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By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.' More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.' This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.' These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer's6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

By P. Chiotti, J. T. Mason

Ther?nal, X-ray, metallographic, and vapor pressure data were obtained to establish the phase diagram and standard free energy, enthalpy, and entropy of formation for the compounds in the Sw-Zn system. Four compounds, SmZn, SmZn2 , SmZn4.s, and SmZn8.5, melt congruently at 960°, 94Z°, 908°, and 940°C, respectively. The cornpounds SlnZns, Sm3Znll, and SnzZn7.3 undergo peritectic decomposition at 855", 870°, and 890C, respectively. Another compound of uncertain stoichiometry, SmZn11, undergoes peritectic decomposition at 760°C. Four entectics were observed with the following compositions in weight percent zinc and eutectic tenzperatures in degrees Centigrade: 12 pct, 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. An allotropic transformation and a composition range were observed for the SmZnz compound. The transfor)nation varies from 905" to 865°C as the zinc content increases from 16.0 to 48.5 wt pct, respectively. The free energy of formation of the compounds at 50PC varies between -15.9 kcal per mole for SmZn to -51.1 kcal per mole for SmZn,.,. Corresponding enthalpies vary between -19.2 to -78.3 kcal per mole. The ther-modynamic properties for the liquid alloys are described by the relations: A search of the literature revealed very little information on the Sm-Zn system. Chao et al.&apos; as well as Iandelli and palenzonai have reported the structure of SmZn to be cubic B2 type and Kuz&apos;ma et al3. have reported the structure of -sm2zn17 to be of the Th2Ni17 type. The purpose of this work was to establish the phase diagram of this system, to determine the zinc vapor pressure over the solid two-phase regions of the SYstem, and to calculate the thermodynamic properties of the compounds. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in this investigation were Bunker Hill slab zinc 99.99 wt pct pure and Ames Laboratory samarium. Analysis of the samarium by chemical, spectrographic, and vacuum-fusion methods gave the following average impurities in ppm: Nd, <200; Eu, <100; Gd, <100; Y, <50;Ca, 225; Ta, 400; Mg, 10; Cu, ~50; 0, 175; H, 20; and N, 15. The elements Fe, Si, Cr, Ni, Al, and W were not detected. The samarium was received as sponge metal and was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys with zinc contents up to the Sm2Znl, stoichio-metry. At higher zinc contents the grain boundaries of the tantalum containers were penetrated by the alloy and the containers failed during prolonged annealing. About 25 g of massive zinc and samarium sponge were sealed in tantalum crucibles equipped with thermocouple wells. These crucibles were in turn sealed in stainless-steel jackets. All closures were made by arc welding under an argon atmosphere. The samples were equilibrated in an oscillating furnace and in some cases were given various heat treatments in a soaking furnace. After appropriate heat treatment the steel jackets were removed and the alloy subjected to differential thermal analysis. The apparatus was calibrated against pure zinc and pure copper and found to reproduce the accepted melting points within 1°C. Alloys were subsequently subjected to metallographic examination and those of appropriate compositions were used for X-ray diffraction analysis and for zinc vapor pressure determinations. The vapor pressures were determined by the dewpoint method. Both the differential analysis and dewpoint measuring apparatuses have been described in earlier papers.4, 5 All alloy samples were etched with Nital (0.5 to 3 pct nitric acid in alcohol) except the samarium-rich alloys. These more reactive alloys were electro-polished in a 1 to 6 pct HClO4 in methanol solution at -700c at a potential of 50 v. EXPERIMENTAL RESULTS Phase Diagram. The results of thermal analysis are indicated by the points on the phase diagram, Fig. 1. Eight compounds and four eutectics were observed. The composition of the compounds and their melting or peritectic temperatures are given on the phase diagram. The four eutectic compositions in wt pct zinc and eutectic temperatures in % are: 12 pct,- 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. The stoichiometry of the most zinc-rich compound is still uncertain, but is very likely either SmZnll or SmZnlz. However, to simplify the presentation which follows it will be referred to as SmZnll. As shown on the phase diagram the phase regions for some of the samarium-rich alloys have not been unambiguously established. A sample of pure samarium was observed to transform at 924°C and to melt at 1074"C, in good agreement with corresponding val-

