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

HE majority of liquidus and solidus surfaces in phase diagrams have been determined by the conventional cooling- and heating-curve techniques.' These techniques have two main shortcomings: 1) the solidus may be in considerable error due to the difficulty involved in completely homogenizing the solid and 2) the determination of liquidus and solidus in more than a two-component system does not enable one to determine tie-lines connecting the specific equilibrium solid and liquid compositions. However, in a recent paper by one of the authors,' a method was suggested whereby the liquidus and solidus surfaces plus tie-lines in an n-component system may be determined. This method utilizes a controlled solidification technique and assumes that interface equilibrium exists during freezing. The present work was undertaken with a twofold purpose; first, to determine the liquidus and solidus lines in the pseudo-binary system Bi2Te3-Bi2Se3 by heating- and cooling-curve techniques and, second, to determine the partition coefficients of Te and Se in the BizTe3-,Sex system by controlled solidifica- tion techniques. The two sets of results can be compared to test the accuracy of the controlled solidification method. EXPERIMENTAL I—The starting materials for this study were 997999 pct Bi, Te, and Se, obtained from the American Smelting and Refining Co. The compounds BizTe, and Bi2Se3 were each prepared by melting together stoichiometric amounts of the elements, followed by twelve zone-refining passes. This produced homogeneous bars of the compounds for use in the phase-diagram studies. The apparatus used to obtain heating and cooling curves is illustrated schematically in Fig. 1. The alloy samples were located in a graphite crucible placed in a stainless steel canister. The canister was supported in a heavily lagged pit furnace by a device which oscillated the canister about its vertical axis at a frequency of about 3 cycles per sec during heating and cooling-curve runs. The graphite crucible was designed to minimize the thermal coupling of the sample to the furnace. A thin graphite sleeve separated the alloy sample from the stainless steel tube that housed the thermo-

Jan 1, 1960

By H. F. Bishop, F. A. Brandt, W. S. Pellini

The solidification mechanism of experimental steel ingots (7x7x20 in.) was studied by thermal analysis. It was determined that solidification proceeds in wave-like fashion at rates which are determined by the carbon level, superheat, and mold thickness. The thermal cycles of the mold walls were related to the course of solidification. ESPITE marked advances in the field of solid state transformation, metallurgical research has contributed comparatively little exact quantitative data on the mechanism of solidification of metals. There is, therefore, a great need for such data in the various metallurgical industries. The mechanics of solidification of ingots have been investigated in the past primarily by studies of the rate of skin formation as indicated by bleeding or "pour out" tests. The "pour out" method, however, is a tool which gives only approximate information. In the case of alloys with wide solidification ranges, such as irons and certain nonferrous alloys, the method will not work at all; in the case of alloys of intermediate solidification ranges, such as commercial steels, the information may be misleading. Thus, the general adoption of this method has resulted in divergent conclusions regarding the solidification process. Chipman and Fondersmith1 by means of bleeding tests have shown that the linear growth of a solidifying ingot wall follows a parabola of the general form, D = K C, with the start of solidification delayed until superheat is exhausted, as indicated by the constant C. These tests were carried only to a wall thickness of about 5 in. using an ingot of approximately 17x39 in. in cross-section; hence the latter stages of solidification were not studied. Matuschka2-3 indicated that linear solidification of ingots is rapid at first, then slow, but toward the end of solidification the rate becomes extremely rapid again. Spretnak's4 bleeding studies indicated that, wall growth is expressed more rigorously by two parabolas, and that their point of intersection corresponds to a change of solidification mode from columnar to equiaxed. Spretnak also showed that the K values of the first parabola are always the same regardless of superheat. Nelson bled ingots of square cross-section and found that linear wall growth is initially rapid but decreases continually until the end of solidification. He also concluded that rate of solidification in ingots of square cross-section increases 2.15 pct for every 10 pct increase in cross-sectional area of the mold. The mold ratios considered (ratio of cross-sectional area of the mold to cross-sectional area of the ingot) were all less than 2 to 1. The subject of solidification has also been treated mathematically in many cases, but because of the lack of accurate thermal constants and the simplifying assumptions required, as their authors generally acknowledge, they represent only approaches to the actual conditions of ingot solidification. A third method of studying solidification is the electrical analogue method promulgated by Pasch-kis6-7 and by Jackson and coworkers.8 This method treats solidification as a heat transfer problem with the solidification cycle synthesized on an electrical circuit. Paschkis in his treatment of solidification considered the fact, which was generally ignored, that solidification of steel is not simply the growth of a plane solid wall but a more complex process occurring over a temperature range as indicated by the constitution diagram. Undoubtedly, the anomalous results obtained by bleeding tests arise from the inability to measure quantitatively this mushy condition. The shape of Paschkis' solidification curves are more nearly in accord with those of Matuschka, in that they indicate rapid linear solidification at the beginning and end of solidification with intermediate solidification occurring at a slower rate. Paschkis indicates a definite lengthening of solidification time with increasing superheat. Thermal analysis is a direct method providing exact information for all types of metals regardless of solidification range and was thus adopted in the present program to follow the entire course of solidification from the surface to the centerline of the ingots. The method has the added advantage of being adaptable to following the thermal cycle of the ingot mold during the course of solidification. Test Methods The ingots studied were of square cross-section, 20 in. long, tapered from 71/4 in. at the top to 63/4 in. at the bottom, and fed with a hot top 7 in. in diam and 12 in. high. The molds were uniform in wall

Jan 1, 1953

By H. F. Bishop, F. A. Brandt, W. S. Pellini

M. S. Fisher and D. R. F. West (Imperial College of Science and Technology, London, England)—It may be of value to compare certain features of the results recorded in this very interesting paper with those of an investigation11 involving determinations of temperature gradients and rates of solidification of steel blocks of 3 in. sq section, cast horizontally in sand molds, some of which contained chills. Castings in plain carbon steels containing up to 0.8 pct C were made and, throughout this range of compositions, both inverse-rate and direct cooling curves, obtained from thermocouples placed within the mold cavity, showed a major arrest, the temperature of which was taken as the "effective liquidus" for the particular steel in question, solidifying under the conditions of the investigation. At the completion of the arrest, the curves showed a comparatively rapid de- crease in temperature. Some of the steels investigated lay within the peritectic region, and a second arrest at 1485°C was detected. In Fig. 15, which shows the effective liquidus temperatures, the limit of the 8 + liquid field has been placed at approximately 0.5 pct C. In inverse-rate curves corresponding to the thermal center of each casting, there was always a discontinuity, viz: an abrupt change of slope, at a temperature about 10 to 20°C below the "liquidus arrest," after which there seemed to be no significant irregularity in the rate of cooling. Curves corresponding to other positions in the casting generally showed some irregularities below the main arrest, probably as a result of heat flow from the solidifying interior. Even the reproducible discontinuity in the curves for the central positions appeared to have no theoretical or practical significance, though it probably corresponded to a stage in the solidification process at which only a relatively small amount of interdendritic liquid remained. Its temperature, rela-

