations of a large number of secondary grains in various sheet thickness were determined by means of the Laue back-reflection X-ray technique. PROCEDURE A vacuum-melted 3 pct Si-Fe alloy containing a nominal impurity content of 0.005 wt pct was processed into strip. A single cold-rolling step of 90 pct reduction was used for each strip regardless of the final sheet thickness. Final strip thicknesses of 0.60, 0.30, 0.15, and 0.075 mm were used. Care was taken to insure that the final strip surface was smooth and flat. All strips of a given thickness were annealed together at 1200°C in dry hydrogen (dew point -70°C) to develop the desired secondary structure and to insure identical environmental annealing conditions. The annealing time was selected to develop a complete secondary structure in the thinner sheets but to permit the thicker sheets (0.60 mm) to have residual primary grains remaining. This was necessary to determine whether growth impingement could lead to one secondary grain consuming another at a greater angular deviation. For the X-ray determination of the surface orientation of the secondary grains, a special specimen holder was used. The camera and holder arrangement could be aligned by X-raying a grain in three positions rotated 180 deg to each other. Thus, with a small beam X-ray focus (1 mm), the surface orientation of any grain could be determined to within one-half a degree. The surface orientations of one hundred cube secondary grains were determined for each sheet thickness. The criteria of a secondary grain were its size relative to the sheet thickness and the number of sides of the grain observed in the sheet surface. (A primary recrystallized grain extending through a sheet will generally have six edges visible in the plane of the sheet, whereas a secondary grain will have many more when growing entirely into primary grains.) Grains were selected as randomly as possible by X-raying every secondary grain found along a line drawn on the strip. No attempt was made to determine the exact orientation of the planes of the surface, as many strips from randomly selected sheets were used. On1y the angular deviation of the surface plane from {100} was measured. In order to assess the volume distribution in the

Jan 1, 1965

By P. E. Doherty, B. Chalmers

Subboundaries may be revealed in aluminum by the formation of pits on the surface during cooling from elevated temperatures. The pits do not form in the vicinity of high- or low-angle boundaries. They are attributed to the condensation of vacancies from a super saturation produced during coolirzg. Using the vacancy pit and Schulz X-ray techniques for observing low-angle boundaries, a study was made of the transition from the nearly perfect seed to the striated structuke characterist-ic of aluminum crystals grown from the melt. It was found that the individual striation boundaries develop by the coalescence of very small-angle boundaries, as well as by the addition of individual dislocations. Several mechanisms for the formation of striations are discussed. Evidence was found suggesting that a super-saturation of vacancies exists near a growing interface, and it is proposed that the resulting climb of existing dislocalions produces "half'-loops" at the interface, which combine to form the low-angle striation boundaries. LINEAGE, or "striation" boundaries, have been studied in detail by Teghtsoonian and Chalmers 1,2 in crystals of tin grown from the melt, and by Atwater and Chalmers3 in lead. They found that single crystals grown from the melt consist of regions which are separated by subboundaries that lie roughly parallel to the growth direction. A difference in orientation of 0.5 to 3 deg exists between the striated regions; the misorientation is such that the lattice of one region could be brought into coincidence with the lattice of its neighbor by a rotation about an axis approximately parallel to the direction of growth of the crystal. They observed an incubation distance for the formation of striations which increased with decreasing growth rate. They also found that in any crystal, the sum of all rotations of the lattice in one sense, in going from one striation to the next, is very nearly equal to the sum of all the rotations in the opposite sense. A striation boundary, which is a low-angle grain boundary, can be described as an array of dislocations. If it is assumed that suitable dislocations are introduced into the crystal during solidification, the formation of striation boundaries can be explained as a result of the migration of the disloca- tions into arrays. The formation of arrays is energetically favorable since the energy of an assembly of dislocations can be reduced by the interaction of the stress fields when a suitable array is formed. This investigation presents and interprets new information concerning the nature and origin of striation boundaries in aluminum. EXPERIMENTAL TECHNIQUE Single crystals of high-purity aluminum (Alcoa 99.992 pct) were prepared by horizontal growth from the melt.'' The specimens were subsequently electropolished in a solution of 5 parts methanol to 1 part perchloric acid kept between -10° and 0°C in a bath of dry ice and alcohol. The current density was approximately 6 amps per sq in. Doherty and Davis9 have shown that in aluminum sub-boundaries with misorientations of not less than several seconds of arc may be revealed by the vacancy pit technique. During cooling from elevated temperatures pits form on electropolished surfaces of aluminum crystals as a result of the condensation of vacancies.11 Pits do not form in the vicinity of small- or large-angle grain boundaries, presumably because such boundaries act as sinks for vacancies. Boundaries of misorientations down to 3 sec of arc are revealed as pit-free regions, see Fig. 1. The Schulz X-ray technique12 was used to determine the angular misorientations of subboundaries. In this method, white radiation from a micro-focus X-ray tube is used to produce an image of a fairly large area of a single crystal surface. Subboundaries cause splitting in the diffracted image, see Fig. 2. Misorientations down to about 15 sec of arc may be observed with this technique. OBSERVATIONS AND DISCUSSION Figure 1 shows a striated aluminum crystal grown at 10 cm per hr etched by the vacancy pit technique. An incubation distance of about 1 cm is observed before the initiation of striation boundaries. Fig. 2 is a Schulz X-ray photograph of a striated crystal similar to that shown in Fig. 1. A large area of the crystal was studied by means of a series of photographs. Fig. 2, which is a reflection from the (100) plane, included about the first 4 cm of crystal to freeze. There is an incubation distance of about 1 cm, and a distance of about 2 cm over which the angle of misorientation builds up to its final value of approximately one degree. Some twist component can be seen in Fig. 2 at the right side of the photograph. From Fig. 2 it can be seen that the sum of all rotations of the lattice in one