Jan 1, 1968

By K. M. Rolls, F. W. Reuter, J. Wulff

The superconducting behavior and microstructural characteristics of a nominal Nb-40 wt pct Ti-0.239 wt pct O alloy were studied as a function of ther mo -mechanical processing treatment. Critical current density us applied transverse magnetic field was obtained for 0.010-in.-diam wires at 4.2°Kin steady fields 14 to 110 kG. Both optical metallogvaphy and transmission electron microscopy were used to delineate the micros tructures of the same wires. It wan found that a 1-hr 500°C precipitation heat treatment after cold drawing to final size led to the highest critical current density. Heat treatment at 600°C also led to a high critical current density, but the precipitate differs in kind and form from that at 500°C. The resistire critical field was also found to be sensitive to precipitation heat treatment since the effective composition of the superconducting phase changes. This is discussed in terms of the oxygen in interstitial solid solution. Two types of high-field superconducting wire are at present used in the construction of high-field superconducting solenoids. These types are solid-solution alloy wire such as Nb-Zr and Nb-Ti and composites of the brittle inter metallic compound Nb3Sn. The latter generally have a high super cur rent-carry ing capacity which is difficult to vary if properly made. The supercur rent- carry ing capacity of the former can be varied drastically and often predictably by suitable thermomechanical processing treatments. In general, the critical current density Jc of the solid-solution type of alloy is increased by cold work and by additions of interstitial elements along with aging heat treatments. The imperfections which result are be-iieved to be responsible for the observed increase in Jc. In 1962 Kneip and coworkers1 found that the critical faurrent density of Nb-Zr alloys could be increased by proper heat treatment preceded and followed by cold work. Betterton and coworkers2 using a Nb-25 at. pct Zr alloy found that small additions of oxygen or carbon enhanced the effect of this heat treatment. They suggested that the interstitials present aided precipitation in the alloy, leading to a filamentary structure with superior properties. If the precipitation heat treatment was omitted, interstitial additions had a negligible effect on Jc. wong3 showed that higher heat-treatment temperatures lowered Jc. Walker and co-workers,4 who studied microstructure (by transmission electron microscopy) as well as superconductivity, found that the Jc anisotropy introduced by cold rolling was itself affected by heat treatment. They were unable to clarify the relation between microstructure and critical current density, although evidence of precipitation was indicated. More recent investigation of Nb-Zr alloys,5,6 besides showing that structural defects and fiber ing due to cold work and precipitation serve to raise Jc, also elucidate important optically observable microstructural changes which occur upon precipitation. In these reports, coarsening of the microstructural features was found to decrease Jc. Vetrano and Boom,7 who studied Ti-20.7 at. pct Nb, found that Jc was increased to a maximum by a 415°C, 3-hr heat treatment following quenching from 800°C and cold working. Heat treatments can also affect the resistive critical field Hr. Final-size heat treatments of Nb-Zr wire can lower Hr drastically if gross phase decomposition occurs5&apos;* or moderately if the effects of cold work are eliminated without changing significantly the composition of the phase of interest.3,5,6,8 The percentage of oxygen which can be added to Nb-Zr alloys to enhance Jc is limited by the difficulty of subsequent cold drawing. Since Nb-Ti and Ta-Ti alloys in contrast can tolerate appreciably higher percentages of oxygen, it was decided to investigate the superconducting behavior of various alloys in these systems. The present paper describes the results of adding oxygen to a nominal 40 wt pct Nb alloy as a function of thermomechanical treatment. I) EXPERIMENTAL PROCEDURE A small alloy ingot was prepared from high-purity niobium, iodide, crystal-bar titanium, and Nb2O5 powder by arc melting on a water-cooled copper hearth in a gettered argon atmosphere. The ingot was turned and remelted fourteen times to insure homogeneity. After final melting and rapid cooling, it was machined round to 0.415 in. diam, jacketed in stainless steel, and cold-swaged to 0.117 in. diam. The jacket was removed and swaging continued to 0.051 in. diam followed by wire drawing in carbide dies to 0.010 in. diam. Although it was intended that about 1500 ppm O (by weight) be added, inert gas fusion analysis indicated a 2390 ppm 0 content, apparently due to additional oxygen pickup in the arc furnace. Even so, the alloy was sufficiently ductile to be cold-worked to greater than 99.9 pct reduction

