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THE CHAIRMAN.-Thank you. Since the papers are rather closely related, I think rather than taking them one at a time we will entertain discussion on any of these problems at this time. W. A. REICH.*-We, of course, quite a while ago got the yellow light that Mr. Cole spoke of, and like everyone else immediately started to study silicon bronzes and brasses. We were interested in the silicon bronzes and brasses because we felt that in order to replace gun metal which makes up a large part of our use we needed something with an elastic limit at least equal to that of gun metal. That means at least 12,000 lb. per sq. in. This study was aimed only at tin conservation. Then we dropped the study of silicon bronzes because high purity copper which is needed in their manufacture became a scarce item. To make a long story short we have recommended to our designing engineers that they use 85-5-5-5 wherever possible because 85-5-5-5 we understand can be made entirely from scrap with little or no tin addition. 85-5-5-5 has a lower elastic limit than 88-8-4, so we felt that we would need another substitute material, a structural alloy with an elastic limit equal to that of 88-8-4, and we immediately turned to the manganese bronze type of alloy. The poor foundry properties of standard manganese bronzes were mentioned by Mr. Thieme and since we feel that high zinc content is largely responsible for this difficulty, our development is directed along the lines of uncovering a material with a lower zinc content and which gains its elastic strength from the addition of other alloying elements, such as, aluminum, manganese and iron. It must be possible to make this alloy entirely from scrap with no additions of scarce high purity material. I would appreciate an expression of opinion on how low we can go in zinc content with this type of alloy without seriously impairing the availability, and how high we can go in aluminum content without making use of aluminum restricted for that use. We assume that the maximum lead content must be placed at 1 ½ per cent to insure good availability and we feel that about I per cent of tin in the alloy would improve salt water corrosion resistance similar to the effect of tin in Admiralty Metal. Has anyone here had experience with the effect of tin and lead on the weldability of such an alloy? C. S. COLE.-What percentage of lead and tin? W. A. REICH.-About 1 per cent of lead and 1 per cent of tin. We are studying the weldability of the alloy but perhaps someone already has the answer. (Pause, no answer) The claim has been made that 1 per cent of lead can be added to certain silicon bronzes without impairing their properties. A silicon bronze with a low zinc content requires high purity copper in its manufacture but if say the 15 per cent zinc, 44 silicon balance copper alloy could be made, with a I per cent lead content, some quantity could be made from scrap. We do not know whether the aforementioned is