Jan 1, 1962

By M. E. Wadsworth, I. B. Cutler, R. W. Bartlett

The oxidation kinetics of ZrC was studied between 450" and 580°C in oxygen pressures from 6.5 x 10-to 1 atm using a ther mogravimetric apparatus and sized powder samples. Two parallel rate controlling processes were observed. A surface reaction occurring at the ZrC-ZrO2 phase boundary accounted for most of the oxidation and had an activation enthalpy of 46 kcal per mole. The other process, believed to be diffusion of oxygen into the ZrC lattice partially replacing carbon, had an activation enthalpy of 53 kcal per mole. The enthalpy for chemisorption of O2 on ZrC was determined to be —13 kcal per mole. Water vapor in the presence of oxygen accelerated the surface reaction rate. THERE has been little reporting of formal rate studies or attempts to ascertain the mechanism of oxidation of carbides. MacDonald and Ransley1 studied the oxidation of titanium carbide which has the same structure as zirconium carbide, fcc. They observed an initial increase in rate with increasing temperature followed by a rapid decrease through a rate minimum and a subsequent second increase at higher temperatures. The discontinuity in the rate rise was attributed to a phase change in the oxide which changed the rate determining step from the surface reaction at the carbide-oxide interface to diffusion through the oxide layer. Samsonov and Golybera 2 studied titanium carbide and reported that during the initial period of oxidation a dense film of Tic-TiO was formed followed by the formation of less adhering layers of higher oxides. The purpose of this investigation was to study the kinetics of oxidation of zirconium carbide and to attempt to gain some knowledge of the mechanism by which oxidation occurs. EXPERIMENTAL PROCEDURE Measurement of the weight gain associated with the oxidation of ZrC was used to determine oxidation rates. The principal experimental parameters were surface area, temperature, and oxygen pressure. Although moderately sized crystals of ZrC can be grown by the Van Arkel method, the only commercially available ZrC is a powder. In using powders, the surface area must be controlled either by fabricating the powder into a sintered pellet with a measurable surface area, relatively fixed during oxidation, or by using sized unconsolidated powder and applying appropriate geometric considerations to the shape of the grains to correct for their diminishing surface areas as they oxidize. Both techniques involve some difficulties. pellets of binder-free zirconium carbide can be made by hot pressing, but it is difficult to obtain densities greater than 90 pct of

Jan 1, 1963

By D. W. Rudd, D. W. Vose, S. Johnson

The permeability of Mo-0.5 pel Ti to hydrogen was investigated over a limited range of temperature and pressuire (709° to 1100°C, 1.i and 2.0 atm). The resulting permeability, p, is found to obey the The experimental data justifies the permeation mechanism as a diffusion contl-olled pnssage of Ilvdrogen atoms through the metal barrier. 1 HE permeability of metals to hydrogen has been investigated by a number of workers and their published results have been tabulated by Barrer' up to 1951. Since most of the work on the permeability has been accomplished prior to this date, the compilation is fairly complete. Mathematical discussion of the permeability process has been reported by Barrer, smithells, and more recently by zener. From these efforts several facts are observed. First, the permeability of metals to diatomic gases involves the passage through the metal of individual atoms of the permeating gas. This is evidenced by the fact that the rate of permeation is directly proportional to the square root of the gas pressure. Second, the gas permeates the lattice of the metal and not along grain boundaries. It was shown by Smithells and Ransley that the rate of permeation through single-crystal iron was the same after the iron had been recrystallized into several smaller crystals. Third, it has been observed that the rate of permeation is inversely proportional to the thickness of the metal membrane. Johnson and Larose5 verified these phenomena by measurirlg the permeation of oxygen through silver foils of various thicknesses. Similar findings were noted by Lombard6 for the system H-Ni and by Lewkonja and Baukloh7 for H-Fe. Finally, it has been determined that for a gas to permeate a metal, activated adsorption of the gas on the metal must take place. Rare gases are not adsorbed by metals, and attempts to measure permeabilities of these gases have proved futile. ~~der' found negative results on the permeability of iron to argon. Also, Baukloh and Kayser found nickel impervious to helium, neon, argon, and krypton. From what was stated above concerning the dependence of the rate on the reciprocal thickness of the metal barrier, it is seen that although adsorption is a very important process, at least in determining whether permeation will or will not ensue, it is not the rate determining process for the common metals. A case in which adsorption is of sufficient inlportance to cause abnormal behavior has been noted in the case of Inconel-hydrogen and various stainless steels.'' APPARATUS The apparatus used in this study is shown in Fig. 1. The membrane is a thin disc (A), but is an integral part of an entire membrane assembly. The entire unit is one piece, being machined from a solid ingot of metal stock. When finished, the membrane assembly is about 5 in. long. Two membrane assemblies were made; the dimensions of the membranes are given in Table I. The wall thickness is large compared to the thickness of the membrane, being on the average in the ratio of 13 to 1. There exists in this design the possibility that some gas may diffuse around the corner section of the membrane where it joins the walls of the membrane assembly, If such an effect is present, it is of a small order of magnitude, as evidenced by the agreement of the values of permeability between the two membranes under the same temperature and pressure. A thermocouple well (B) is drilled to the vicinity of the membrane. The entire membrane assembly is then encased in an Inconel jacket and mounted in a resistance furnace. The interior of the jacket is connected to an auxiliary vacuum pump and is always kept evacuated so that the membrane assembly will suffer no oxidation at the temperatures at which measurements are taken. The advantages of this configuration are: 1) there are no welds about the membrane itself, so that the chance of welding material diffusing into the membrane at elevated temperatures is remote. 2) It is possible to maintain the membrane at a constant temperature. Since the resulting permeation rate is very dependent upon temperature, it is advisable to be as free as possible from all temperature gradients. 3) It is possible to obtain reproducible results using different specimens. The only disadvantage to this configuration is the welds (at C) in the hot zone. The welding of molybdenum to the degree of per-

