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By M. E. Wadsworth, R. C. Peterson, W. M. Fassell

The temperature and pressure dependence of the reaction of tantalum in oxygen were investigated from 500° to 1000°C at pressures from 10 mm Hg to 600 psi total oxygen pressure. Tantalum was found to oxidize linearly under the above conditions. Three distinct regions of temperature dependence were found with different energies of activation. From 500° to 600°C the rate of oxidation of tantalum was found to be essentially independent of the oxygen pressure at the pressure investigated. The oxidation rate increases rapidly with an increase in pressure from 600' to 800°C. The dependence of the oxidation rate on the bulk concentration may be expressed by V = k'?, where k' is the specific rate constant and ?=k1Co2/(l + K1Co2), where k, is the equilibrium constant for the adsorption of oxygen on tantalum. ONLY a limited amount of data has been presented in the literature on the oxidation behavior of tantalum metal. Some values of its oxidation rate were reported in the Corroston Handbook' and by McAdams and Geil.' The first extensive investigation of tantalum was the work of Gulbransen and Andrews." They determined the reaction rates of tantalum in O2 and N2. Their results indicate that this metal follows the parabolic law in the temperature range of 250" to 450°C in O2 at pressures of 7.6 cm Hg with an activation energy of 27,400 cal per mol. In nitrogen, the metal follows the parabolic law from 500" to 800°C at 7.6 cm pressure. All experimental determinations were of 2 hr or less duration and deviations from the parabolic rate conceivably could occur at longer times. A spectrophotometric study of the oxidation of tantalum by Waber, Sturdy, Wise, and Tipton' indicated good agreement between this method and the microbalance technique. The experiments were conducted in air from 220" to 350°C. The metal was found to follow the logarithmic law up to 320°C and the parabolic law at higher temperatures. The activation energies in the logarithmic region were reported as 12.57 kcal per mol and 12.0 kcal per mol, respectively, for the microgravimetric and spectrophotometric methods. In the parabolic region the activation energy was found to be 27.2 kcal per mol, in good agreement with the value of Gulbransen and Andrews." The present paper is concerned with the behavior of tantalum from 500" to 1000°C in oxygen at pressures ranging from 1/2 to 40.8 atm pressure. Earlier preliminary data by McKewan5,6 indicated the following facts concerning the behavior of tantalum: 1—At temperatures from 500" to 600°C, the metal followed the linear law. 2—At 575°C the rate of oxidation was found to increase with O2 pressure. 3—The Arrhenius plot in this temperature region was nonlinear. The nonlinearity of the Arrhenius plot was indicative of a more complex behavior than originally suspected for this metal.

Jan 1, 1955

By Charles E. Lundin

Pressure-temperature-composition data were obtainedfor the Er-H system. Measurements werecar-ried out in the temperature range of 473° to 1223°K, the composition range of erbium to ErH,, and the pressure range of 10-5 to 760 Torr. Solubility relationships were established from these data throughout the system. Three solid-solution phases were delineated: metal solid solution, dihydride phase, and trihydride phase. The trihydride Phase decomposes at about 656°K and 1 atm pressure. The dihydride phase is stable to about 1023°K, but becomes more deficient in hydrogen above this temperature. The equilibrium decomposition pressure-temperature relationships in the two-phase regions, erbium solid solution plus dihydride and dihydride plus trihydride, were deter- The differential heats of reaction in these two regions are AH = - 52.6 * 0.3 and - 19.8 i 0.2 kcal per mole of Hz, respectively. The differential entropies of reaction are AS = - 35.2 * 0.3 and - 30.1 * 0.4 cal per mole HZ.deg, respectively. Relative partial molal and integral thermodynamic quuntities were calculated in the system to the dihydride phase. RARE earth metal-hydrogen systems have been the subject of general survey,1"4 and all have been found to form hydride phases. The heavy rare earths, of which erbium is a member, form dihydride and trihydride phases with different crystal structures, whereas the light rare earths form only a single-phase dihydride which expands without structure change, as hydrogen is added, to the trihydride composition. These materials are of interest primarily because of their theoretical properties, such as bonding, defect structure, and thermodynamic and electronic characteristics. Erbium has been studied in several previous investigations.5, 6 It was deemed desirable to more thoroughly and accurately define the system, both for the phase equilibria and the thermodynamic properties. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure hydrogen, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GM 100A and CVC, GM 110). Pure hydrogen was obtained by passing hydrogen through a heated Pd-Ag thimble. The hydrogen was analyzed and found to have only a trace of oxygen and nitrogen. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit hydrogen to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to ±1°K. An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to ±0.5 Torr and in the McLeod range (10-4 to 10 Torr) to ±3 pct. The hydrogen compositions in erbium were calculated in terms of hydrogen-to-erbium atomic ratio. These compositions were estimated to be ±0.01 H/Er. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9 pct +. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<1 vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the pressure-temperature-composition relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 grain for each loading of the reaction chamber. The procedure employed to obtain the pressure-temperature-composition data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen of erbium was wrapped in a tungsten foil capsule to prevent contact with the quartz tube. After loading the specimen, the system was evacuated to less than l0-6 Torr, flushed several times with high-purity hydrogen, and evacuated again ready for the start of the experiment. The furnace was then brought to the desired temperature. A measured amount of hydrogen was admitted into the chamber. Equilibrium was allowed to be attained, the pressure read, and the process then repeated many times until 1 atm of gas pressure was finally reached. Other isotherms were then developed in the same manner. The partial pressure plateaus were determined by another manner. In the solid solution-dihydride region a composition of approximately 1.0 H/Er was selected on the plateau. The temperature was varied throughout the range of interest. At each temperature level, equilibrium was achieved, the pressure read, and the next temperature attained. The temperature was cycled both up and down. In the dihydride-trihy-dride region, the plateaus were determined in the 473" to 651°K range only by heating to the desired temperature and not by both heating and cooling. The data were much more reproducible in this manner. Equilibrium required long periods of time. Specimens were initially hydrided to 2.8 H/Er, so that at the higher

