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By J. L. Wyatt

The electrical resistance of titanium as a function of purity and temperature was measured from —325" to 2800°F. Two points of inflection in the data plots were found, and an increase in resistance with increase in temperature above the transformation was observed. IN 1948 Greiner and Ellis' reported on the thermal and electrical properties of titanium, including a study of the effect of temperature on the electrical resistance. The materials used in the research were obtained from the United States Bureau of Mines, where powder metallurgy techniques were being employed for consolidation purposes. These authors found a decreasing resistance with increasing temperature above 1625°F, and concluded that the latter temperature represented the point of transformation from hexagonal close-packed to body-centered cubic structure on heating. They reported a specific resistivity value of 55x10-6 ohm-cm, and showed that dp/dt was positive, decreasing with increasing temperature above ambient. In one of his early texts Hume-Rothery2 mentioned that certain metals, including titanium, exhibited minima in plots of resistance vs temperature. He indicated that this occurred at 212°F. Reporting many years ago on the effect of temperature on the electrical resistance of zirconium, de Boer and Fast³ showed that phase transformation in this sister metal occurred over a range of temperatures, the extent varying with its purity. Graphs of resistance vs temperature, showing transformation effects over a range of several hundred degrees, were presented for relatively impure metal. In the latter case the resistance decreased with increasing temperature throughout the region of partial phase transformation, thereafter increasing as predicted for normal metals by modern theories of the solid state. Since the quality of metal used in previous studies was substandard compared with iodide-type titanium, and in view of the fact that there seemed to be some rather unusual observations in the reported literature, it was decided to undertake a more extensive study of the thermal effects using high purity titanium, and to include temperature ranges beyond those which had been studied in order to ascertain whether or not the characteristics of zirconium would be duplicated. Experimental Materials Materials used in this investigation included commercial quality titanium (Ti-75A produced by the Titanium Metals Corp. of America) in the form of ¼ in. diam rods, and high purity iodide titanium (produced by the Foote Mineral Co.) in the form of crystal bar of irregular size. The latter was cold-swaged into rod form and machined to the desired size. Lead wires to all specimens consisted of 18 gage Ti-75A. Chemical analyses of the stock materials are given in Table I. Experimental Procedures Specimens 2½ to 3 in. in length were prepared with diameters nominally 0.15 to 0.20 in. Two holes,

Jan 1, 1954

By B. D. Cullity, J. T. Norton, M. Telkes

THIS investigation of antimony-selenium alloys was undertaken in an attempt to find a suitable material for use in power-generating thermocouples. The chief requirements for such a material are high thermoelectric power, low electrical resistivity and low thermal conductivity. Measurements of the first two properties mentioned are usually sufficient to determine whether or not a material is suitable for use in a thermoelectric generator. As a first approximation the requirements are: 1. Thermoelectric power greater than 200 microvolts per °C. 2. Electrical resistivity less than 0.002 ohm-cm. 3. Thermal conductivity less than 0.015 watt per cm per "C. These quantities are averages for the Operating temperature range. Previous Work Experimental investigations of equilibrium in the antimony - selenium system have been summarized by Han-sen². These investigations extended from 1906 to 1921. In Hansen's judgment, the most accurate phase diagram is that determined by Parravano, in 1913 and this is reproduced in the upper part of fig. 1. The most notable parts of this diagram are the liquid miscilibility gap, extending from about 12 to 36 wt pct selenium, and the intermediate phase Sb2Se3 containing 49.3 wt pct selenium. The crystal structure of Sb2Se3 has not been determined. Pelabon3,4 made measurements of the electrical resistivity of a few antimony-selenium alloys but his investigation was not very complete. He found that the resistivity increased with the selenium content and became very large as the composition of Sb2Se3 was approached. For alloys containing less than 50 at. pct (39.3 wt pet) selenium, he found that the resistivity increased regularly with temperature. For alloys containing larger amounts of selenium, he found various results: in some cases, the resistivity decreased with increas-

Jan 1, 1951

By B. D. Cullity, J. T. Norton, M. Telkes

M. Balicki—As one who some years ago spent much time searching for an alloy with high thermoelectric power that would be suitable for heat energy-electric energy converter based on the principle of a thermoelectric pile, I would like to make a few comments touching upon that aspect of this excellent paper. The specifications which one of the authors has formulated so aptly do not appear to me as complete, and I would like to add to them the following two demands: (1) Melting point not less than 500°C and (2) elongation on 2 in. at least 5 pct. Condition 1 would insure good thermodynamic efficiency of the pile by permitting a reasonably high temperature of the hot junction and at the same time making it suitable for such application as salvage of vast amounts of energy which is lost in the form of sensible heat of waste gas leaving industrial and other furnaces. Condition 2 is also a very important one; particularly, because of the fact that all elements and alloys which exhibit attractive thermoelectric properties seem to be as a rule very brittle. The design, erection, and maintenance of a pile incorporating a brittle material in one of the most crucial parts of the converter would be a very difficult and costly affair indeed. To illustrate this point I may mention great difficulties I encountered when trying to make thermocouples of silicon. Casting of 1/4-in. rods in iron or graphite mould yielded only broken pieces which had to be welded into a bar. Such a bar had to be handled very carefully during the determinations. Raising the molten silicon by vacuum into a silica tube and solidifying it there solved the problem of stability as well as that of electrical insulation of a bar. On tests this bar (98.5 pct Si) showed dE/dT = — 275.5 microvolts per degree C vs. copper. Thermocouples made of this grade of silicon and pure nickel developed 0.39 v when temperature of the hot junction was approximately 1000°C. The possibility Dr. Gonser has mentioned of trying to impart to metals good thermoelectric properties by alloying them with silicon, has been considered. The preliminary survey which I have made was, however, disappointing. Perhaps, it will be advisable to record the results obtained (table VI), as this might save repetition of search in fields already covered.