Jan 1, 1967

By W. J. Helfrich, R. A. Dodd

Binary aluminum solid-solution alloys containing various amounts of silver, magnesium, and zinc were prepared by careful directional solidification, and the hydrostatic and X-ray densities were compared. With the exception of the Al(Ag) alloys, the X-ray densities were consistently greater than the hydrostatic measurements, in agreement with earlier observations by Ellwood. In contrast to Ell-wood&apos;s interpretation in terms of vacant lattice sites associated with Brillouin zone effects, a tentative explanation based on the existence of solidification microshrinkage was favored. This hypothesis was confirmed by an examination of Al(Zn) alloys prepared by vapor diffusion of zinc into aluminum. The hydrostatic and X-ray densities were now in very close agreement, and it was concluded that the filling of Brillouin zones in aluminum solid-solution alloys does not necessarily result in the formation of defect structures containing an excess of vacant lattice sites. ThE existence of defect structures of the vacancy type in alloys in which the excess vacancies have an electronic rather than a thermal or mechanical, and so forth, origin is well recognized. Examples of incomplete lattices of this type are to be found in the Ni-Al,1-3 Fe-Ni-A1,4 c~-Ni-Al,5 Fe-Cu-Al,= and Co-A17 systems. These defect structures are of a special kind in that the intermediate phases possess an ordered atomic arrangement or superlattice, and in some instances the vacancy concentration may be unusually large, e.g., at 45.25 at. pet Ni in NiA1, approximately 8.8 pet of the lattice sites are unoccupied. Ellwood8-10 has reported similar defect structures in the aluminum solid solution alloys of the Al-Zn and A1-Mg systems and in alloys of the Au-Ni system." In Al(Zn) the (apparent) vacancy concentration rose, somewhat irregularly, to a maximum of about 2 pet vacant sites at 25 at. pet Zn, while in Al(Mg) the (apparent) vacancy concentration increased continuously to 1.7 pet at 15 at. pet Mg. An explanation in terms of Brillouin zone overlap was attempted, although Pearson12 has pointed out the difficulty of reconciling the observations with zone theory. However, the possibility of the effect being caused by the Fermi surface just touching a plane of energy discontinuity inside a prominent Brillouin zone has, in general, been accepted. In fact, Massal-ski13 has interpreted Ellwood&apos;s8 observations as confirmation of Leigh&apos;s14 theoretically predicted zone overlap occurring at approximately 2.67 electrons per atom. Unfortunately, Massalski was apparently unaware that Ellwood9 had revised his earlier results considerably, and the revised data did not confirm Leigh&apos;s analysis. Ellwood&apos;s clata were reexamined by the present authors who noted a possible correlation between the percentage defects as a function of alloy composition and the temperature interval of solidification measured from the respective equilibrium diagrams. This suggested an explanation in terms of shrinkage porosity rather than vacant lattice sites, and pointed to the desirability of reexamining appropriate alloy systems using: both Ellwood&apos;s method of specimen preparation (casting followed by wrought fabrication) and alternativ&apos;e methods, i.e., diffusion, which might be expected to minimize, or even completely obviate, microporosity. ALLOY PREPARATION 1) Cast Allolys and Aluminum Single Crystals. Al(Ag), Al(Mg;l, and Al(Zn) alloys of various compositions up to 20 at. pet silver, 13.5 at. pet mg, and 30 at. pet Zn were prepared by melting under helium and casting into graphite molds. In the first two systems, the maximum alloying addition was quite close to the limit of solid solubility, but the possibility of transformation to a&apos; during quenching somewhat restricted the suitable Al(Zn) composition range. The alloys were prepared from high-purity aluminum, a lot analysis showing 0.002 wt pet Cu, 0.002 wt pet Fe, and 99.996 wt pet A1 by difference. The silver, magnesium, and zinc were of 99.99+, 99.98+, and 99.998 wt pet respectively. Each composition was analyzed chemically. The as-cast ingots measured 7/16 in. diam and 5 in. length. One in. was removed from the top of the ingot, and the bottom 3 in. was machined to 0.275 in. diam; a point was also machined on the smaller diameter end. The remainder of the original ingot served as a top riser during subsequent remelting and controlled solidification. The machined ingots were now remelted using a Bridgman soft-mold technique to ensure directional solidification and, therefore, a minimum of micro-shrinkage. Alumina powder was used as mold material contained in an alundum thimble, and this crucible was placed in a helium-filled Vycor tube. The assembly was lowered through a suitable temperature gradient at approximately 0.5 in. min-l, and the risered portion of the casting was subsequently removed by sawing.