Jan 1, 1943

By K. M. Busen, J. Lindmayer

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

Jan 1, 1965

By R. F. Mehl, C. E. Birchenall

R. E. Hoffman and D. Turnbull—The authors have presented evidence which they have interpreted as indicating that the rate of self diffusion is not intrinsically more rapid at grain boundaries than within the grain. Grain-size effects which apparently exist are attributed rather to impurities concentrated at the grain boundaries. In view of our own experiments and the existing evidence, we believe that the support for this hypothesis is not convincing. We have in progress an investigation in which the rate of self diffusion of silver is being measured over an extended temperature range in both single-crystal and polycrystalline specimens. The results of the single-crystal experiments and some preliminary data on fine-grained polycrystalline specimens have already been reported:' and it is anticipated that a complete report will be published in the near future. The self-diffusion coefficient of large-grained polycrystalline silver (1 grain per sq mm) has previously been measured by Johnson" between 730" and 940°C. The diffusion coefficients which we have measured in single crystals (210 plane normal to diffusion direction) agree within experimental error with values calculated from an extrapolation of Johnson's curve down to temperatures as low as 500 °C. However, it has been demonstrated that the overall self-diffusion rate in fine-grained polycrystalline specimens (initial grain size of 0.003 cm) becomes measurably larger than the overall rate in a single crystal at a temperature of 600°C, and the discrepancy between the two rates becomes greater as the temperature is further decreased. In fact, it has been possible to obtain satisfactory penetration curves for polycrystalline specimens using the sectioning technique at temperatures as low as 400°C. At this temperature, the penetration is 50 to 100 times greater in the polycrystalline specimens than in a single crystal. Fisher" has developed an analysis whereby the ratio of the rate of the unit diffusion process at the grain boundary to the corresponding rate within the grain can be calculated from the penetration curves and an assumption as to the width of a grain boundary. This analysis applied to our data indicates that the unit process at the grain boundary is faster by a factor of 10' at 475°C when the grain boundary width is taken to be 5. The silver used in most of these experiments was obtained from the Handy and Harmon Co. and listed as 99.97 pct pure. Preliminary experiments on 99.999 pct silver from the Jarrel-Asch Co. indicate a grain-size effect of the same order of magnitude as in the less pure silver. Nominally, these purities are as good, at least, as that of the carbonyl iron used by the authors, but of course if an impurity effect does exist its magnitude might be very dependent upon the nature of both major and minor constituents. The authors have cited the work of other investigators who have found no grain-size effects. Neither Steigman, Shockley and Nix" nor Maier and Nelson8 were able to correlate self-diffusion coefficients of copper with grain size. However, all their measurements were performed at or above 750°C; and on the basis of our work with silver, no grain-size effect would be expected at temperatures above about 0.7 of the absolute melting temperature unless the grain size were exceedingly small. Likewise, in the investigation of the self diffusion of lead by Seith and Keil,14 the lowest temperature at which the diffusion coefficient was measured in polycrystalline specimens was 207°C, which is still sufficiently high so that the lack of a grain-size effect is not surprising. Finally, in those experiments on iron from which they concluded that there was no grain size effect, Drs. Birchenall and Mehl seem to have no information as to the actual grain sizes immediately prior to and following the diffusion anneal. Without this information, we believe that their own experiments offer little support for their hypothesis. F. S. Buffington, I. D. Bakalar, and M. Cohen—The results given in this paper agree in order of magnitude with those tentatively reported by us.27 However, significant differences exist in the two sets of data, and it may be well to make an explicit comparison. The diffusion studies at M.I.T. were conducted on somewhat higher purity iron (99.98 pct Fe) than the grades used by the authors, but this is undoubtedly not the answer. Fig. 4 shows the diffusion results of both laboratories for the gamma phase, omitting the authors' data on the commercial steels, while fig. 5 presents a similar comparison for the alpha phase. The divergence is much more marked in the latter case than in the former. In connection with the M.I.T. determinations, all of the runs in the gamma range and those above 800 °C in the alpha range were conducted with specimens having a relatively thick (0.002 cm) electrodeposit of radioactive iron. This practice minimizes any possible error due to extraneous diffusion that may occur during the heating to and cooling from the operating temperature. An exact solution of Fick's law for these boundary conditions was used in calculating the diffusion coefficients. At a later time, three runs were made below 800°C, using very thin electrodeposits similar to those of the authors, and the points fell considerably below the values expected from the extrapolation of the results based on the specimens with the thick deposits (compare dash-dot line in fig. 5). However, in the runs with the thin deposits, deviations of 100 pct were found between the individual specimens, whereas the maximum deviation with the thick deposits was less than 25 pct. Accordingly, it is not known at the moment whether the M.I.T. points below 800 °C should be given as much weight as those above 800°C. If this were done, the frequency factor would be of the order of 400 cm2 per sec, which is quite high. In other metals, the frequency factor for self diffusion lies between about 0.1 and 10 cm2 per sec. As the points below

Jan 1, 1951

By C. E. Wood

THIS paper is a brief report of experimental work undertaken to determine whether barium oxide in any quantity increases the desulfurizing action of blast-furnace slags. Industrial furnace operation with slag containing small quantities of barium oxide, referred to later, interested S. A. Sanford of the Commercial Chemical Co., Youngstown, Ohio, to conduct experiments to furnish comparative results on desulfurization with normal slag and slag containing small quantities of barium oxide. The U. S. Bureau of Mines agreed to assist on the problem because of the possible saving in fuel if the desulfurizing action of blast-furnace slag can be substantially increased, also because the experiments would yield new information on sulfur elimination in general, a matter of economic importance in furnace practice. A more complete and fundamental study of desulfurization of iron by slag is in progress.

Jan 1, 1929

By Myron A. Pugacz, Frank S. McKenna, Clarence E. Jackson

The notched-bar impact test has proved worth while in certain applications as a test for control of the quality or the heat-treatment of steel. In view of the serious thought that even so simple a test as the tensile test has evoked during the past years, it is not surprising that the notched-bar impact test should have inspired much experimental work. The correlation of the great number of data has not been successful, although steady progress has been made toward a better understanding of this test. Progress has been made, especially, in the isolation of the effects of the many variables that control the results. The stress system imposed on a specimen with a notch is so complicated and unpredictable that no simple evaluation of the test has been possible. Because of this uncertainty, many engineers hesitate to use the notched-bar impact test, and this attitude may well continue until a better understanding of the effects of the variables in the test are available. Without doubt, any additional data that may be presented should be accompanied by as complete a description of the - details of test as possible, so that it may be added to the general fund of information that is to serve as the basis for the theory of the notched-bar impact test. The many factors that may control the test results have been pointed out repeatedly. The importance of the effect of the type and dimensions of the specimen has been recognized. Most of the work reported by American investigators has been limited to small-size (Charpy) specimens tested as a simple beam; two types of notches (Fig. I) have been commonly used. Considerable data have also been presented by many investigators using a small specimen tested as a cantilever beam; this commonly being called the Izod test. Here, however, a shear component of stress makes the stress system even more complex than that present in the simple beam type of test, hence a critical analysis is difficult. Much work has also been reported by investigators using the tension type of specimen. A second variable that must be controlled is the testing temperature. An indication that the tests were performed at room temperature is not sufficient, since in many steels a variation of a few degrees in the actual testing temperature may be sufficient to give an entirely different range of results. Other factors, such as the composition and condition of the material being tested and the speed of test, should also be considered. Many investigators have contributed data and theoretical discussions on the problems encountered in notched-bar test-