Jan 1, 1951

By F. W. Glaser

Iron-silicon alloys have had a great influence, in many ways, in modern industry. Silicon steels have been used almost exclusively for the construction of electrical machinery, but have also become an important material for structures which benefit by the high tensile and yield strengths of this material. In elaborating on the early history of work done on iron-silicon alloys, Greiner, Marsh and Stoughton1 went back as far as 1808, and pointed to Berzelius as the first producer of ferrosilicon. During the last twenty years some very important contributions in the form of studies of the iron-silicon system, as well as of the physical properties of these alloys, have been published. In consideration of the brit-tleness and poor machinability of alloys containing more than 5-6 pct Si, commercial interests have stimulated the research done on iron-silicon alloys, but mainly in the range of 0 to 6 pct Si. Yensen2 has shown the influence of im- purities, such as carbon, sulphur and phosphorus on the magnetic properties of 2, 4, and 6 pct Si alloys. Corson3 extended his investigation of physical properties to approximately 32 pct Si, and attributed the brittleness of the high-silicon material to the particular constitutional features of the alloys. Though mentioned earlier in the literature, the effect of nitrogen on crystal growth and magnetic permeability of iron-silicon alloys has been demonstrated recently by Morrill4 and Rostoker,5 respectively. In all the above quoted investigations, except that of Rostoker,5 sand or chill casting processes were employed for the preparation of samples. A major advantage of the powder metallurgy process is that it does away with time-consuming machining in many applications. The powder metal industry is always interested in pro- ducing a finished product employing a material which has presented considerably greater difficulties in manufacture by other methods. Steinit26 described preparation and testing of various Fe-Si alloys which were produced by the powder metallurgy process for the manufacture of armatures for small electric motors or generators. While Steinitz investigated alloys up to 6 pct Si, Rostoker5 went as high as 9 pct Si. The author7 previously discussed the diffusion of iron-silicon compacts containing 6 and 10 pct silicon. It is the object of this paper to study the progress of diffusion occurring in iron-silicon alloys by electrical resistivity measurements. All samples were prepared by pressing and sintering of compacts. Iron, silicon, and Fe-Si powders of various mesh size and compositions were employed to obtain test samples. It was assumed that complete diffusion had been obtained when the electrical resistivity reached a constant value characteristic for that particular alloy. To this end, electrical resistance measurements were used to follow the progress of alloying under various conditions.

Jan 1, 1950

By W. R. Hibbard

THE classical work on the electrical conductivity of alloys was carried out by Matthiessen and his coworkers1 in the early 1860's. He attempted to correlate the electrical conductivity of alloys with their constitution diagrams, but the information regarding the latter was too meager for success. Guertler2 reworked Matthiessen's and other conductivity data in 1906 on the basis of volume composition (an application of Le Chatelier's principle with implications as to temperature and pressure effects), and obtained the following relationships between specific conductivity and phase diagrams (plotted as volume compositions) : 1—For two-phase regions, electrical conductivity can be considered as a linear function of volume composition, following the law of mixtures. 2—For solid solutions, except intermetallic compounds, the electrical conductivity is lowered by solute additions first very extensively and later more gradually, such that a minimum occurs in systems with complete solid solubility. This minimum forms from a catenary type of curve. Intermetallic compound formation with variable compound composition results in a maximum conductivity at the stoi-chiometric composition. Landauer" has recently considered the resistivity of binary metallic two-phase mixtures on the basis of randomly distributed spherical-shaped regions of two phases having different conductivities. His derivation predicts deviations from the law of mixtures which fit measurements on alloys of 6 systems out of 13 considered. Volency (Ionic Charge) Perhaps the first comprehensive discussion of the electrical resistivity of dilute solid-solution alloys was presented by Norbury' in 1921. He collected sufficient data to show that the change in resistance caused by 1 atomic pct binary solute additions is periodic* in character. The difference between the period and/or the group of the solvent and solute elements could be correlated with the increase in resistance. Linde5-7 determined the electrical resistivity (p) of solid solutions containing up to about 4 atomic pct of various solutes in copper, silver, and gold at several temperatures. He reported that the extrapolated"" increase in resistance per atomic percent addition is a function of the square of the difference in group number of the solute and solvent as follows: ?p= a + K(N-Ng)2 where a and K are empirical constants and N and Ng are group numbers of the constituents. This empirical relation was subsequently rationalized theoretically by Mott,8 who showed that the scattering of conduction electrons is proportional to the square of the scattering charge at lattice sites. Thus, the change in resistance of dilute alloys is propor-t,ional to the square of the difference between the ionic charge (or valence) of the solvent and solute when other factors are neglected. Mott's difficulty in evaluating the volume of the lattice near each atom site where the valency electrons tend to segre-gate: limited his calculations to proportionality relations. Recently, Robinson and Dorn" reconfirmed this relationship for dilute aluminum solid-solution alloys at 20°C, using an effective charge of 2.5 for aluminum. In terms of valence, Linde's equation becomes ?P= {K2 + K1 (Z8 -Za)2} A where K1 and K2 are coefficients, A is atomic percent solute, Z, is valence of solvent, and Zß, is valence of solute. Plots of these data for copper, silver, gold, and aluminum alloys are shown in Fig. 1. The values of K1 and K2 are constant for a given chemical period (P), but vary from period to period. The value of K, increases irregularly with increasing difference between the period of the solvent and solute element (AP), being zero when AP is zero. The value of K, appears to have no obvious periodic relationship. All factors other than valence that affect resistivity are gathered in these coefficients. Because of the nature of the coefficients, Eq. 1 is of limited use in estimating the effects of solute additions on resistivity unless a large amount of experimental data are already available on the systems involved. It is the purpose of the first part of this report to investigate the factors that may be included in the coefficients of Linde's equation. On this basis, it is hoped that the relative effects of solute additions on resistivity can be better estimated from basic data, leading to a more convenient alloy design procedure. It is well 10,11 that phenomena that decrease the perfection of the periodic field in an atomic lattice, such as the introduction of a solute atom or strain due to deformation, will also increase the electrical resistivity. Thus, in an effort to relate changes in electrical resistivity to alloy composition, it appears appropriate to consider the atomic characteristics related to solution and strain hardening