Jan 1, 1962

By George V. Smith, Daniel E. Sonon

Various mechanical properties of the Ni-Co-C alloy system were investigated to delineate the strengthening effect of carbon. Carbon concentration, cobalt concentration, vain size, temperature, and strain rate were varied so that thermal activation analysis and the Hall-Petch analysis could be used to evaluate the strengthening effect of carbon. Increasing carbon increased the strength of nickel and a Ni-60 pct Co alloy , with the effect becoming more pronounced at lower temperatures. Yield stress depended linearly on carbon concentration in nickel, but it depended on the square root of carbon concentration in the Ni-60 pct Co alloy. The Hall-Petch slope of nickel increased with carbon concentration; however, that of the Ni-60 pct Co alloy did not. The yielding behavior of these alloys was sensitive to composition, grain size, and temperature. Cobalt eliminated serrations in the flow curve of carbon-containing nickel at 300&apos; and weakened them severely at higher temperatures. Pairs, or clusters, of carbon atoms appear to be responsible for the observed strengthening behavior. FLINN&apos; conducted several experiments with carbon in nickel in an effort to provide information on the strengthening effect of interstitial impurities in solid solution in fcc metals and alloys. Strengthening which increased with decreasing temperature led him to conclude that carbon causes Cottrell locking in nickel. Fleischer2 analyzed Flinn&apos;s data and calculated that the strengthening effect of carbon in nickel was smaller by a factor of fifty than the strengthening effect of carbon in a! iron. Fleischer2 termed the magnitude of strengthening of carbon in nickel "gradual" and that of carbon in a! iron "rapid". He attributed "gradual" hardening to hydrostatic strains and localized changes in modulus of elasticity around solute atoms, whereas he attributed "rapid" hardening to tetragonal strains around solute atoms. Sukhovarov et a1.3-7 reported strain aging and serrated plastic flow in nickel, both of which they attributed to the presence of carbon. Serrated plastic flow has been rationalized by a process involving a series of dislocation pinning and multiplication steps.8, This process is more probable when screw dislocations are strongly pinned. Screw dislocations cannot be pinned by pure hydrostatic forces from the symmetrical strains of an interstitial impurity in an fcc lattice, except for small, second-order effects. However, they might be pinned by localized changes in modulus of elasticity around solute atoms,&apos; by the pinning of the edge components of the partial dislocations of an extended screw dislo~ation,&apos;~ or by clustered groups of solute atoms whose net elastic stress field is unsymmetric. The purpose of the present work was to investigate various mechanical properties of the Ni-Co-C a1loy system which are sensitive to pinning effects in order to delineate the specific pinning mechanism of carbon. Carbon concentration, grain size, temperature, and strain rate were varied so that thermal-activation analysis and the Hall-Petch analysis could be used to evaluate the pinning mechanism. Cobalt was added to lower stacking fault energy so that the number and extension of split, screw dislocations would be increased in order to test the possibility of pinning by carbon at extended screw dislocations. EXPERIMENTAL PROCEDURE Nickel and cobalt (both 99.98 pct-. pure) were melted with graphite in stabilized zirconia crucibles and cast at lo-&apos; Torr to form Ni-C and Ni-60 pctCo-C alloys. Two ingots were heated to 1250°C and were forged to 1-in.-sq bars. These bars were machined to 4-in.-round bars, and then swaged cold to 0.144-in. -diam rods. Reductions in area of approximately 75pct were used with intermediate anneals at 900°C for 1 hr. The carbon content of batches of 0.144-in.-diam rods from each ingot was reduced to two levels by annealing 5-in. lengths in palladium-purified, dry hydrogen at 1100°C for 25 and 100 hr. The remaining material from each ingot was annealed at 10"5 Torr for 1 hr at 1100"~. These treatments gave a total of three carbon levels for both the nickel and the Ni-60 pct Co alloy. The 0.144-in.-diam rods were swaged to 70-mil wire, cut into test specimens, and then re crystallized at lom5 Torr in capsules for 1 hr at temperatures ranging from 760" to 1050" ~. The capsules were broken and the specimens were immediately quenched into water. Average grain size was measured using Hilliard&apos;s method of circular intercepts." Annealing twin boundary intercepts were counted in addition to grain boundary intercepts to establish an average grain size. Average grain sizes ranged from 5 to 140 p depending on the cobalt concentration and re-crystallization temperature. Tension tests were made in duplicate at various temperatures at a crosshead speed of 8.34 x 10"4 in. per sec with an Instron Universal Testing Machine. Specimens of 1-in. gage length with soldered ball ends were used at atmospheric and cryogenic temperatures. Pinch grips were used on specimens at elevated tem-