Jan 1, 1953

By Donald Jaffe, Michael B. Bever

The solidification of Al-Zn alloys (2 to 70 pct Zn was investigated at different rates of solidification. The resulting structures were studied; the amounts of nonequilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography after activation of the zinc by neutron irradiation. These compositions were also determined from microhardness values. IN a recent investigation of the soltdification of aluminum-rich AI-Cu alloys,' the amounts of non-equilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography. The work reported here extends the investigation of nonequilibrium solidification to the Al-Zn system in the range from 2 to 70 pct Zn. In addition to autoradiography, microhard-ness values were used to determine compositions on a micro scale. Solidification Experiments The alloys contained approximately 2. 6, 12, 20, 30, 50, and 70 wt pct Zn and the balance aluminum. According to published diagrams the eutectic reaction occurs at 382°C between the eutectic liquid (95 pct Zn), a (82.8 pet Zn), and $ 498.9 pct Zn). Solid-state reactions at lower temperatures (due to the miscibility gap between 350" and 275"C, the eutectoid at 275'C, and the precipitation from supcrsaturated a) did not affect this investigation. Even if they occurred to any appreciable extent, they did not alter the evidence pertaining to the solidification structures. The alloys had to be of high purity to avoid radioact~ve contamination during activation. The aluminum analyzed 0.015 pct Si, 0.009 pct Fe, less than 0.004 pct Cu, and less than 0.006 pct Mg with traces of sodium and titanium; the zinc was reported to be at least 99.99 pct pure with traces of iron and magnesium. The alloys were prepared under argon in an induction-heated, bottom-pouring furnace, and poured into a coated steel mold, which could be preheated to temperatures up to 700°C in order to control the rate of solidification. The pouring temperatures ranged from about 40" above the liquidus for 2 pct Zn alloys to about 130°C above the liquidus for 70 pct Zn alloys. As soon as the melt entered the mold, the readings of a thermocouple placed % in. above the bottom of the mold were recorded by a recording potentiometer. Cooling at the rate induced by the initial temperature of the mold was continued to a temperature 100°C below the liquidus; the mold with its contents was then quenched in icy brine. Quenching from a fixed interval below the liquidus was used to provide a standardized procedure, since the solidus and liquidus temperatures and the interval between them vary greatly over the composition range investigated. The temperatures from which the samples were quenched were below the equilibrium solidus, but under nonequilibrium conditions some liquid was still present. This residual liquid solidified during the quench. The samples measured 314 in. diam and 11, in. height. Drillings for chemical analysis were taken

Jan 1, 1957

By D. Turnbull, J. H. Hollomon

THERE is a large body of evidence'" indicating that solidification during the liquid-solid transition is usually induced by heterogeneities present in the liquid. By dispersing liquid metals into small droplets, the impurities responsible for catalyzing solidification are isolated within a small number of these droplets. The effect of the foreign body therefore is restricted to a single drop by this technique. Thus upon cooling below the melting temperature, solidification is initiated by homogeneous nucleation in the majority of the droplets that do not contain impurities. In the case of solidification of liquid metals, the activation energy for nucleation is so great that its rate changes by orders of magnitude for a change in temperature of only several degrees centigrade.' Effectively homogeneous nucleation occurs at a critical temperature upon continuous cooling. Thus by microscopic observation of single particles during cooling, a temperature at which the rate of homogeneous nucleation becomes sensible can be determined.3 since at the temperatures at which nucleation occurs in the absence of impurities the rate of crystal growth is extremely rapid, the temperature at which the entire particle solidifies is very nearly the temperature at which the nucleation of the solidification occurs. Thus for liquids that freeze at high temperatures the onset of nucleation can be established by simply observing the temperature at which the marked heat evolution and increase in brightness of the particle occur. For liquids that freeze at lower temperatures the onset of nucleation can be determined by a rumpling and change in shape of the particle resulting from its solidification. The microscopic technique for observing the solidification of small particles has already been described." In earlier papers the nucleation of solidification of pure metals 5,6 and of alloy systems7 showing complete liquid and solid solubility have been described. In the present paper, the observations are extended to a simple eutectic system (Pb-Sn) where the possibility of the formation of two solid phases exists. Metals for the investigation were obtained from the American Smelting and Refining Co. in the form of pure lead and pure tin, 99.8 and 99.9 pct purity, respectively. An ingot of each of the pure metals was made into shot by heating the metals at a temperature about 50 °C in excess of the melting point and pouring the liquid slowly into a container of water at 15°C. Samples of the shotted pure metals were weighed out to make alloys containing 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, and 90 atomic pct Pb. Samples of each alloy were then melted in separate beakers. Each melt was poured through a pyrex funnel into a cylindrical mold (% in. ID). The casting solidified in 10 to 20 sec. The inside of the mold as well as the funnel through which the metal was poured were coated with graphite to eliminate adherence of the metal. Analyses were performed on some of the compositions and are given in Table I. The compositions also were checked for these samples and for those that were not analyzed by determining the spread between the liquidus and the solidus upon melting the small metal particles. These measurements agreed as well with the nominal compositions as the analyses listed above. Results The results of the supercooling experiments for the several alloys are summarized in Table II and plotted on the constitution diagram in Fig. 1. Data for the pure lead and pure tin were taken from earlier investigations. The values for the maximum supercooling of the several alloys are the average of several determinations on a number of drops of each alloy. The maximum value in any determination was within about 2 pct of the average. For the alloys containing from 20 to 60 atomic pct Sn, inclusive, two marked changes of the surface structure were observed upon cooling. At the higher temperature, after the first appearance of the solid phase it continued to grow slowly at a constant temperature and then stopped. At the lower temperature the alteration of surface structure was abrupt. For the alloys containing from 70 to 95 atomic pct Sn, inclusive, an abrupt change in surface structure was observed at a single critical temperature.

