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By M. T. Hepworth, T. P. Papazoglou

Hydrogen diffusion in hcp and bcc titanium in the temperature range 610° to 900°C was measured by reacting cylindrical specimens of high-purity titanium at constant temperature with small constant pressures of hydrogen of the order of a few Torr. In the range 0 to 6.7 at. pct H in hcp titanium, the diffusion coefficient D in sq cm per sec is given by: where T is in °K and R in cal per g-atom OK. Only three measurements of diffusivity in bcc titanium were made: at 900' : the diffusivity in ß titanium was found to be 1.8 x 10-4 sq crn per sec. McQUILLAN1 has studied the constitution of the Ti-H system and reported the concentration of hydrogen as a function of pressure of hydrogen and temperature. He found hydrogen absorption was reversible and rapid at temperatures above 500°C in both crystallographic modifications, the a (hcp) phase and the ß (bcc) phase, with the latter phase stabilized by hydrogen additions. Wasilewski and Kehl 2 measured the diffusivity of hydrogen in hcp and bcc Ti-H alloys. For bcc alloys, they reacted cylindrical specimens of titanium with hydrogen gas at 1 atm pressure. They measured the rate of absorption of hydrogen isothermally on specimens ranging from zero hydrogen content when above the transformation temperature to hydrogen contents sufficient to stabilize the bcc phase when below the transformation temperature. By integrating Fick's second law for a cylindrical geometry, assuming a diffusion coefficient independent of composition, they calculated diffusivities as a function of temperature. In the range 650" to 1000°C their results in bcc titanium yielded the expression: where D is in sq cm per sec, T in OK, and R the gas constant in cal per g-atom-OK. Their studies on the hcp a phase were conducted by exposing long cylindrical titanium specimens to hydrogen at a sufficiently high pressure to establish a surface layer of fl phase 80 to 120 u thick for the duration of an isothermal experiment. Concentration profiles were then determined by hydrogen analysis from chips obtained upon machining quenched specimens. The diffusivity of hydrogen was then calculated yielding the expression: The present investigation was undertaken principally to redetermine the diffusivity data on a titanium by a direct absorption from the gas phase at sufficiently low hydrogen pressures to avoid the presence of a surface bcc phase and also to check the diffusivity data at low hydrogen concentrations in the bcc stmcture. EXPERIMENTAL PROCEDURE High-purity electrolytic sponge titanium (99.9 pct) of BHN 91 was arc-melted, forged, rolled, and machined into cylinders of final hardness, upon annealing, of BHN 92. Cylindrical specimens of two sets of dimensions were used: 1.524 by 2.931 cm and 1.905 by 3.663 cm diam and length, respectively. The experimental apparatus used for annealing specimens and for admitting known amounts of hydrogen at constant pressure is shown in Fig. 1. In a typical experiment, a specimen was lightly abraded with fine-grain silicon carbide, washed with water and detergent, and then thoroughly degreased with reagent-grade tri-chlorethylene and acetone. The specimen was suspended by a Chrome1 wire in the center of a quartz furnace tube, without contact with the tube, and heated to 925°C (as measured by a thermocouple adjacent to the specimen, outside the tube) for a period of at least 4 hr under a vacuum of from 10-6 to -7 Torr as measured by an ionization gage. The furnace temperature was then adjusted to the temperature chosen for the particular diffusion study and the specimen allowed to equilibrate thermally. Hydrogen was then ad-

Jan 1, 1969

By E. C. W. Perryman

IN spite of the large amount of work which has been carried out on the recrystallization of aluminum and its alloys, there has been no complete investigation of the recrystallization characteristics of A1-Mg alloys. The most complete investigation is that reported by Bungardt and Osswald' who, working with commercial-purity materials, found that the temperature both of beginning and of complete recrystallization increased with magnesium content up to about 2 pct Mg, then decreased with a further increase in magnesium up to 5.0 pct, and thereafter increased again. Michaud and Segolz working with 99.93 pct A1 also found the temperature of beginning of recrystallization to decrease as the magnesium content increased from 2.13 pct to about 4.5 pct. Chossat3 using aluminum of 99.99 pct purity found that 0.12 pct Mg had no effect but that 0.4 pct Mg increased the recrystallization temperature by about 30°C. That no effect was found for 0.12 pct Mg does not agree with the later results reported by Demer and Beck4 who found that 0.025 pct Mg in 99.99 pct A1 increased the time for complete recrystallization and furthermore increased the activation energy for the recrystallization process. Kratz" using 99.997 pct A1 found that 0.5 pct Mg increased both the temperature of beginning and of complete recrystallization by 100°C. Chadwick and Hooper" working with commercial-purity material found that 1 pct Mg increased the temperature of complete recrystallization by about 40 °C for cold reductions in the range 17 to 72 pct. With smaller amounts of cold work produced by stretching (10 pct strain), they found no significant effect of magnesium. The latter result agrees with that obtained by Williams and Eborall' who found no effect of 2 pct Mg on the recrystallization temperature of commercial-purity aluminum strained 10 pct or less by stretching. Experimental Procedure Material Used: The chemical analyses of the materials used throughout this investigation are given in Table I. Fabrication: The alloys were cast in iron molds which had been washed thoroughly with alumina. After scalping, the ingots were annealed for 16 hr at 450°C, pressed, annealed at 450°C for 16 hr and hot rolled to 0.25 in. After hot rolling, the slabs were alternately annealed and cold rolled to 0.036 in. Cold-rolling reductions between intermediate anneals were kept at about 30 pct and a high intermediate annealing temperature of 450°C was used so as to obtain, as nearly as possible, similar starting grain sizes for the different materials. All intermediate anneals were done in a salt bath and were followed by cold-water quenching so as to retain all the magnesium in solid solution. The final cold reductions investigated were 20, 30, 40, 50, 60, and 80 pct. The initial grain sizes, that is, the grain size before the final cold reduction, were all very similar. Annealing Procedure: Specimens, 1 in. sq, were cut from the 0.036 in. sheet and annealed in a salt bath, the temperature of which was controlled to k2"C. Separate specimens were annealed for different times at 350°, 375", 400°, and in one or two cases at 415°C and after annealing were quenched in cold water. The time taken for a specimen to reach temperature was approximately 5 sec. Metal-lographic examination after annealing showed that no precipitation of Mg+413 occurred during cooling. Procedures Used for Determining Recrystallization Characteristics: All specimens were electrolyti-cally polished and etched by the method described previously1° and polishing was continued until about 0.002 in. had been removed from each side of the specimen. Using this technique, the smallest recrys-tallized grain which could be observed with cer-