Jan 1, 1969

By R. H. Jamison

A relatively new haulage system is described. Employed by the Delmant Fuel Co.. the "Full Dimension" system provides an uninterrupted flow of coal from a loader or continuous miner at the face to the main line transportation system. This system is said to provide a higher percentage of recovery as well as additional safety and production. Delmont Fuel Co. is employing a comparatively new system of transportation known as a Full Dimension system. Cne of these systems has been in operation for a year at the company&apos;s 10-B Mine as a part of a conventional section. A second was installed at the No. 10 mine in late 1960 to handle the production of a Colmol in a pillar section. SYSTEM COMPONENTS A Full Dimension system is a haulage system that provides an uninterrupted flow of coal from a loader or continuous miner at the face to the main line transportation system. The equipment required for this system consists of a series of interconnected chain conveyors that are mobile and articulated. They will retract or extend a sufficient distance for the development of a five-entry system; or, in the Colmol pillar section, it provides reach of 210 ft in all directions from the section belt. The components of this system are: l)One 160-ft chain line placed in tandem with the belt conveyor. It has a self-propelled drive, is 20 in. wide and 9 in. deep. Moving this conveyor requires the assistance of a loading machine or cutting machine. 2) One 40-ft piggyback that discharges along the entire length of the 160 ft chain conveyor. 3) A mobile bridge carrier, which is a self-propelled conveyor with four wheel steer and four wheel drive, twenty-eight feet long, it delivers coal to the receiving end of the piggyback. Axles steer individually making possible almost lateral movement. 4) Another 40-ft piggyback, duplicate of item 2 that delivers coal along the entire length of item 3 (mobile bridge carrier). 5) A second mobile bridge carrier, similar to the first, which deliver coal to the piggyback (item 4). 6) A third 40-ft piggyback, duplicate of items 2 and 4. This pig is attached to the loading machine and delivers its coal along the length of the second mobile bridge conveyor. Since the original preparation of this paper, the Delmot Fuel Co. has been able to eliminate the 160-ft chain conveyor. This was accomplished by connecting the outby piggyback directly to a loading machine with an extended boom. The loading machine loads directly onto the belt. This change has resulted in a substantial reduction in moving time and greatly increased flexability. A single trailing cable powers the entire string of equipment. It is attached to the side of the equipment in such a way as to keep it off the ground and afford maximum protection. The tramming rate of this equipment is 90 fpm. The conveyor capacity in a conventional section at Delmont&apos;s mines is 7.5 tpm and in the Colmol section is 5.5 tpm. This regulation is a simple function of conveyor speed. To visualize operation of this equipment, it would be well for me to touch briefly on local conditions in the Upper Freeport seam in which we mine. (Also, see the photographs of some of the equipment in use.) DELMONT&apos;S TOPOGRAPHY The Delmont Fuel Co. operates two mines in this seam in Westmoreland County, Pa. The No. 10 mine, which was opened in about 1912, is now almost worked out. Depending on economics in the industry, it has a life of two to four years on a declining production basis. A year ago a new drift mine was opened which is called No. 10-B. It is about two miles from the cleaning plant and is connected thereto by an overland belt conveyor. The new mine is being developed at a rate calculated to take up the slack as the old mine plays out. The Upper Freeport seam averages 4.2 ft in thickness in the area of the Delmont mines. It carries 4 in. of boney coal at the top of the seam and a middle man of from 2 to 4 in. We mine just above a 1-in. slate parting which has 4 to 6 in. of highly laminated coal beneath it. This material normally makes a very firm bottom. The roof varies from dark shale to sand rock and 36-in. bolts are placed on 4-ft centers for roof support. All working places are driven 20 ft wide on development and 25 ft wide on retreat. Selection of mobile chain conveyor equipment when it became available, was a very natural move for Delmont Fuel to make, because chain conveyors and piggybacks had been in use at the company&apos;s mines for about 12 years. Grades in the new mine

Jan 1, 1961

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200&apos;K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:&apos;4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3&apos;7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By S. Storchheim