Jan 1, 1944

By Frank S. McKenna, Myron A. Pugacz, Clarence E. Jackson

The notched-bar impact test has proved worth while in certain applications as a test for control of the quality or the heat-treatment of steel. In view of the serious thought that even so simple a test as the tensile test has evoked during the past years, it is not surprising that the notched-bar impact test should have inspired much experimental work. The correlation of the great number of data has not been successful, although steady progress has been made toward a better understanding of this test. Progress has been made, especially, in the isolation of the effects of the many variables that control the results. The stress system imposed on a specimen with a notch is so complicated and unpredictable that no simple evaluation of the test has been possible. Because of this uncertainty, many engineers hesitate to use the notched-bar impact test, and this attitude may well continue until a better understanding of the effects of the variables in the test are available. Without doubt, any additional data that may be presented should be accompanied by as complete a description of the - details of test as possible, so that it may be added to the general fund of information that is to serve as the basis for the theory of the notched-bar impact test. The many factors that may control the test results have been pointed out repeatedly. The importance of the effect of the type and dimensions of the specimen has been recognized. Most of the work reported by American investigators has been limited to small-size (Charpy) specimens tested as a simple beam; two types of notches (Fig. I) have been commonly used. Considerable data have also been presented by many investigators using a small specimen tested as a cantilever beam; this commonly being called the Izod test. Here, however, a shear component of stress makes the stress system even more complex than that present in the simple beam type of test, hence a critical analysis is difficult. Much work has also been reported by investigators using the tension type of specimen. A second variable that must be controlled is the testing temperature. An indication that the tests were performed at room temperature is not sufficient, since in many steels a variation of a few degrees in the actual testing temperature may be sufficient to give an entirely different range of results. Other factors, such as the composition and condition of the material being tested and the speed of test, should also be considered. Many investigators have contributed data and theoretical discussions on the problems encountered in notched-bar test-

Jan 1, 1944

By Henry M. Howe

This paper is a discussion of the extremely valuable one of Mathewson and Phillips, The Recrystallization of Cold-Worked Alpha Brass on Annealing,1 which not only gives us a wealth of important data reached with great intelligence, but also shows both uncommon powers of imagination and a perfectly fair spirit. Let me try to analyze some of their results, and to enunciate some of the laws to which these results point. For brevity I refer to them as "The Authors." The page numbers in parentheses refer to their paper. 1. The Visible Aspects of Recrystallization.—Plastic deformation in a single direction, as in cold-rolling, draws the grains out in that direction, that is, inequiaxes them, without destroying their apparent individuality. Each grain seems to endure the drawing out without changing either its volume or its orientation materially, for the etching tint of each grain seems to be as uniform after as before the drawing out, save for the "etch bands,"2 shown in Figs. A to D of the Authors' Plate I. As the drawn-out metal is heated progressively, on reaching a certain "disintegration temperature" these old grains seem to break up, probably into submicroscopic fragments, and this apparent disintegration is followed by a coalescence of these fragments, so that their number decreases and their size increases, till they may become very much coarser than before the drawing out. Ruder3 coarsened the grains of silicon steel in this way till single grains reached an area of 50 cm. (7.75 sq. in.). The deformation itself probably breaks each grain up into many very small fragments, but the fact that each grain continues to have a uniform etching tint different from that of its neighbors indicates that these fragments retain the initial common orientation of the grain. The apparent disintegration which we observe, then, is rather an abandonment of community of orientation for individuality of orientation, by the fragments formed earlier during the deformation. Hence we