Jan 1, 1956

By J. F. Kemp

PAGE I. Introduction,.......269 11. Topogmphical Features,.....270 III. Geological Relations of the Mineralized Area,.272 1. Structural Features,.....272 2. Occurrence of the Copper,....274 3. Granite-Contacts,.......274 IV. Descriptions of the Rocks,.....274 1. Granite,........274 2. Limestone,.......276 3. Porphyritic Eruptions,.....278 (a) Quartz-Porphyry,.....278 (b) Trachyte-Porphyry,.....280 V. Contact Phenomena,......285 1. Comparative Immunity of the Limestone, . 285 2. Contact Phenomena in the Quartz-Porphyry,.... 285 3. The Form and Distribution of the Ore-Bodies,290 VI. Method of Deposition,......293 I. Introduction. The White Knob copper-deposits are situated about three miles south of Mackay, on the Salmon River branch of the Oregon Short Line Railroad, in Custer county, Idaho. An outline-map of this district is given in Fig. 1. The deposits have been known and spasmodically worked for many years, and a total of over 3.5 miles of tunnels, shafts and other workings has been driven with a view to their development. These extensive excavations have exposed the deposits sufficiently to permit a careful geological examination. The peculiar features which give special interest to this paper are the branching, tree-like form of the ore-bodies; the absence of zones of secondary enrichment in the partly oxidized pyritic deposits, and the fact that while the deposits are associated in a general way with the contact of an eruptive rock with limeetone, which it penetrates, the garnetization has taken place not in the limestone, as is the usual case, but in the igneous

Jan 1, 1908

By Benjamin Moore

AT present the demands of the United States for strontium are met by imports from Germany, England and Canada, which vary considerably in proportions of ore and finished salts, in tonnage and in value. Statistics for the period 1926-1932 are given in Table 1. Domestic deposits are TABLE 1.-Strontium Imported into the United States, 1926-1932° Ore Chemicals Year Short Tons Value Pounds Value 1926 2,200 $58,159 5,433,044 $115,436 1927 1,356 58,711 4,233,816 149,383 1928 759 31,157 3,380,464 136,561 1929 973 45,505 4,578,327 196,233 1930 220 10,459 2,153,788 104,807 1931 (260 lbs.) 123 1,742,714 83,564 1932 5 276 469,481 20,910 a Mineral Industry (1934) 42, 61. known in many states, but the larger and purer ones are in the West, particularly in the desert region of southeastern California and western Arizona. These deposits are large enough to command interest, par-ticularly in consideration of future cheap power at the Boulder Dam. The deposits described in this paper were examined during an investi¬gation of the, mineral resources of the Boulder Dam region by the United States Geological Survey for the United States Bureau of Reclamation' in the spring of 1934. Mr. D. F. Hewett, who had general charge of the investigation, Mr. W. T. Schaller and Mr. M. I. Goldman contributed many helpful suggestions. Mr. N. H. Harshman assisted efficiently during the field work.

Jan 1, 1935

By John W. Tieman

Coal is a term applied to vegetable matter (trees, grasses, etc.) which was subjected to heat and pressure through geologic ages. This resulted in a change in both the physical and chemical properties. Because its chemical composition is variable, geologists classify coal as a heterogeneous mineral rather than a homogeneous mineral. Peat represents the initial, unconsolidated stage in the development of coal. This coalification continues with time and the application of temperature and pressure to lignite, subbituminous, bituminous, and anthracite toward the theoretical graphite end member. PHYSICAL PROPERTIES OF COAL The physical properties are concerned with the characteristics of coal in its natural state, or prior to its end use as a fuel. For example, the hardness and grindability of coal determine the maintenance cost for coal mining, handling, and pulverizing equipment; the specific gravity of coal and its associated minerals determines the coal preparation technique used in a cleaning plant as well as the capacity of coal bins, boats and size of cargo, and other coal storage facilities. The physical properties are, of course, dependent on the chemical constituents of coal, and all properties are interrelated. Specific Gravity The specific gravity (sp gr) of a solid is the ratio of the weight of a cubic foot of the solid to the weight of a cubic foot of water. The specific gravity of pure coal has been reported to range between 1.23 to 1.72 and increases with the change in rank from lignite to anthracite. This means that it is 1.23 to 1.72 times heavier than water.

Jan 1, 1981

By Bernard Moore

AT present the demands of the United States for strontium are met by imports from Germany, England and Canada, which vary considerably in proportions of ore and finished salts, in tonnage and in value. Statistics for the period 1926-1932 are given in Table 1. Domestic deposits are TABLE 1.-Strontium Imported into the United States, 1926-1932a Ore Chemicals Year Short Tons Value Pounds Value 1926 2,200 $58,159 5,433,044 $115,436 1927 1,356 58,711 4,233,816 149,383 1928 759 31,157 3,380,464 136,561 1929 973 45,505 4,578,327 196,233 1930 220 10,459 2,153,788 104.807 1931 (260 lbs.) 123 1,742,714 83,564 1932 5 276 469,481 20,910 a Mineral Industry (1934) 42, 61. known in many states, but the, larger and purer ones are in the West, particularly in the desert region of southeastern California and western Arizona. These deposits are large enough to command interest, par-ticularly in consideration of future cheap power at the Boulder Dam. The deposits described in this paper were examined during an investi-gation of the mineral resources of the Boulder Dam region by the United States Geological Survey for the United States Bureau of Reclamation in the spring of 1934. Mr. D. F. Hewett, who had general charge of the investigation, Mr. W. T. Schaller and Mr. M. I. Goldman contributed many helpful suggestions. Mr. N. H. Harshman assisted efficiently during the field work.