Jan 1, 1952

By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956

By S. H. Moll, R. E. Ogilvie

The investigation of solid-state diffusion phenomena may lead to much information concerning binary alloys. In particular, a study of the concentration gradients present in multiphase diffusion couples can lead to the determination of the solubility limits of the single-phase fields in the phase diagram. The specific concentration gradient which results from the heat treatment of a diffusion couple depends not only upon the time and temperature of diffusion, but also upon the number of phases existing in equilibrium at the diffusion temperature. Such concentration gradients possess sharp discontinuities whose terminal points correspond to the solubilities existing at the limits of the two-phase field in the phase diagram at the diffusion temperature. In general, there will be a discontinuity in the concentration curve for each two-phase field which exists in the phase diagram between the concentration limits of the couple. A number of investigators have analyzed the gradients present in multiphase diffusion couples. 1-8 The iron-titanium phase diagram exhibits a y loop in the temperature range from 900" to 1400°C, and the limit of the a + y field lies at some composition which is less than 1 wt pct Ti for any temperature. It was felt that a diffusion study could yield values not only for the diffusion coefficients involved, but also for the chemical solubilities in the phase diagram. The concentration gradients were analyzed by an X-ray absorption technique developed by Ogilvie.6 The absorption of a monochromatic X-ray beam is measured in steps parallel to the diffusion direction and the resulting intensity gradients are transformed into concentration gradients by applying the laws of X-ray absorption in a binary system. This technique has been applied by ogilvie6 to the systems Ni-Au, Cu-Au, Fe-Cr, and Ni-Cr; by Gelles7 to the systems Be-Fe, and Be-Ni and by Hilliarde to the system Al-Zn. Linear X-Ray Absorption Analysis—The use of X-ray absorption analysis as a tool for determining concentration gradients arises from the fact that the beam is absorbed according to the quantity and species of elements present in the sample and not according to their state of aggregation. This method is more advantageous than the chemical analysis of machined layers since it is less time consuming and less expensive and can analyze a very small area. IF a homogeneous binary alloy (A + B) is analyzed with two different monochromatic X-ray beams I0(2) and lo(2) the following relation between the transmitted intensities, the intrinsic absorption coefficients of A and B for the two different radiations and the weight fraction of each element may be derived.' In (I/Io) (a+b) xa(u/p)a(2) + xb(u/p)8(2) Eq. [1] is independent of specimen thickness and density, but requires that either element A or B possess an absorption edge between the wavelength limits of the two monochromatic beams. I, is evaluated for each radiation by measuring the transmitted intensity through a varying number of foils of a suitable absorber. A plot of the natural logarithm of the transmitted intensity as a function of the number of foils, when extrapolated to zero foils, yields the value of I,. If a plot of the ratio in Eq. [ I] is calculated as a function of xA, then a master curve results. From

Jan 1, 1960

By R. W. Fountain, John Chipman

The solubility of nitrogen in Fe-B alloys (0.001 to 0.91 pet B) is determined by the Sieverts' technique for temperatures of 950° to 1150°C. The activity coefficient of nitrogen is decreased by boron. The three-phase equilibrium between ? iron, BN, and gas is established and also the four-phase equilibrium between iron, BN, Fe2B, and gas. The above equilibria are calculated for a iron. The relation of these data to hardenability and strain aging of boron-treated steels is discussed. BORON additions are known to enhanbe the hardenability of heat-treatable steels and to assist in the control of strain aging in sheet steel for deep drawing. The increase in hardenability is explained by the theory that adsorption of boron on austenite grain boundaries reduces their free energy and thus retards ferrite and upper bainite nucleation.l,2 Digges and Reinhart3 have shown that the full effectiveness of boron in commercial steels is achieved only when strong nitride formers such as titanium and zirconium are also present. The influence of nitrogen on eliminating the boron contribution to hardenability was also demonstrated by Shyne and Morgan.4 These workers prepared Ni-Mo steels containing either nitrogen or boron or nitrogen plus boron. The nitrogen-plus-boron steels showed the lowest hardenability which was attributed to the presence of stable nucleating particles, presumably nitride. Morgan and Shyne5-7 have shown that boron in the amount of 0.007 pet will completely eliminate strain aging due to nitrogen in low-carbon, open-hearth steels. In addition, by proper control of the boron additions, a rimming steel can be produced. Since the effectiveness of boron on hardenability and eliminating strain aging is influenced by the amount and distribution of the nitrogen in the steel, the present study was. undertaken to determine the influence of boron on the solubility of nitrogen in iron. EXPERIMENTAL PROCEDURE The solubility of nitrogen in Fe-B alloys was measured by the method of Sieverts, which consists of determining the amount of gas dissolved by the metal in a constant volume system. The apparatus employed in this investigation and the experimental details have beendescribed previously.B AMcLeodgage was added to the apparatus to allow measurements at very low pressures. The alloys were melted at reduced pressure in a basic-lined induction furnace using electrolytic iron and ferroboron. Ferroboron was added after the primary deoxidation of the iron with carbon. Since it was difficult to attain a constant low level of oxygen by this procedure, silicon was added after the carbon deoxidation and prior to the ferr obor on addition. The alloys were castas 2-in. sq ingots, heated in argon at 1050loC, and forged to 1/4-in. plate. After forging, 1116 in. was machined from each side of the plate to remove any possible contamination, and it was then cold-rolled to 0.010-in. sheet. The sheet was cut into approximately 1/4-in. squares and pickled in an inhibited H2SO4 solution to ensure a clean surface. In the case of the boron alloys, a hydrogen treatment could not be used for surface cleaning because boron losses resulted. The composition of the alloys is given in Table I. For a solubility determination, a 75-g sample was inserted in a quartz tube and sealed in place in the apparatus. The entire system was evacuated at room temperature and leak tested for 24 hr. If no leaks were observed, the system was heated to the temperature of measurement and again leak tested for 24 hr. If no leaks were detected, the hot volume and solubility determinations were begun. The hot volume was determined at a constant temperature for each run by admitting successive amounts of argon and recording pressure vs volume, which, in all cases, resulted in a straightline relationship. The argon was then removed and the procedure repeated with nitrogen. Successive additions were made until the desired nitrogen content of the metal and equilibrium pressure of the system were obtained. The