Jan 1, 1969

By A. F. Witt, A. M. Gaudin, A. K. Biswas

Finite contact angles in the rutile-water-organic liquid system are traceable to contamination or are due to addition of a surface-active agent. Finite contact angles are invariably accompanied by hysteresis.1-7 Besides surfactant concentration and pH, the nature of the organic liquid is found to be a factor influencing the magnitude of contact angle hysteresis. In a recent paper the authors have reviewed principles and applications of measurement methods for contact angles and their hysteresis.22 In this paper, these methods are applied to a system consisting of rutile, an organic liquid (benzene, decane, or dode-cane) and water. Surfactant (dodecylamine hydro-chloride) was used at various concentrations and various pH values. MATERIALS A synthetic rutile crystal supplied by the Linde Co. was used. It is a cylinder 1/2 in. diam, with faces cut perpendicular to the c-axis. The crystal is stated to be alumina-free and to be 99.9% pure. Rutile is a high surface energy solid, its calculated average field strength being 2.7 x 105 e.s.u.,9 its dielectric constant10 is 114. The zero point of charge of rutile was measured11 and found to be at pH 6.0. The atomic distances and bond angles of the tetragonal crystal of rutile have been precisely determined.l2 The organic liquids were specially purified. Reagent grade benzene was repeatedly shaken with concentrated sulfuric acid to remove thiophene, then neutralized with sodium hydroxide solution, rinsed with distilled water, dried overnight over anhydrous calcium chloride and filtered. The refractive index of this chemically purified benzene was 1.4977 (at 25°C) - very close to that of pure benzene (n25 1.4979).13 Both n-decane and n-dodecane were washed with aqueous sodium hydroxide, concentrated sulfuric acid (repeatedly, until the acid layer was colorless) and again with alkali, to free the organic hydrocarbon from fatty acids and unsaturated hydrocarbons. The organic phases were subsequently washed with distilled water and dried over anhydrous sodium sulfate. The filtered hydrocarbons were then distilled under vacuum (9-10 mm pressure). Decane, thus purified, showed traces of unsaturated and of carboxylic compounds. On gas chromatographic analysis the purified n-dodecane showed the presence of two impurities. However, the relative retention times of these components did not change substantially when measured on a polar or a nonpolar column. This indicates that the compounds were probably in the same polarity class, i.e. the components were nonpolar like dodecane. Conductivity water has always been one of the liquids. Conductivity of the water used was 10-6 ohm-&apos; cm". Dodecyl ammonium chloride was prepared from pure amine (supplied by Armour and Co., Chicago), by Li in the MIT Mineral Engineering Laboratory.14 The critical micelle concentration at 25°C is known, 0.0138 mol per liter15 or 3.06 gpl. All our experiments have been done at concentrations lower than the critical micelle concentration. The glass vessels, glass drop holder and the rutile crystal were all cleaned with hot chromic acid followed by distilled water, concentrated hydrochloric acid, and again distilled water, and conductivity water. During the experiments, a nitrogen atmosphere was maintained. For this purpose, commercially purified nitrogen was further purified by passing it over hot copper wire at 450°C, then through columns of acidic chromous chloride solution, concentrated alkali solution and distilled water. APPARATUS AND METHODS Hysteresis was produced by the "captive drop" or constant volume drop method as well as by the "expanding-contracting drop" or variable volume drop method. The image of the drop while it is expanding, contracting or moving is projected on a screen and photographed. The developed film is projected through an enlarger and the contact angles measured with a protractor.

Jan 1, 1964

By W. F. Holbrook, C. E. Wood, E. P. Barrett

THE high-frequency laboratory induction furnace with a rotating liquid crucible enables research workers to conduct certain investigations heretofore very difficult or impossible to realize because vessels are not obtainable that are capable of resisting the physical conditions or the chemical actions to which they are subjected. Applications for patents covering commercial uses of centrifugal liquid crucibles were filed in the United States in 1919,1 in France in 1925, in the United States and Germany in 1926,2 and in France in 1927.3 In 1928, Schuette and Maier,4 of the Bureau of Mines, reported the construction of a whirling table beneath a high-frequency induction furnace. SHAPE AND SIZE OF CENTRIFUGAL LIQUID CRUCIBLES When a vessel containing a liquid is rotated, the inner surface of the liquid takes the shape of a paraboloid under the simultaneous action of centrifugal force and gravity. The internal dimensions of the paraboloid rotating liquid crucible are governed by the diameter of the container and .its speed of rotation. Melted Wood&apos;s metal was poured into cylinders 2 1/2 in. in diameter, which were rotated at 180, 300, and 468 r.p.m. When the metal was solid, a slurry of plaster of Paris was added, and rotation continued until the plaster had set. Fig. 1, a photograph of sections of the cylinders, shows the effect of speed of rotation of the containers upon the shape of the inner surface of the rotating liquid crucibles. TYPES OF FURNACES Three types of high-frequency induction laboratory furnaces using liquid-metal crucibles were designed and constructed by the Blast