Jan 1, 1917

By Ben-Zion Weiss, Melvin R. Meyerson

FATIGUE crack propagation in some aspects can be viewed as being a result of localized plastic deformation concentrated near the tip of the crack.' Deformation is influenced by microstructure which in turn can affect the fatigue crack growth significantly. To study the effect of localized microstructural changes on fatigue crack propagation, cantilever-type notched specimens were subjected to cyclic bending at constant load amplitude. The extent of fatigue crack propagation was obtained by measuring the length of the crack by periodic observation with a microscope on the polished side of the sample,2"4 and these data were used in preparing the curves in the figures which follow. Figs. 1 (solid lines) and 2 show experimental results obtained in austenitic type 302 stainless steel containing higher than standard carbon (0.24 pct C) and 310 stainless steel. Both steels were homogenized for 8 hr at 1120°C and then water-quenched in order to prevent the precipitation of carbides. Fig. 3 shows experimental results obtained on 9440 low alloy steel in the normalized condition and in the quenched and tempered (580°C) condition. Indications of microstructural influence can be seen in scattering of the experimental data. The degree of scattering depends on both the microstructure and the amount of cyclic stress applied to the sample. For microstructures which are more easily deformed plastically, e.g., normalized or annealed as compared with hardened and tempered structures, the scattering is greater. Similarly, higher stresses produce greater scattering in the results, regardless of whether the cause of the stress increase is due to initial loading conditions or the growth in crack length. Scattering is believed to be a result of partial redistribution in the stress field around the tip caused by plastic deformation. This opinion is borne out by much smaller scattering of experimental results in the austenitic 302 high-carbon (0.24 pct C) steel. In this steel, plastic deformation in the neighborhood of the crack causes partial mar-tensitic transformation of metastable austenite,5 which in turn restrains further plastic deformation. As a result, the stress redistribution around The tip is reduced. Partial martensitic transformation was confirmed

Jan 1, 1969

By Lawrence B. Wright

THE Republic district, Washington, is of new interest because of the discovery of new gold-silver ore within a unique structural pattern. The camp was revived in 1937 following installation of a plant to treat low-grade disseminated ore at Knob Hill and further stimulation followed discovery of "cross vein" breccia ores in 1939. Previous writers 1-2 ascribed the quartz veins to a latite porphyry stock, but are in disagreement as to its precise location and extent. This study leads to the conclusion that the ores have a more profound parentage linked to a broad system of thrust faults and folds, the mechanical origin of which is related to a southward trending (Sanpoil) syncline connecting with the Lewis and Clark zone of shift described by Billingsley and Locke3 in 1939. The Republic anticline and a cross anticline recumbent against Cretaceous granodiorite, and involving some 4000 ft of Eocene andesite flows and early Miocene lake beds, localize the ores, mainly along the east flank, in a series of openings simulating drag folds and steeper than the folded flows. These broad structural features no doubt reach deeply into the basement rocks, where at appropriate crossings and junctions it is suggested that heat effects gave rise to oremaking materials, including, in this instance, intrusive breccias that later were mineralized, and comprising the broader bodies of new ores. The breccia ore is seen crosscutting the earlier narrow quartz veins with a welding of the two at junction areas by a second surge of ore minerals. The ore mined and developed since 1937 equals district production from 1896 to 1937. The ores are typified by cherty quartz, adularia and some barite, with fine pyrite and marcasite, polybasite, pyrargyrite, tetrahedrite and gold. Selenium is present, possibly with gold, as a normal selenide. The disseminated ores, as well as the vein and breccia ores, are localized principally in one 500-ft flow (Knob Hill andesite), which has been traced around the crest of the low northward-plunging Republic anticline. The gold-silver ratio in the earlier narrow veins is about 1 to 4 and in the disseminated and breccia ores, 1 to 7. The latter higher silver ratio is deemed to reflect the character of the second surge of mineralization. Sills and dikes of the Columbia River (Miocene) basalt cut the folded structure and ore, thus placing the mineralization in the middle Miocene.

Jan 1, 1947

By E. M. Norris

During the winter and spring of 1917, an unprecedented number of underground fires occurred in the Butte district. With one exception, these fires were caused by the failure of electrical equipment, and called attention to the increased fire hazard in underground mining operations occasioned by the extensive use of electricity. Five local conditions that contributed toward a heavy fire risk were: (1) The heavy continuous timbering necessary for mine supports; (2) the strong ventilating pressures in the shafts and main airways; (3) the subsidence and faulting movements in the country rock, which ruptured cables and displaced trolley and lighting wires; (4) the strongly acid mine waters, which quickly developed any weak points in the electrical insulation; (5) oxidation in old stopes containing large amounts of timber. In the summer of 1917, a comprehensive plan of fire prevention was begun by the Anaconda Copper Mining Co., which involved a thorough and intensive development of the preventive measures then in use. These were as follows: Fireproofing, remodeling and strengthening electrical insulations, extension of underground water system, control of ' ventilation, maintaining efficiency of fire-fighting crews, and reorganization of fire patrol. In considering the problems of fireproofing, it was immediately apparent that some method of applying a durable coat of fireproof material to the mine timbers was needed. The first experiments were made with a plaster composed of one part cement, one-half part fireclay, and three parts sand. This was applied by hand to a thickness of 1 in. (2.5 cm.) over a reenforcement of herringbone metal lath. It made a very satisfactory covering for fan stations, but was too soft and friable for traveling ways, where it was subject to abrasion. The cement gun was tried next with a three to one mixture of sand and cement. A 1/2-in. coating of gunite applied over poultry netting or metal-lath reenforcement proved