Jan 1, 1962

By P. D. Hunt, I. Johnson, M. G. Chasanov, H. M. Feder

The solubilities of the transition metals from scundium to nickel, inclusive, in liquid cadmium were determined by sampling saturated solutions. At 400°C these solubilities (ppm) are:Sc, Co, 22; Ni, 12000. Relative partial molal enthalpies and excess partial molal entropies at infinite dilution for the solutes Cr, Mn, Fe, and Co are compared zoitlz similar data for the post-transition metals. Three new intermetallic phases, ScCd,, TiCd, and Ti,Cd, encozaztered in the course of this work, are reported. Measurements of the solubility of the 3-d transition metals in liquid cadmium have been reported' only for iron. The present measurements for the entire series were made as an aid to the study of the systematics of alloy formation. EXPERIMENTAL The apparatus and sampling techniques used for the solubility determinations were similar to those described by Martin etal.' Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple sheathed in recrystallized alumina and immersed in the solution. The thermocouple was recalibrated periodically during the course of the investigation. Thermocouple voltages were measured to the neares 0.01 mv with a Rubicon model 2732 potentiometer. A scaled-down version of the apparratus, in which the total metal charge was about 90 g, was employed to measure the solubility of scandium. Two-mm ID Vycor filter pipets were used to sample the scandium-cadmiurn solutions; the samples weighed about 2g- Cadmium with a minimum purity of 99.95 pct was used; the only impurities detected spectrochem-ically were C'u and Mg, both less than 10 ppm. The purities of the other metals were: scandium, 99.9 pct; titanium. 99.92 pct; vanadium, 99.9 pct; chromium, 99).99 pct; manganese, 99.9+ pct; iron, 99.90 pct; cobalt, 99.95 pct; and nickel, 99.96 pct. Solidified melts were routinely analyzed spectro-graphically. No significant contamination by the crucible, sampling pipets, or other materials of construction was observed. The entire specimen obtained by sampling was dissolved to preclude analytical errors due to segregation on cooling. Colorimetric methods3 were used for the analyses of cobalt (2-nitroso-l-naphthol), manganese (permanganate), nickel (dimethylglyoxime), titanium (peroxide), and vanadium (thiocyanate).4 Chromium, iron, and scandium were neutron-irradiated to produce The dissolved samples were gamma-counted to determine solute concentration.For the separation of intermediate phases from cadmium-rich alloys selective leaching by saturated ammonium nitrate solutions was employed. The concentration of cadmium in the successive leaches was followed polarographically and the process was terminated when the rate of cadmium dissolution decreased markedly. For the further investigation of intermediate phases 1/4- in. diam powder compacts were pressed at 80,000 psi and annealed in argon at 315" to 330°C for 10 days. Larger quantities of alloys were prepared in sealed tantalum capsules heated in a rocking furnace.

Jan 1, 1962

By G. K. Manning, W. E. Few

T has been known for some time that both'inter-granular carbide and intergranular oxide phases cause brittleness in molybdenum. Parke and Ham' indicated that 0.0025 pct 0 present in molybdenum after solidification from the melt was sufficient to induce intergranular brittleness during forging. However, material containing 0.06 pct C could still be forged. However, adding this amount of carbon to insure deoxidation causes the formation of carbides on freezing. These carbides are precipitated at grain boundaries, and Rengstorff and Fischer' have shown they have an unfavorable effect on the room-temperature ductility of molybdenum. Take? in 1928 proposed that the solubility of carbon was a constant value of 0.30 pct from room temperature up to 1800°C. In 1935, Sykes, Van Horn, and Tucker' obtained X-ray data suggesting that the solid solubility of carbon in molybdenum was between 0.07 and 0.09 pct at temperatures from 1500" to 2100°C. The a-solubility line for carbon was included in the Mo-C diagram given in the Metals Handbook as a tentative line based on the data of Sykes, Van Horn, and Tucker. In order to determine the partial phase diagrams for these systems, it was necessary to construct a high-temperature furnace suitable for heat treating molybdenum at temperatures up to 4000°F. A molybdenum resistance furnace was built for this purpose in which samples could be heat treated in a purified atmosphere and quenched from any desired temperature.' Experimental Work Solubility of Carbon: Arc-cast molybdenum supplied by the Climax Molybdenum Co. and 18-gage molybdenum wire samples produced by powder metallurgy at the Fansteel Metallurgical Co. were used in determining the a-solubility line for the MO-C system. The cast molybdenum contained 0.032 pct C initially. Two lots of 18-gage wire were used, one containing 0.011 pct C and the other 0.005 pct C initially. All material contained a carbide phase as received. Fig. 1 illustrates the carbides found in the untreated material. Heat treatment in a purified hydrogen atmosphere was found to reduce the carbon content in the as-cast molybdenum. Purified argonT also decarburized molybdenum samples at temperatures above 3500°F; however, the carbon content remained constant during heat treatment in purified argon at lower tem- peratures. The argon was purified by passing it over titanium at 750 °C and then through a magnesium perchlorate drying tower. The hydrogen was purified by passing it through a commercial hydrogen deoxidizer, followed by a drying tower. Specimens having different initial carbon contents were heat treated in argon at 3500°F for periods ranging from 5 min to 5 hr and were analyzed for carbon. Samples of the same final carbon content had the same microstructures regardless of time at temperature. Furthermore, a gradient between center and surface in the amount of undissolved carbide particles present was never observed. It was concluded that at these low carbon levels, and at the high temperatures involved, diffusion proceeds so rapidly that the specimen is always substantially homogeneous in carbon content, in spite of the gradual loss in carbon. Based on the above findings, the following procedure was used to determine the carbon-solubility limit at 3000°, 3500°, and 4000°F. At each of these temperatures, a number of samples were heat treated, as shown in Table I, and rapidly cooled to room temperature. Since the samples lost carbon in proportion to the length of time heated, a series of samples were obtained of varying carbon contents. By use of a rapid cooling rate, the phases present at the high temperature were retained at room temperature. All samples were examined microscopically. Those found to contain either no excess carbide phase or only a very small amount were then analyzed for carbon. The samples actually analyzed for carbon