MORE and more attention is being paid to the bonding of metals in their solid states. For a better understanding of this technique for joining metals and how it is affected by changes in temperature, pressure, and time at temperature and pressure, a detailed report concerning nickel to aluminum bonding has been published.&apos; In order to broaden the knowledge accrued, some additional work concerning solid state joining of aluminum to copper and aluminum to zirconium was performed. The investigation of the Al-Cu system was considerably more extensive than the investigation of the Al-Zr system. For the A1-Cu system, not only were tensile sudies made but intermetallic penetration rate investigations also were carried out. The effect of temperature on intermetallic penetration rate for the A1-Cu system was determined at 11 tsi pressure, held 2 min. Procedure Apparatus: The hot pressing technique was the means of solid state reaction used and required the equipment depicted in Fig. 1. The following procedure was involved: The two metals to be reacted were placed in an aquadag-lubricated 18-4-1 tool steel die, 16 in. high by 1.440 in. ID, between punches of 1.366 in. diam made of the same material. A thermocouple well was located in the die body 3½ in. down from the top of the die, while another well was located centrally in the bottom punch 8½ in. from the bottom of the die. This die assembly was located in three cylindrical ceramic heating furnaces placed in tandem. Each furnace was controlled individually by a Variac power transformer. In turn, the die and furnaces were placed in a water-cooled stainless steel pot which could be evacuated. A cover, which contained a centrally located Wilson seal with an 18-4-1 1 in. diam ram running through it, was bolted on the pot. After sealing, the pot was evacuated by a roughing pump to 200 microns pressure, after which a diffusion pump was used to bring the pressure down to 5 to 15 u. At this pressure, the furnaces were turned on. As soon as they started to heat, out-gassing of the entire unit raised the pressure to 30 to 400 p. By the time the specimens were at temperature ready to be pressed, approximately 4/2 hr, the vacuum pumps had re-established the 5 to 15 u pressure. Once the desired temperature was reached, the required pressure was applied for a predetermined length of time to the 1 in. ram, through to the top punch, and to the specimen. When the time for keeping the specimen under pressure had elapsed, the pressure was released, the energizing coil current turned off, and the assembly allowed to cool. After cooling, the die was removed from the pot and the specimen was ejected. Specimen Preparation: Two different types of specimens were made for this investigation. One was for subsequent tensile testing, while the other was for determination of intermetallic alloy zone penetration into the parent metals. Tensile Bars—Commercially rolled copper pieces in. thick or zirconium sheet pieces 1/32 in. thick and 1.366 in. diam were placed between commercial 2-S aluminum rod 1 in. thick and 1.366 in. diam. This sandwich in turn was slipped into a 2-S aluminum sleeve 1.438 in. OD and 1.370 in. ID. This sleeve lined the couple up and prevented the aquadag lubricant from getting in between either the A1-Cu or Al-Zr interfaces. Immediately prior to the specimen assembly, the copper or zirconium was abraded on the flat surfaces with 320 grit silicon carbide paper, producing clean smooth surfaces. The aluminum was chemically cleaned just before assembly by: l—degrease in acetone, 2—distilled water rinse, 3—immersion for 3 min in 5 pct NaOH at 70" to 80°C, 4—distilled water rinse, 5—immersion for 2 min in 50 pct HNO3 solution at room temperature, 6—distilled water rinse, and 7—drying in a blast of gas. After the A1-Cu sandwiches were hot pressed and ejected, the specimens were machined such that the aluminum sleeve was removed, and the remaining aluminum was then threaded; the bar so produced was tested later for tensile strength. In all the instances where Al-Cu couples were tested, the specimens broke during the test at the Cu-A1 interface and never within the aluminum or copper. The ultimate tensile strength values at times showed considerable scatter for a set of given reaction conditions. Because of this, as many as three to five specimens were made for a particular set of conditions. The trend of the average tensile strengths obtained was not as conclusive as was the trend of the maximum tensile strengths, the latter values being obtained under optimum reaction conditions. Therefore, the values of ultimate tensile strength given herein are maximums.