Jan 1, 1935

By John W. Tieman

Coal is a term applied to vegetable matter (trees, grasses, etc.) which was subjected to heat and pressure through geologic ages. This resulted in a change in both the physical and chemical properties. Because its chemical composition is variable, geologists classify coal as a heterogeneous mineral rather than a homogeneous mineral. Peat represents the initial, unconsolidated stage in the development of coal. This coalification continues with time and the application of temperature and pressure to lignite, subbituminous, bituminous, and anthracite toward the theoretical graphite end member. PHYSICAL PROPERTIES OF COAL The physical properties are concerned with the characteristics of coal in its natural state, or prior to its end use as a fuel. For example, the hardness and grindability of coal determine the maintenance cost for coal mining, handling, and pulverizing equipment; the specific gravity of coal and its associated minerals determines the coal preparation technique used in a cleaning plant as well as the capacity of coal bins, boats and size of cargo, and other coal storage facilities. The physical properties are, of course, dependent on the chemical constituents of coal, and all properties are interrelated. Specific Gravity The specific gravity (sp gr) of a solid is the ratio of the weight of a cubic foot of the solid to the weight of a cubic foot of water. The specific gravity of pure coal has been reported to range between 1.23 to 1.72 and increases with the change in rank from lignite to anthracite. This means that it is 1.23 to 1.72 times heavier than water.

Jan 1, 1981

By R. J. Borg, C. E. Birchenall

The self-diffusion coefficients for a iron have been deternzined between 980° and 1167° K using Fe55 as the tracer. With decreasing temperature the diffusivity was found to decrease more rapidly than predicted by the Arrhenius equation in the region of the Curie temperature. The diffusion coefficients obtained well above the temperature of the magnetic transformation are more precise ard differ substantially from all the previously reported values. In the temperature region beginning at least 50" above T,, the diffusion coefficient is given by D = 118 (±2) exp 1 HE self-diffusion coefficients for a iron have been reported previously as the result of four independent investigations The general lack of agreement and the poor precision of most of the previous work prompted the redetermination by the present authors. The possible effect of the onset of ferromagnetism upon the diffusivity5 provided an additional impetus for this investigation. The earlier measurements of Birchenall and Mehl1 gave low values for the diffusion coefficient at temperatures below the Curie temperature, Tc. However, the precision of these measurements is not sufficient to establish an indisputable correlation between the low values and the magnetic transformation. The results of this investigation along with all the previous ones are shown in Fig. 1. EXPERIMENTAL Small rectangular samples, approximately 1 by 0.5 by 0.3 cm, of high-purity iron (Vacuum Metals Corp., "Ferrovac") are first heated in hydrogen at 900°C for24hr in order to remove possible trace amounts of dissolved carbon and oxygen. The small

Jan 1, 1961

By W. M. Lehrer

RECENT development of high-temperature brazing alloys has required information regarding the eutec-tic temperature and composition of the Pd-rich section of the Pd-B system.. Literature on this subject was found to be scanty with no complete system yet determined. Buddery and welch1 report an inter-metallic compound occurring in the Pd-B system at 6.33 wt pct B (PdsBz). Another source, Sieverts and Bruning,2 indicates that after annealing at 700°C, a 1.6 and a 2.0 wt pct B alloy were two phase whereas a 0.75 pct B alloy was single phase. Recent work3 using a hot-stage microscope has proposed a eutectic temperature of 743OC. This method utilized the observation of the onset of incipient melting at grain boundaries. The eutectic composition, however, was not determined. METHODS AND PR0CEDURES Five alloys were prepared by triple inert arc-melting high-purity palladium (95.98 pct) with additions of 2 to 6 pct purified amorphous boron. The alloys were crushed within a hardened steel mortar with a steel pestle. The 2 pct alloy, however, was too tough to be crushed in the above manner so was crushed by successive reductions through a rolling mill. Approximately 17 to 18 g of the crushed alloy was used in the thermal analysis. The alloys were melted in pure quartz crucibles. The thermocouple protection tubes were also of quartz and fused along the inside wall of crucibles to prevent floating of the thermocouple. This was an expediency as centering of the thermocouple in the melt would have been preferable. Melting was done in a tube furnace with a slow flow of tank helium maintained as a protective atmosphere. Heating and cooling rates were maintained at 3.5OC per min through the critical temperature ranges by means of a synchronous motor hook-up to a furnace controller. All specimens were heated to 100°C over the indicated liquidus on heating prior to reversing to the cooling cycle. Specimens emerged from the furnace with mirrorlike brightness attesting to the protective quality of the helium atmosphere. Thermal arrests were detected by the differential thermocouple technique using chrome l-alumel couples and nickel as the reference specimen. Arrests were recorded on a Leeds-Northrup automatic X-Y recorder. The specimen temperature and temperature difference were read to + 7.5OC and ± 1.5OC, respectively. These readings were well within the sensitivity of the instrument amplifier. Chromel-alumel couples were used in lieu of Pt-Rh as very few arrests were contemplated in excess of 1200" to 1300°C, the approach of instability. No standardization was performed on these thermocouples subsequent to their use. RESULTS The thermal arrest temperatures obtained are plotted in Fig. 1 as a function of wt pct B. The composition function was obtained by chemical analysis of portions of the specimens after the thermal analysis was completed. The 2 to 6 pct nominal alloys were found to have 1.80, 2.35, 3.65, 4.18 and 5.90

