Search Documents

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970

By E. A. Gulbransen, W. S. Wysong

The behavior of molybdenum and its surface oxides in oxidizing and reducing gas atmospheres and in high vacua at elevated temperatures is a question of scientific and technical importance. The use of molybdenum as a metal or as an important component in alloys in oxidizing atmospheres at elevated temperatures has been limited because of the unprotec-tive nature of its oxide film and the volatility of this oxide at moderate temperatures. This communication will present results of a vacuum microbalance studyl, 2 of the following problems: (I) the oxidation kinetics in the temperature range of 250°to 450°C; (2) the reduction with pure hydrogen of thin oxide films formed on molybdenum; (3) the volatility of the thin oxide films; and (4) the vacuum oxidation of molybdenum at high temperatures. Molybdenum is an interesting metal to study for the following reasons: (I) although the oxide-to-metal-volume ratio is greater than one, the metal is not considered protective; (2) the metal oxidizes readily at temperatures of 2 50°C and higher; (3) the oxides of the metal are reduced at temperatures as low as 500°C by pure hydrogen; (4) the oxide Moo3 melts at 795°C; and (5) the oxides of molybdenum are volatile at moderate temperatures. The following variables are studied in the oxidation kinetics: time, temperature, pressure, surface preparation, surface area, concentration of inert gas in the lattice, cycling procedures in temperature, vacuum effect and high temperature vacuum oxidation. The general interpretation of many of these factors has been previously discussed. Literature The oxidation of molybdenum has not been studied critically. Although many studies have probably been made on the kinetics of the oxidation process, none has been reported in the literature available to us. The crystal structures found in the oxidation of molybdenum have been studied by Hickman and Gulbransen." Their results showed that Moo2 is the oxide which is stable in contact with the metallic substrate throughout the temperature range 300 to 700°C. As the film thickens in the low temperature range, MoO3 becomes predominant on the surface. Above 400°C, Moos is no longer observed, MoO2 being the only oxide found. Hagg and Magneli6 have shown from an X ray study that the a-phase, orthor-hombic Moo3 is stable up to 1050°C. Two other phases, ß and ß with compositions close to MoO2.90 are also obtained. The formula for the 0 phase is not given but that of the ß phase is defined as Mo9O26 The 0&apos; phase is found to be built upon a monoclinic unit cell. A ?-phase is isolated from a preparation MoO2.75 heated for 17 hrs at 670°C. This phase is

Jan 1, 1949

By Robert L. Dean, Michael Hoch, Samuel M. Wolosin, Chung K. Hwu

The general shape of the 1450°C isotherm of the Ti-TiO-ZrO2-Zr region was evaluated from the surrounding binary phase diagrams and from thermo-dynamic data on the metal-oxygen binaries. The phase boundaries were accurately determined using X-ray and metallographic techniques. At 1450°C the system shows a large bcc ß field, which extends from the two metal-oxygen binary systems as a Gaussian error function, and is stable up to 30 at. pct 0 when Ti and Zr are present in equal amounts. At higher O Concentrations, the ß field is in equilibrium with t-ZrO . The following four regions, with three solid phases, are present: two a ß t-ZrO,, a TW t-ZrO,, and TiO t-ZrO2 c-ZrO2. On cooling the ß phase transforms into the a phase, going through the w transition phase. The isotherm at 1500°C for the region TiO-TiO,-ZrO, was obtained by using X-ray diffraction. At 1500°C a large c-ZrOz region is present as well as a large two-phase field, Ti0 c-ZrO,. The following regions, with three solid phases in equilibrium, were found These regions are relatively small. The solidus and liquidus relationships were determined by observing samples suspended in a tungsten crucible by means of a fine tungsten wire and heated in vacuum. Eleven univariant points were found. C-ZrO, decomposes through a peritectic reaction into liquid t-ZrO2. The activities of Ti and TiO in the TiO t-ZrOz and in the two a ß t-ZrO regions were measured using the Knudsen effusion method. In the a TiO t-ZrO, region the activities of Ti and Ti are the same, as in the a — Ti TiO binary. In the two a t-ZrO, regions, the Ti activity is high and the Ti0 activity very low, although all phases present contain at least 30 at. pct 0. This indicates a short-range order in the solid phases, Zr atoms being preferentially surrounded by 0. 1 HE system Ti-Zr-0 is of interest because of the wide ranges of solid solubility exhibited by the boundary systems; as titanium and zirconium both belong to the same group of the periodic table, large single-phase regions should occur within the system, with a great variation of properties (as the composition changes within the single-phase region). Furthermore, the possibility of modifying ZrO, to make it a more usable refractory by the addition of other metals makes this system also of interest. Because of the high affinity of titanium and zirconium for oxygen, the oxygen partial pressure is very low at all compositions; thus, there exists a ternary metal-metal-oxygen system in which the oxygen pressure is not an important variable, so long as it is low enough. When a sample is heated in vacuum to a temperature high enough for vaporization to occur, the vapor phase will consist of metal and metal-oxide gas, the oxygen concentration being very low. The phase relationships in the surrounding binary systems have already been reported in the literature; therefore, the study of the ternary diagram