Jan 1, 1923

By E. M. Norris

During the winter and spring of 1917, an unprecedented number of underground fires occurred in the Butte district. With one exception, these fires were caused by the failure of electrical equipment, and called attention to the increased fire hazard in underground mining operations occasioned by the extensive use of electricity. Five local conditions that contributed toward a heavy fire risk were: (1) The heavy continuous timbering necessary for mine supports; (2) the strong ventilating pressures in the shafts and main airways; (3) the subsidence and faulting movements in the country rock, which ruptured cables and displaced trolley and lighting wires; (4) the strongly acid mine waters, which quickly developed any weak points in the electrical insulation; (5) oxidation in old stopes containing large amounts of timber. In the summer of 1917, a comprehensive plan of fire prevention was begun by the Anaconda Copper Mining Co., which involved a thorough and intensive development of the preventive measures then in use. These were as follows: Fireproofing, remodeling and strengthening electrical insulations, extension of underground water system, control of ' ventilation, maintaining efficiency of fire-fighting crews, and reorganization of fire patrol. In considering the problems of fireproofing, it was immediately apparent that some method of applying a durable coat of fireproof material to the mine timbers was needed. The first experiments were made with a plaster composed of one part cement, one-half part fireclay, and three parts sand. This was applied by hand to a thickness of 1 in. (2.5 cm.) over a reenforcement of herringbone metal lath. It made a very satisfactory covering for fan stations, but was too soft and friable for traveling ways, where it was subject to abrasion. The cement gun was tried next with a three to one mixture of sand and cement. A 1/2-in. coating of gunite applied over poultry netting or metal-lath reenforcement proved

Jan 1, 1923

By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.' Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.' STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

For the first time, the attendance at the meetings of the Institute passed the thousand mark; as is shown by the following table: REGIS- AT BANQUET DID TOTAL TERED NOT REGISTER Men :..:... 703 76 806 Women 195 61 256 1062 The names of the members and guests who registered or attended the banquet but did not register are: A A. D. Beers C. A. Adams Hans Behr Thos. J. Adams Edgar G. Bell Lawrence Addicks Donald A. S. Bell H. T. Abrams W. de LeBenedict G. Aertsen G. B. Bertelli M. M. Albertson Charles P. Berkey James Aldrich Clinton Bernard D. C. Alexander, Jr. W. N. Best W. H. Alexander Robert M. Betts A. W. Allen Christopher H. Bierbaum F. D. Aller Paul Billingsley R. H. Allport R. A. Bingham F. C. Alsdorf R. M. Bird Capt. M. Altmayer John L. W. Birkinbine A.' W. Ambrose G. S. Bisey Henry M. Ami Charles W. Boise F. L. Antisell J. J. Blackmore R. S. Archer A. E. Blackwood Paul' Armitage Capt. C. K. Blatchly Andrew B. Armstrong E. L. Blossom Clifton T. Armstrong C. A. Bohn Ralph Arnold James M. Bonsall R. M. Atwater, Jr. E. E. Boon Joseph E. Aue Gail Borden A. M. Austin R. S. Botsford W. S. Ayres John M. Boutwell