Jan 1, 1938

By R. C. Hirschfeld, H. H. Einstein, R. W. Bruhn, R. A. Nelson

The objective of the model studies described in this paper is to determine the effect of planar discontinuities on the strength and deformability of a rock mass. A model material was used because it satisfied concurrently three requirements that available natural-rock samples did not: (1) low strength, which was desirable for minimizing the loads that had to be applied in the laboratory; (2) ease of producing test specimens with geometrically regular joint patterns; and (3) uniformity of the test specimens. The model tests were performed on specimens made from a single modeling material and tested under triaxial stress conditions with [u,=u,]. Results are presented in this paper for tests on specimens that had (1) a single joint set inclined at several angles to the major principal direction, including 0º and 90°, and (2) two joint sets that were mutually perpendicular, one set perpendicular to and one set parallel to the major principal direction. Several different joint spacings were used in each series. Future tests will include a series with two sets of joints that make oblique angles with each other and with the major principal direction. The results of model tests and tests on cores of jointed rock by several investigators (e.g., Müller and Pacher,l Moore,2 Krsmanovic and Milic,3 Hayashi,4 Rosenblad,5 Jaeger,6 and Lane and Heck 7, have contributed significantly to the design of these experiments, which are believed to be the first in which a comprehensive study has been made of the combined effects under triaxial loading of joint spacing and joint orientation (Fig. 1).

Jan 1, 1970

By J. D. Lubahn, R. P. Carreker, J. G. Leschen

THE formation of slip bands in crystalline solids undergoing plastic deformation has recently been treated as a problem of nucleation and growth.1 A simplified theory was developed and shown to be qualitatively consistent with certain experimental observations reported in the literature, such as the frequent failure of slip bands to traverse the entire crystal, the effect of specimen diameter and temperature on the yield stress, and the occurrence of incubation periods in the deformation of suddenly loaded crystals. The theory further predicts the appearance of transients in the rate of strain of a crystal when the applied stress is suddenly changed from one constant value to another. A transient consists of a discontinuous change in the strain rate followed by a gradual approach to a steady-state value. Such transient behavior apparently has not been recognized in previous experimental work. The preliminary experiments reported in the present paper were undertaken to confirm the existence of the predicted transients and thus to determine whether a more detailed treatment of the nucleation theory of slip might be theoretically and experimentally fruitful. EXPERIMENTAL PROCEDURE A simple creep apparatus was assembled as shown in Fig 1. Very little insulation was used on the furnace in order to facilitate rapid changes of temperature. Temperature was measured with a thermometer placed in the center of the furnace and was [ ] controlled by adjusting the Variac setting. The specimens were cold-headed in split-cylinder grips. The strain was measured as total elongation by a dial gauge sensitive to 1/10,000-in. movement of the weight pan. Since the specimen gauge lengths were

Jan 1, 1948

By E. W. Wagy

The year 1927 witnessed numerous developments of significance in California. The State&apos;s shut-in production increased from an average of 58,000 bbl. daily in January to a maximum of 93,000 bbl. daily in August, and a total of about 25,000,000 bbl. was withheld from the market during the year. This not only lessened the effect of large production at Hunt-ington Beach, Seal Beach and Alamitos Heights, but also was a most effective conservation move. Since 1922, it is estimated that approximately 100,000,000 bbl. of oil that would otherwise have been produced have been held in the ground. I. Outstanding Field Developments of 19271 1. Long Beach Deep Sand. 2. Rincon (Seac1iff)Discovery. 3. Alamitos Heights Discovery. 4. Ventura Avenue Extension. 5. Round Mountain Discovery. 6. Mt. Poso Extension. 7. Potrero (Cypress) Discovery. 8. Buttonwillow Gas Development. 9. Goleta Discovery. 10. Union Avenue, Edison and Fruitvale Areas. (See Fig. 1.) II. Crude Production The most important factor in new crude production in 1927 was the Seal Reach field with its adjacent Alamitos Heights townlot area. Production increased from about 10,000 bbl. daily in January, to a peak of 66,000 bbl. in June. Huntington Beach finished the year 1926 with a production of 102,000 bbl. daily, which declined to 60,000 bbl. by the end of 1927. Due to production in these three areas and the tempering effect of shutting in numerous wells, the California production curve for 1927 was held at a fairly even level. Fig. 2, shows the State&apos;s production in 1927 and 1926 as compared with 1923, which was the year of excessive

Jan 1, 1928

By P. W. George

THE rapid increase in cost of discovering new orebodies by churn drilling in the Tri-State district has led to some attempts to lessen the expense by using geophysical methods. Electrical prospecting was tried three or four years ago, but no successful results were recorded. In 1926, the Federal Mining and Smelting Co. engaged the North American Exploration Co., of Houston, Texas, to make some tests with the torsion balance. At first, it was thought that the most favorable conditions for discovery of ore deposits with the torsion balance would be in locations where the ore was known to occur at rather shallow depths, FIG. 1.-CROSS-SECTION OF DUENWEG LEASE. therefore the first trial was made at Duenweg, east of Joplin, where some zinc ore had been developed at a depth of 130 ft. The gravity gradients at 61 stations on a tract of about seventeen acres indicated plainly one large zone of maximum gravity and a smaller narrow zone of minimum gravity. Fourteen churn-drill holes, half of which struck ore, show that all the ore found was located outside the zones of maximum and minimum gravity. In the zone of maximum gravity the limestone beds were closest to the surface, and the first chert beds encountered were at the greatest depth. The results (shown in Table 1) indicated that the gravity of the limestone was greater than the gravity of the fractured chert together with its orebodies, and probably also greater than the bouldery soil and clay on top of the limestone. A cross-section of the Duenweg lease is shown in Fig. 1.