Jan 1, 1962

By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan&apos; presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner&apos;s contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-&apos; demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann&apos; and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,&apos; who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970

By N. A. Gokcen, S. Fujishiro

The dissociation pressure of Cr3C2 has been measured in the range of 1908" to 2237°K by means of graphite Knudsen effusion cells. It has been found that Cr3C2 vaporizes according to the following reaction: 1/3 Cr3C2 (s or 1) = 2/3 C (graph.) + Cr (g). The equilibrizcm pressure, P, of Cr (g) is found to be log Ps=- - (21,194/T) + 6.525 over solid Cr3C2 and estimated as log P, = - (19,535/T) + 5.76 over liquid Cr3C2. CARBIDES of chromium are of great importance in alloy steels and cemented carbides. The published data on their therm odynamic properties at high temperatures, however, are meager. The heat capacity and change in entropy of Cr3C2 were determined calorimetrically by Kelley and Moore1 in the range of approximately 50" to 300°K, and by Oriani and Murphy2 from 297" to 1188°K. The standard entropy of Cr3C2at 298.15°K, obtained by Kelley.7 was later confirmed by DeSorbo.4 Equilibrium in the reaction was investigated by Boericke.5 A recent tabular summary

Jan 1, 1962

By N. A. D. Parlee, E. M. Sacris

OVER 55 years ago, Sieverts and Hagenacker1 and Donnan and shaw2 made determinations of the solubility of oxygen in liquid silver, over a rather short range of temperatures (973° to 1125°C), using quartz bulbs, mainly at 1 atm. From the results of their investigations, Mizikar, Grace, and parlee3 plotted % O vs 1/T and obtained the following straight-line equation for solubility at 1 atm: log % O = 723.7/T - 1.0949 Recent work on the kinetics of the Ag-O2 system394 indicated there might have been some error due to reaction with the direct heated silica bulbs. Thus it became important to redetermine the solubility with the silver contained in a better refractory such as alumina, and by induction heating where the walls of the container were not so strongly heated. It was also desirable to extend the temperature range. A modified Sieverts apparatus of fairly standard type was used except that a special type of reaction tube was employed, Fig. 1. Dried argon with a guaranteed purity of 99.9 pet, and dried medical-grade oxygen with a guaranteed purity of 99.6 pet containing a little nitrogen, were the gases used. The measuring system consisted essentially of a manometer and a water-jacketed 100-cc gas buret with an open-end vertical tube parallel to the buret. This tube has the same diameter as the buret in order to give the same capillary effect on the mercury. A screw leveling device was used with the buret leveling bulb to help provide accurate pressure readings. A 2-mm ID capillary line connected the buret to the reaction chamber, helping to reduce the dead volume, which was determined with argon. The heating medium was a 2.5-kw output induction furnace. The induction coil was made of a 3/16-in. copper tubing with eight turns and an inside diameter of 4 cm. The reaction bulb was made of a quartz tube 18 cm long and 3 cm in inside diameter, Fig. 1. Inside the quartz tube were two alumina crucibles (Mor-ganite Triangle RR, XN10 and XN5) one inside the other. Below these two was an alumina disk. The disk prevented the corners of the outer crucible from expanding against the quartz tube. The solid sample (99.994 + pet Ag), which had been previously cleaned by air oxidation and repeated removal of scum, was placed inside the inner crucible. An alumina disk with a hole at the center covered the two crucibles. In order to decrease the dead volume, an evacuated quartz "filler" tube was placed on top of the crucible cover. The part of the reaction tube above the spherical joint was made up of Pyrex glass with a flat glass top. It was here that a prism was placed to facilitate the use of an optical pyrometer, previously calibrated at the freezing point of silver. This type of reaction bulb and furnace assembly was specially designed for this work, and used in preference to the relatively new water-