Jan 4, 1919

By Ellen H. Richards

It is of importance to analysts to have a ready means of detecting the presence of small quantities of titaninm in iron ores and in certain fluxes and slags. The method given in Elderhorst's Blowpipe Analysis (fusion with potassium hydrogen sulphate) requires considerable practice, in order so to regulate the heat that the titanium oxide shall become soluble. In Brash's Determinative Mineralogy is found a method which, at least in inexperienced hands, has given better results, i. e., fusion of the substance to be tested with sodium carbonate on charcoal in the reducing flame. The solution in hydrochloric acid of the bead thus obtained, boiled with tin or zinc, gives the characteristic violet color; but when the mineral contains less than four per cent. of titanium oxide, long boiling and consequent concentration is necessary. In fact the test would seem to be much less delicate than is generally supposed. In the course of some analyses I quite accidentally found that a peculiar color is given to turmeric paper by solutions of titanium chloride. This color is hard to describe, being modified by the quantity of ferric chloride present in the solution ; but it is neither the orange of zirconia nor the red of' boron. It is rather a dull shade of purple, arid is easily recognized when the paper is dried, although the color fades in a few hours. By this means a solution containing .015 per cent. of titanium oxide can easily be tested. The same solution, treated with tin, required to be concentrated to one-tenth its bulk before a decided color could be obtained. The color given to turmeric paper is intensified after the solution has been treated with tin. This and some other indications show that the best shade of color is given by the titanons chloride rather than by the titanic chloride, and no other salt of titanium than the chloride has been found to give the color. Another peculiar property of titanium salts has come tinder my observation. When titaniferous minerals are soluble in nitric acid, and the solution is subjected to the action of the battery, the soluble titanium salt is converted into the insoluble oxide and appears on the electrode, in some cases, as a white coating; this

Jan 1, 1883

By John W. Burd

A system is described for the simultaneous deposition of epitaxial layers on as many as eight substrates. A high degree of uniformity of both physical and electrical characteristics is achieved in the films. Variation of film thicknesses is consistently less than ±10pct within a wafer and from wafer to wafer within a run with the variation typically on the order of 55 pct. Composition variation of GaAs1-x PX layers within a wafer and from wafer to wafer within a run is consistently less than 51 pct. Electrical evaluation of the films by several techniques indicates excellent doping uniformity within a wafer and from wafer to wafer within a run. Mobilities for lightly doped GaAs films at 300°K are consistently >6000 cm2 v-1 sec-1 and mobilities > 7000 cm2 v- 1 sec-1 are regularly attainable. Techniques for the preparation of material with carrier concentrations from 1 x 1015cm-3 to 1 x 1019 cm-3 n-type and 5 x 1016 to 5 x 1018 cm-3 p-type are discussed. METHODS for the preparation of 111-V compounds by vapor phase reactions have been extensively reported in the literature.1-6 Almost all of the apparatus described for these various methods are suitable for processing one or at the most a very limited number of wafers simultaneously. With the recent rapid advances in the use of vapor grown GaAs for microwave oscillators and GaAs1-xPx as visible light emitters the requirements for these materials are steadily increasing. In order to satisfy these requirements it is necessary to move from a laboratory scale apparatus to one which is capable of processing a large number of wafers simultaneously. Desirable features would be a high degree of uniformity among the wafers and good reproducibility from run to run. The apparatus to be described fulfills these requirements very well. DISCUSSION The various methods reported in the literature can be classified under three headings: 1) closed tube, 2) open tube, and 3) the close-spaced method. Of these three the open-tube method is the most amenable for scale-up to a manufacturing process. It is the most versatile and the various operating conditions can be more precisely controlled than with the other two methods. A number of chemical reactions may be used to achieve vapor-phase growth of 111-V compounds. Sev-era1 of the more generally used reactions are shown in Fig. 1. All of these reactions have the following points in common: 1) generation of a volatile group III(Ga) species by the reaction of the transport agent (halide or HC1) with either Ga or GaAs, 2) introduction of the Group V(As and/or PI component, 3) a method of adding dopant, if desired, and 4) a region in which deposition from the vapor will occur and form as a single crystal epitaxial film on the substrates. The laboratory scale reactors permit the hot re-actant gases to flow into the relatively cooler deposition zone and pass successively over the several substrates which are arrayed along the long axis of the tube parallel to the gas flow. With this arrangement the composition of the reactant stream is continually changing as solid material is deposited on each successive substrate. As a result of this changing gas composition the reaction driving force also changes from substrate to substrate and the degree of uniformity of layer thickness, doping level, and so forth, is poor. This effect can be partially overcome by imposing a controlled temperature gradient along the deposition region to compensate for change in gas composition. However, even when this is done variations in layer thickness on the order of 30 to 40 pct are common and as high as 50 pct are frequently experienced between adjacent wafers in the tube. To expand this arrangement to a large number of wafers would only increase the nonuniformity from the first to last wafer in the line. From the above discussion the two undesirable features of changing gas composition and temperature gradient become evident. A reactor system which eliminates or minimizes these undesirable features is one in which the apparatus is mounted vertically as shown schematically in Fig. 2. The vertical mounting permits the disposition of a number of substrates on a suitable support so that all wafers are at the same vertical height in the furnace and hence at essentially the same temperature. By using only a single row of wafers the reactant gas mixture passes over only one substrate in its path through the reactor. Thus the two undesirable features of changing gas composition and temperature gradient are minimized. An additional design feature which further minimizes temperature variations is rotation of the substrate holder. Rotation serves to integrate any radial temperature gradient existing around the resistance heated furnace. A photograph of a reactor assembly at the completion of a run is shown in Fig. 3. MATERIAL PREPARATION Apparatus. Although any of the several chemical systems shown in Fig. 1 are adaptable for use in this apparatus the one generally used is System 2, the hydride synthesis system. This system has been de-