Jan 1, 1928

By Norman Brown, J. V. Rinnovatore

Substructures in explosively deformed and annealed ß brass have been examined by electron microscopy. In the explosively deformed condition, the structure contains a large density of straight screw type dislocations. Subsequent annealing up to 300oC produces low angle boundaries, which are characterized by superlattice dislocations, and expanded and contracted nodes. Evidence is given where two a(111) superlattice dislocations combine to form two a(001) superlattice dislocations. It is also shown that annealing at 400°C the networks disappear and that quenching from 400" C produces square and circular prismatic dislocation loops that lie on (100) and (111) planes, respectively. THE purpose of this work was to determine the effects of explosive deformation and subsequent annealing in a superlattice using electron microscopy. One of the first observations of explosively deformed structures was made by Hornbogen1 on a iron. Hornbogen found that screw dislocations were most prominent in the explosively deformed structure. He explained this result by suggesting that the edge components of dislocation loops move with the velocity of the shock front leaving a trail of extended screw components. Kressel and Brown2 observed explosively deformed Fe3A1, which is basically a body-centered type of superlattice in terms of dislocation geometry, and found that, as in the case of iron, screw dislocations were most prominent. It was also observed2 that, in cold-rolled and explosively deformed nickel, screw dislocations did not predominate, but rather a uniform network of dislocations was present in which the orientation of the dislocations was random. (Cell structures also have been observed by Nolder and Thomas3 for copper and by Johari and Thomas* for nickel). Kressel and Brown2 discussed the difference between dislocation morphology for bee and fee metals in terms of dislocation mobilities. They suggested that edge dislocations have a greater mobility than screw dislocations in bee metals but not in fee metals. Thus, the idea offered originally by Hornbogen1 is not valid since it should apply equally to fee and bee systems but does not. The results of recent work by Mikkola and cohens on explosively deformed Cu2Au are consistent with other observations for fee metals. They found that dislocations were randomly arranged but there was no significant cell formation. At high shock pressures, deformation twins are produced in fee metals.&apos; High pressures in bee metal should induce the bee — fee transformation while the metal is under pressure. EXPERIMENTAL PROCEDURE The Cu-Zn alloy used in this work contained 51.4 wt pct Cu. Specimens of 0.5 in. diam and 0.012 in.

Jan 1, 1968

By P. W. George

THE rapid increase in cost of discovering new orebodies by churn drilling in the Tri-State district has led to some attempts to lessen the expense by using geophysical methods. Electrical prospecting was tried three or four years ago, but no successful results were recorded. In 1926, the Federal Mining and Smelting Co. engaged the North American Exploration Co., of Houston, Texas, to make some tests with the torsion balance. At first, it was thought that the most favorable conditions for discovery of ore deposits with the torsion balance would be in locations where the ore was known to occur at rather shallow depths, FIG. 1.-CROSS-SECTION OF DUENWEG LEASE. therefore the first trial was made at Duenweg, east of Joplin, where some zinc ore had been developed at a depth of 130 ft. The gravity gradients at 61 stations on a tract of about seventeen acres indicated plainly one large zone of maximum gravity and a smaller narrow zone of minimum gravity. Fourteen churn-drill holes, half of which struck ore, show that all the ore found was located outside the zones of maximum and minimum gravity. In the zone of maximum gravity the limestone beds were closest to the surface, and the first chert beds encountered were at the greatest depth. The results (shown in Table 1) indicated that the gravity of the, limestone was greater than the gravity of the fractured chert together with its orebodies, and probably also greater than the bouldery soil and clay on top of the limestone. A cross-section of the Duenweg lease is shown in Fig. 1.

Jan 1, 1928

By Robert W. Fullerton, Donald T. King

INTRODUCTION AND THEORY by Robert W. Fullerton In coal preparation plants, as in any industrial operation where raw materials are handled, nuisance problems arising from the generation of dust are inevitable. Devices for the control or collection of dust are there- fore essential components of the plant process equipment. The general term "aerosol" is applied to small particles suspended in a gaseous medium, usually air, whose velocity under the force of gravity is small enough that the particles remain suspended for a reasonable length of time. Aerosols can be classified as dust, smokes, fumes, mists or fogs. Dust includes particles originally formed by pulverization of materials by such processes as crushing, grinding, drilling, blasting and abrasion. Smoke includes particles formed from the burning of organic materials. Fumes are particles formed by processes such as condensation and sublimation, usually at high temperatures. Mists or fogs are particles formed by the condensation of water or other vapors on some nuclei. The size of aerosol particles is generally designated in units of microns, there being 1000 microns to a millimeter and 25,400 microns to an inch. Particles of about 10 microns or above are visible to the naked eye. Table 14-1 shows size characteristics of the general classifications of particles discussed above and includes typical examples of particles commonly en- countered. Table 14-1 also shows the relationship between micron size and standard screen mesh sizes. Smoke and fume are usually in the range of 0.01 to one micron, dusts are in the range of one to 400 microns, mists are in the range of 0.1 to 100 microns, and fogs are in the range of one to 100 microns. For purposes of dust control, particles greater than 10 or 20 microns in size are considered large, particles one to 10 microns are considered fine and particles below one micron are ultrafine. Sources of Dust Because coal is relatively friable, the mining and subsequent handling operations break part of the coal into dust that can be readily carried by currents of air. In a coal preparation plant mechanical handling operations such as unloading, transferring from one belt to another, screening, cleaning, and crushing in a dry state result in the generation and release of varying amounts of additional dust. The dust problem, of course, is much less serious in plants employing entirely wet processing. In addition to dust from handling operations, thermal drying of the fine coal product frequently presents another dust collection problem. Most coal driers are