Jan 1, 1962

By D. E. Etter, J. E. Selle

The Pu-Ce phase diagram was determined by differential thermal analysis, metallography, and elechm-nricroprobe analysis. The dingram is chararterized by a eutectic with extensive solid solubility in the cubic Phases of both cerium and plutonium. No intermediate phases were found. Cerium is soluble in e plutonium to 16.0 at. pet Ce at 626OC nnd in d plcltoniurn to 23.0 at. pet at 613 "C, decreasing to 17.5 at. pet at room temperature. No solubility in the a, ß, or ? phases was jound, and the mininum cerium required to stabilize 5 plutonium to room temperature is 3.2 at. pet. The maximum solubility of plutonium in 6 cerium is 19.5 at. pet at 721OC, and the maximum soluhility of plutonium in ? cerium is 34.5 at. pet. Invariant points in the system are: a) eutectic at 626oC, L16.5 = E Pu16.0 + y Ce65.5; b) peritectoid at613oC, e Pu13.5 -y Ce65.5- d Pu23.0. AS part of a program aimed at the determination of the phase equilibria in the Pu-Ce-Cu ternary system, preliminary investigations were made of the three binary systems. A survey of the Pu-Ce binary system by differential therma1 analysis indi- cated several areas of disagreement with the published diagram,' primarily in the shape of the liquidus surface. Consequently, a thorough investigation of the system was undertaken, and this report presents the results of the study. EXPERIMENTAL PROCEDURE Three methods of investigation were used: differential thermal analysis (DTA), metallography, and analysis with electron-microprobe X-ray analyzer (EMX). The EMX analysis was particularly useful for the determination of solvus lines. The DTA method was most useful for the determination of the liquidus curves. Metallography complemented both of these techniques. Materials. The cerium metal used for most of this work had a freezing point of 805°C. This material showed 15°C premelting, and was found metallographically to contain some unidentified in~lusions.2 The temperature of premelting is defined as the point at which the DTA curve breaks away from the base line, analogous to a curve obtained from a solid-solution alloy. Several compositions were prepared near the cerium end of the diagram with higher-purity material which had a freezing point of 800°C. etallographic analysis showed this material to be relatively free of inclusions and only 8°C premelting was observed. Major impurities were found by spectrographic

Jan 1, 1964

By R. F. Mitchell, G. F. Dillon, A. F. Armington

In this paper the present methods of boron preparation are discussed with emphasis on the iodide intermediate. Several methods of boron triiodide preparation were investigated, the most satisfactory method being the preparation from the elements. A yield of 60 pct based on iodine is found for this method. Zone-refining, sublinzation, distillation, and fractional-recrystallization results are given for the boron triiodide, with distillation producing the best results. Several methods of decomposition are also discussed. The purity of the resulting iodide boron approximates the puritjl of the best available bromide boron, ELEMENTAL boron has been suggested as a possible high-temperature semiconductor by several workers,' but has never been exploited as a device material. The principal difficulty with boron is the unavailability of pure crystalline material from which accurate information on electrical properties could be obtained. Most boron crystals presently produced are very imperfect in structure and of questionable purity, particularly in relation to carbon content. Several methods of boron purification have been reported in the past few years, all of which produce material with a purity better than 99.0 pct. Most of these methods have been the subject of a recent review by Starks' and will not be elaborated upon in this report. However, of all the purification methods reported, only those using halide intermediates produce a purity approaching that usually required for electronic applications. The bromide intermediate has been most used for the preparation of high-purity boron.'y3 This material is easily prepared from the elements and can be effectively purified by distillation and decomposed by hydrogen reduction. The resulting product contains a trace of silicon, and an uncertain amount of carbon, believed to be approximately 100 ppm. It has been recently reported by Russian workers that high-purity boron can be produced using an iodide intermediate.' In the work cited, boron is reported free of spectro-scopically determined impurities, but the reported detection limits are quite high (- 100 ppm). In addition, no data is given on the carbon content of the product. In the present paper, boron triiodide was chosen as the intermediate for several reasons. First, carbon tetraiodide, which could be a major impurity, is reported to be unstable above 200" and hence could be easily separated from the boron triiodide by its decomposition, since temperatures greater than this are attained during the purification process. The low melting point (45°C) and boiling point (20B°C) and the relatively high vapor pressure of boron triiodide should allow the application of any physical purification technique to the material. The possibility of a lower decomposition temperature than that used for the bromide process is another advantage which might cut down extraneous contamination. The iodide, however, does have certain disadvantages when compared with the bromide, the production cost being the most significant. This is the result of a higher halide-to-boron weight ratio, which means more intermediate must be employed. The cost of the starting material is also greater for the iodide. This cost could be considerably reduced however, by recycling the iodine byproduct. Epitaxial growth of boron, which is probably the best method of producing junctions, should be possible with either the bromide or the iodide as the intermediate. However, this has been attempted only on a limited scale up to the present time because of the unavailability of good crystals. The authors have been relatively successful in laying down a heterotaxy of boron on silicon, however. This will be reported at a later date. Several crystalline modifications have been reported for boron, four of which are now believed to be real.' These are the a! and 0 rhombohedral and the a, and 0 tetragonal. In general, the a! rhombohedral is the low-temperature form and the B rhombohedral is the high-temperature form. The tetragonal structures are detected between 1000"