Jan 1, 1953

By E. W. Filer, R. P. Smith, L. S. Darken

The solubility of nitrogen gas in purified iron and low alloy steels is determined for the y region (930° to 1350°C). The diffusivtiy of nitrogen is estimated from the rate of approach to equilibrium. The investigation of aluminum-killed steels, held in nitrogen, discloses precipitation of aluminum nitride, the solubility of which is determined. ALTHOUGH several investigations of the solu-bility of nitrogen gas in y iron have been reported, all have made use of the method adopted by Sieverts in his classic work, whereby the solubility is determined by the pressure or volume change of the gas. The agreement between different investigators* is rather poor, particularly as compared to the self-consistency of results of several individual investigators. The present report represents a portion of our investigation of the equilibrium of nitrogen and nitrogenous atmospheres with iron and steels. The method adopted in this temperature region (910" to 1400°C) consists of holding the specimen in gaseous nitrogen, quenching (or cooling), and determining the nitrogen content by direct analysis (solution in acid followed by distillation and titra-tion of the ammonia).** Up to 1050°C a 20 in. vertical wire-wound (Kan-thal) furnace was used; this was wound in three sections so that by proper adjustment of relative currents, and use of a modulator1 and a commercial controller (using a chromel-alumel control couple), a zone almost 6 in. long could be maintained uniform within a few tenths of a degree. Since the temperature coefficient of the nitrogen solubility is low, the full precision was not utilized and a variation of l° to 2" was tolerated; a variation of a similar amount also occurred occasionally between the beginning and end of the experiment. At higher temperature a vertically mounted, tubular Globar furnace and control unit was used; the zone of uniformity (l° to 2"C) was here limited to about 2 in.; fluctuations with time were comparable to those in the wire-wound furnace. Reported temperatures were measured by use of a platinum-platinum-rhodium thermocouple, which was frequently com- pared with a similar standard couple which was calibrated at the gold and palladium points and also compared with one certified by the Bureau of Standards; error from this source is believed to be less than 1 "C. Nitrogen gas from a commercial cylinder was mixed with slightly over 1 pct H by use of a gas mixer described previously.' This mixture was passed over hot copper and through ascarite and phosphorus pentoxide to remove oxygen and water vapor. The purified gas contained 1.05 pct H. This procedure was adopted to prevent the formation on the specimens of oxide film, which is well known to be nearly impervious to nitrogen; its success was attested by

Jan 1, 1952

By N. J. Grant, W. R. Opie

THE amount of hydrogen that will dissolve in lead has been considered negligible. However, a limited number of measurements made recently using apparatus built for determining hydrogen solubility in aluminum alloys' indicate that liquid lead will hold a small but appreciable amount of hydrogen in solution. The apparatus used was similar to that developed by Sieverts.' This consists of a bulb to hold the molten metal, a gas burette for introducing a measured quantity of gas into the bulb and a manometer for measuring the gas pressure in the bulb. Measurements are made by introducing enough of an insoluble gas (helium) to fill the system at a given temperature and pressure, thereby determining the hot volume of the bulb. This gas then is pumped out and hydrogen is introduced until the same pressure is reached, the metal being maintained at the same temperature while in contact with each gas. The difference between the volumes corrected for pressure is then the hydrogen solubility. A more detailed account of the procedure can be found in refs. 1 and 2. The lead was melted in an alundum crucible by induction heating to provide uniform temperature and an important stirring effect. The metal was the purest obtainable, 99.999 + , prepared especially by the research department of the American Smelting and Refining Co. Measurements were made by approaching the equilibrium value from high and low temperatures during the constant pressure runs, and from high and low pressures when the temperature was held constant. Thus a number of measurements were made on each of two large samples which weighed 336 and 398 g. The gases were purified as .described in ref. 1. The effect of temperature on the solubility was studied with the pressure held constant at 760 mm of Hg. To show the effect of pressure, solubility measurements were taken at two constant temperatures, 600" and 900°C. Results The effect of temperature on hydrogen solubility is shown in Fig. 1. The curve representing the data is parabolic, as are plots of hydrogen solubility vs. temperature for other metals and alloys (aluminum,' copper," and iron,& for example). Fig. 2 shows the relationship that exists when the solubility is

Jan 1, 1952

By C. Wert, P. Bunn

Determination of the solid solubility of gases in metals is usually done by one of two methods. The first is an additive method, in which measurement is made at temperature of the maximum amount of gas absorbed by an initially degassed piece of the metal. Gas additions are made until the dissolved gas first comes into equilibrium with a compound. This method is most useful at relatively high temperatures where the amount of gas absorbed is relatively large and where equilibration of the dissolved gas with the gas atmosphere can be achieved in a relatively short time. The second is a precipitation method. A supersaturated solution of the gas in the metal is held at temperature until equilibrium is established between the gas atoms in solution and a compound. The quantity of dissolved gas is then determined by some physical measurement which is sensitive only to the gas in solution. This method is generally useful in low temperatures. This paper describes measurement of solubility of nitrogen in tantalum whereby measurements at low temperatures using internal-friction methods are plotted together with existing measurements at high temperatures. The solubility is thereby known from less than 0.5 at. pet at 350°C to near 13 pet at 2300°C. Several measurements have been reported of the solubility of nitrogen in tantalum. These are collected in Fig. 1. Three single determinations by Ke,1 Andrews,2 and Brauer and zapp3 are plotted along with a series of measurements by Vaughn, Stewart and schwartz4 and Gebhardt, Seghezzi, and Fromm.5 Although not much doubt exists about the solubility being in excess of 10 at. pet above 2000°C, the solubility indicated at low temperatures depends on whose data are selected as being most reliable. The variation is enormous, being at least an order of magnitude at 500°C. Accordingly, a measurement was begun to examine this discrepancy. The method of measurement finally selected was that of internal friction. A solid solution of nitrogen in tantalum was prepared by heating a tantalum wire in a dilute at-