Jan 1, 1968

By C. A. Queener, W. L. Mitchell

In recent years bismuth telluride has received considerable attention, primarily due to its value as a thermoelectric material. Since there seems to be little dependence of thermoelectric effect upon crystal orientation1 many of those who have previously worked with this material have been unconcerned with knowing its crystallographic angles to any degree of accuracy. However, when one studies deformation modes, lattice stresses, or the aniso-tropy of mechanical properties of a material, knowledge of the interplanar angles and their relationships as depicted in a stereographic projection becomes essential. Lange2 originally published crystallographic data which described the structure of bismuth telluride as rhombohedral with the space group A more recent work by Francombe3 presented data which corroborated and refined the original findings of Lange. In addition, Francombe established that there is no coexistence of rhombohedral and hexagonal lattices in bismuth telluride as was suggested by Vasenin and Konovalov,4 and that the structure can be treated as a pseu do hexagonal structure with an axial ratio, c/a, of 6.95 for convenience of presentation and study. The interplanar angles and standard projections for several unalloyed hexagonal metals have been previously published,5-9 but the present work appears to be unique in that it presents data for a rhombohedral compound in pseudohexagonal form. As a pseudohexagonal structure, this material has an extremely large axial ratio as compared to the usual range of approximately 1.5 to 1.9 for the hexagonal metals. Since the interplanar angles are a function only of c/a, the angular relations between various planes for Bi,Te3 will be grossly different

Jan 1, 1965

By J. O. Betterton, D. S. Easton

A detailed investigation was made of the phase diagram of silver-zirconium, particularly in the region 0 to 36 at. pct Ag. The system was found to be characterized by two intermediate phases Zr2Ag and ZrAg and a eutectoid reaction in which the -zirconium solid solution decomposes into a-zirconium and Zr2Ag. It was found that impurities in the range 0.05 pct from the iodide-type zirconium were sufficient to introduce deviations from binary behavior, and that with partial removal of these impurities an increase in the a-phase solid solubility limit from 0.1 to 1.1 at. pct Ag was observed. The phase diagram of the silver-zirconium system is of interest as an example of alloying a transition metal from the left side of the Periodic Table with a Group IB element. Silver would normally act as a univalent metal, its filled 4d-shell remaining undisturbed during the alloying. However, there is a possibility that some of the 4d electrons might transfer to the zirconium. An insight into such a question can occasionally be obtained by comparison of phase diagrams. The silver-zirconium system forms part of a more complete review of various solutes in zirconium in which these valency effects were studied.&apos; Earlier work on the silver-zirconium system was done by Raub and Enge1,2 who investigated the silver-rich alloys. After the start of the present experhents, work on this system was reported by Kemper3 and by Karlsson4 which for the most part agrees with the phase diagram presented here. EXPERIMENTAL PROCEDURE The alloys were prepared by arc casting on a water-cooled, copper hearth with a tungsten electrode and in a pure argon atmosphere. Uniform solute composition was attained by multiple melting on alternate sides of the same ingot. Progressive improvements in the vacuum conditions inside the apparatus during the course of the experiments reduced the Vickers hardness increase of the pure zirconium control ingot from 10 to 20 points, observed initially, to negligible amounts at the end of the experiments. Such hardness changes in zirconium are a well known indication of purity. For example, -01 wt pct additions of oxygen, nitrogen, and carbon increase hardness by 6, 10, and 3 VPN respectively. &apos;9&apos; Further verification that the final casting technique did not add a significant quantity of impurities was obtained when pure zirconium was arc cast and then isothermally annealed in the vicinity of the allotropic transition. The transition was always observed to take place over the same temperature range as in the original crystal bar. The alloy ingots were annealed in sealed silica capsules for times and temperatures which varied between 1 day at 1300°C and 60 days at 700°C. The best method found to prevent the reaction of the zirconium with the silica was foil wrapping of molybdenum or tantalum. With this method, samples of pure zirconium were found to be unchanged in hardness after annealing for 3 days at 1200°C. In most of the experiments the protection of these foils was supplemented by an additional layer of zirconium foil inside the molybdenum or tantalum foil. The alloys, foil, and the capsule were outgassed at pressures in the range 10 to l0-7mm Hg in the temperature range 800" to 1100°C before each anneal in order to remove hydrogen and other impurities, and to provide a suitable container for the high purity, inert atmosphere, which is essential in the annealing of zirconium. The temperature measurements were made with Pt/Pt + 10 pct Rh thermocouples calibrated frequently during the experiments against the melting points of zinc, aluminum, silver, gold, and palladium. For the longer anneals the sum of various temperature errors was generally well within ± 2°C. For short-time anneals and during thermal analysis the overall temperature error is considered to be within ± 0.5°C. The compositions of the alloys from the quenching experiments were determined by chemical analysis at Johnson Matthey and Company, Ltd., under the direction of Mr. F. M. Lever. The actual metallo-graphic samples were individually analyzed in every case, and prior to the analyses two or more sides of each specimen were examined to insure that the specimen was not segregated. The sum of the solute and solvent analyses was in each case within the range 99.9 to 100.1 pct. In the course of the experiments, minor impurities in the range 0 to 500 ppm were found to have significant effects on the zirconium-rich portion of the phase diagram. Similar effects had been encountered previously in other zirconium phase-