Jan 1, 1955

By R. J. Wasilewski

Electrical resistivity variation with temperature was measured on a series of alloys containting up to 33 at. pct of oxygen over the range 77° to1500°K. The resistivity behavior is highly anomalous and itzconsistent with simple metallic conduction. Both composition and temperature-depended resistivity singularities were observed. A few experiments carried out on Ti-N and Zr-O alloys indicate the presence of similar anomalies. These observations, together with the published data on effects of substi-tutional alloying on the resistiuity of titanium, suggest that the anomalies are inhevent in the electron structure of this group oj metals. The existence of two-band conduction, and a significant shift of bands relative to each other with temperature and/or the electron concentration are suggested. CONSIDERABLE advances have been made in recent years in the alloy theory of simple metals. Very little, however, is known about the bonding in transition metals and their alloys.&apos; Titanium, with its relatively few electrons, may be expected to show simpler alloying behavior than the more complex transition elements. Its alloys with the interstitial elements appear particularly attractive in an investigation of bonding characteristics because of a) the simple nature of the solute elements, b) the remarkable similarity between the equiatomic structures Tic, TiN, and TiO, and c) the extensive solid solubility ranges of oxygen and nitrogen in a titanium reported.2,3 The Ti-O system was chosen for the most extensive investigation because of the relative ease of preparation of suitable specimens. Since the main object of the work was to obtain data on the bonding and its changes on alloying, electron-sensitive properties were primarily investigated. The present work describes the investigation on the electrical resistivity-temperature-oxygen content relationships. A few experiments were also carried out at selected compositions in the Ti-N and Zr-O systems. EXPERIMENTAL Materials and Method. Polycrystalline specimens were prepared in the form of hairpin strips some 50 by 5 by 0.15 to 0.50 mm by direct metal-gas reaction. This was carried out by controlled oxidation followed by a homogenizing anneal at a higher temperature. All the test specimens were fully homogenized as judged from the uniform microstructure and microhardness. To avoid preferred orientation, each strip specimen was annealed in the ß range prior to the oxidation, this procedure assuring random orientation in the strip;4 hence any texture resulting from the oxidation reaction itself affected all the specimens to a similar extent. Titanium used was of high purity (66 DPN, 10 Kg load; major impurities 0,-43G ppm, N,-70 ppm, C-25 ppm, Fe-14G ppm). The solute content of the alloys was determined by weighing, after the reaction with a known amount of oxygen. The specimens in which the discrepancy between the volumetric and gravimetric measurements exceeded 2 pct (or 0.2 mg for the low oxygen alloys) were rejected. The mean between the two measurements was then taken as the oxygen content of the alloy. Check analyses showed no measurable nitrogen contamination. All oxygen contents are given in atomic percent. Zr-O alloys were prepared in identical manner from hafnium-free crystal bar metal, cold-rolled to strip 0.25 mm thick. Ti-N alloys required very long reaction times at the maximum temperature available (1250°C). In order, therefore, to detect possible oxygen contamination, duplicate specimens were reacted in every experimental run, and one of these was analyzed both for oxygen (vacuum fusion) and for nitrogen (Kjeldahl). Only the specimens in which the check analysis showed < 1000 ppm O were then used for resistivity investigation. Since only relatively high nitrogen alloys (7.1 at. pct; i.e., 2 wt pct N,) were investigated, this oxygen contamination was considered permissible. Dc resistance was measured by the four-probe method as previously described.= The temperature was determined with a calibrated thermocouple placed in the center of the specimen hairpin. The errors in the specimen resistance values thus obtained were estimated at 1 pct due almost exclusively to the finite thickness of the potential wires and the consequent uncertainty as regards the true resistance length of the specimen. For the calculation of the specific resistance, however, no dimensional measurements could be carried out on most of the

Jan 1, 1962

By Malcolm McColl, C. A. Mead

Thin films (of mica have unique attributes that are exceptionally good for studies of high-field conduction mechamisms in thin-film insulators and the quantum mechanical tunneling of electrons from metal to metal. The principal advantages of using mica films are that the films are crystalline and the cleavage planes occur every 10Å. This property results in films whose thicknesses are integral multiples of 10Å and whose surfaces are uniformly parallel over sizable areas. Hence, very well-defined metal -mica-metal structures are possible. Furthermore, the fact that the insulator is split fro??! a bulk sample allows the index of refraction, dielectric constant, forbidden energy gap, and trapping levels and their density- to be obtained directly from measurements performed on thick samples Of mica rather than requiring that these properties be interred from the conduction characterrsties alone. In the work to he described, all the cleaving was done in a high vacuum just prior to the evaporation of metal elertrodes so as to avoid air contamination at the interfaces. Results of these studies indicate that the current through the 30 and 40Å films exhibited quantitative agreement with the theoretical voltage and temperature dependence derived by Strallon for the tunneling of electrons directly from metal to metal. Thicker films at room temperature exhibited volt-ampere curves suggesting Schottky emission of electrons from the cathode into the conduction band of mica. However, the thermal activation energy was smaller than that found from other measurements, and the experimsntal Schottky dielectric constant was larger than the square of the index of refraction. These facts would indicate that the electrons were being injected into polaron stales ill the iusulator. At low temperatures and high fields, the current through the thicker films did not exhibit the Fowler -Nordheim dependence as would be predicted by a simple extention of the theory of field emission into a vacuum. THE mechanism of electrons tunneling through insulating films has received considerable attention in the last few years due to the devices possible utilizing tunneling&apos;-4 and the success of tunneling in the study of superconductivity.5,6 Until the recent paper by Hartman and chivian7 on the study of aluminum oxide, there had been no reported successful quantitative experimental fit to the theory. Their method of fabrication necessarily results in a polycrystalline insulator, the stoichiometry of which is nonuniform from one side to the other. This structure also introduces complications to the shape of the barrier which is set up by the insulator since the insulator possesses a spatially nonuniform band structure and dielectric constant. Due to these facts an analysis of the data in terms of a pviori barrier shape is of questionable validity. The use of muscovite mica not only overcomes these disadvantages but, as an insulating thin film, provides physical properties (dielectric constant. trapping levels and their densities, forbidden energy gap, and so forth) that are identical to the easily measured values of the bulk sample. Furthermore, it is a single-crystal insulator whose cleavage planes (10Å apart8,9) provide uniformly parallel surfaces of well-known separation. This material is therefore ideally suited to the study of electron-transport phenomena. Von Hippel10 using a 6.5-µ-thick sample was the first to observe the high-field conductivity (=5 x l06 v per cm) of mica. No attempt was made to develop an empirical formula, but Von Hippel concluded from intuitive arguments that the current was being space-charge limited by trapped electrons. Mal&apos;tsev11 in a more recent investigation at high fields observed a dependence of the conductivity a on the field F of the form exp(ßF1/2). This dependence was attributed to the Frenkel effect,12,13 a Schottky type of emission from filled traps. No mention in the English abstract was made of the thicknesses of his samples or, and more important, of how well the value of ß fit Frenkel&apos;s theory. In 1962 Foote and Kazan14 developed a technique for splitting mica to a thickness of less than 100Å and observed a dependence of the current density j on the field of the form j = jo exp(ßF1/2) on a thin sample thought to be 40Å thick. Assuming that this was a Schottky emission process and that the appropriate dielectric constant for such a mechanism would be closer to a low-frequency value of 7.6, Foote and Kazan calculated from ß an independent thickness of the mica of 36Å. No further investigation was made of the phenomenon. However, the work reported in this paper indicates that the film measured by Foote and Kazan was probably 60Å thick, the error arising from the measurement of the very small metal-insulator-metal diode areas that were used, along with the diode capacitance and dielectric constant, to calculate the thickness. In the research reported in this paper, Foote and Kazan&apos;s technique was modified to cleave muscovite in a vacuum of 10-6 Torr, immediately after which metal electrodes were evaporated creating Au-mica-A1 diodes. Aluminum was chosen because of its strong adhesion to mica, as necessitated by the