Jan 1, 1970

By J. K. Edgar

FOR a number of years the production and use of super-purity aluminum (better than 99.99 pct) has been steadily increasing. High-grade lots of such aluminum show certain outstanding characteristics not found in lower grades containing principally silicon, iron and copper as impurities. One such characteristic is the so-called "self annealing," that is, the recrystallization of the heavily cold worked metal at room temperature.' Interest therefore is aroused as to the effects of the impurities. It is well known that the amounts of silicon and copper which occur in aluminum of better than 99.95 pct are completely soluble, at least at elevated temperatures (above 200°C). Iron, on the other hand, is known to be fairly insoluble in solid aluminum. Thus, a knowledge of the limits of this solubility would be of considerable use in studying the characteristics of the high purity metal. All investigators have agreed that iron has very low solubility in solid aluminum. Rosenhain, Archbutt and Hanson2 reported traces of an aluminum-iron phase in the "purest samples of aluminum obtainable." Gwyer and Phillips3 reported that an iron constituent was visible under the microscope in metal containing ".0088 per cent iron." Roth1 found that in the solid state the solubility of iron in high purity aluminum was 0.01, 0.01, 0.017 and 0.022 pct at 225, 320, 500 and 600°C respectively. Dix5 working with alloys containing less than 0.03 pct impurities, concluded from microscopic and chemical analyses of eutectic areas that the eutectic composition was close to 1.7 pct iron. Dix placed the eutectic temperature at 655°C'. Archer and Fink,6 using high purity aluminum-iron alloys, found that the hypoeutectic liquidus intersects the eutectic horizontal at 1.7 pct. This is in fair agreement with the investigation of the aluminum-iron system by Gwyer and Phillips who placed the eutectic at 1.89 pct iron with a freezing point of 653° PREPARATION AND CHEMICAL ANALYSIS OF ALLOYS Electrolytically refined aluminum (99.991 pct aluminum) and a high purity aluminum-iron alloy (11.45 pct iron) were used in the preparation of the alloys for this investigation. To aid in controlling the iron content of the experimental alloys, an alloy of lower iron content was prepared first from these materials. The high purity aluminum was melted and heated to about 700°C in a plumbago crucible coated with alundum cement and the aluminum-iron alloy was then added. The alloy was thoroughly stirred, fluxed and skimmed and then chill-cast into notch bars. The analyses of the three materials are given in Table I. The alloys for the determination of the solid solubility of iron in aluminum were prepared by melting 600 g total of the aluminum plus the required quantity of the aluminum-iron alloy (No. 92531). These

Jan 1, 1948

IN order not to deviate from the proposed order both in speaking of melts and of things necessary for guns, I shall tell you at present the method by which iron balls are made. This is surely a very fine invention and a horrible one because of its very powerful effect. It is a new thing in warfare,* because (as far as I know) iron balls shot from guns were never seen in, Italy before those that King Charles of France brought here for the conquest of the Kingdom of Naples against King Ferrandino in the year 1495. Now, although I spoke to you briefly of these when I told you above of the purification of iron, it seems to me necessary to show you again in more detail here how they are made. Therefore I tell you that in addition to iron, bellows, blast furnace, and charcoal, it is necessary to have the moulds, without which they could not be cast. At first, when this work was begun in Italy, it was customary to make these moulds of bronze so as not to be obliged always to be making them of clay. Now the present masters cast the moulds of the same iron in order to save expense. Although I am aware that you should already know how to make these from the methods of moulding taught you before, still I shall tell you the method that is followed in making these, because in the practice of every particular thing there is some divergence from the general procedure. For these balls, first make a ball of wood or of clay, or have one made of lead or iron, round and of exactly the dimensions that you wish. This is if you wish to make only one in your mould; otherwise take as many as you wish it to contain. Bury half of this, or these, in a board or in clay and, having greased them with oil or lard, make a mould over them of plaster of Paris, or of clay if you have no plaster, exactly as you wish it to be in iron or bronze. Then make the other half opposite this. After having taken out the balls make little openings for the gates and vents and like- wise four holes for pegging the parts together. At the back make a stud or