Jan 1, 1960

By R. L. Stephenson

The effect of fabrication variables on the creep-rupture properties of TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C), Cb-TZM [columbium-modified TZM (7140-1.5 pct Nb-0.5 pct Ti-0.8 pct Zr-0.05 pct C)], and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C) has been studied at 982º. 1093º, 1204º, and 1315°C for rupture times up to 1000 hr. The creep tests were performed in vacuum creep furnaces, employing cold-trapped oil-diffusion pumps, operating at pressures 2 X 10-7 tory. After-test chemical analyses showed no significant changes in interstitial content. The creep-rupture properties of TZM, fabricated according to current mill practice, were determined in the stress-relieved and in the re crystallized conditions to provide control data. Specimens of TZM, Cb-TZM, and TZC fabricated according to each of two experimental fabrication schedules were then tested. The schedules differed in terms of in-process annealing temperatures and warm -working temperatures. The data make several conclusions evident. Fabrication variables do indeed have a profound effect on the long-time creep-rupture properties of molybdenum alloys. Strengths of these alloys compare very favorably with those of other refractory metal alloys in the temperature range studied. FOR several years we have been engaged in the evaluation of the creep-rupture properties of promising refractory metal alloys. We consider the determination of these properties to 1000 hr at several temperatures necessary for a valid comparison. Such an evaluation indicated that the creep strengths of Mo-0.5 pct Ti and TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C) compare favorably with those of other refractory metal alloys. Tensile and recrystallization data of other investigators1,2 show an effect of fabrication variables. More specifically, those fabrication schedules which produce high strength through work hardening exhibit the least thermal stability. A similar conclusion was reported by perkins3 for Cb-TZM. This would lead one to expect that, in terms of creep, those materials showing higher strength at short times and low temperatures would exhibit lower strength at long times and high temperatures. If these expectations were fact, a substantial improvement could be made in these alloys by optimizing their fabrication schedule in terms of their anticipated service temperature. We therefore undertook a study of the effect of fabrication variables on the long-time creep properties of TZM, Cb-TZM (Mo-1.5 pct Cb-0.5 pct Ti-0.08 pct Zr-0.05pct C) and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C). MATERIALS All materials used were supplied by the Climax Molybdenum Co. of Mich. Our original intention was to test the same heat of each alloy in different conditions. Fabrication difficulties prevented this; however, heats with nearly identical analysis were selected. The compositions of the materials used are listed in Table I. All materials were supplied in the

Jan 1, 1970

By Mark D. Tabak

Measurments of the transient photoconductivity in fillns of amorphous selenium with blocking- contacts haue been used in studying the transport properties. The results shozu that the transport of free carviers cannot be explained in terms of a model using bulk trapping. Measurments of the photocurrent-applied field characteristic as a unction of sample thickness do not pvoduce the scaling lau,s approps-iate lo a range-limited model. THE investigation described here was undertaken to explore the mechanisms of transport in amorphous selenium films. These films are used in xerography, where a photoconductor is charged electrostatically and then exposed to light to form a latent image. The sensitivity that one can expect when operating in this mode is directly related to the transport properties of the photoconductor material. The study of photoconductivity at high fields in insulating materials is often complicated by contact effects. Injection from the contacts can easily mask the fundamental transport processes that are being studied. A technique is described in this paper that allows a study of photoconductivity and transport processes in amorphous selenium films without the complicating effects introduced by contacts. Accordingly, the samples are prepared using insulating films between the sample and the metal electrodes, where the electrodes are capacitively coupled to the surfaces of the sample under study. A transient measurement is performed with pulsed light, and the photocurrent measured near the beginning of the pulse before the field is distorted by polarization at the blocking elec- trodes. A similar method has been described by Manyl using pulsed electric fields in studying the high field transport in insulating cadmium sulfide. EXPERIMENTAL It is possible to eliminate undesirable contact effects and maintain uniform high fields across the sample by using blocking electrodes and measuring the current-field characteristic under transient conditions. The sample configuration is shown schematically in Fig. 1. Each of the gold electrodes is separated from the amorphous selenium film by a layer of insulating plastic (Formvar) approximately 2000~ thick. The electrode on the front surface is semi-transparent to allow illumination of the sample. The whole configuration is mounted on a KEL-F substrate, which is a transparent insulating plastic having a thermal expansion coefficient that allows low-temperature measurements without cracking the selenium film. Fig. 2 shows a block diagram of the measurement apparatus. Light was obtained from a 450-w Xenon arc lamp, the intensity of which was controlled by stainless-steel screen filters and monitored by a pho-tomultiplier which was calibrated periodically against a thermopile. A camera shutter operated at 1/200 sec provided the light pulse and a synchronized signal to the oscilloscope. The photocurrent transient is ob-served with a high-speed picoammeter (response time of 1 msec) the output of which is displayed on an oscilloscope. The applied voltage is constant throughout the transient measurement. The selenium films were prepared by evaporation of four 9's pure selenium shot supplied by Canadian Copper Refiners. Spectrographic analysis showed about 1 ppm of Te and Fe, 5 ppm of C1, and 0.05 ppm