Jan 1, 1965

By Goro Shimaoka, Kichizo Niwa

IN the past, the crystalline states of graphite in cast iron have been studied by many investigators. Recently several authors 1-4 have published interesting information on the crystal texture of the individual graphite grain, especially spherulites in nodular cast iron. In regard to the crystal structure of graphite, Lipson and Stokes0 howed by powder X-ray analysis that most of the crystals contain about 14 pct rhombohedra1 structure (ß-form) which differs from the hexagonal structure (a-form) in the sequence of layer stacking. Hoerni6 onfirmed the existence of the ß-form in a single crystal with electron diffraction by Kossel-Moellenstedt&apos;s method. Furthermore, Hoerni and Weigle7 found extra reflections in electron diffraction patterns, which are given by a unit cell twice as large as the usual one in the basal plane. Recently, Lukeshs observed graphite twinning and satellite reflections in his X-ray work and considered them as evidence for the existence of an orthorhombic superstructure. Owen and Street" and Matuyama" studied the structures of graphite crystals in several types of cast iron, using the X-ray powder method, and they showed that the graphite crystal contains a certain amount of the ß-form, an amount which varies with the sources of the cast iron used. The present study was made in order to secure structural information on graphitization in cast iron. Electron diffraction studies on the structure of single graphite flakes segregated from molten carbon or silicon-rich iron at 1200" to 1500°C are reported. Experimental Honkeiko pig iron (4.05 pct C, 1.59 pct Si, and 0.65 pct Mn) was used as the solvent of carbon or silicon. The pig iron was melted in an open furnace and a small quantity of metallic silicon was added to the melt at 1300°C. The melt was heated to 150O°C, and then retort black carbon or metallic silicon was added little by little. The components added to the bath contained approximately 5.0 pct C and 2.0 pct Si in the carbon-rich material, and 3.8 pct C and 5.4 pct Si in the silicon-rich iron. These two types were held at 1500°C and then cooled without graphitizing by cutting the heat sup-

Jan 1, 1958

By S. B. Lement

THE nature of the carbides that form during the tempering of martensite is a subject of continuing controversy. The only direct methods of identification available are X-ray and electron diffraction. These methods are subject to several difficulties. Only a relatively few diffraction lines of appreciable intensity emanate from carbide phases that are formed at low tempering temperatures. Furthermore, some overlapping of carbide and matrix lines occurs. There is also the problem that numerous lines in the patterns of possible carbide phases that may be present have about the same d-spacings. Increasing the number of carbide lines and eliminating the matrix lines can be accomplished by extraction techniques. However, there is always the possibility that a change in carbide structure will occur as a result of removal from the parent matrix. Therefore, such techniques as electrolytic extraction and making extraction replicas should be checked by other methods. For identifying small amounts of carbide in a tempered martensitic matrix, electron diffraction carried out in reflection is more advantageous than X-ray diffraction. To properly prepare a specimen for reflection electron diffraction, an etchant that will selectively attack the matrix and thereby cause the carbide particles to stand in relief should be used. With an electron beam directed at a grazing angle to the specimen surface, the major contribution

Jan 1, 1960

By L. Delisle

This work represents the first step of an attempt to test the applicability of the electron microscope to the study of subgrain structures in copper. Observations on annealed and deformed single crystals and polycrystalline samples of copper are described. IN the course of study of the structure of fine tungsten wires and tungsten rods with the electron microscope, well defined subgrain structures were observed. The size, size distribution, and orientation uniformity of the etch figures varied widely in different samples. Figs. 1 and 2, electron micrographs of a tungsten wire and of a tungsten rod, respectively, are illustrations of the difference in size and size distribution of the etch figures in different samples of the same metal. The observed differences, as pointed out in a previous paper,&apos; appeared to be related to the heat and mechanical treatments of the samples. They were also consistent with the results reported in the literature on the mosaic structure of metals.&apos; For that reason a program of research was initiated in an effort to obtain more systematic evidence of the possible relation of heat and mechanical treatments to the subgrain structure of metals as observed in the electron microscope. The purpose of this paper is to present observations made on the effect of cold work on the subgrain structure of copper. Procedure Starting Materials: Copper was the metal studied because it can be obtained in a high degree of purity, much information is available in the literature on its properties and its response to cold work and heat treatment, it shows no allotropic change, and it is sufficiently hard to be handled without great difficulty. Two groups of specimens were used: 1—single crystals cast from spectroscopically pure copper and 2—polycrystalline samples of oxygen-free high conductivity copper. Single crystals were studied because it was hoped that the elimination of a number of variables, such as grain boundaries, orientation differences, degree of purity, would simplify the problem and perhaps permit a better understanding of the phenomena that would be observed. The polycrystalline samples were designed to give a general picture of the changes considered. The single crystals were made of copper which analyzed spectroscopically to better than 99.999 pct Cu. They were cast in vacuum, by the Bridgman method, in crucibles made of graphite with a maximum ash content of 0.06 pct. The mold design is shown in Fig. 3. It permitted casting crystals of the size and shape required for the experiments, so that the danger of introducing cold work in the original samples by cutting or other machining would be eliminated. The polycrystalline samples were pieces, 3/4 in. long, cut from a rod of oxygen-free high conductivity copper, % in. in diameter. A flat surface, 1/4 in. wide, was milled along the rods, polished, and etched. The samples were then annealed in vacuum at 850°C for 1 hr. Polishing and Etching: Work previously done on tungsten,&apos; polished mechanically and etched chemically," had shown that: 1—the general appearance of the etch figures of a given sample was not altered by repeated polishings and etchings under similar conditions; 2—variations in the time of etching and the concentration of the etchant changed the definition of the etch figures, but did not alter their general size nor orientation distribution within the limits of observation. Further work confirmed the reproducibility of the subgrain structures observed in, 1—single crystals and polycrystalline samples of copper when polishing and etching were repeated under similar conditions, and 2—specimens of tungsten and polycrystalline copper when electrolytic polishing and etching were substituted for mechanical polishing and chemical etching, respectively. On the strength of these observations, it was felt that, if conditions of polishing and etching were kept constant, changes observed in the subgrain structure of a sample upon deformation and annealing would be attributable to such treatments. For that reason the conditions of polishing and etching were kept as constant as possible. The single crystals were polished electrolytically in a bath of orthophosphoric acid in water, in the ratio of 1000 g of acid of density 1.75 g per cc to 1000 cc of solution, under a potential drop of 1.6 to 1.8 V. Electrolytic polishing was selected to prevent the formation of distorted metal in polishing. The same samples were etched by immersion in a 10 pct aque-