Jan 1, 1956

By B. L. Averbach, M. F. Comerford, M. B. Rough

The volume fraction of ß phase was determined in a Ti-6Al-4V alloy by measurements of integrated diffraction intensities. The (0002), and (100)ß diffraction lines were chosen because this combination minimizes the errors resulting from preferred orientation. The difficulties arising from fluorescence radiation were eliminated by use of a diffracted beam monochromator. A specimen quenched from 1475OF (800°C) contained approximately 5 pct ß, but in specimens quenched from higher temperatures no ß was found. The ß phase formed during aging, and in specimens solution treated at 1570oF (855oC) approximately 10 pct ß was present after aging at 1000°F (540°C) for 24 hr. This ß appears to form by decomposition of martensitic a&apos;. ThE kinetics of the reactions which occur during the heat treatment of titanium alloys are complex &apos; and not completely understood. It has been proposed that hardening occurs in some alloys&apos; on aging by the precipitation of a transition phase w followed by the formation of the stable a and ß phases. It has been proposed for other alloys2 that the a&apos; marten-site decomposes by precipitating finely dispersed a particles. Most investigations have been hampered by the difficulties of determining quantitatively the amounts of the various phases present. This paper is concerned with the measurement of the amount of ß phase by an X-ray method, similar to one developed for the determination of retained austenite. The principal new feature was the use of a mono-chromator in the diffracted beam in order to reduce the fluorescence arising from the sample. EXPERIMENTAL PROCEDURE The experiments were carried out on an alloy of nominal composition Ti-6Al-4V (actual weight percentages: 6.2 Al, 4.1 V, 0.02 Mn, 0.17 Fe, 0.005 H, 0.03 C, and 0.02 N). The material was received as 5/8-in.-diam centerless ground rods in the annealed condition. The heat treatments were carried out in a vacuum of approximately 0.03µHg. The X-ray intensity measurements were made on 3/8-in. thick discs. The surface was prepared by grinding off about 0.060 in. and electropolishing in a solution af 60 ml (70 to 72 pct) perchloric acid in 1000 ml glacial acetic acid with a current density of 0.5 amp per sq cm.q The X-ray determination is based on the proportionality of the diffracted intensity of each line to the volume fraction of the corresponding phase. In calculating the intensities for a powder sample it is assumed that a large number of grains con- tributes to the diffracted intensity and that the grains are oriented at random. The presence of preferred orientation introduces serious errors in the relative intensities. The material used in this investigation exhibited a strong preferred orientation, which could not be removed by heat treatment. Other investigators have also found that preferred orientation may be retained after phase transformations. Glen and pugh5 performed a detailed analysis of the randomness expected after several allotropic transformations, but stated that this is not observed. Burgers,6 and Burgers and Ploos van Amstel,7 found that, in zirconium, the original orientation is retained after two phase transformations. Newkirk and Geisler8 observed similar behavior in titanium. On the basis of this evidence, it appears that, in the absence of plastic deformation, textures present in annealed titanium alloys are retained. Heating an a-ß alloy to the all-ß region and subsequent cooling to room temperature do not make the orientation of the mar-tensite different from that of the original a phase. In the present investigation it was possible to take advantage of the crystallographic relationships involved in the martensitic transformation to minimize the errors associated with preferred orientation. The relative orientation for titaniu-m marten-site9 takes the form (0001), 11 (110)ß; [1120], 11 [lll]ß. The same relationship has been proposed for zirconium&apos; and certain titanium-base alloys.10-12 Additional sets of approximately parallel planes have been determined for titanium-nickel alloys." The influence of preferred orientation can be minimized by comparing intensities from parallel planes in the two related phases. If it is assumed that each family of planes in a given phase is equally well populated, the effect of preferred orientation can be eliminated by using the normal multiplicity for the family of planes since each set of parallel planes is equally preferred for any orientation of the sample relative to the X-ray beam. The most suitable combination of reflections in the Ti-6A1-4V alloy appeared to be (0002), and (110)ß It must be recognized that the ß formed during aging of the Ti-6A1-4V alloy is a precipitate rather