Jan 1, 1959

By W. A. Wood, W. H. Reimann, K. R. Sargant

A study is made of the microstructural changes produced in armco and pure iron subjected to alternating torsion at amplitudes above and below the knee of the S/N curve. The aim was to identify the basic mechanisms of fatigue and to find why they should give rise to a sharp S/N knee in contrast to the type of S/N curve shown by fcc metals. It is found that the basic structural change above the knee in the iron is a pronounced cell formation in the grains, which determines irregular micro-cracks, and below the knee a dispersion of fine slip that determines a dispersed pore formation in the grains. Comparison of these changes with those in fcc metals similarly tested shows that they do not include an intermediate structural change, a concentrating of slip in narrow bands with associated slip-band cracking, that characterizes the fcc metals and accounts for their different type of S/N curve. RECENT conferences on basic mechanisms of fatigue emphasize that fatigue damage takes many forms: for example, cracking in slip bands (Thompson1), at grain boundaries and inclusions (Hempel&apos;), at precipitation zones in alloys (Han-stock, Forsythe), or at surface notch-peak effects, both hypothetical (Mott, cottrel16) and observed (Wood). Evidently it is not easy to see in this diversity a basic mechanism. At the same time the contributions suggest that some reconciliation may be possible if distinctions are drawn between three phases of the fatigue process: initiation of damage at nuclei, distribution of these nuclei, and the final macroscopic crack system. In initiation, the relevant features appear to be that nuclei may appear early, at least by 1/100th to 1/1000th of the life of a test specimen; that they may do so at many independent centers, appearing according to some observationsa as pores or voids; and that they are not necessarily self-propagating, damage spreading rather by their multiplication. In distribution, the relevant feature appears to be that they form preferentially in zones where the microstructure becomes abnormally strained (as defined more closely below). Now in these two phases the basic fatigue process should be systematic. But, at the same time, the "abnormal strains" in particular set the stage for considerable diversity in the final phase of macroscopic cracking, for where zones of abnormal strain develop will depend on what kind of fatigue deformation is applied and what kind of prior processing the test material has had. On this view it seems desirable to know what in

Jan 1, 1964

By Franz R. Dykstra

DEFINITIONS The ores of iron are classified in three general categories: direct shipping, concentrates, and agglomerated-i.e., pelletized or sintered. Direct Shipping As the name implies, direct-shipping ores are shipped as mined or, perhaps, after screening. Generally, direct-shipping ores are hematitic (R203), magnetitic (R304), or limonitic (2Fe2O3.3H20) in nature. Grades of direct-shipping ores vary widely. Prices are frequently related to the historical Mesabi standard of 51.5% iron, although certain premium lump ores may contain up to 68% iron. The use of direct-shipping ores is diminishing as the advantages of beneficiated ores become evident and reserves are depleted. Concentrates Where the nature of the deposit and economics allows, certain ores are upgraded. This may include no more than washing and screening, or may be as elaborate as fine grinding followed by magnetic, gravity, or even flotation procedures for separation. Coarser concentrates may be smelted "as is.&apos;; Fine concentrates usually are sold as sinter feed. (Sinter, as used here and in the following, refers to a process by which a fine ore-carbon mixture is agglomerated at elevated temperatures on a direct-fired moving grate to eliminate fines and improve chemical and physical homogeneity.) Agglomerates-Pellets or Sinter The development of economic techniques of mining and concentrating taconite (fine-grained, ferruginous jasperoids) led to the introduction of the iron-ore pellet, which is now becoming the major form in which iron is introduced into the furnace. The tremendous reserves of magnetic taconites of the northern United States and Canadian Precambrian shield had been recognized for many years. A century of mining has seen the reserves of the direct-shipping or "red ores" of the Minnesota, Michigan, and Wisconsin ranges approach depletion. Research started in the 1930s has seen the evolution of motives and techniques to concentrate these stubborn refractory ores. The efficacy of concentrate pellets in iron-making has been such as to induce mines throughout the world to grind, concentrate, and pelletize otherwise shipping-grade ores. Table 14.1A.1 shows typical analyses of iron ore. Marketing-Prices of iron may be quoted on a value per long-ton (2240 lbs) or metric-ton (1000 kg or 2204 lb) basis, or on a value per long-ton-unit or metric-ton-unit basis. One iron unit represents 1 % of contained iron per ton. (Thus, a price of $0.45 per iron unit for ore containing