Jan 1, 1954

By W. R. McMillan, E. A. Gulbransen, K. F. Andrew

Annealed and electrolytically polished pure iron was oxidized between 650° and 850°C at oxygen pressures of 0.1 to 2 microns Hg. Electron optical studies showed that oxidation occurs discontinuously over the surface and orients crystallographically with the substructure of the metal grains. IN previous papers&apos;, " the authors described the formation of oxide films on high purity iron at norrnal pressures and at temperatures below 300°C. Electron optical studies showed that the oxide film consisted of many individual oxide crystallites having nearly random orientation on each metal grain. The size of the oxide crystallites depended upon the temperature and upon the extent of oxidation. In these studies the crystallite size varied from 250 to 1800Å. Recently, Bardolle and Benard3 studied the crystal habit of the oxide crystallites formed on Armco iron between 650" and 850°C in what might be defined as a "poor vacuum" atmosphere in which the pressure could be varied between 10-1 to 10-3 mm of Hg. Their results showed that, at 850°C and a vacuum of l0-2 to 10-3 mm of Hg, a few well oriented nuclei of oxide were formed on the metal grains. At pressures between l0-1 to 10-2 mm of Hg, many oriented nuclei of oxide were formed. At 750°C the metal surface was bright although an oxide was present. Unfortunately, the extent of oxidation, the oxygen pressure, and the influence of carbon in the metal were not determined, and it was, therefore, impossible to give a theoretical interpretation to the very beautiful light micrographs. Bardolle and Benard used the light microscope to determine the crystal habit of the oxide and X-ray diffraction to determine the orientation relationships. It was believed that the use of controlled amounts of oxidation at high temperature is an important method for the study of the initial stages of oxidation of metals at high temperatures. This paper presents the first results of an electron optical study of this problem for iron. Since the electron microscope and electron-diffraction methods using stripped oxide films and surface replicas yielded finer details of the crystal habit and structure of oxide film, these methods were used in this study. Two types of iron having different carbon contents were used: Puron and Armco* iron. A com- parison of the results for these materials made possible a study of the influence of the surface oxide-carbon reaction on the initial stages of oxidation. Before discussing the experimental results, the thermodynamic equilibria of 1—the oxidation reaction, 2—the surface oxide-carbon reaction, and 3—the solubility of oxygen in iron, will be considered. In addition, it is important to consider the kinetic-theory predictions on the rate of collision of oxygen with the iron surface. Thermodynamic and Kinetic-Theory Calculations Only one type of reaction is usually considered in the oxidation of iron at normal pressures at high temperatures: Fe(a) + 1/2O2(g) = FeO(s) 3Fe(a) + 2O2(g) = Fe3O4(s) 2Fe(a) +3/2O2(g) = a-Fe2O3(s). [11 However, two other reactions may occur: FeO(s) + C (solid solution in Fe) + Fe(a) + CO(g) [2] and Fe(a) + O2(g) e Fe(a) (solid solution of 0,). [ 3 ] In addition, iron will react with the higher oxide at certain temperatures to form FeO. For a complete interpretation of the oxidation of iron at low pres-

Jan 1, 1955

By R. Casting, J. Philibert, and C. Crussard

APPARATUS described in this paper uses the properties of X-radiation, emitted by substances under electron bombardment, as a means of rapid chemical point analysis. The method is based upon the principles of emission X-ray spectrography pioneered by Moseley in 1913. A very finely focused beam of electrons—the electron probe—is projected on the surface of a sample, which has a very large area compared with the beam diameter, at the point where it is desired to know the chemical composition. The minute volume of the sample which is thus irradiated emits a complex X-ray spectrum consisting principally of the characteristic radiations of the elements present in the volume. Measurement of the wavelength and intensity of each component of this spectrum thus affords a simple method of determining the chemical identity and concentration of these elements. The volume of sample which is analyzed at each position of the beam is limited by the diffusion of electrons in the sample. For an accelerating potential of the electron beam of about 30 kv, which is a convenient value for producing the characteristic radiation, this diffusion extends over a diameter of about 1 µ normal to the beam, and about 2 µ in the direction of the beam. Thus a beam of 1 µ in diameter leads to a volume of about 2 µ in diameter being irradiated. The limits of the analyzed region are thus considerably smaller than those obtained by using spark or arc emission spectrometry, which must extend to about 50 µ at right angles to the beam, and those obtained in X-ray fluorescence analysis, where the penetration of the specimen is considerably greater. The apparatus itself consists of three main parts: an electron optical system. an X-ray spectrograph and an optical microscope. The electron opticai system consists of a tungsten cathode emitting the electrow and a pair of magnetic lenses which focus the electron beam on the specimen to be analyzed. The specimen is prepared in the usual way, as in optical micrography. The X-radiation, emitted at the focal spot where the electrons strike the sample, is analyzed with a curved crystal, Geiger-Müller counter, vacuum spectrograph. The light microscope, designed to observe the surface of the sample in the region to be analyzed, is provided with a reflecting objective placed on the axis of the second magnetic lens. Its magnification is X450. The quantitative determination of an element A in the analyzed region is made by measuring the intensity I, of a strong characteristic line of the element, as emitted from the sample, and then the intensity I (A) of this same line as emitted from a