Jan 1, 1965

By T. J. Woodside

A. E. LEE*—One question of the flue leading to the tube coolers. What gas velocity is maintained to prevent settling of the finely divided fume ? T. J. WOODSIDE (author&apos;s reply)— 30 fps. Of course some fume settles out, but is immediately carried away by the screw conveyors. H. R. BIANCO —How effective are the soot blowers ? Do you have to use any hand lancing? T. J. WOODSIDE Only one point, which is right at the top of the economizer and which the soot blowers do not reach, we occasionally hand lance. But everywhere else the soot blowers have been very effective and no hand lancing has been done. L. V. DAVIDSON*—Do you have considerable variation in the lead content of the fume collected if the lead is higher, and is there greater tendency for the fume to stick on the boiler tubes ? T. J. WOODSIDE—There is very little variation in the lead content. From 5 to 7 pct is the widest range variation we have had and we have noticed no difference in the behavior of the fume. C. R. KUZELL—Mr. Woodside has been quite generous with data pertaining to metal and fuel economics. I think he stated that the coal consumption of the furnace was 21/10 21/10 for a pound of zinc recovered. I take it that that is the gross coal input to the furnace. I wonder what the net fuel consumption in terms of coal might be after crediting the fuel equivalent of the waste heat steam recovered? T. J. WOODSIDE—The fuel value of the waste heat steam is approximately 42 pct of the heat input to the furnace. A very large part of the heat, of course, goes out in jacket water—44 pct. A. D. TERRELL*—I would like to know how much lead is in the deleaded material. T. J. WOODSIDE—It is a little less than 2 pct now.

Jan 1, 1950

By T. E. Eagan, W. R. McCrackin

IN dealing with segregation in babbitt, and its effect on the final cast structure, which is a bearing, it is obviously impossible to cover all of the compositions manufactured. Each composition, of course, will exhibit certain specific types of segregation. However, as examples,, two compositions of babbitt are presented: one a tin-base of well-known analysis and the other a lead-base, which in the past few years has found wide usage. Bearings usually are cast either statically or centrifugally; therefore the effect of these two methods on segregation is presented. EXPERIMENTAL PROCEDURE A slab of babbitt 1/2 in. thick by 5 in. wide and 17 in. long was cast, using a book mold with the long edge vertical. An A.S.T.M. grade 2 babbitt was used (3.5 per cent copper, 7.5 per cent antimony, remainder tin), to which 0.10 per cent tellurium had been added. Unfortunately, no metal without tellurium was available. The mold to hold the babbitt was heated to approximately 300°F., the temperature being judged by the babbitter. The pouring temperature of the babbitt was 875°F. (470°C.). One slab was made by allowing the babbitt to cool without stirring. The other slab was stirred during the entire cooling cycle. This stirring consisted of a vigorous churning or puddling into the mold until complete solidification had taken place. Three samples were removed from these slabs. One was taken at the extreme bottom, another half way to the top, and another at the extreme top, all at the center of the width. Chemical, macroscopic and microscopic examination was made of all samples. Table I shows the chemical analyses obtained at the described positions [ ] in the slab. The analyses show no serious amount of gravity segregation. Microscopic examination from edge to edge of the slab showed little change in structure. From top to bottom there was a progressive coarsening of the grain size in the stirred slab but little change in the slab that was not stirred (Fig. I). No definite exhibit of segregation could be detected. In line with our experimental study on the tin-base babbitts, we cast an almost duplicate slab using A.S.T.M. Alloy No. 15, containing 0.9 to 1.25 per cent tin, 14.75 to 15.5. per cent antimony, 0.80 to 1.25 per cent arsenic and 0.4 per cent copper. The slab was 16 in. long and 3/8 in. thick, cast with the long side vertical. One slab was allowed to cool normally and the other was stirred continually during cooling. The pouring temperature of the babbitt was