Jan 1, 1964

By J. W. Rutter, K. T. Aust

In previous studies of grain boundary migration in zone-refined lead, the authors used bicrystal specimens consisting of a striated crystal which was grown from the melt, and an adjacent striation-free crystal, introduced by artificial nucleation and growth.1 While this method permits the study of the motion of individual grain boundaries, it does not provide control of the relative orientations of the grains. The present note will describe a technique for controlling the orientations of the two crystals in this type of specimen. The technique consists essentially of placing a striated crystal and a striation-free crystal of controlled orientations end-to-end in a graphite trough, then melting a short zone at the junction of the two crystals and allowing it to freeze to form the desired grain boundary. The apparatus used to carry out this process is illustrated in Fig. 1. It consists of a trough milled from high-purity graphite,with grooves in the underside for the placement of thermocouples. The graphite piece fans out on one end at the level of the bottom of the trough; the sides of the trough are completed in this region by the attachment of a mating plate with a slot cut at any desired angle to permit reorientation of the crystal placed at this end of the assembly. The joint between the crystals is made at or near the point where the slotted plate joins the rest of the trough. The thermocouple slots are deepened in this region so that the thermocouples are separated from the melt by only 1/32 in. of graphite. An induction heater, with suitable temperature control, is used to obtain the molten zone. The two single crystals used are first chemically polished in a solution consisting of eight parts glacial acetic acid and two parts 30 pct hydrogen peroxide. They are then placed in the trough with the ends to be joined at the position of the thermocouples. Next, cooling is applied to the two crystals by means of air

Jan 1, 1962

By T. E. Leontis

Several publications1-7 during the past few years have demonstrated the markedly greater effect of cerium, as compared to all other alloying elements, in enhancing the strength and creep resistance of magnesium at elevated temperature either with or without the presence of other elements. In the work reported in Ref. 1-6, the cerium was added in the form of Mischmetal, which contains all the rare earth elements in essentially the same proportions as they occur in monazite sand, the principal ore of these metals. Mellor and Ridley7 have presented the creep characteristics at 200°C of magnesium alloys prepared both with pure cerium and with Mischmetal. Up to the present time, however, no comprehensive study of the effect of the various component elements of Mischmetal on the properties of sand-cast magnesium has been made. This hiatus in magnesium technology undoubtedly is associated with the difficulty in obtaining the rare earth metals separately. This investigation provides such a survey, the object of which was to determine which of the elements present in Mischmetal contributes the greatest effect in developing high strength and high resistance to creep at elevated temperatures. Toward this end the compositional variation of these properties has been determined as a function of temperature in the following alloy systems: 1. Magnesium-Mischmetal 2. Magnesium-cerium-free Misch- metal 3. Magnesium-didymiuin 4. Magnesium-praseodymium- lanthanum 5. Magnesium-cerium 6. Magnesium-lanthanum This designation, based on the names of the metals as furnished by the producer, is used throughout the paper in order to avoid the complicated system of listing all the elements present in the more complex alloys. The composition of the metals and the alloys is discussed in detail below. Preparation of Alloys ALLOYING INGREDIENTS The chemical composition of each of the six alloying ingredients used to prepare the alloys reported in this paper is given in Table 1. In each case, the percent total rare earths, percent cerium, percent neodymium, percent praseodymium, and percent thorium were determined in addition to the listed impurities. The percent lanthanum was determined by difference from the total rare earth content and consequently includes the other elements (samarium, terbium, yttrium, etc.) present in Mischmetal. These additional elements, however, seldom amount to more than 1 to 2 pet of the total rare earth content of Mischmetal. The iron content of the Mischmetal is considerably lower than that of the other metals. This grade of Mischmetal is now readily available. The metals are listed in the order of decreasing complexity. Elimination of the cerium from Mischmetal results in what the trade calls "Cerium-free Mischmetal." Carrying the separation a step further by eliminating the lantha-

Jan 1, 1950

By R. J. Allio, C. H. Randall

An automatic system for the quantitative analysis of microstrulcture has been developed. The method is based upon a statistical model of microstructure and employs phase intercept fractions as fundamental random variables. Structure-sensitive properties can be related explicitly to parameters derived from the distribution of phase intercept fractions in a matevial. THE properties of mechanical dispersions and of multiphase alloys art: intimately related to the amount, distribution, and intrinsic properties of the dispersed material. In many instances, the amount and distribution of the dispersed substances have greater influence on the over-all system properties than do the properties of the dispersed substance-Such properties as average particle size, particle size distribution, homogeneity of dispersion, volume per cent of dispersed phase, and mean free path between dispersed particles thus become critical in any evaluation of the properties of a dispersion. Unfortunately, techniques for evaluating quantitatively the microstructural characteristics of dis~ersions rapidly and accurately have not been available. If necessary, qualitative or semiquantitative devices can be utilized. Some such devices are based merely upon comparison of the specimens in question with arbitrary standards. Other techniques involve superposition of grids and tabulation of particles observed in different portions of the grid. Still other methods based upon lineal analysis entail counting lines or points at random upon the specimen to be examined; the number of intersections of the line with a given phase, the proportion of line or number of points which are covered by given phase are variously recorded. The mathematical basis for most of the techniques of quantitative metallography have been amply reviewed in the literature.'l2 without exctption, however, the standard techniques for quantitative metallography are either imprecise or are exceedingly tedious to apply. For example, tranverse integrating stage for rapid manual areal fraction measurement has been designed by Smith.3 Howerer, as in the case of any device based upon visual eslimation, operator bias may cause appreciable error. Various flying spot devices, on the other hand register particle size distributions in 2-dimensions, from which it is difficult to derive other properties of the dispersion. Thus, e.g., the 3-dimensional distribution cannot be inferred unless certain rather broad assumptions are made concerning the randomness of distribution and geometrical configuration of dispersed phase. Many limitations to the application of quantitative structural analysis can be overcome by the use of the microdensitometer, which is essentially an automated areal analysis device. Data obtained in the form of a distribution of phase intercept values are