Jan 1, 1958

By H. A. Domian, H. Biloni, G. F. Bolling

Jan 1, 1965

By V. A. Phillips

Transmission-electron micrographs of electro-thinned samples of bulk-aged Cu-3.1 pet Co alloy show an aging sequence, supersaturated solid solution — coherent particles — quasi -coherent particles — noncoherent particles. Hardening is due to precipitation of coherent spherical fee coball-rich particles showing coherency strain fields, which are resolved at between 15 and 30A diameter. Loss of- full coherency did not occur until well into the overaged region, even with the assistance of deformation after aging. Different average particle diameters of 123, 92, and 149 ± 10Å were observed in samples aged to peak yield strength at 600°, 650°, and 700°C, respectively, indicating that there is no critical size for peak hardening. Noncoherent particles tended to develop (111) faces and became octahedral in shape. Dislocations tended to nucleate spherical coherent particles which eventually grew together forming large elongated particles. The surface energy of a noncoherent (low-angle) inter-phase boundary is estimated to he about 50 ergs per sq cm. A number of particle lining-up phenomena were observed. Overaging is principally attributed to increase in particle spacing, progressive loss of coherency, and increase in amount of discontinzdous precipitation. COPPER dissolves about 5.6 at. pet (5.2 wt pet) of cobalt at 1110oC1 and the solubility decreases to 0.75 at. petl (0.54 at. pet)2 at 650°C and to 0.1 at. pet or less at lower temperature.&apos; It has been known for many years3-5 that Cu-Co alloys are capable of age hardening. Since cobalt is fee above 417°C and its atom size is only about 2 pet smaller than that of copper, precipitation of coherent particles would be expected. The equilibrium phase precipitated at 700°C and below contains about 10 pet Cu in solution which tends to stabilize the fee structure, lowering the transformation temperature to 340oc.l The alloy is known to undergo discontinuous precipitation in addition to general precipitation; while the former can be seen with an optical microscope, the latter precipitates are not visible except in the grosly overaged condition.5, 6 Extensive use has therefore been made of the ferromagnetic properties of the precipitate in order to follow the course of aging, and it has proved possible to measure the average particle size, spacing, approximate shape, and volume fraction and to determine that the particles are coherent without ever seeing a particle (see for example Refs. 2, 7, and 8). The magnetic measurements of particle size are limited to diameters below about 120Å.7 The present study was undertaken using the techniques of transmission-electron microscopy in order to check the above conclusions, to extend the previous magnetic work to larger particle sizes, and to attempt a more detailed correlation of properties and structure. A portion of this work has already been published.9-11 The present paper is concerned with the metallographic features of precipitation in relation to aging curves. Bonar and Kelly12&apos;13 have published preliminary results of a similar study on single crystals of Cu-2 at. pet Co. EXPERIMENTAL Preparation of Alloy. A Cu-Co alloy, containing 3.12 wt pet (3.36 at. pet) Co by analysis, was prepared from 99.999 pet purity oxygen-free copper and electrolytic-grade cobalt. The alloy was melted and cast in vacuo in a high-frequency furnace using a graphite crucible and mold: Analysis showed chat 0.004 pet C was picked up during melting. The 1-1/2-lb ingot was homogenized in hydrogen for 24 hr at 1000°C. Slices were cold-rolled to 0.005 or 0.003 in. thickness, with an intermediate 650°C anneal in hydrogen at 0.080 in. thickness. Batches of six to ten strips were solution-treated in sealed-off quartz tubes in high vacuum in a vertical furnace and quenched by dropping into iced brine containing a device which snapped off the nose of the tube. Solution treatment consisted of 1 hr at 990°C or 2 hr at 965°C. The latter was employed for all mechanical-property studies, since a tendency was noted for the higher temperature to give porous material. Strips were usually aged individually in a horizontal vacuum furnace, inserting into the hot zone and withdrawing into a cold zone without breaking the vacuum. This method gave a rapid heating rate, permitting the use of short aging times. In some cases, particularly for the longer aging times at the higher temperatures, samples were sealed individually in quartz tubes in high

Jan 1, 1964

By John D. Verhoeven, Edward E. Hucke

An experimental technique has been developed for the measurement of the rate of electrotransport to a precision of 1 pct in the molten Bi-Sn system. Results are presented across the phase diagram from 30°C above the liquidus to 520°C. A phenomenological description is presented and the data on Bi-Sn are thereby converted to the effective charge, Analysis of the data indicates the true charge of the migrating tin species in bismuth to be +1.8 at 500°C. The data agree well with the recent work of Belashchmko. fieldintensity. The resistivity of the molten Bi-Sn system is also presented. WHEN an electric field is applied to a metal, a relatively large current is produced due to the ease with which electrons move within the metal. The electric field also produces a force on the ions which might cause them to migrate. Such a migration of metallic ions has been detected under certain conditions. This electromigration of the metallic ions will be referred to herein as electrotransport. The study of electrotransport in metallic systems has a rather long history dating back to the initial work of Gerardin1 in 1861. General reviews of electrotransport in liquid and solid metals have been published by Schwarz,2 Jost,3 Seith,4 and Heumann.5 In reviewing the literature it is apparent that the theoretical developments are not yet complete. The difficulty arises in describing the momentum transfer between the migrating ions and the electrons. In addition, there is a lack of good quantitative electrotransport data at high temperatures, especially in liquid metal systems. This work was undertaken to establish quantitative electrotransport data in a liquid metal system which might serve as a critical test of the theoretical developments. The Bi-Sn system was chosen for analysis, and the rate of electrotransport was determined as a function of temperature and composition. THEORETICAL CONSIDERATIONS If all of the atoms of a metal are considered to be positively charged due to the loss of electrons to the