Jan 1, 1944

By Herbert H. Uhlig

Although the mechanical properties of high-carbon manganese-iron alloys, particularly the Hadfield manganese steels, have been established, the literature discloses discrepancies in the reported properties for the low-carbon alloys. Hadfieldla summarized the existing data up to 1927, including the investigations of Guillet, Arnold, Strauss, Burgess and Aston, and reported his own values for alloys containing for the most part from 0.06 to 0.I5 per cent carbon. He noted: From these comparisons it wil! be seen that while there is a broad and general agreement as to the character of the alloys at the different manganese percentages, there are disparities in individual cases, especially as regards the degree of toughness or brittleness displayed by an alloy with certain percentages and with particular types of treatment. These differences are not always readily explainable.lb His data showed that alloys containing 4 to 10 per cent manganese water-quenched from Iooo°C. were brittle and hard with maximum brittleness at about 7 per cent. Slight improvement in ductility was obtained with compositions from 10 to 17 per cent manganese. Alloys containing up to 17 per cent manganese slowly cooled rather than quenched from 87o°C., he found, were slightly improved in ductility with significant improvement in alloys analyzing 4.1 and 4.8 per cent manganese. Recently Walters, Kramer and Loring2 reported mechanical properties for alloys made up from electrolytic manganese and ingot iron and containing from 0.02 to 0.04 per cent carbon. They showed that a tempering treatment at 54o°C. (Iooo°F.) for one hour significantly improved the ductility of compositions ranging from 6.7 to &apos; 20.7 per cent manganese. The differences of these compared with Hadfield&apos;s results they considered to originate in this tempering treatment plus the fact that Hadfield&apos;s alloys contained higher carbon and phosphorus (0.06 to 0.I5 per cent C; 0.06 to 0.07 per cent P compared with 0.02 to 0.04 per cent C, <o.ooI per cent P). In this paper it is shown that of the low-carbon alloys (0.02 to 0.03 per cent) containing from 3.3 to 21.5 per cent manganese moderately or rapidly quenched from IOOO°C. some are brittle or ductile, depending on presence or absence of hydrogen. Hydrogen is readily absorbed at high temperatures, and much of it is retained when the alloys are cooled to room temperature. The presence of hydrogen in the range of composition from 10 to 18 per cent manganese is a major factor in determining relative ductility. At 22 per cent manganese, and also at compositions below 10 per cent manganese, factors other than or in addition to hydrogen play a role. These are discussed. Also data are presented to show that hydrogen absorbed by the high-carbon alloys of Hadfield composition is without effect on their mechanical properties.

Jan 1, 1944

By Herbert H. Uhlig

Although the mechanical properties of high-carbon manganese-iron alloys, particularly the Hadfield manganese steels, have been established, the literature discloses discrepancies in the reported properties for the low-carbon alloys. Hadfieldla summarized the existing data up to 1927, including the investigations of Guillet, Arnold, Strauss, Burgess and Aston, and reported his own values for alloys containing for the most part from 0.06 to 0.I5 per cent carbon. He noted: From these comparisons it wil! be seen that while there is a broad and general agreement as to the character of the alloys at the different manganese percentages, there are disparities in individual cases, especially as regards the degree of toughness or brittleness displayed by an alloy with certain percentages and with particular types of treatment. These differences are not always readily explainable.lb His data showed that alloys containing 4 to 10 per cent manganese water-quenched from Iooo°C. were brittle and hard with maximum brittleness at about 7 per cent. Slight improvement in ductility was obtained with compositions from 10 to 17 per cent manganese. Alloys containing up to 17 per cent manganese slowly cooled rather than quenched from 87o°C., he found, were slightly improved in ductility with significant improvement in alloys analyzing 4.1 and 4.8 per cent manganese. Recently Walters, Kramer and Loring2 reported mechanical properties for alloys made up from electrolytic manganese and ingot iron and containing from 0.02 to 0.04 per cent carbon. They showed that a tempering treatment at 54o°C. (Iooo°F.) for one hour significantly improved the ductility of compositions ranging from 6.7 to &apos; 20.7 per cent manganese. The differences of these compared with Hadfield&apos;s results they considered to originate in this tempering treatment plus the fact that Hadfield&apos;s alloys contained higher carbon and phosphorus (0.06 to 0.I5 per cent C; 0.06 to 0.07 per cent P compared with 0.02 to 0.04 per cent C, <o.ooI per cent P). In this paper it is shown that of the low-carbon alloys (0.02 to 0.03 per cent) containing from 3.3 to 21.5 per cent manganese moderately or rapidly quenched from IOOO°C. some are brittle or ductile, depending on presence or absence of hydrogen. Hydrogen is readily absorbed at high temperatures, and much of it is retained when the alloys are cooled to room temperature. The presence of hydrogen in the range of composition from 10 to 18 per cent manganese is a major factor in determining relative ductility. At 22 per cent manganese, and also at compositions below 10 per cent manganese, factors other than or in addition to hydrogen play a role. These are discussed. Also data are presented to show that hydrogen absorbed by the high-carbon alloys of Hadfield composition is without effect on their mechanical properties.