Jan 1, 1962

By G. R. Speich, R. A. Oriani

The rate of coarsening (Ostwald ripening) of copper precipitate Particles in an a-iron matrix has been studied in three Fe-Cu alloys containing 2.3, 4.0, and 5.4 wt pct Cu in the temperature range 730° to 830°C. The kinetics of Ostwald ripening ohevs the law as deduced by Lifshitz and Wagner so that matrix diffusion controls the process. The equilibrium shape of the particles is that of rods with hemispherical caps, and is due to the BOTH Lifshitz and slyozov and wagner3 have recently solved the complex problem of determining the rate of coarsening of an assembly of precipitate particles. Both workers, although using somewhat different mathematical approaches, arrive at the same equation for the relation between the mean radius 7 of a distribution of spherical particles and the bulk solubility co, diffusivity D in the matrix, large anisotropy in the copper/a iron interfacial free energy (y,/y, = 4). A Lifshitz -Wagner equation, modified for both the nonsphericity of the diffusion field and the reformulation of the Gibbs-Thomson equation for the case of nonsphencal particles, is derived. Using the modified equation, the calculated values of the mean radius are smaller than those observed by a factor of about one -half. absolute temperature T, gas constant R, surface free energy y of the precipitate/matrix interface, and the time t of aging: where V, is the molar volume of the precipitate and v is a stoichiometric factor. Wagner's treatment is restricted to the case of spherical particles growing in a liquid matrix where strain energy is not a factor. Lifshitz and slyozov have discussed the effect of anisotropic particle shapes and internal strains on the rate of coarsening. Oriani4

Jan 1, 1965

By E. P. Abrahamson

The effect of transition element binary solid solution additions upon the recrystallization temperature of titanium has been investigated. All additions, except columbium and tungsten, raised the recrystallization temperature. A correlation is obtained between the logarithm of the absolute rate of change of recrystallization temperature with atomic percent solute and the number of uuter d shell electrons attributed to the free atom of the solute element in its ground state. The work of Abrahamson, et aL.1-6 on dilute binary solid solution alloys indicated a correlation between the free atom ground state electron configuration of the solute and both the brittle-ductile transition and recrystallization temperature. It is shown in these studies that the number of outer s and d electrons in the solute are of prime importance in determining the absolute rate of change of recrystallization or transition temperature with composition. Furthermore, the limit of initial linearity (in the curve of recrystallization temperature vs at. pct solute) has been shown to be a function of the number of d shell electrons in the solute for dilute iron- and vanadium-base alloys. To date no complete systematic recrystallization study of dilute binary titanium base alloys has been made. This study together with that of zirconium base alloys 6 will provide the data for the comparison of the effect of the same solutes upon two solvents with the same number of outer d shell electrons.

Jan 1, 1962

By O. N. Carlson, S. A. Bradford

Discontinuous yielding in tensile tests was observed in V-O alloys in the temperature ranges of 150° to 175°C and also 350° to 400°C. The magnitude and intensity of the serrations were found to vary considerably with oxygen content. Maxima were observed in tensile and yield strengths and in the strain-hardening coefficient at the higher temperature only. The strain rate sensitivity was observed to be negative between 150° and 400°C. THIS investigation was undertaken to study the effect of oxygen on the tensile properties of iodide vanadium in the temperature range of 25o to 450°C. Brown1 observed an increase in strength between room temperature and 400°C in vanadium metal, and found that oxygen and nitrogen had a rather pronounced effect on the strength and ductility. A maximum in the tensile strength was observed by Rostoker et al.2 near 300oC and by Pugh3 around 450°C for calcium-reduced vanadium. Pugh also found a maximum in the yield strength and in the strain-hardening exponent, and minima in the elongation and strain rate sensitivity at the same temperature. Eustice and Carlson4 reported the appearance of serrations in the stress-strain curves between 140° and 180°C in iodide vanadium containing 600 ppm O. These anomalies in the mechanical properties indicate that strain aging occurs in vanadium, but the impurity or impurities responsible for the above-mentioned effects have not been identified. The phenomenon of strain aging is usually characterized by the return of the yield point after interruption of a strength test. In the temperature range where strain aging occurs, the yield and tensile strengths attain maximum values, elongation and strain rate sensitivity exhibit minima, and discontinuous yielding is generally observed in the stress-strain curve. Cottrell5, 6 has postulated that strain aging is due to the migration of solute atoms to dislocation sites to produce locking after the dislocations have broken free from their impurity atmospheres during the initial yielding. At the strain-aging temperature the process is a dynamic one in which the solute impurity atoms diffuse to the vicinity of the moving disloca- tion producing "locking" which gives rise to maxima in the tensile strength and serrations in the elongation curves. Cottrel17 has noted that discontinuous yielding in iron occurs when the diffusion coefficient of nitrogen, D, and the strain rate, i, are related by D = 10-9 €. EXPERTMENTAL PROCEDURE The vanadium metal employed in this study was prepared by the iodide refining process as described by Carlson and owen.8 A representative analysis of the vanadium used in this investigation was: 150 ppm O, <5 ppm N, <1 ppm H, 150 ppm C, 150 ppm Fe, 70 ppm Cr, <50 ppm Si, 30ppm Cu, 20 ppm Ni, <20 ppm Ca, <20 ppm Mg and <20 ppm Ti. Alloys containing from 200 to 1800 ppm O, all of which lie in the solid solution range of the V-O system, were prepared by arc melting vanadium together with portions of a high-oxygen master alloy. The master alloy was prepared by tamping pure V2O5 into holes drilled in a vanadium ingot and arc melting this five or six times in an inert gas atmosphere, inverting the button between each melting step. The oxygen content of the master alloy was then determined by vacuum fusion analysis. Vanadium containing less than 150 ppm O was prepared in the following manner. A bar of iodide vanadium was deoxidized by sealing it in a tantalum crucible with a few grams of high-purity calcium. This was held at 1100°C for 4 days to allow time for the oxygen to diffuse to the surface and to react with the calcium vapors. The calcium oxide product was later dissolved from the surface of the bar with dilute acetic acid. In this way vanadium containing from 20 to 50 ppm O was prepared. Sample Preparation. The are-melted ingots were cold swaged into 3/16-in. diam rods and these were machined into cylindrical tensile specimens with a reduced section of 1.00-in. length and 0.120-in. diam. The test specimens were annealed for 4 hr at 900°C in a dynamic vacuum of mm of Hg to remove hydrogen from the metal. This recrystal-lization treatment produced a uniformly fine-grained structure with a mean grain size of approximately 0.06-mm diam. The oxygen contents reported in this paper were determined by a vacuum fusion analysis of the tensile specimens after testing. Analyses for other interstitial or metallic impurities showed no significant changes from that of the original material. Tension Tests. Tension tests were performed on a screw-driven tensile machine at a constant cross-head speed of 0.01 in. per min. Tests at elevated temperatures were carried out by heating the