Jan 1, 1964

By A. U. Seybolt

The solubility of oxygen in a iron has been determined in the range between 700° and 900°C. The solubility is a function of temperature and varies from about 0.008 pct oxygen at 700°C to atureandabout 0.03 pct at 900°C. The heat of solution is approximately +15,500 cal per mol. AS pointed out in a recent paper by Kitchener et al.,1 there has been a lack of agreement among many investigators even as to the order of magnitude of the solid solubility of oxygen in the various forms of iron. This lack of agreement is attributable in large part to the difficulties in the determination of a small oxygen solubility; but because the problem has remained so long unsettled, it also indicates a lack of interest which is rather surprising when the demonstrated importance of small amounts of soluble nonmetallic impurities in iron is considered. The work of Kitchener et al. apparently leaves the solubility of oxygen in iron in a satisfactory state, but no attempt was made to investigate the solubility in a iron. The solubility of oxygen in a iron is actually of greater interest, since it is in this form that iron and mild steels are employed ordinarily. That the effect of oxygen in iron is of more than theoretical interest has been well established by Fast,' and more recently by Rees and Hopkins," who demonstrated that oxygen in the range between 0.0008 and 0.27 wt pct has a pronounced effect upon the mechanical properties. Previous Work and Methods Used To report in detail the literature relating to the solubility of oxygen in a iron would require an inordinate amount of space. For those interested in reviewing this work, a bibliography4-13 of the more significant papers is appended. In general, two methods of studying this problem have been used. One is the gas-metal equilibrium method where the H2O-H2-Fe or the CO2-CO-Fe equilibria have been used. The other is the more direct approach of the oxidation of thin strips of pure iron by packing in mill scale or by air or gaseous oxygen at some desired temperature. In this method oxygen is allowed to oxidize the surface and then to diffuse inward until saturation is obtained. In the gas-metal equilibrium method the oxygen dissolved in solid iron at a given temperature is proportional to the ratio of the water vapor-hydrogen pressures or the CO2-CO pressures over the sample for small ratio values. If the ratio becomes higher than a critical value, then an oxide phase makes its appearance (the solution becomes supersaturated). In principle, it is possible to use a series of H2O/H2 or CO2/CO ratios and to find by analysis the corresponding amounts of oxygen in solid solution at constant temperature. At the point where a very small increase in the gas ratio (increase in oxidizing powder) produces a large increase in oxygen content, the solid solubility limit is reached. Alternately, if the critical ratio is known, it is possible to use the procedure of Kitchener et al.1 and to use a ratio which is near but below the critical one. The solubility corresponding to this lower ratio will not be the saturation solubility at the temperature employed, but the saturation solubility can be calculated by multiplying the measured solubility by the critical ratio over the ratio used. However, in the case where oxygen gas is the oxidizing medium, the saturation solubility is not a function of pressure, providing the pressure exceeds the dissociation pressure of FeO in equilibrium with iron. This is 1.2x10-16 mm at 800 °C, according to Dushman." As pointed out by Darken17 in discussing the FeO phase diagram, most of the possible errors tend to yield high values of oxygen solubility. For example, one circumstance which evidently caused the reporting of many high values was the use of finely divided or powdered iron in the gas equilibrium method. Because of the large surface area of such a sample, and the likelihood of some surface contamination if only by exposure to air, the results tended to be high. The direct oxidation method which was used in this work has the advantage in that it is simple and direct, but it suffers from one disadvantage: equilibrium can only be approached from the low oxygen side. The important factors to be kept under control are the following: 1—use of high purity iron to avoid internal oxidation (oxidation of readily

Jan 1, 1955

By A. U. Seybolt

Since the time this topic was originally treated in 1954, more recent French3,1 work has been published making it advisable to repeat the earlier oxygen solubility experiments, but using iron of a higher purity. Upon repeating oxygen saturation experiments with zone-refined iron, it was found that the oxygen solid solubility was at least an order of magnitude less than previously observed. SINCE the publication of an earlier paper1 (1954) on this subject by the present author, several contributions on this topic have appeared. Meijering2 in 1955 attempted to reconcile recent conflicting solubility data, without reaching any definite conclusion. sifferlen3 (1955) found that iron of high purity appeared to absorb a quantity of oxygen (0.005 to 0.025 pct) approximately proportional to the structural imperfections present, such as polygonization and grain boundary area. However, he also indicated that purity itself was a significant factor. He concluded that very pure iron nearly free of lattice imperfections would have essentially zero oxygen solubility. His second paper4 (1957) supported this contention since a zone-melted iron containing initially 0.0007 pct O analyzed only 0.0006 pct 0 after prolonged soaking at 850°C with an FeO layer on the surface. Because of the discrepancy between the results of Ref. 1 and those of Sifferlen, it seemed desirable to attempt to resolve this disagreement. EXPERIMENTAL PROCEDURE AND MATERIALS The experimental method used by sifferlen3,1 was essentially the same as that of Ref. 1. In this technique thin iron strip with a surface layer of FeO is soaked for prolonged periods at an elevated temperature in order to saturate the iron with oxygen. After two days at temperatures near 800° to 900° C, one would expect that the iron would be in equilibrium with the surface FeO. In the work reported in Ref. 1 there was evidence that two days holding at 8000to 900°C was more than sufficiently long for saturation. Sifferlen used 48 hr at 850°C. Because of the evidence presented by Sifferlen that the apparent oxygen solubility is a function of iron purity, three grades of iron were used as indicated in Table 1. The Bureau of Standards wire was used only for resistivity tests, while the other two irons were used for saturation-analysis tests of the type described above.