Jan 1, 1944

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who called at Institute headquarters during the period Jan. 10, 1916 to Feb. 10, 1916: William Rettie, Yonkers, N. Y. Wallace E. Pratt, Manila, P. I. R. V. Norris, Wilkesbarre, Pa. T. Skewes Saunders, El Oro, Mex. Fred MacCoy, El Oro, Mex. M. L. Requa, San Francisco, Cal. Reno H. Sales, Butte, Mont. R. W. Schultz, Ravenna, O. R. T. White, Batourn, Russia. H. J. Brown, Chester, Pa. David T. Day, Washington, D: C. A. M. Van Rensselaer, New Rochelle, N. Y. H. M. LaFollette, LaFollette, Tenn. Norman C. Stines, Russia. F. N. Speller, Pittsburgh, Pa. Howard R. Hughes, Houston, Tex. Robert W. Hunt, Chicago, Ill. C. F. Schnepp, Ridgefield Park, N. J. B. E. Fernow, Toronto, Ont., Can. George L. A. Thomson, Elizabeth, N. J. A. F. Bennett, New York City. Jasper T. Robertson, Chicago, Ill. J. C. Ralston, Spokane, Wash. J. B. Tyrrell, Toronto, Ont., Can. George J. Lyon, Schenectady, N. Y. H. G. Officer, New York Cty. Jesse C. Porter is now superintendent of the San Fernando Mine, Hoyo de Manicaragua, Santa Clara Province, Cuba.

Jan 3, 1916

By P. G. Sprang, S. Rosen

The Y-Al- C ternary phase diagram for the com -position range from 55 to 100 at. pct Y and for a temperature of 950°C has been constructed from metallographic and X-ray diffraction data. The significant features of the isothermal section which is presented are the small solubility of aluminum in the binary Y3C phase and the presence of a ternary carbide phase with a small homogeneity range around the composition Y3AlC. The similarity in structure and composition between these two carbide phases is discussed in the light of the misci-bility gap which exists between room temperature and 1300°C, which was the temperature range studied. THE occurrence and stability criteria of ternary T3BC, carbide phases having the L&apos;12 structure and the general formula T3BCx have been discussed in detail by stadelmaier1 and more recently by the present authors., Stadelmaier found many representatives of these phases formed between the T metals Mn, Fe, Co, and Ni and the B metals Mg, Al, Zn, Ca, Ge, Cd, In, Sn, Hg, T1, and Pb. The present authors reported on a new series of iso-structural carbide phases formed between the T metals of the Sc group and the B metal, aluminum. These new phases are unique in that many of the Sc group elements form stable binary carbide phases which occur about the composition T3C and which crystallize with a structure similar to that of the T9BCx ternary carbide phases. Furthermore, these binary and ternary phases are found to coexist in equilibrium with each other. The similarity in structure and composition between, for example, Y3C and Y3AlC in the light of the mis-cibility gap which had been found to exist between these two phases indicated a need for a more thorough knowledge of the phase relations which occur in alloys based upon these compositions. Consequently, an investigation of the phase equilibria in the yttrium-rich portion of the Y-A1-C phase diagram was undertaken. The limiting Y-A1 binary diagram determined by Lundin and Klodt3 and the results of Spedding et al.4 governing the Y3C phase were used as guides in , constructing the diagram. EXPERIMENTAL Alloys weighing about 10 g were prepared by arc-melting powder compacts made from the various components on a water-cooled copper hearth using a tungsten electrode in a gettered argon atmosphere. Good homogeneity was obtained by melting the alloys three times. The purity of the yttrium used was 99.9 pct (0.07 pct rare earths). The purity of the aluminum and the carbon was 99.99 pct. The results of chemical analysis on five representative alloys showed that losses during the alloying process were predominantly carbon losses and that in no instance did the measured concentration of this component differ by more than 3 at. pct from the intended composition. For this reason the alloy compositions which are reported are those of the charges prepared for melting. Three alloys which were analyzed for copper, tungsten, nitrogen, and oxygen compositions showed that no contamination had occurred either during casting or during the subsequent annealing treatments. For the major part annealing treatments were carried out on specimens which were placed in

Jan 1, 1965

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-&apos;. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.&apos; and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner&apos;s3 data for cation self-diffusion, D:, using Wagner&apos;s theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner&apos;s data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-&apos; at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By R. N. Edmondson, L. Mair, M. Tenenbaum