Jan 1, 1942

By Cuppam Dasarathy

The incidence of liquid inzmiscibility in binar)) indium alloys has been theoretically analyzed on the basis of the Hildebrand-Alott equation. Bedictions of miscibility or otherwise Imve in general been found to agree with those phase diagrams that are already publislzed in the literature. Out of a total of 27 systems, where either the complete phase diagrams are published or liquid immiscible behavior is reported, the Predictions agree with the experimental data in 25 systems, the exceptions being the Te-In and Ni-In systems. According to the equation, liquid immiscibility is also indicated in the binary alloys of indium with K, Rb, Cs, Na, Sr, Ba, Ti, Zr, V. Nb(Cb), Ta, W, U, Re, Ru, Rh, Os, and Ir. RECENT investigations by the author have shown that indium when alloyed with iron, chromium, and cobalt shows liquid immiscible behavior.1"3 The Fe-In phase diagram shows a wide range of compositions where the liquids are immiscible.4,5 No intermediate phases are present in this system. No precise information is available about the extent of liquid immiscibility in the Co-In system. However, it is certain that there is a range of compositions where the liquids are immiscible and that there are two or three intermediate phases,376 in the system. Liquid immiscibility is also strongly indicated in the Cr-In system and no evidence was obtained in the brief investigation to indicate the presence of intermediate Cr-In phases.2 The present paper deals with a theoretical analysis of binary alloys of indium with certain elements of the periodic table and indicates the systems where liquid immiscibility may be expected. The incidence of liquid immiscibility in binary systems has been theoretically examined by many workers and many excellent papers are available on the subject. In this paper, the alloy systems are examined on the basis of the more recent ideas proposed by Mott.7,8 It has been claimed8 that the Mott parameter predicts the incidence of miscibility or otherwise with reasonable accuracy and consistency. BACKGROUND TO MOTT&apos;S APPROACH Hildebrand applied his immiscibility rule for non-polar liquids to various alloy systems.9 The basis of this rule is that the equation for the excess free energy of formation of a liquid solution is rather similar to the theoretical expression for the energy of mixing of a regular solution. He postulated that when the heat of mixing is sufficiently high, separation into liquid phases will occur and the condition for complete CUPPAM DASARATHY is at the Research Centre, British Steel Corporation, (South Wales Group), Port Talbot, Glamorgan, Great Britain. Manuscript submitted March 12, 1969. IMD miscibility was shown as where VA and VB were the atomic volumes of the components A and B, and ?EV the energy of vaporization of the component. The term (?EVA/VA)1/2 was regarded as a measure of the binding energy of the component A and was called the L&apos;solubility parameter" 8A. On this basis immiscibility occurs when 1/2(VA+VB)(bA-bBf > 2RT [2] Apparently, however, there were several inconsistencies in that according to Eq. [2] several systems known to be miscible in the liquid state were predicted as immiscible. MOTT&apos;S ANALYSIS ~ott&apos;" regards that the reason for the inconsistencies arising out of Hildebrand&apos;s equation was largely due to the electrochemical attraction between the two elements, not being considered. Hence, Eqs. [I] and [2] were modified by taking into account the electro-negativities of the two elements XA and XB, and Mott arrived at an equation for immiscibility, i(VA + VB)(6A - aB)2 - 23,Q60n(XA - XBf > 2RT [3j which can be written as i **&£*&* >&apos;*°™- &apos;• HI T being the melting point of the more refractory component of the system. In Eq. [4], the numerator was called the Hildebrand term, the denominator, the electronegativity term, and their ratio, the Mott number. Mott observed that if the Mott number of a given binary system was greater than the maximum number of Pauling bonds which the two metals could form, then liquid immiscibility could be expected. The maximum number of bonds formed by a given metal was considered to be directly related to the number of bonding electrons available, i.e., to its maximum valency. Since the valencies of the elements considered vary from 1 to 6, Mott assumed that if the ratio of the Hildebrand term to the electronegativity term was >6, then immiscibility could be expected. On the contrary, if the ratio is <1, the metals should be miscible. Further, the alloying behavior is not only influenced by the valencies of the two elements but also by the relative atomic sizes that influence the types of packing and hence the coordination number. Mott considers that on average the maximum number of near neighbors of unlike atoms is 6. Thus, on both valency and size factor considerations, Mott concludes that the maximum number of bonds&apos; possible in any system was 6, this being the upper limit of the Mott number for miscibility. In considering the alloying behavior of systems with Mott numbers between 1 and 6, Mott plotted the num-

Jan 1, 1970

By J. F. Enrietto

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

Jan 1, 1962

Readers of recent Bulletins have doubtless observed that the problem of improving both material and moral condition of employees is receiving close attention from influential members of the Institute. This will lend interest to certain developments and investigations that have been reported elsewhere.

Jan 5, 1918