Jan 1, 1962

By K. M. Busen, J. Lindmayer

A heterojunction model is suggested for descrihzng the electronic conditions at oxide -semiconductor interfaces. Detailed study of the silicon oxide-silicon interface shows that the heterojunction model explains many experimental facts; however, it is necessary to assume that a transition layer exists at the interface. It will he demonstrated that ionic contrbution way also he present. Extended low-temperature heating stabilizes the oxide to a charge carrier density in the order of 10&apos; cln-: determined by the heterojuncton model. OXIDIZED semiconductor surfaces are widely used, since they offer technological advantages and "passivate" the surfaces of semiconductor devices. However, it has been recognized that there are always n-type inversion layers formed in the silicon oxide-silicon system, which must be regarded as a definite disadvantage. An added complication is the "instability" of these inversion layers;&apos; the inversion layer appears to vary with the processing and they change at temperatures as low as 100" to 200°C This paper will point out that the inversion layer is a result of the dissimilarity of the contacting materials and therefore must always be present. The dissimilarity is the essence of the heterojunction or electronic model and involves directly the structure of the materials involved. In addition, one finds the contribution from ions; this disturbance, however. can be eliminated for the case of silicon oxide-silicon interface. The strength of the inversion layer or channel will be expressed in terms of the density of elementary charges per square centimeter, N*, maintaining the channel. The next section contains the formulation of the heterojunction model by assuming a contact between two homogeneous materials. This calculation should not imply that silicon oxide is homogeneous; it serves only to point out the general properties of the electronic model. Following the electronic model, the practical case of the silicon oxide-silicon interface will be discussed. I) THE HETEROJUNCTION MODEL Contacting an oxide with a semiconductor, a work-function difference must be accommodated. Fig. 1 represents the oxide and the semiconductor before and after contact. When the contact has been made, one finds that qVi + qV, = A@; i.e., the work-function difference is distributed between the oxide and the semiconductor. Normally, the work-function difference appears on the wide-bandgap material, but in the present case the oxide is thin and far from being a single crystal. Accordingly, a significant fraction of the work-function difference must appear on the semiconductor. The work function of silicon2 is about 4.8 ev, but we shall not assign any particular work function for the oxide as it may vary. However, oxides usually have lower work functions and therefore the potentials must build up in the manner shown in Fig. 1. Such an argument predicts that the inversion layer must be n type, as opposed to the clean surface which is p type. Another important factor to be considered is that the oxide is disorderly and therefore contains many trapping levels. As a result, the charges in the oxide arise primarily from the change in trap occupation, while on the semiconductor side the space charge is composed of mobile free electrons. The consequence of this fact is that a change to another thermal equilibrium will require some time, dictated by the traps in the oxide. The conditions can easily be calculated on the semiconductor side. Assuming an intrinsic semiconductor, Poisson&apos;s equation is