Jan 1, 1963

By E. J. Whittenberger

OVER the past two decades, the Cr-Ni stainless steels, popularly termed 18-8 steels, have been used in ever increasing amounts in the aircraft, automotive, chemical, transportation, and building industries.&apos; The contribution of nickel to these steels is associated with its strong austenite forming tendencies which assure good hot and cold forming characteristics, and with its beneficial influence upon corrosion resistance, especially in oxidizing acids. The adjustment of the chromium and nickel contents has been used advantageously in controlling the rollability and the response of the mechanical properties of these steels to cold reduction. With the advent of the jet age and the government stockpiling of nickel, considerable emphasis has been placed upon the development of satisfactory low nickel or nickel-free substitute austenitic stainless steels, especially for nonmilitary applications.2 Fer-ritic 17 pct Cr (AISI Type 430) stainless steel has been effectively substituted for the austenitic grades in applications with mildly corrosive exposure. However, the limited formability and ferromagnetic behavior of this grade do not permit its satisfactory use for many applications. To achieve better formability in a nenmagnetic steel and conserve nickel, a number of low nickel substitute austenitic grades of stainless steel have been developed in recent years. In most of these steels, manganese and nitrogen have been substituted for a portion of the nickel content, for example, 17 pct Cr-4 pct Ni-6 pct Mn (AISI Type 201), 18 pct Cr-5 pct Ni-8 pct Mn (AISI Type 202), and 16 pct Cr-1 pct Ni-17 pct Mn, all of which contain approximately 0.15 pct N.1 The precipitation of ferrite when large ingots of these Cr-Ni-Mn-N steels are heated to temperatures high enough for conversion to slabs on conventional universal slabbing mills has seriously affected the hot workability of these steels. This has been especially true in the case of the 16 pct Cr-1 pct Ni-17 pct Mn (sometimes referred to as 15 pct Cr-1 pct Ni-15 pct Mn) composition." Because it is possible that little, if any, nickel will be available for nonmilitary stainless steel applications in the event of a national emergency, a need has existed for a nickel-free austenitic stainless steel containing hot and cold forming characteristics similar to 18-8 steels and corrosion resistance at least comparable to the 17 pct Cr ferritic steel. The aforementioned deleterious effect of ferrite upon the hot working characteristics of the 16 pct Cr-1 pct Ni-17 pct Mn, steel indicates the importance of establishing the austenite-austenite plus ferrite phase boundaries as the first step in the development of nickel-free or low nickel substitute steels. This paper presents the data collected in an elevated temperature constitutional study of the Cr-Ni-Mn-N system at the South Works of the United States Steel Corp. Experimental Procedure The 300 compositions used in the investigation were melted in a 26 Ib induction furnace and cast in 3 14 in. diam by 18 in tall hot-tcpped ingot mo1ds.

Jan 1, 1958

By W. L. Phillips

The plastic properties of lithium fluoride and magnesium oxide under compression were investigated in the temperature range 25° to 1000°C. At the higher test temperatures, the critical resolved shear stress and the rate of work-hardening of both materials decreased. At the same time, the number of stress lines decreased and the individual stress lines became wider. The density of dislocations decreased for a given strain the higher the test temperature for lithium fluoride. The decrease in the critical resolved shear stress as a function of temperature could be fitted by the equation 7 = Toe-KT. THE influence of temperature on the stress-strain curves of a variety of metal single crystals has been studied for a wide range of temperature.1"5 In general, it has been found that both the critical resolved shear stress and the rate of work-hardening decrease rapidly with increasing temperature and fall to a value of essentially zero well before the melting point is reached. AS the test temperature is increased, the density of slip lines has been found to decrease, while the width of the individual lines increases. Recently, Gallagher,&apos; Graf et al.,7 and Pate1 and Alexander8 have found that single crystals of germanium and silicon, which have a covalent bond, can be plastically deformed at elevated temperatures. In compressing germanium it has been found that the strain-hardening coefficient decreased very rapidly as the temperature was increased. The coefficient did not tend to zero, however, as the melting point was approached. The plastic properties of ionic crystals at elevated temperatures have not been extensively investigated. In the only work previously reported Tamman and salge9 and Theile10 have shown that the yield point of sodium chloride single crystals tested in tension and compression decreased slowly with increasing temperature, falling to zero at the melting point. As the temperature was increased, they found a substantial increase in the amount of plastic deformation that could be sustained before fracture; and at temperatures above 400°C in tension tests there was an obvious necking which produced local extensions of up to 3000 pct. The purpose of the present work is to extend the knowledge of high-temperature deformation to the ionic crystals, lithium fluoride and magnesium oxide. The following were investigated: 1) The gross shape of the stress-strain curve at several temperatures. 2) The change in the critical resolved shear stress as a function of temperature. 3) The appearance of slip bands and the density of dislocations as a function of strain and temperature. EXPERIMENTAL TECHNIQUES The lithium fluoride and magnesium oxide used in this investigation were purchased from the Harshaw

Jan 1, 1961

By C. A. Bruch, W. E. McHugh, R. W. Hockenbury

Commercially pure molybdenum specimens were irradiated in the Materials Testing Reactor for an estimated exposure of 1.9 to 5.9x10 20 thermal nvt. Prior to irradiation, the material was ductile in the tension test; whereas after irradiation, it was brittle. The results of tension tests conducted at various temperatures revealed that the transition temperature for this material had been increased from —30&apos; to +70°C as a result of the radiation exposure. From metallographic studies, it is concluded that the embrittlement is due to submicroscopic changes which raise the flow stress-temperature curve of the material. PRIOR to ten years ago, the bombardment of metals with high speed heavy particles such as protons, deuterons, a particles, and neutrons was primarily of academic interest. These particles existed in extremely small numbers in a few laboratories and only under very special conditions. With the introduction of the nuclear power reactors, these particles are now available in enormous quantities and it has become important from a practical standpoint to learn how well metals withstand severe reactor radiations. The principal radiations of concern in reactors are neutrons and y rays, since the heavier charged particles exist only in limited regions of reactors. Seitz,&apos; in a theoretical approach, has shown that all of these high energy particles, except y rays, have enough energy to knock atoms from lattice sites and that these knocked-on atoms have enough energy to cause additional displacements of neighboring atoms. The result of this process would be a lattice containing many imperfections in the form of interstitial atoms and vacancies. Hence, it would be expected that the properties of metals can be changed by reactor radiations, and such has been found to be the case. Only a limited amount of data have been published in the open literature,2,3 and these data have been for relatively low integrated-neutron-flux exposures. In general, one effect of reactor radiations on the mechanical properties of metals has been to increase strength and decrease ductility. It is now possible to irradiate specimens in the Materials Testing reactor at much higher fluxes and to higher integrated exposures than previously possible.&apos; The data which are being presented here describe the effects of a relatively high exposure on some mechanical properties of molybdenum. Experimental Procedures Material: The molybdenum used in this investigation was obtained from the Climax Molybdenum Co. The two heats from which the material originated were melted under a vacuum of 5 to 30 microns and cast in 7 in. diam water-cooled copper molds. One ingot contained 0.061 pct C and the other 0.066 pct. Both ingots were hot worked by extrusion and rolling into % in. diam rods, after which they were annealed and straightened. The rods were subsequently heated to 1100°C in a hydrogen atmosphere and swaged to ½ in. diam rods at the Research Laboratory of the General Electric Co. The resulting material had an average hardness of 264 VPN, or 99.2 Rb, and had an average of 5000 grains per sq ml in the transverse section, Test Specimens: Substandard-size tensile specimens were prepared according to the specifications shown in Fig. 1. These specimens were used also for hardness measurements. The metallographic specimens were small disks which were polished, etched, and photographed at X1000 prior to irradiation. The field studied was