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhord Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chipmon, Vice President; T. D. Jones, Treosurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. w. Thornton, Chairman; Dennis Carney, John Chipman, J. C. Fulton I. H. Hollomon H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supenision of the following Publications Committees: Extractive Metallurgy Division: T. 0. King Chairman; S. J. Dickenson, R. P. Hermsdorf R. Schuhmann. Jr.. and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman F. Lincoln Vogel Jr., Vice-chairman, W. A. Baikofen, R. W. Boliuffi J. H. Bechtold M. B. Beyer. R S. Busk, C. G. Gaetzel, Paul Gordon C. D. Groham, Jr., Robert F. Hehe-mann,&apos; R. I. Joffee, F. c. Joumot Jr lrving R. Kramer A. J. Lena Harold Morglin, C. J. McHargue, Russell A: Meussner, J. B. Newkirk H. W. Paxton, G. E. Pellissier, I. S, Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B King, F. C. Langenberg, W. 0.. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining Metallurgical and Petroleum Engineers Inc., 29 West 39th Street, New York 18, N. Y. Telephon: pEnnsvlvanio 6-9220. Subscription 522 Per year for non-AIME members in United States and North South and Central America; $25 foreign;, $5 for AIME members. Single copies, 54.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed In its publications . . . Copyright 1958 by the American lnstltute of Mining Metallurgical and Petroleum Engineers Inc. . . . Registered cable address AIME New York , . . lndexed in Engineering Index Industrial Arts Index and Chemical Abstrats . . . Application for second class mail privileges ii pending at New York, N. Y. Volume 212, Number 4.

Jan 1, 1959

MEMBERS, JUNIOR MEMBERS, ASSOCIATES AND JUNIOR ASSOCIATES LIST OF MEMBERS ALPHABETICALLY ARRANGED EXPLANATION OF SYMBOLS ** Junior Member. t Associate. || Junior Associate. Members are not marked. Capital letters signify Honorary membership. Student Associate and Rocky Mountain members on pages 165-167. Abadilla. Quirico A Catanawan. Tayabas, P. I. Abbey. Robert Graham. District Mgr The W. W. Sly Mfn. Co., 60 Church St New York. N. Y. Abbott. A. N Mines Supt Mazapil Copper Co Ltd . .Conception del Oro. Zac., Mexico. Abbott. Ckrence E Mgr Mines & Quarries, Tenn. Coal. Iron & R. R. Co 1242 Brown Marx Bldg Birminrham. Ala. Abbott. Louie Benjamin. Chief Enar Consolidation Coal Co Elkhorn Div .Jenkins, KY. Abeel. Gsorge H Jr., Cons. Min. Enar .Box 427. Santa Monica. Cal. Abel. Albert E Asst. to Pres Valley Mould & Iron Corp Hubbard. Ohio. Abel. Raymond L. Asst. Prof., Dept. of Pet. Refin Univ. of Pittsburgh Pittsburgh. Pa. Abernathy. George Elmer. Prof. of Geol. & Min Kansas State Teachers College. Pittsburg. Kans. IlAbernethy. D. Carl, Jr. Min. Engr Hudson Coal Co .Scranton. Pa. Abey, Hiroshi. Min. & Met. Engr., Min. & Met. Dept., The Higher Technical School, Osaka. Japan. tAbarn, Robert H Instructor in Met Harvard University Cambridge, Mass tAbozeid,Mahmood. Pet. Production E r . . Marland Oil Co. Ponca City, Okla. Abraham. Arthur W Geol., Richfield Oil Co Box 788. Bakersfield, Cal. Abraham, W. E. V Member, Staff of Burmah Oil Co Ltd. Nyaunghla. Upper Burmz, India. Abrahams. Alexander I Gen&apos;l Mgr., Racon Electrical Co Slough, Bucks England. tAbrahammn. C. W Min. Engr The Mond Nickel Co Ltd . Coniston, Ont Canada. IlAbmn. Guy W., Asst. Metallographist, Youngstown Sheet & Tube Co., Research Dept., Youngstown. Ohio. Abstein. Henry T., Engr. & Mgr Profile-Tamarack Mines Co . .Yellow Pine, Idaho. tAcker. E. O&apos;C Met I28 East Washington Lane. Germantown, Philadelphia. Pa. Ackerman. D. E Met. Research Lab International Nickel Co Inc Bayonne. N. J. tAbckerman. Ernest R Pres., Lawrence Portland Cement Co . .Plainfield. Union Co N. J. ||Ackerman. George F Jr. Min. Engr El Potosi Min. Co. .Apt. 13. Chihuahua, Chih Mexico. Acres, T. H Geol. Dept Valuation & Pet. Engr., Richfield Oil Co. 655 S. Flower St Los Angeles. Cal. Adachi. Jinzoo Address Wanted. Adair. Arthur C Valuation Enar., Internal Revenue. Treasury Dept., Washington, D. C. Adam. John. Min. Ennr., The Zinc Corp. Ltd., Box 4 C. Broken Hill, N. S. W Australia. Adami. Arthur E V. P Montana State School of Mines.Butte, Mont. Adami. Charles J Min. Ensr St. Joseph Lead Co 4540 Lindel Blvd., St. Louis, Mo. Adams. C. W.729 South Normandie St LaGranada Apt Los Angeles, Cal. Adams. Cmyler Geerwwd. Minn. Adams. F. J Gen&apos;l Anent. Gulf Production & Pipa Line Cos .Fort Worth. Tex. ADAMS. FRANK DAWSON. Logan Prof. of Geology and Dean, Faculty of Applied Science, McGill Univ Montreal. Que Canada. Adama, Gale L Research Enar., General Pet. Corp. of California, Higgins Bldg Los Angeles. Cal. Adams. George I, Prof. of Geol. & Mineralogy Univ. of Alabama, Tuscaloosa, Ala. Adams. H. H Cons. Geol Room 416, W. T. Waagoner Bldg Fort Worth. Tex. Adams, Henry. Cons. Min. Ennr 1050 Edgewood Ave., Plainfield, N. J. Adams, Henry H.285 Madison Ave., New York. N. Y. Adams, Henry Farnum. Engr., Charge. Experimental Work. Inspiration Concentrator, Inspiration Cons. Copper Co Box 354. Inspiration. Ariz. Adams. Huntington. Min. Enar I41 Broadway, New York. N. Y. Mama, Leland D., V. P., Leslie-California Salt Co 166 Montgomery St., San Francisco, Cal. Adams, Louis W., Illinois Steel Co .Gary. Ind.