Jan 1, 1965

By A. H. Daane, W. J. Wunderlin, B. J. Beaudry

The solid solubility of holmium in copper, silver, and gold, determined using metallographic techniques, was found to be a maximum of 0.06, 2.4, and 3.2 wt pct, respectively, nt the eutectic temperatures. The temperatures of these eutectic horizontals, determined by differential thermal analysis, were found to be 868", 787", and 778"C, respectively. The first compound on the silver-rich side of the Ag-Ho system was found to be A&Ho2. In a study by Gold et al.,&apos; on the effect of small amounts of soluble impurities on the electrical resistance and thermoelectrical properties of copper, traces of iron were shown to have drastic effects on the thermoelectric power due to the magnetic scattering of the conduction electrons. Since little is known about the state of the iron ion when dissolved in copper, Gold had hoped to repeat these experiments using certain rare earths as the magnetic scattering centers; because of the tightly bound 4f electrons it is not expected that their spectroscopic state would be affected by alloying. In such an experiment the sole role of the trace rare-earth impurity would be to magnetically scatter the copper conduction electrons without producing appreciable distortions in the otherwise pure copper matrix. Since holmium was chosen for such a study because of its high magnetic moment, it was necessary to establish precisely its solid solubility in copper. The study was extended to include the solvents silver and gold, so that an evaluation of the data using classical solubility parameters could be made. No previously reported work on the systems of holmium with copper, silver, or gold was found in the literature. Information on the solubility of other rare earths in these three metals is also very meager. The solubility limit of yttrium in copper was reported as less than 1 wt pct2 and the solubility of praseodymium in gold as 0.35 wt pct,3 while no references were found on solubility studies of rare earths in silver. EXPERIMENTAL Materials. The materials used in this investigation were distilled holmium prepared in this Laboratory, OFHC* copper, electrorefined silver (99.9 *OFHC = oxygen-free high conductivity. pct), and gold with the analyses given in Table I. Sample Preparation. Samples weighing 1 to 2 g were prepared by arc-melting the components together on a water-cooled copper plate under purified argon atmosphere. The samples, turned and remelted at least five times to ensure homogeneity, showed weight changes of less than 0.1 wt pct after melting. Samples containing less than 0.7 wt pct Ho were prepared by diluting 1 to 2 wt pct Ho alloys with the pure solvent, while samples with concentrations greater than 0.7 wt pct Ho were prepared directly from the metals. The samples were wrapped in tantalum foil, sealed in outgassed Vycor tubing under helium, annealed at the desired temperature for at least 24 hr, and then quenched by shattering the Vycor tube in cold water. Metallographic Methods. Standard mechanical polishing methods were used in preparing the silver and gold alloys for examination, while the copper alloys were electropolished using a 40 pct solution

Jan 1, 1963

By J. F. Enrietto

Internal friction measurements were used to determine the effect of manganese on the solubility and precipitation kinetics of nitrogen. Manganese, in concentrations up to 0.75 pct, has little effect on the solubility at temperatures above 250°C. On the other hand, at Concentrations as low as 0.15 pct, manganese inhibits the formation of iron nitrides, especially Fe4N, even though it may not form a precipitnte itself. The precipitation and solubility of carbides and nitrides have been extensively investigated in the pure Fe-C and Fe-N systems.1-3 In recent years, some effort has been ispent in studying the influence of substitutional alloying elements on the behavior of carbon and nitrogen in ferrite.4 -7 In particular Fast, Dijkstra, and Sladek have investigated the effect of 0.5 pct Mn on the internal friction and hardness during the quench aging of Fe-Mn-N alloys.&apos;, &apos; They found that at low temperatures (below 200°C) the presence of 0.5 pct Mn greatly retarded quench aging. For example, after 66 hr at 200°C very little precipitation had taken place in the iron alloyed with manganese, whereas precipitation was complete after a few minutes in a pure Fe-N alloy. The effect of varying the manganese content and the details of the precipitation process were not mentioned in these papers. Fast&apos; postulated that manganese causes a local lowering of the free energy of the lattice with a resulting segregation of nitrogen atoms to these low energy sites. The segregated nitrogen atoms are bound so tightly to the manganese atoms that they cannot form a precipitate. The internal friction measurements of Dijkstra and Sladek tended to confirm the concept of segregation of nitrogen around manganese atoms, and the increase in free energy on transferring a mole of nitrogen atoms from a segregated to a "normal" lattice site was computed to be - 2800 cal. Dijkstra and Sladek9 distinguished between two types of precipitates: ortho, a nitride of appreciably different manganese content than that of the matrix, and para, a nitride with a manganese content essentially that of the matrix. With each type of precipitate a solubility, again designated ortho or para, can be associated. Since the internal friction maximum in alloys which were aged several hours at 600" C dropped almost to zero, Dijkstra and Sladek9 concluded that the ortho solubility must be very low. The effect of temperature on the ortho and para solubilities has no1: been investigated. There are obviously several gaps in our knowledge concerning the influence of manganese on the behavior of nitrogen in a-iron. It was the purpose of the experiments described in this paper to determine the following: 1) The ortho and para solubilities of nitrogen as a function of temperature. 2) The details of the precipitation process at elevated temperatures. 3) The effect of varying the manganese concentration on the above phenomena. EXPERIMENTAL PROCEDURE Internal friction is conveniently employed in studying the precipitation of nitrides and/or carbides from a -iron because it is one of the few parameters, perhaps the only one, which is not affected by the presence of the precipitate itself. For this reason, internal friction techniques were heavily relied upon in the present experiment. A) Preparat of -. All specimens were prepared from electrolytic iron and electrolytic manganese. Alloys containing 0.15, 0.33, 0.65, and 0.75 wt pct Mn were vacuum melted and cast into 25 lb ingots. After being hot rolled to 3/4 in. bars, the ingots were swaged and drawn to 0.030 in. wires. The wires wen? decarburized and denitrided by annealing at 750° C for 17 hr in flowing hydrogen saturated with warer vapor. To obtain a medium grain size, - 0.1 mm, the wires were then heated to 945oC, allowed to soak for 1 hr, furnace cooled to 750°C, and water quenched. Subsequent internal friction measurements showed that this procedure reduced the nitrogen and carbon concentrations of the alloys to less than 0.001 wt pct. The wires were nitrided by sealing them in pyrex capsules containing anhydrous ammonia and annealing them for 24 hr at 580°C, the nitrogen being retained in solid solution by quenching the capsule into water. Immediately after quenching, the wires were stored in liquid nitrogen to prevent any precipitation of nitrides. By varying the pressure of ammonia in the capsule, it was possible to produce any desired nitrogen concentration. B) Internal Friction. The internal Friction measurements were made on a torsional pendulum of the Ke type,&apos;&apos; a frequency OF 1. or 2 cps being used. For