Jan 1, 1968

By D. F. Kaufman, E. D. Levine, L. R. Aronin

ThE primary slip plane in hcp metal crystals can usually be inferred from the c/a ratio. Basal slip is the primary system at room temperature for zinc, cadmium, magnesium, cobalt, and rhenium, all of which have a c/a ratio greater than 1.60. Zirconium and titanium, on the other hand, each with a c/a ratio of 1.59, deform primarily by (1010) [ll20] prismatic slip. The increasing tendency toward prismatic slip in these materials is generally thought to be associated with the increase in atomic density on (10i0) as c/a is reduced. Beryllium, with a c/a ratio of 1.57, would, according to the above scheme, be expected to exhibit prismatic slip. However, in beryllium of commercial purity, the primary deformation mode at room temperature is basal slip.' The ratio of critical shear stress for prismatic to that for basal slip at room temperature is approximately 5:l. The critical shear stress for prismatic slip decreases quite rapidly with increasing temperature, however, and at 500°C the ratio is approximately unity. The apparently anomalous behavior of beryllium has led to speculation that prismatic slip in this material may be restricted by an anisotropic effect of impurities,' and that, if beryllium could be purified to a sufficient extent, prismatic slip might predominate at room temperature. In such a case, the conditions under which basal cleavage can occur would be suppressed, and enhanced low-temperature ductility might result. With the advent of the floating-zone method for purification of beryllium,3 it has become possible to determine experimentally the effects of purification on basal and prismatic slip. Tensile tests were performed at room temperature on single crystals oriented favorably either for basal or prismatic slip. The crystals had been purified to various extents by zone-refining, employing procedures that have been described elsewhere.4 Relative purities of the crystals were estimated by measuring the ratio of electrical resistance at 4.2"K to that at 298°K. Typical values ranged from 0.40 for commercial-purity material to 7.7 X 10"4 for crystals prepared from vacuum-distilled beryllium and subjected to six zone-refining passes. The purity dependence of the critical shear stresses for basal and prismatic slip is shown in Fig. 1. In the purity range studied, the critical shear stress for basal slip is decreased from 1.4 to 0.14 kg per sq mm. The critical shear stress for prismatic slip is decreased from 6.7 to 5.3 kg per sq mm. The decreases in critical shear stress for each deformation mode, therefore, are approximately equivalent. No purification anisotropy is observed. Because of the absolute magnitudes of the critical stresses, the ratio of the critical shear stress for prismatic slip to that for basal slip actually increases from 5:l to 38:l at the highest purity level studied. It is evident, therefore, that basal slip is the primary deformation mode in high-purity beryllium. This fact must be accounted for in any rationalization of the deformation behavior of hcp metals. This work was performed at Nuclear Metals, Inc., under the sponsorship of the U.S. Atomic Energy Commission.

Jan 1, 1964

By N. S. Stoloff, R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-Co and Fe- V alloys containing up to 25 pct solute have been studied in the temperature range 25° to - 196°C. The microyield stress is independent of temperature for all alloys studied, while the temperature dependence of the ordinary yield stress is large and comparable to that for unalloyed iron. An alloy-softening phenomenon is observed for many alloys relative to unalloyed iron, and appears to be a consequence of removal of inter-stitials from solution and their subsequent agglomeration. The ductile to brittle transition temperature is increased markedly by both cobalt and vanadium. Transmission electron microscopy observations reveal that cross slip and cell formation are restricted with increasing solute, which can account for many aspects of yielding and fracture behavior. IRON and other metals of bcc structure slip on many planes of the (111) zone at moderate and elevated temperatures, giving rise to wavy glide. At low temperatures, however, there is a tendency for slip to be restricted to planes of only one or two crystallographic types; in the case of Fe-Si alloys for example, (110) glide predominates, giving rise to planar slip bands."' Restriction of cross slip at low temperatures in iron has been linked by Brown and Ekvall3 to increased strain hardening in the preyield microstrain region, leading to an apparently large temperature dependence of the yield stress. Support for this view has been provided by Lawley and Gaigher4 from a transmission electron microscope study of molybdenum. They concluded that dislocations at lower temperatures, by virtue of their inability to change planes readily, are unable to interact and annihilate, leading to an increase in internal stress and work-hardening capacity. Restriction of cross slip at low temperatures has also been suggested to be an important factor in determining the ductile to brittle transition of single-phase solids, including metals of bcc structure.5 It is pertinent to note that most solute elements tend to raise the ductile to brittle transition temperature of poly crystalline ferrite,6,7 although in some cases, e.g., Fe-Cr7 and Fe-Al,8 the dilute alloys may actually yield at lower stresses than unalloyed iron. It appears, therefore, that solute elements may have an effect analogous to lowering the test temperature with regard to restricting cross glide. Such an effect has indeed been observed in the ionic alloy system KCl-KBr,9 in which bromine atoms, although causing little misfit and consequently little effect on the yield stress of KC1, have a pronounced effect in restricting wavy glide and inducing brittleness. The purpose of the present investigation was to determine the effects of selected solute atoms on the yield stress and fracture behavior of iron, and to elucidate in turn how the slip character was related to these properties. Since it is known that interstitial atoms exert a strong influence on the mechanical behavior of iron, the solute elements chosen for study were vanadium, which reacts strong with interstitials,10 and cobalt, which does not form highly stable interstitial compounds." EXPERIMENTAL PROCEDURE Four-pound ingots of each of the following alloys were vacuum-melted in zirconia crucibles: Fe-1, 5, 10, 25 at. pct Co, and Fe-1, 4, 10, 20 at. pct V. An ingot of unalloyed iron from the same original stock as that used for the alloy was remelted under similar conditions to eliminate variations in interstitial content arising from differing thermal histories. Chemical analyses of the iron, cobalt, and vanadium melt stock are listed in Table I. All ingots were rolled and swaged, commencing at 850°C, to 1/4-in.-diameter bar. The bars were then annealed at 850°C for 1 hr (except that the 10 and 20 pct V alloys were heated for 2 hr) to give a uniform equiaxed grain size of about 0.05 mm. Tensile samples of 0.125 in. diameter by 0.8 in. gage length were utilized for studies of the ductile to brittle transition. A second set of tensile samples were utilized for microstrain experiments in which strain sensitivity of 1 x 10"6 was achieved by a capacitance method.3 Cylindrical compression samples 0.250 in. diameter by 0.4 in. long also were prepared to study the influence of composition on the macroscopic yield stress, and for metallographic analyses of defor-