Jan 1, 1976

By D. C. Ganow, N. J. Grant, I. R. Silver, A. R. Chaudhuri

The structural changes that result when a metal is "cold worked" lead to higher values of yield and tensile strength on subsequent deformation at room temperature. Further it has been shown that the beneficial effects of cold work are, to some extent, maintained even at elevated temperatures. The strength improvements from prior cold work decrease as the temperature is raised and are a function of grain size, amount of cold work, and strain rate (or time of test). If recrystallization occurs during test, the cold-worked material may even show weaker stress-rupture properties than the annealed material. A question that arises is whether there is a significant effect on the subsequent creep behavior if the prior deformation is performed under creep conditions at high temperatures not too different than the test temperature, but at significantly different strain rates and for various amounts of strain. An answer to this question was sought in the work described in the present paper. PROCEDURE Two materials were used in this work, high-purity aluminum and a solid-solution A1 2 pct Mg alloy. The compositions are shown in Table I. The grain size in the two materials was 0.2 to 0.3 mm. The deformation for both the prestraining and for the creep tests was at constant stress. The procedure adopted was to prestrain a specimen to the desired elongation, remove the load, and cool to room temperature rapidly by spraying. the test bar with cold water. The specimen was then placed in a creep machine, held at the test temperature for less than 5 min, and loaded. Less than 15 min was required to bring the specimen to temperature. The creep stress was based on the diameter resulting from the prior strain, and values of elongation at fracture listed in the tables do not include the respective elongations resulting from the prestrain. The choice of the stresses for the prestrain and for the creep tests was made so that the tests could be completed in relatively short times to maximize any effect of prestrain. The specimens had a gage length of 1 in., the pure aluminum specimens having a diameter of 0.150 in. and the alloy specimens a diameter of 0.125 in. For pure aluminum, prestrain was at 400&apos; and 600°F with testing at 500°F; for the alloy, prestraining was at 700°F and testing at 600°F. RESULTS The prestrain conditions for the aluminum and the alloy specimens are shown in Tables I1 and IV. In addition to showing the time required to achieve the desired prestrain, the expected rupture Lives are given which would have resulted had the creep prestrain been continued to fracture. The prestrained and the annealed specimens were then tested in creep to fracture; the temperature and stress for the pure aliminum specimens being 500o F and 1800 psi and for the alloy, 600&apos; F and 3400 psi. The creep curves for the prestrained and the annealed specimens of pure aluminum showed all three stages of creep; hence in addition to the effect of prestraining on the rupture life, it was also possible to determine the effect of prestraining on the minimum creep rate, and on the time and elongation at the end of each of the three creep stages. The results are shown in Fig. 1 and Table 111.

Jan 1, 1960

By R. L. Skaggs, D. T. Peterson

The effect of carbon in solid solution on the plastic behavior of thorium was studied by measuring the flow stress of Th-C alloys from 4.2" to 573°K and at several strain rates. Carbon was found to strengthen thorium primarily by increasing the thermally activated component of the flow stress. The strengthening due to carbon was directly proportional to the carbon content and decreased rapidly with increasing temperature up to 423" K. The flow stress also increased with increasing strain rate. The strengthening appears to be due to a strong short-range interaction between carbon atoms and dislocations. A yield point was observed in the Th-C alloys which increased with increasing carbon content. JTREVIOUS study of the mechanical properties of thorium has been confined largely to the measurement of the engineering properties. Work prior to 1956 has been summarized by Milko et al.1 who reported that additions of carbon to thorium sharply increased the room-temperature strength. In addition, the yield strength was observed to decrease rapidly over the temperature range from 25" to 500°C. In 1960, Klieven-eit2 measured the flow stress of thorium containing 400 ppm C. He found that over the temperature range from 78" to 470°K the flow stress was strongly dependent on temperature and rate of deformation. A drop in the load-elongation curve, or a yield point, was observed over most of the above temperature range. Above 470°K, the flow stress was nearly independent of temperature and strain rate. This strong temperature and strain rate dependence of flow stress is not generally observed in fcc metals. It is, in fact, more typical of the behavior reported for bcc metals. Bechtold,3 Wessel,4 and conrad5 have pointed out the striking difference between the commonly studied bcc metals and fcc metals in regard to the effect of temperature and strain rate on the flow stress. Zerwekh and scott6 studied the plastic deformation of thorium reported to contain 12 ppm C. They found that this material did not obey the Cottrell-Stokes law as expected for fcc metals. In addition, they found values of the activation volume smaller by an order of magnitude than expected for an fcc metal. They concluded that thorium was strengthened by a randomly dispersed solute. Thorium differs from many other fcc metals that have been studied extensively in that it shows a relatively high carbon solubility at room temperature. Mickleson and peterson7 report the solubility limit at room temperature to be 3500 ppm C. The lowest value reported is that of Smith and Honeycombe8 who report the limit to be 2000 ppm C at 350°C. The pres- ent investigation was a systematic study of the flow stress and yield point phenomenon of thorium over a broad range of carbon content, temperature, and strain rate. EXPERIMENTAL PROCEDURE The thorium used in this investigation was produced by the reduction of thorium tetrachloride with magnesium as described by Peterson et a1.&apos; Chemical analysis of the original ingot after arc melting and electron beam melting is shown in Table I. Alloys were prepared by arc melting this thorium with high-purity spectrographic graphite. Threaded specimens with a gage length 0.252 in. diam by 1.6 in. long were used for the constant stress or creep measurements. These specimens were machined from rod which had been cold-rolled and swaged to % in. diam. Tensile specimens were prepared by swaging annealed 3/8 -in.-diam rod to 0.102 *0.001 in. The as-swaged wire was cut to lengths of 2 in., annealed, and the center 1-in. gage length elec-tropolished to 0.100 ±0.001 in. The specimens were gripped for a length of 3 in. at each end by a serrated four-jaw collet which was tightened by a tapered compression nut. No slipping occurred in the grips and negligible deformation was observed outside the 1-in. gage length. Both the creep and tensile specimens were annealed at 730°C under a vacuum of 1 x X Torr. The resulting structures consisted of equiaxed recrystallized grains with a grain size of 3200 grains per sq mm for the tensile specimens and 2200 grains per sq mm for the creep specimens. After the specimens were prepared, samples were analyzed for nitrogen, oxygen, and hydrogen. The results of these analyses are given in Table 11.