Jan 1, 1929

By K. P. Gupta

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

Jan 1, 1962

By Avnulf Muan, P. V. Riboud

The effect of Cr2O3 on melting relations of iron oxide at oxygen pressures slightly above those prevailing in contact with metallic iron has been determined. Liquidus and solidus temperatures of wüstite are raised by the addition of Cr2O3, from 1385°C for pure iron oxide to 1420°C at the peri-ledie point where wüstite, iron chromite, liquid, and gas coexist in equilibrium under the atmospheric conditions used in the present investigation (CO2/H2 = 1). It has been shown in a previous investigation1 that the liquidus and solidus temperatures of iron oxide are drastically increased by the addition of Cr2O3 under the relatively oxidizing conditions prevailing in air. This is to be expected in view of the easy substitution of cr3+ for Fe3+ in crystalline oxide structures which are stable at high oxygen pressures, as demonstrated for instance by the completeness of the solid solution series Fe2O3-Cr2O3 at high temperatures (>1000°C). The stable phase of iron oxide at oxygen pressures approximating those prevailing when metallic iron is present is wüstite. This phase, although commonly represented by the simplified formula FeO for sake of convenience, in reality has a defect structure in which a part of the iron ions are present as Fe3+. It is to be expected that at least a limited amount of cr3 ions will substitute for Fe in this structure when Cr2O3 is added to wüstite. Depending on the ease of this substitution in comparison with that of cr3 substitution for Fe in iron oxide-Cr2O3 liquids under the same atmos- pheric conditions, the liquidus and solidus temperatures of wüstite may increase or decrease upon addition of Cr2O3. The methods of establishing these melting relations and the results obtained are presented in the following. I) EXPERIMENTAL METHOD 1) General Procedure. The quenching technique was used in this study. Oxide mixtures were heated at chosen constant temperatures in an atmosphere consisting of equal parts of CO2 and H2 until equilibrium was established among gas and condensed phases. The samples were then quenched in mercury to room temperature, and the phases present were determined by microscopic and X-ray investigation. 2) Preparation of the Mixtures. Starting mixtures were prepared by weighing and thoroughly mixing Fe2O3 and Cr2O3, or wüstite and Cr2O3. The Fe2O3 and Cr2O3 used were "Baker Analyzed" reagent grades, whereas wüstite of composition was synthesized by reducing Fe203 at 1325°C in an atmosphere consisting of equal parts of CG andHz. In order to avoid contact with crucibles, the equilibration runs were made with small pellets suspended from thin (-0.004-in.) platinum wires. Mixtures made from FOs and Cr203 were readily pelletized at a pressure of 500 atm in a 9.5-mm die, whereas mixtures made from wüstite and Cr203 when treated identically were too weak for handling. In order to obtain a stronger product, these pellets were sintered by heating for 2 min at -1200°C in the same atmosphere as was subsequently used for the equilibration runs (CG/H2 = 1:1). During the sintering, these pellets were wrapped in thin (0.0004-in.) platinum foil, which was stripped off before the equilibration runs. In order to reduce the time needed for equilibrium to be attained, preliminary equilibration of relatively large pellets of each mixture was carried out at -1200°C for 4 to 12 hr. Smaller pellets