Jan 1, 1962

By M. E. Nicholson

The solubility of carbon in Ni-Cu alloys was determined at 1000°C. The factors which limit solid solubility are discussed with particular reference to the influence of electronic factors. The results indicate the extent of solid solubility is a function of the density of states at the Fermi surface. THE solid solubility of an interstitial element is primarily limited according to Seybolt and Fullman1 and Speiser and Spretnak2 by (a) the strain energy produced when the solute atom takes its interstitial position, and (b) the partial molal free energies of the solid solution and the coexisting phases. In several binary systems of a transition and a noble metal, where there are no abrupt changes in strain energy or free energies of coexisting phases, the solid solubility of an interstitial third element drops abruptly to a negligible value at a composition corresponding to a complete filling of the "d-band." Such a decrease occurs in the case of hydrogen in the Pd-Ag system at 60 pct Ag.3,4 The solubility of carbon in Ni-Cu alloys seems to vary in a similar manner as indicated by the embrittling effect of carbon on these alloys. These al- loys are embrittled by slow cooling due to the precipitation of graphite. This embrittlement can be removed by heat treatment if the carbon content is less than the solid solubility limit at the heat-treating temperature. If the carbon content of the alloy exceeds the solid solubility at the heat-treating given temperxture, the embrittlement cannot be eliminated by solution heat treatment.&apos; Since pure nickel has a carbon solubility of 0.25 wt pct6 at 1000°C, embrittlement is easily removed from commercial nickel and nickel-rich alloys, which may contain of the order of 0.10 wt pct C. Embrittlement due to carbon cannot be removed from Ni-Cu alloys containing 70 to 80 wt pct Cu by annealing unless: the carbon content is of the order of 0.04 wt pct CL or less."&apos; Thus, it appears that the

Jan 1, 1962

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös&apos; law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By A. J. Shaler, H. Udin, J. Wulff

In the study of the sintering of meta powders, we have come to the conclusion in this laboratory that further progress requires a more basic understanding of the operating mechanisms. This is emphasized in detail by Shaler. He has shown that a knowledge of the exact value of the surface tension is imperative for a solution of the kinetics of sintering. This force plays a principal role in causing the density of compacts to increase.2 Furthermore, a knowledge of the surface tension of solids is also applicable to other aspects of physical metallurgy. C. S. Smith3 points out the relation between surface and interfacial tension and their function in determining the microstructure and resulting properties of polycrystal-line and polyphase alloys. This paper describes one group of results of an experimental program designed for the study of the surface tension in solid metals. As a by-product of this work, considerable information has been obtained on the rate and nature of the flow of a metal at temperatures approaching the melting point and under extremely low stresses, a field of mechanical behavior heretofore scarcely touched by metallurgists. The importance of this additional information to students of powder metallurgy need not be stressed. Theoretical Considerations Interfacial tension arises from the condition that an excess of energy exists at the interface between two phases. Gibbs proves that this energy is a partial function of the interfacial area; thus: ?F/?s = ? where ?F/?s is the rate of change of free energy of the system with changing surface area, at constant temperature, pressure and composition, and ? is the interfacial tension, or interfacial free energy per unit area. If one of the phases is the pure liquid or solid, and the other the vapor of the substance, ? may properly be termed "surface tension," and is a characteristic of the solid or liquid. The attempt of a body to lower its free energy by decreasing its surface gives rise to a force in the surface which is numerically equal in terms of unit length to the free energy per unit area of the surface. Thus ? may be expressed either in erg-cm-² or in dyne-cm-1. Similarly, surface tension may be determined either by a thermo-dynamic measurement of the surface energy or by a mechanical measurement of the surface force. We have chosen the latter approach. Tammann and Boehme4 determined the surface tension of gold by measuring the amount of shrinkage or extension of thin weighted foil at various temperatures and interpolating to zero strain. The method is of questionable accuracy because of the tendency of foil to form minute tears when heated under tension. Their assumption of F = 2W?, where W is the width of the foil, is unsound, as the foil can decrease its surface area by transverse as well as by longitudinal shrinkage. Although their experimentation was meticulous, the paper does not include details of the sample configuration required for recalculating ? on a correct basis, even if such a calculation were possible. In the experimental procedure chosen here, a series of small weights of increasing magnitude are suspended from a series of line copper wires of uniform cross-section. This array is brought to a temperature at which creep is appreciable under extremely small stress. If the weight overbalances the contracting force of surface tension, the wire stretches; otherwise, it shrinks. The magnitude of the strain is determined by the amount of unbalance, so a plot of strain vs. load should cross the zero strain axis at w = F?. If balance is visualized as a thermodynamic equilibrium, the critical load is readily calculated. At constant temperature, an infinitesimal change in surface energy should be equal to the work done on or by the weight: ds = wdl [A] For a cylinder, s = 2pr2 + 2prl [2] If the volume remains constant, r = vV/pl [31 s = 2vpl+2V/l [4] ds = vpv/l - 2V/l²) dl [5] Substituting [5] into [I] gives for the equilibrium load, w = ?(z/rV- 2V/12) [6] and, again expressing V in terms of r and l, w = pr?(1 - 2r/l [7] Here the end-effect term, 2r/l, is neglected for thin wires in subsequent work. Eq 7 can be confirmed by means of a stress analysis. If the x-axis is chosen along the wire, then the stress is 2pr? - w pr² pr2 [8] A cylinder of diameter dis equivalent to a sphere of radius r, insofar as radial surface tension effects are concerned.³ Thus xv = 2?/d = ?/r = sz [9] For the case of zero strain in the x direction, the strain will also be zero in the y and z directions. Since the wire is under hydrostatic stress, Eq 8 and 9 are

Jan 1, 1950