Jan 1, 1956

By W. H. Class

The embrittling effects of oxygen, ozone, nitrogen, air, and surface residues, on NaCl has been investigated. The embrittlement by ozone and oxygen was found to be associated with the formation of a NaClO3 surface compound. In these cases the initial crack that was responsible for fracture (in a bend test) always nucleated at the corners between the tension and side faces. The behavior of air was very erratic and on certain days did not produce enzbrittlement. During these periods, crystals that had become embrittled by the ozone treatment completely recovered their ductility after a short exposure to the ambient atmosphere, It was established many years ago1 that considerable ductility could be obtained in NaCl single-crystal specimens if the crystal surfaces were dissolved in water either during or immediately prior to the test. The original interpretation of this effect by Joffe attributed the enhanced ductility to the removal of surface microcracks by dissolution. Later investigations2&apos;3 have suggested that the exclusion of air from the specimen surface is the criterion for extensive plastic flow prior to fracture. The air em-brittlement in this later work was attributed to the diffusion of gaseous atoms into the surface layers of the crystal, thereby impeding the movement of dislocations. This model satisfactorily accounts for the reembrittlement observed after further air exposure subsequent to the water dissolution treatment. However, the situation has recently become more complex by the observations in several laboratories4-t that under certain conditions air exposure does not impair the ductility of NaC1. It has also been recognized5 that improper drying operations after water dissolution can leave surface precipitates that lead to embrittlement. Cleavage defects on as-cleaved crystals can often be another source of embrittlement. In the present work the effect of the gaseous atmospheres nitrogen, argon, air, oxygen, and ozone, on the ductility of rock salt was studied extensively. The embrittlement resulting from oxygen and ozone exposures was found to be associated with the formation of a NaC1O3 surface film. It is suggested that certain atmospheres, one of which often can be ambient air, which inhibit the formation or favor the decomposition of this compound, can promote ductility. Thus one aspect of the Joffe effect is certainly related to the removal of surface compounds or complexes by water dissolution. The effect of surface precipitates that remain after drying operations and of cleavage defects were also studied. In neither of the latter cases was the embrittlement as severe as that found with a NaClO3 surface layer. PROCEDURE AND SPECIMEN PREPARATION The nature of the embrittlement produced by the agents mentioned above was studied by means of microscopy, mechanical testing, and X-ray diffraction. Specimens were cleaved from large crystals of optical quality sodium chloride obtained from the Harshaw Chemical Co., and, except for those tested in the as-cleaved condition, were given a 15- to 20-sec immersion in distilled water followed by a rinse in absolute methyl alcohol. The specimens were then blotted on a soft, absorbent paper, and dried by a few seconds exposure to a stream of warm, dry air. Such a procedure was found to give a control surface which was microscopically free of residues. (A few crystals were intentionally painted with a concentrated NaCl solution in order to investigate the effect of surface residues). All specimens were of 0.140 sq in. cross-section. Crystals prepared in the above manner were immediately placed in a gas train where they could be exposed to the desired gases for preselected periods of time. For the oxygen and nitrogen exposures, pure reagent-grade gases were employed. The ozone was provided in the form of an ozone-oxygen mixture (approximately 10 pct ozone) prepared by passing commercial grade oxygen over a strong ultraviolet light source. All gases were dried prior to their introduction into the train. Since argon was found to be completely inert in its behavior (i.e., residue-free specimens that were exposed to argon were not embrittled), it was periodically utilized to check the control specimen surfaces as well as the condition of the gas train used for aging the specimens. After exposure to the gaseous media in question, the crystals to be used for the measurement of the strain to fracture were transferred from the gas train to a protective oil bath (without further exposure to the atmosphere) where the tests were conducted in three-point bending. The apparatus was so adjusted that the load could be applied at a constant, continuous rate. Other Snecimens from the gas train were deformed

Jan 1, 1962

By W. F. Carew, F. A. Crossley

IT has been reported that the Ti-8 pct A1 alloy is ductile as water quenched from 800°C but brittle as annealed at 650 °C." The present, somewhat limited, investigation was undertaken to discover the cause of the embrittlement. In order to evaluate to some extent the continuity of the embrittling phenomenon, alloys of 6, 8, and 10 pct A1 were studied. Subsequent to the completion of most of this work, Ence and Margolin reported that a Ti,A1 phase exists and that two or more unidentified compounds may exist in the Ti-A1 system.&apos; Materials, Equipment, and Techniques The alloys were prepared using Kroll process sponge of 124 Bhn hardness. In addition, some 8 pct A1 material was made with iodide titanium. The sponge-base alloys were prepared as melts of 4 lb or more by double arc melting. The iodide Ti-8 pct A1 alloy was prepared as 200-g buttons. The alloys were forged at temperatures of 980" to 1150°C. Results of chemical analyses are given in Table I. A Baldwin-Southwark 60,000-lb capacity tensile machine, equipped with an autographic stress-strain recorder, was used for the tensile tests. Standard tensile test specimens, 0.252 in. diam, were used. Standard Charwy V-notch impact specimens were tested using a -kiehle machine. specimens were sealed in evacuated Vycor bulbs for heat treatment. Powder samples for Debye-Sherrer anal- ysis were prepared by filing and screening through 325 mesh. The —325 mesh fraction was taken in an effort to concentrate a microstructural constituent assumed to be less ductile than the a phase. The powder samples were stress relieve2 by annealing

Jan 1, 1958