Jan 1, 1965

By D. W. Fuerstenau, P. C. Kapur

The kinetics of green pelletization in a laboratory balling drum have been studied, using pulverized limestone as a model system. The growth characteristics of green pellets were found to be extremely sensitive to the moisture content of the material. Empirical kinetic equations, which incorporate a function of specific surface of the pellets as the criterion for growth potential, have been found to describe growth in a nucleation region and in a ball growth region. The rate constants in the kinetic equations are strongly dependent on the moisture content of the material being pelletized. Size distributions of the balls at different stages of pelletiz-ing are also discussed. In many industrial chemical processes, particulate matter can only be utilized if it is in an agglomerated form, such as pellets. Pelletizing is now widely used in iron ore technology1, and it has also been applied to a number of diverse fields such as the production of cement-kiln feed2, fertilizers3, and fluorspar4. Recently, it has been proposed to pelletize dispersion-type ceramic nuclear fuel elements5. In iron ore technology, for example, the production of agglomerates by pelletizing involves two major steps: 1) the preparation of green balls by rolling particles in a suitable balling device and 2) the firing of the green balls to form compact, strong bodies upon sintering. The critical step in a successful iron ore pelletizing operation is generally considered to be the balling operation1. In this paper, which is not concerned with the sintering of green pellets, the words green pelletizing and balling will be used interchangeably. Green pelletizing, or balling, will be defined as the process of forming larger bodies by rolling fine particles on a surface without the application of direct pressure. Two recent literature surveys6" indicate that in spite of the considerable amount of industrial pelletizing, very little is known about the fundamental principles of balling and its kinetics. The first reported research on the kinetics of pelletizing is the work of Newitt and Conway-Jones8. Using silica sands of different sizes in a batch laboratory balling drum, they found that the average green pellet diameter increased linearly with time at constant drum speed, and qualitatively the growth rate increased with moisture content. Generalized conclusions cannot be drawn from their research since the materials which they pelletized were sand and sand-silt mixtures rather than comminuted materials. Moreover, Newitt and Conway-Jones used testing sieves to estimate the size distribution of the green pellets, and this technique limited the range over which they could study the growth kinetics of the pellets. Bhrany and co-workers9 investigated the kinetics of balling iron ore fines on disk pelletizers ranging in diam from 1 to 18 ft. In their investigation, balling was carried out as a continuous operation, and growth kinetics were studied in terms of retention time of the material on the disk. Although the feed material in their study was quite coarse (the maximum size being about 1/2 in.), they also found qualitative relationships between pellet growth and water content, and feed size. In the present investigation, a number of innovations were introduced that refined the experimental measurements and established the reproducibility of balling experimentation. This enabled extension of the range of measurements to include study of agglomerate nucleation phenomena in the fractional mm size. This paper presents a detailed analysis of the nucleation and growth of green pellets in a laboratory balling drum. MATERIALS AND METHOD Pulverized limestone of specific gravity 2.72 was used as a model system in these studies. It has already been established that the balling characteristics of limestone and silica are similar to those of iron ore concentrates 2,8,10, depending on physical, rather than chemical, properties of the particles. The size distribution of the limestone was determined by a wet-dry sieving technique in the sieve range and by a sedimentation balance in the sub-sieve range. Fig. 1 presents the size distribution of the limestone used in this research. This figure shows that the material is finer than 200p (65 mesh) and that 25% of it is finer than 12. The specific surface area of this powder, as measured by BET gas adsorption methods,

Jan 1, 1964

By W. A. Jr. Slippy, E. P. Dahlberg, R. B. Reed-Hill

A large room-temperature mechanical-hysteresis effect under cyclic tensile loading was observed in zivconium specimens prestrained at 77°K so as to form large numbers of (1121) twins. The observed hysteresis loss was a maximum when the prestrain was just under 1 pct It also depended strongly on the maximum applied cyclic stress, but only moderately on loading rate and temperature (-72°to 100°C). The phenotnena have also been studied in terms of the elastic aftereffect where the data has been found to cotlforln closely to the functional relationship between strain and time, c = -RT/a In tank ft. t to)/Zr, for strains cts large as about 10-4 This eyication can be derived directly from the strain-rate equation There may be important commercial implications to the present discovery since it appears that within rather wide limits it may be possible to obtain any desired magnitude of damping capacity in zirconium melal. The damping propevties may also be given directional characteristics. It is shown that the observed anelaslic phenomena can he explained on the assumiplion that they are the resuilt of stress-induced twin-boundary movements in which the average twin increases its thickness by only a few percent. In polycrystalline zirconium, a grain is least favorably oriented for slip when its basal plane, containing the (1130) slip directions, lies nearly perpendicular to the principle normal stress. Mechanical twinning is favored by this orientation and under simple tensile deformation at room temperature the primary twinning mode is {1012).' The (1012) twinning shear is small (0.17) so that, during deformation, twin growth does not greatly enhance ductility. At 77°K, on the other hand, the predominant twinning mode shifts to {1121), and many thin (1121) twins can form at small strains.' Twins thus nucleated can grow readily during subsequent room-temperature deformation and permit easy deformation in unfavorably oriented grains. In addition, the (1131) twinning shear is large: 0.63. These facts have lead to a process' for greatly improving the room-temperature ductility of zirconium when it contains a sizable fraction of grains with basal planes nearly normal to the stress axis. Optimum results are obtained by slightly less than 1 pct prestrain. The effect is large so that a 50 pct elongation increase is readily attained. A large room-temperature mechanical-hysteresis effect has also been observed in zirconium specimens prestrained at 77°K. The present paper is concerned with some aspects of this effect which the experimental observations strongly indicate is primarily the result of strain-induced {1121) twin-boundary movements. This clearly suggests that mechanical twins formed by plastic deformation can cause anelastic effects similar to those previously observed2 for annealing twins and twins associated with phase transformations. EXPERIMENTAL PROCEDURES All specimens were prepared from arc-melted sponge zirconium plate stock as previously described,3 which has a preferred orientation with basal planes aligned parallel to and uniformly distributed around the rolling direction. Both lonti-tudinal and transverse tensile specimens, with axes parallel and transverse, respectively, to the plate rolling direction, were cut from this plate. In a longitudinal specimen most grains are favorably oriented for slip, while in a transverse specimen a large fraction are unfavorably oriented. Prestraining at 77°K was performed in two ways. In one, annealed zirconium plate stock was cooled in liquid nitrogen and then rolled in the transverse plate direction to strains varying from 0.5 to 12 pct. Cylindrical 1/8-in.-diameter by 1-1/4-in.-gage-length tensile specimens were machined from this material. In the other, previously machined tensile specimens were prestrained in tension at 77°K between 0.2 and 3.8 pct. Type FA 25-12 SR4 strain gages were cemented to all specimen gage sections. All tests were performed on an Instron testing machine of 10,000-lb capacity. EXPERIMENTAL RESULTS Fig. 1 shows a typical two-cycle room-temperature stress-strain diagram for a specimen prestrained 0.65 pct by rolling at 77°K. The maximum stress in both cycles was 14,500 psi. Note that in the first cycle the loading and unloading curves are unsymmetrical so that a residual strain, er, remains after unloading. In the second cycle the stress-strain curves form a nearly symmetrical hystere-