Jan 1, 1960

By D. G. Westlake, D. T. Peterson

The saturation solubility of thorium dihydride in thorium was studied by saturation of samples and subsequent analysis. The solubility increased from about 1 at. pct at 300°C to above 20 at. pct at 800 °C. Over this temperature range the log of the solubility was a linear function of the reciprocal absolute temperature for thorium of good purity. The heat of solution of thorium dihydride was found to be 7.9 kcal per atom of hydrogen in crystal bar thorium and 6.6 kcal per atom of hydrogen in Ames thorium, The important effect of hydrogen on the physical and mechanical properties of many metals is receiving increasing recognition. The basic physical and chemical data necessary to help explain the observed effects of hydrogen on the mechanical proper ties of metals are all too often not available. The solubility of hydrogen in thorium metal was determined to provide a portion of this basic data for the thorium-hydrogen system. The absorption of hydrogen by thorium metal and the formation of thorium hydrides was studied by several investigators, beginning in 1891, and their work is summarized in Gmelin's Handbuch.1 No effort was made to determine the extent of solid solubility in the metal in these early investigations and the impure metal available made interpretation of the results uncertain. Nottorf2 reported the results of a careful study of pressure-composition isotherms for the thorium-hydrogen system. The principal interest in this work was in the composition and dissociation pressures of the thorium hydrides. Mallett and campbel13 reported the pressure-composition isotherms for the thorium-hydrogen system up to the composition of thorium dihydride. The saturation solubility of thorium dihydride in thorium was reported to be 13 at. pct at 650°C and 23 at. pct at about 900° C. Mallett and Campbell used thorium metal which had been prepared by the calcium reduction of thorium tetra-fluoride or thorium oxide. The results obtained with thorium of these two types agreed within the experimental error. PROCEDURE AND MATERIALS Procedure—The method used to determine the solubility was to saturate a sample of thorium with hydrogen and analyze a portion of the saturated sample. This method was chosen rather than a determination of pressure-composition isotherms since it was much less time consuming and could be applied at temperatures at which the equilibrium hydrogen pressure was too low to measure. The

Jan 1, 1960

By L. M. Pidgeon, K. T. Aust

There has been considerable interest in the possible use of titanium in magnesium alloys.' Zirconium has shown some promise in this connection2 and its general similarity with titanium suggests that the latter might act in a similar manner. A literature survey revealed that quantitative data on the Mg-Ti system was unavailable. Several patents3 have claimed that titanium additions from 0.2 to 4 pct to magnesium alloys were possible, but no mention was made as to the form in which the titanium existed in the alloy. Kro114 succeeded in introducing only traces of titanium into magnesium by bubbling TiCl4 through the metal under argon or by reacting it with sodium titanium fluoride. The application of theoretical data given by Carapella5 based on Hume-Rothery's principles, involving atomic size factor, crystal structure, valency and the electro-chemical factor, suggests that a Mg-Ti alloy is a favorable case, and the system appeared to warrant experimental examination. Experimental Procedure and Results THERMAL ANALYSIS If titanium is appreciably soluble in magnesium, a change in the melting point of the magnesium might be detectable using standard cooling curve methods. Magnesium was melted in graphite crucibles under an argon atmosphere, the assembly being enclosed in a silica tube. Graphite thermocouple protection tubes served also to stir the melts. The apparatus was very similar to Fig 1, with the addition of a refractory and baffle system to prevent undue heat losses from the top of the crucible. Chromel-alumel thermocouples were calibrated using Al of 99.97 pct purity. Dominion Magnesium Limited sup- plied redistilled high purity magnesium of the analysis given above. Titanium was added in three different forms: 1. Titanium powder —100 mesh, from the Titanium Alloy Manufacturing Co., Niagara Falls, N. Y. 2. Sheet titanium from the U.S. Bureau of Mines, produced by Mg reduction of TiCl4. 3. Magnesium —50 pct titanium master alloy from Metal Hydrides Inc., Beverly, Mass. The melting point of the high purity magnesium used was measured experimentally as 651.0°C. More than a dozen tests were conducted using titanium from the three sources referred to above, in calculated additions up to 20 pct titanium, at temperatures between the melting point and 1000°C and holding periods up to 6 hr. In no case was evidence obtained of solubility of titanium in magnesium, using inverse-rate and time-temperature curves. The melting point of the magnesium was unchanged within the accuracy of measurement, namely -+0.5°C; and no other thermal arrests were detected. Metallographic investigation of the thermal analysis billets indicated that the titanium additions were apparently mechanically entrapped in the magnesium in segregated areas. Consequently, these samples were not analyzed for titanium. The master alloy proved to be a mechanical mixture of titanium particles in a magne- sium matrix. These results indicated that the titanium solubility, if such existed, could not be obtained by the usual thermal methods. X RAY DIFFRACTION INVESTIGATION In an effort to detect solubility of titanium in magnesium, samples were investigated using both the Debye-Scherrer and the Focusing Back-Reflection methods. Filings from samples of the thermal analysis billets and from pure magnesium were annealed in argon one hour at 350°C to relieve mechanical strain. Measurements made of the interplanar spacings showed no difference between the Mg-Ti samples and pure magnesium. The interplanar spacings could be measured to within 0.0002A, and the greatest variation found was 0.0004A, in the back-reflection method. The diffraction lines for magnesium were not shifted by the titanium additions indicating that the solid solubility of titanium in magnesium is of a very low order—less than 0.5 pct. From both diffraction methods, a d or interplanar spacing of 0.817A was obtained for the redistilled high purity magnesium. This latter value is not given in the standard X ray diffraction cards for magnesium metal or vacuum distilled magnesium. Theoretical calculations for a close-packed hexagonal space lattice for magnesium indicate that the planes {2134) should give a line which was found. The relative intensity for this reflection at 0.817A is slightly less than that at 0.870k for magnesium. SOLUBILITY OF TITANIUM IN LIQUID MAGNESIUM The Mg-Mn system was examined by Grogan and Haughton6 who were