Jan 1, 1964

CONTENTS PAGE World-V. R. Garfias 3 Russia-R. C. Beckstrom 6 Rumania-I. I. Gardescu 11 Germany-W. Kauenhowen 14 France, Italy and Poland-W. P. Haynes 20 Persia-Sir John Cadman 23 Iraq-E. B. Swanson 27 Burma and India-L. D. Stamp 30 Venezuela-H. Sherman 37 Trinidad-H. W. Reid 44 Colombia-O. C. Wheeler 47 Peru-O. B. Hopkins 50 Mexico-V. R. Garfias and R. V. Whetsel 51 Canada-L. C. Snider 55

Jan 1, 1933

LIST OF MEMBERS AND ASSOCIATES ARRANGED ACCORDING TO STATES AND TOWNS ALABAMA Aldrich, Aldrich, W F Anniston, Noble, A E, Smith, N B Aibacoche, Bradley, D II Bessemer, Fergusson, V Birmingham, Aldrich, T H, Aldrich, T H, Jr, Bowron, J, Bowron, C E, Davis, F H, Dimmick, F D, Hillman, McCarthy, M E , McCormack, McCrery, Ramsay, E, Shook, A M Bridge¬port, Wheeler, S K Ensley, McDonald, S, Shook, J W Fanbanks, Hamil¬ton, A L Helena, Squire, J Huntsville, Moss Lehigh, Toulmin Oxmoor, Green¬amyer, A G Plasma, Gage Rock Run, Garvin Sheffileld, Miller, D I Tuscaloesa, Lodge, J University, McCalley Woodward, Bukofzer, Woodward, A H ALASKA Dawson, Buck Douglas Island, Corbus, J P , Macdonald, J Hames, Le Wald, E A Jualin, Hoggatt, W B Juneau, Denby, Gaifield, Garside, Hamp¬ton, W H Rodman Bay, Phillpots Snettisham, Tisdale Sumdum, Thane Tel¬ler, Hirshberg, M R Treadwell City, Batcheller, J H , Kinzie Valdez, Esterly, G M Yukon, Dawson, Elmer, J M ARIZONA Bisbee, Clark, G C, Coombs, H L , Douglas, W, Hoatson, Parnall, S A, Pelton, R T, Ricketts, L D, Sherman, G F G, Smith, F W, Smith, H A Black Diamond, Bagge Blanchard, Cummins, Murray, J J Casa Grande, Rich¬mond, A B Clifton, Colquhoun, Grabill, Murray, H T , Plater, Smith, J D A, Veitch, Watson, W S Congress, Goodloe Crown King, Alexander, G E Douglas, Cornell, Kraemer, E L, Lee, G B, Rutherford, F Globe, Berray, Hoar, Snell Harrisburg, Smith, F C Jerome, Clark, W A, Thomas, C A Kingman, Treadwell, Wallace, J P Kirkland, Bretherton, G K Kofa, Lamp¬shire, J O , Pomeroy, H G Mayer, Haggott, E A Metca j, Blumenkranz, M , Forbes, D L H Morenca, Clark, C D, Fleming, J B, Honey man, Mills, C E, Wallace, L R Morristown, Stevens, H W Nogales, Glove, H G, Sandoval, A , Sandoval, P Octave, Rose, G W Phoenix, Armstrong, T , Butler, C E, Defty, Lindsay, L Prescott, Blauvelt, H , Bunker, C E, Claypool, W M , Drescher, F M , Fairbank, Nissen Tombstone, Gage, Poindexter, C L , Staunton, Walker, E W Troy, Cutting Tucson, Blake, W P, Burgess, De Lashmutt, I, McCleary, Mann, Prout, J W , Jr ARKANSAS Fayetteville, Purdue Fort Smith, Bache, F , Denman, H Little Rock, Fordyce, Scholz CALIFORNIA Alameda, Arents, King, L Arnador City, Downs, Tregloan Angeles Camp, Dig¬gles, R N , Kenney, C E Antioch, Belshaw Auburn, Coe, I J Ballarat, Thorns Berkeley, Abadie,, Christy, Dozier, Hall, F F , Hersam, Landfield, Lind¬say, L , Mansfield, N T, Morley, W S , Sharwood, W J Bag Oak Flat, Dron Bodae, Hamilton, W R, Hoover, T, Hoover, T J, Jackson, B L , Nutter , E, H Bullion, Power, H T Callahan, Scott, E H Campo Seco, Baird Cartero,

Jan 1, 1910

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansenl and Haughton,² the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 157.3²C O.l°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys, 4,6 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157. ²°C ± O.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4°C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. Thermal Analysis Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high- flash point was used. A platinum-platinum rhodium thermocouple of fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermocouple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.²°Cl and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it scems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16 in. thick, sufficed to give a cooling rate of from I° to ²°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947