Jan 1, 1965

By A. H. Daane, W. J. Wunderlin, B. J. Beaudry

The solid solubility of holmium in copper, silver, and gold, determined using metallographic techniques, was found to be a maximum of 0.06, 2.4, and 3.2 wt pct, respectively, nt the eutectic temperatures. The temperatures of these eutectic horizontals, determined by differential thermal analysis, were found to be 868", 787", and 778"C, respectively. The first compound on the silver-rich side of the Ag-Ho system was found to be A&Ho2. In a study by Gold et al.,' on the effect of small amounts of soluble impurities on the electrical resistance and thermoelectrical properties of copper, traces of iron were shown to have drastic effects on the thermoelectric power due to the magnetic scattering of the conduction electrons. Since little is known about the state of the iron ion when dissolved in copper, Gold had hoped to repeat these experiments using certain rare earths as the magnetic scattering centers; because of the tightly bound 4f electrons it is not expected that their spectroscopic state would be affected by alloying. In such an experiment the sole role of the trace rare-earth impurity would be to magnetically scatter the copper conduction electrons without producing appreciable distortions in the otherwise pure copper matrix. Since holmium was chosen for such a study because of its high magnetic moment, it was necessary to establish precisely its solid solubility in copper. The study was extended to include the solvents silver and gold, so that an evaluation of the data using classical solubility parameters could be made. No previously reported work on the systems of holmium with copper, silver, or gold was found in the literature. Information on the solubility of other rare earths in these three metals is also very meager. The solubility limit of yttrium in copper was reported as less than 1 wt pct2 and the solubility of praseodymium in gold as 0.35 wt pct,3 while no references were found on solubility studies of rare earths in silver. EXPERIMENTAL Materials. The materials used in this investigation were distilled holmium prepared in this Laboratory, OFHC* copper, electrorefined silver (99.9 *OFHC = oxygen-free high conductivity. pct), and gold with the analyses given in Table I. Sample Preparation. Samples weighing 1 to 2 g were prepared by arc-melting the components together on a water-cooled copper plate under purified argon atmosphere. The samples, turned and remelted at least five times to ensure homogeneity, showed weight changes of less than 0.1 wt pct after melting. Samples containing less than 0.7 wt pct Ho were prepared by diluting 1 to 2 wt pct Ho alloys with the pure solvent, while samples with concentrations greater than 0.7 wt pct Ho were prepared directly from the metals. The samples were wrapped in tantalum foil, sealed in outgassed Vycor tubing under helium, annealed at the desired temperature for at least 24 hr, and then quenched by shattering the Vycor tube in cold water. Metallographic Methods. Standard mechanical polishing methods were used in preparing the silver and gold alloys for examination, while the copper alloys were electropolished using a 40 pct solution

Jan 1, 1963

By H. A. Bourne, E. L. Haden, D. R. Reichmuth

A circumferential-toothed bit with novel tooth form gave improved penetration performance. In this design the exterior flank of all teeth were vertical when in rolling contact with the hole bottom. Rock chips were generated by the interior flank of the tooth displacing the rock inwardly and downslope toward the center of the hole. A unique two-cone laboratory bit assembly enabled evaluation of numerous cone and tooth configurations. Some of the variables investigated, in addition to weight on bit, rotary speed and rock type, were tooth interference, percent tooth, hole bottom angle, attack angle and relief angle. Most tests were conducted dry on a brittle synthetic sandsone or a ductile quarried limestone. Tooth configurations were found to be more significant in the ductile material. This was attributed to the deeper tooth penetration before rock failure. These studies showed that the attack angle (angle beween interior flank of the tooth and rock surface) was the controlling variable; changing the tooth configuration from the assymetric or semi-wedge to the more conventional symmetric or wedge form reduced penetration performance; and penetration performance of circumferential-type cutters was directly proportional to rotary speeds up to 200 rpm. INTRODUCTION Much of the published literature on rock-chisel interactions describe experiments wherein symmetrical wedges are vertically loaded or impacted against a smooth rock surface.1-6 are is usually taken to insure that the indentation is not made near the edge of the rock specimen less erroneous data be obtained. The literature describes relatively few studies in which the investigator deliberately attempted to take advantage of an edge or free surface. In contrast, anyone who chips ice or breaks up a concrete sidewalk almost always works near an edge. Chisel "indexing," which has been considered by some investigator1,2,6,7 makes limited application of an edge or free surface. Probably the best documented investigation into applying this idea to drilling was that of Drilling Research Inc. at Battelle Memorial Institute.' Their "annular wing" percussion bit consisted of paired asymmetric chisels oriented so as to produce and move chips to the center of the hole. They predicted that the lowest energy requirement for chip generation would be achieved with a stepped hole bottom having a median angle of 45" to the horizontal. Results from limited tests showed that approximately 50 percent of the rock fragments were large and semi-circular in shape, as would be expected by a chisel impact near an edge. The remaining 50 percent were fine chips produced by the chisels in re-establishing the steps or ledges. Initial penetration rates with this bit were high, but they rapidly decreased. This was the result of excessive tooth wear caused by the constant friction on the gauge surfaces. The basic idea — circumferentially placed asymmetric chisels — still appears to have merit. If the concept could be applied to a rolling cutter bit, two of the shortcomings of the fixed chisel design could be overcome: (1) reduction in tooth friction, and (2) greatly increased cutter surface. Adapting asymmetric chisels to cutters rolling on an inclined hole bottom is restricted by bit geometry. The basic elements of roller rock-bit construction prevents the practical attainment of a 45" hole bottom angle. Nonetheless, experimentally it was considered desirable to investigate the influence of hole bottom angle to at least 40". This paper describes the laboratory studies conducted in evaluating the circumferential-toothed roller cutter rock bit. EXPERIMENTAL APPARATUS AND PROCEDURE BIT ASSEMBLY The cost of constructing a sufficient number of conventional three-cone rock bits to investigate circumferential cutter performance was prohibitive. Instead, a novel two-cone laboratory assembly which used an external bearing system was designed and constructed. The external bearings made it possible to alter the journal bearing angles and thus allow a wide flexibility in cutter configuration. Fig. 1 shows the laboratory bit assembly, the various bearing mount plates and the appropriate roller cutters for drilling shallow holes having hole bottom angles of 0, 10, 20, 30 or 40". The bit was limited to a drilling depth of 1 1/2 in. at the gauge teeth and a hole diameter of 43/4 in. This more or less intermediate size bit was chosen because it gave a more realistic match between bit teeth and the rock than would a microbit. Also, the rock sample size required was convenient and easy to obtain. CIRCUMFERENTIAL CUTTERS The tooth configuration used in our initial studies is shown in the upper half of Fig. 2. All cutters used in this series had the same tooth form — 43" included tooth angle, 2" positive relief angle and a horizontal tooth flat width of 1/32 in. Each cone cuts alternate rows except for the gauge row. The row-to-row spacing in view was 1/4 in. Static loading tests conducted earlier with asymmetrical chisels had been used to establish this spacing. These tests showed energy requirements for chip production increasing rapidly as the distances to the edge increased beyond