Jan 1, 1950

By J. T. Norton, A. L. Mowry

The monocarbides of the A subgroup elements in the fourth and fifth group of the periodic table in addition to being hard and refractory are of special interest in that they are isomorphous in crystalline structure. They are cubic with a sodium chloride type structure in which the metal atoms are essentially close packed in a face-centered cubic arrangement with the carbon atoms placed in the interstices between. Interstitial structures of this close packed type were first investigated systematically by Egg1 and he gave the rule for their formation, stating that the radius ratio of the nonmetal to the metal atom should not exceed the value of 0.59. The carbides of interest are those of titanium and zirconium of the fourth group and vanadium, columbium and tantalum of the fifth group. Table 1 shows the radius ratio using the Goldschmidt radii for 12 coordination for the metal atoms and the diamond radius for the carbon atom. It will be noted that while there is considerable variation in the size of the metal atom, in all cases the ratio is smaller than the limit of 0.59 placed by Hägg. It has been known for some time that these cubic carbides are soluble in one another, at least to some extent or, in other words, the metal atoms can be replaced, one by another without destroying the stability of the structure. Since the stability of these close packed interstitial substances appears to depend more upon geometry than upon the exact chemical nature of the atoms involved, it is of interest to examine the possibilities of replacement in these carbides in some detail. Hume-Rothery2 has pointed out the importance of the difference in size of solute and solvent atom as a factor in limiting the solubility in simple binary solid solutions. Largely on an empirical basis, he states that if the difference in size between solvent and solute atom is more than 14-15 pct of the solvent atom, the range of solubility is very restricted. The atom size was based on the distance of closest approach in the elements involved. While there is some question as to how one should calculate the size of the metal atom in the carbide structures, reference to Table 1 will show that zirconium is the largest and vanadium the smallest of the group and that the difference is about 15 pct. The Ti-Zr difference is about 9 pct and the others are smaller. Thus one would predict that if the size factor controls the solubility, all of the pairs except VC-ZrC would have wide or complete solubility whereas this latter pair is on the border line and might have restricted solubility. The purpose of the present investi- gation was to examine the solubility of the several pairs of carbides by heating them together until equilibrium was established and then examining the product by X rays. Previous Work Agte3 and his associates prepared various transition metal carbides and determined the melting points of binary mixtures. He concluded from the shapes of the melting point curves that there was extensive solubility in the case of the cubic carbides. Umanskii and his colleagues made an investigation of a number of pairs of the cubic carbides, using X rays and plotted lattice parameter vs. composition curves for the systems TaC-Tic, CbC-Tic, TaC-ZrC and CbC-ZrC. All pairs showed a continuous series of solid solutions. The first two pairs gave a linear relation while the latter two showed a negative deviation from Vegard's law. Kiefer and Nowotny, in a paper which became available after the present work was well advanced, investigated the binary pairs of the five cubic carbides by means of X rays. Relatively few points were obtained and results indicated that in some cases, at least, equilibrium was not reached at the temperatures used. The results indicated that solubility in the VC-ZrC system was not complete. All of the results of previous investigations indicated the desirability of a more detailed study. Materials The raw materials used were mono-carbides of titanium, zirconium, vanadium, columbium and tantalum and were the purest which could readily be obtained commercially. Spectrographic qualitative analysis showed that the CbC and TaC contained less than 1 pct

Jan 1, 1950

By J. T. Norton, A. L. Mowry

S. J. SINDEBAND*—(1) Discussing the properties of the powders used, Mr. Rostoker mentioned a silicon powder as being between 150 and 325 mesh. We always had much difficulty in measuring particle size of silicon powder by screen analysis, because of its tendency to agglomerate. I would be interested in the method used to measure these particle sizes. (2) Mr. Rostoker maintains that the measurement of magnetic properties is more accurate in determining complete homogenization of an alloy, than is the X ray diffraction technique. I wonder whether this is really true. Even when diffusion is complete, magnetic properties will change during continuation of the heat treatment, due to change in density and pore shapes, as has been demonstrated by Mr. Rostoker himself. Which effect is faster, the diffusion of the alloy components or the attainment of final density, will, in my opinion, depend very much on initial material and sintering conditions used. For magnetic applications, of course, the magnetic measurements are most suited for determining the point at which equilibrium conditions are reached. (3) I was glad to see that Mr. Rostoker had used sample sizes which are similar to those I had used previously, and I believe that ring samples of about 2 in. od will become more or less standard samples for the determination of magnetic properties of powder metallurgy products. I should like to ask how the density was changed for the samples on which the effect of porosity was investi- gated, and, further, why the sintering temperature used for this series of experiments was so low. It is somewhat surprising that a 24-hr treatment at 850°C acts so much more to spheroidize the pores than a treatment for 1 hr at 1100°C. But the effect seems to be indisputable. I have made an investigation of the influence of sintering temperature for longer times on the maximum permeabilities of iron powder compacts which was presented at the International Powder Metallurgy Conference in Graz, in 1948, and I hope that these results will be published here within a short time. The results of this investigation are confirmed by Mr. Rostoker's findings that the change of time from 1 to 24 hr changes the permeability behavior considerably in the direction as indicated by Polder and Van Santen for spheroidiza-tion of pores. I do not quite understand Mr. Rostoker's explanation of the influ-

Jan 1, 1950

By Allan Martin, R. A. Swalin

Diffusion rates of manganese, aluminum, titanium, and tungsten in nickel were measured at temperatures between 1100° and 1300°C. Activation energies, Q, and values of the frequency factor, Do, were calculated for each system. Values of Q were found to be within 15 pet of that for self-diffusion of nickel in agreement with present theories of diffusion. ONE of the most interesting problems in diffusion concerns factors governing the order of diffusion coefficients of various solutes in a common solvent metal at low solute concentrations. An early suggestion by Rhines and Mehl' was that diffusion coefficients might each approach that of the self-diffusion coefficient of the solvent itself. Later Thomas and Birchenall' pointed out correlations between the order of the diffusion coefficients and the freezing point depressions of the solvent by the various solutes. Other correlations have been sought. To settle this question it seems likely that much more data will be needed and, in particular, data collected at low solute concentrations. This type can be obtained by special analytical techniques as well as by use of radioactive tracers. The following study was made of diffusion of manganese, aluminum, titanium, and tungsten in a common solvent, nickel, at relatively low solute concentrations: 1—Production of alloys of nickel with manganese, aluminum, titanium. and tungsten at concentrations of the order of 1 atomic pet. 2—Use of pressure-welded diffusion couples in cylindrical form. 3—Diffusion anneals in the temperature range of 1100" to 1300°C. 4—Lathe sectioning of the diffused couples. 5—Spectrophotometric analyses of lathe turnings for the solute being studied. 6—Calculation of the diffusion coefficient for each of the solutes as a function of temperature. 7—Interpretation of results with current theories of diffusion. Experimental Work Materials—Two types of nickel were used in this research. The grade designated as Vacuum melted Mond nickel was used for all diffusion systems except the Mn-Ni system for which the Vacuum melted electrolytic nickel was used. Analyses of the two grades are given in Table I. The manganese used in making alloys was 99.9 + pet pure, aluminum 99.99 pet pure, titanium 99.9 pet pure, and tungsten of C.P. grade powder. Alloys used in this investigation were prepared by melting in vacuo or under a low pressure of argon. After melting, all heats except those of nickel-manganese were poured into a cylindrical copper mold 3 in. long and 1 in. ID. In the case of nickel-manganese, the alloys were solidified in the melting crucible. For nickel-aluminum heats alumina crucibles were used and for all other heats, zirconia crucibles.

Jan 1, 1957