Jan 1, 1969

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.&apos; The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By C. H. Lee, R. Maddin

The diffusion rates of Ag110 in cylindrical single crystals of 99.99 pct pure silver, which were twisted to a total surface strain of 0.91 during the diffusion anneal at temperatures of 700°, 750°, and 800°C, were measured by sectioning and counting as a function of the strain rates. The ratio of the diffusivities while strain ing occurred (Ds) to those of the unstrained specimens varies linearly with the rate of twisting and attains values of near 100 for some of the rates used. The enhancement of diffusion by straining is inversely proportional to the temperature at which diffusion occurs. The activation energy for diffusion determined from the data plotted as a function of the rate of twisting decreases from 44,090 cal per mole for zero strain, to an asymptotic value of 21,000 cal per mole for the strain rates of 22 x it)"5 see-l. Qualitative explanation for the observations based on the generation of nonequilibrium number of defects by plastic deformation will be discussed. The initial research of Buffington and cohen1 on self-diffusion in a iron under compressive stresses contributed the first quantitative information concerning the effect of applied stresses on diffusion. These results were obtained from radioactive Fe55 plated on one of the horizontal surfaces and compressing the large-grained specimens while the diffusion-anneal was occurring. Enhancement of diffusion of a maximum of seventeen times was observed provided the strain was in the tertiary stage of creep and the rates of straining were at least as fast as rates used in the normal creep test. On the other hand, Darby, Tomizuka, and Balluffi,2 extending silver single crystals up to 30 pct elongation at rates of straining about equal to those used by Buffington and Cohen observed no effect. For the past two and a half years at the University of Pennsylvania, we have been investigating the effect or torsional strains on self-diffusion in silver single crystals. If enhancement is observed as has been reported1 a possible explanation may be based upon the generation of fairly large numbers of point defects and their role in the diffusion process. Hence, since torsion should produce an abundance3 of point defects, an increase in the diffusivity while the crystal is being twisted should easily be measured. EXPERIMENTAL PROCEDURE Our research uses single crystals of silver prepared from 99.99 Ag by the Bridgman method in a dynamic vacuum of less than 25 µ. As grown, they are about 25 cm long by 1.3 cm in diam. The crystals are cut into 7.5 cm lengths with a jeweler&apos;s saw and machined to the shape shown in Fig. 1. The test length of the crystal is machined to a 0.6 cm diam after which the ends are masked and the test section etched heavily in HNO3, and KCN:(NH4),S2Os , solution to remove the effects of machining. The specimen is then annealed in vacuum for 8 to 12 hr at 800°C to remove any residual stresses and also to recrystallize the end sections. The recrystallized ends are necessary since experiments showed that single-crystalline end sections are too soft to transmit the desired torque. Occasionally, recrystalliza-

Jan 1, 1960

By F. J. Meringer, C. W. MacGregor

Various investigations have been carried out to determine the effects of cold-rolling on the common physical properties as represented by the yield strength, tensile strength, percentage of elongation and ordinary reduction of area. Very little information is available in the literature with reference to the effects of cold-rolling on the true stress-strain properties. Since the ordinary physical properties base both the stresses and the strains on the original dimensions of the test piece, which are greatly changed during the test, they are essentially empirical values and do not represent physically either true stresses or true strains. Consequently, they do not give an accurate picture of the effects of different conditions, both mechanical and metallurgical, on the strength and ductility of the material. It is not, however, the purpose of this paper to review the various advantages accruing from the use of true stress and true strain values, since these have been shown elsewhere,1-l2 but to utilize them in representing the various effects considered. The true stress S and true strain (e = q&apos;) values mentioned above for the tension test are defined by1 S =1/A and where P, A, Ao are the axial load, the instantaneous area and the original area of cross section, respectively. From simultaneous readings of the axial load and the dimension or dimensions determining the instantaneous area of cross section, the true stress-strain curve is constructed by using the relations given in Eq. I. It is then the object of this paper to discuss the general effects of cold-rolling on the true stress and strain values for a low-carbon steel together with the effects of age-hardening and directionality on these properties. Preliminary Investigations The material considered throughout the paper is a low-carbon steel of the following chemical analysis: C, 0.19 per cent; S, 0.118; P, 0.092; Mn, 0.85; Si, 0.01. The stock was received in bars, 7 by 3/4 in., and was first annealed for one hour at 1650°F. followed by a furnace cool. Photomicrographs of this material showed considerable directionality even in the annealed condition. In view of the possible effects of the nonhomogeneity and directionality in this material, it was considered important to investigate their influence on the true stress-strain diagrams. In addition, the effect of strain-aging in this steel was also made the subject of a preliminary study. Effect of Aging on True Stress-strain Properties Since a certain time element would elapse between the cold-rolling operation and the final tension tests, it was determined to investigate the aging character-

Jan 1, 1945