By J. L. Taylor, P. Duwez

The phase boundaries in the ternary system Ti-Cr-Al have been established at 1800° and 1400°F for alloys containing more than 60 pct Ti. The martensite transformation temperature has been measured for the titanium-rich alloys. THE studies of binary alloys of titanium with the transition elements which have been published so far1-0 ndicate clearly that the solubility of these elements is always much greater in the high temperature body-centered cubic form of titanium (ß phase) than in the low temperature hexagonal form. In this category of alloying elements are iron, nickel, chromium, manganese, vanadium, molybdenum, tungsten, columbium, and tantalum. Although studies of the nontransition elements have been rather limited, early work on titanium binary alloys'" has shown that most of them were not very soluble in the a form, with the exception of aluminum, for which the solubility in a is about 25 pct.13, 12 In addition to this large solubility in a, aluminum is also soluble in ß titanium to the extent of about 35 pct and the transformation temperature from ß to a is raised with aluminum content. This effect is also typical of aluminum, in contrast with that found for the transition elements which lower the ß to a transformation temperature. Therefore, it may be anticipated that tprnarv titanium alloys with aluminum and any one of the transition elements will constitute a class of ternary alloys having characteristic features absent in alloys involving two transition elements. Chromium was chosen as a typical transition element for the present study because ternary alloys of Ti-Al-Cr commercially produced have been found to possess very interesting physical properties (MST-3 pct A1-5 pct Cr of Mallory-Sharon).'" Binary Systems The binary systems Ti-A1 and Ti-Cr have been established recently by several investigators. The data used in this investigation were taken from the complete diagram of Bumps, Kessler, and Hansen." This diagram agrees quite well with earlier investigations." For the Ti-Cr system, the phase boundaries at 1800" and 1400°F were taken from refs. 6 and 7. The binary system Cr-A1 has been studied recently by Bradley." This system is rather complex and contains not less than seven intermediate phases. The present study was limited to the titanium corner of the ternary system (less than a total of 40 pct Cr plus Al) and none of the phases present in the Cr-A1 binary alloys were found in the ternary alloys investigated. Experimental Technique Microscopic observation and X-ray diffraction measurements were used to identify phases and de-

Jan 1, 1954

By J. B. Cheatham

The influence of friction on the force required for an idealized bit tooth to penetrate a "plastic" rock is analyzed. The rock is assumed to obey the Coulomb-Mobr yield criterion and the tooth is represented by a two-dimensional sharp wedge. At the tooth-rock interface the stress field not only satisfies the yield condition but also is such that the ratio of the shearing stress to the normal stress is equal to the coefficient of friction. The solution relates the force on the tooth to the depth of penetration, the tooth angle, the coefficient of friction between the rock and bit tooth and the angle of internal friction and compressive strength of the rock. INTRODUCTION Most rocks are brittle at atmospheric pressure but exhibit ductility and increased strength as the confining pressure is increased. In a previous analysisl the force required for a bit tooth to penetrate a rigid-plastic rock was computed for two limiting conditions: (1) a perfectly lubricated tooth-rock interface which should correspond to a lower limit for the penetrating force, and (2) a perfectly rough interface which should provide an upper limit. Experimental results2 for rock indentation under confining pressure have confirmed that the analysis generally predicts upper and lower limits for the penetrating force as a function of rock properties and tooth angle. The present analysis extends the previous work to account for the friction between the rock and the tooth. ANALYSIS The force required for incipient plastic flow of an idealized model of a rock under a bit tooth is computed subjected to the following assumptions. BIT TOOTH 1. sharp two-dimensional wedge (end effects neglected) 2. rigid tooth (elastic deformation of tooth neglected) 3. displacement of tooth is normal to rock surface 4. friction exists between tooth and rock ROCK 1. semi-infinite, isotropic and homogeneous 2. rigid-plastic (elastic deformation of rock neglected) 3. non-work hardening (horizontal stress-strain curve) 4. Coulomb yield condition* (linear Mohr envelope) 5. smooth, flat surface According to the Mohr theory of failure it is assumed that failure occurs when the state of stress is such that the Mohr stress circle becomes tangent to an experimentally determined envelope. The Mohr failure curve is frequent1y approximated by a straight line and referred to as the Coulomb-Mohr failure criterion. If the rock is under sufficient pressure to be ductile we can use the linear envelope as a yield condition. The Coulomb-Mohr yield criterion is illustrated by Fig. 1 and is expressed by the following equation:l

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;'-' and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967