Jan 1, 1960

By J. T. Norton, N. J. Grant, A. R. Chaudhuri

MOST of the recent work to establish the mech-anism of creep in metals at high temperatures has utilized aluminum as the experimental material. It was thought desirable to initiate an investigation of a hexagonal close-packed metal, because of the relatively simple slip system, and compare the observed deformation characteristics with those that have been observed for the face-centerd cubic metals. High-purity magnesium was chosen for this purpose, first, because its strength and other mechanical properties are similar to those of aluminum in the same temperature range, and second, because the existing equipment was ideally suited to observe magnesium during creep. It is proposed in this paper to present a pictorial and qualitative account of the changes that high-purity magnesium undergoes during creep at 500°F. The characteristics of deformation of aluminum described below have been observed by various workers and accounts of these may be obtained from the papers of Chang and Grant.&apos;- These characteristics are: slip, subgrain formation, grain boundary sliding and migration, fold formation, deformation bands, and kink bands. It is well known that in a flat magnesium specimen, slip on the basal plane (0001) in the [1120] direction results in the formation of straight bands on the surface of the specimen. Schmid and co-workers&apos; have shown that this system is operative in the temperature range of -185" to 300°C (-300° to 572°F). They have also shown that a second system, slip on the pyramidal planes {1071} or {1012} in the [1120] direction, is operative at temperatures higher than 225°C (437°F). Between 225° and 300°C (437" to 572°F), therefore, deformation by both these systems is expected. Bakarian and Mathewson5 confirmed the occurrence of pyramidal slip on the {1011} plane and found that it resulted in irregular markings on the surfaces of their specimens. Burke and Hibbard6 obtained evidence of pyramidal slip in single crystals of magnesium deformed at room temperature. Bakarian and Mathewson5 suggested that the irregular appearance of these bands was due to slip on both of the pyramidal planes occurring simultaneously but in the same direction, the close angular relationship between the planes making this process possible. Furthermore, since neither of these planes is close enough to the basal plane, slip on the latter does not exhibit the irregular appearance of slip bands resulting from pyramidal slip. Experimental Procedure High-purity magnesium, supplied by the Dow Chemical Co., was used in these experiments. The analysis was as follows: Al, 0.0002 pct; Mn, 0.0018; Fe, 0.0024; Cu, 0.0002; Sn, 0.001; Ca, 0.01; Ni, 0.0003; Zn, 0.01; Pb, 0.0005; Si, 0.001; and Mg, 99.972. The magnesium was supplied in the form of 1/2 in. diam rods. The specimens had an overall length of 21/4 in., the round ends being threaded to fit the specimen holders. The previously round 3/16 in. diam gage section of the specimen had two parallel flats machined on opposite sides for microscopic observation, yielding a test zone having the dimensions of lx3/16x7/64 in. The specimens were electrolytically polished (without prior mechanical polishing of the machined flats), in a solution composed of 375 ml of ortho-phosphoric acid and 625 ml of ethyl alcohol.&apos; The cathode was a stainless steel sheet bent so that the specimen was completely surrounded. The voltage for successful polishing was 1.5 v at 100 to 300 milli-amp current. Electropolishing for about 45 min sufficed to obtain a good metallographic surface on the specimens after they had been machined. The creep tests were performed under constant load, and two types of equipment were used. In the first, designed by Servi and Grant,V he specimens were beam-loaded, and a furnace could be lowered to surround the specimen. As the microstructural changes could not be observed during the course of the test, the tests had to be interrupted periodically by removing the specimen for microscopic examination. The second unit was a high temperature microscopy furnace designed by Chang and Grant.&apos; The furnace was fitted with an optically flat quartz window having area dimensions 1.25x0.5 in., so that the whole test portion could be viewed through it at magnifications up to x240. The metallurgical microscope had three mutually perpendicular axes of motion, and, in addition, it was possible to measure angular displacements by rotation of the eyepiece. It was thus possible to make precise observations of the specimen during creep, and micrographs could be taken by attaching a camera to the eyepiece of the microscope. The average grain size of the specimens that were tested was about 1 to 3 mm. This grain size could

Jan 1, 1954

By S. G. Proctor, D. L. Baaso, W. V. Conner

A double crucible system was developed for I-g scale plutonium reductions. The equipment consists of an inner MgO crucible, an outer MgO crucible, and a stainless steel pressure vessel. The reduction charge is PIaced in the inner crucible and the annulus between the inner and outer crucibles is filled with a mixture of calcium and iodine. The exothermic reaction between the calcium and iodine in the annulus supplies the heat required for complete reaction of the reduction charge ana&apos; good metal coalescence. Metal yields of 80 to 85 ,pct were obtained from I-g scale reductions and yields as high as 97.5 pct were obtained from 0.5-g scale reductions. The system was used to reduce charges containing as little as 0.1 g of Pu resulting in metal yields up to 90 Pct. THIN metal foils of highly enriched plutonium isotopes are used as targets for cross section and other measurements. The isotopes are separated in the calutrons at Oak Ridge and are very expensive to prepare. Often, only 1 or 2 g of material are available thereby emphasizing the need for a method of preparing these small quantities of metal. Procedures for 1-g scale plutonium reductions have been described, but these procedures require elaborate or expensive equipment. For example, the procedure described by Anselin et al.1 requires an inert atmosphere glovebox and induction heating equipment. The procedure described by Baker2 also uses induction heating equipment to obtain the recommended heating rates and liner temperatures. Baker&apos;s procedure also requires high purity PuF4 with very little PuO2 present. The procedure described in this paper resulted from a search for a simple and inexpensive method for making 1-g scale plutonium reductions. EXPERIMENTAL Equipment. The equipment required for the double crucible system consists of a pressure vessel, two MgO crucibles, a MgO crucible lid, and a resistance-heated, vertical crucible furnace. The crucibles were slip cast from high purity MgO and were supplied by the Coors Porcelain Co. and the Norton Co. The pressure vessel and lid were fabricated from 316 stainless steel. Materials. The PuF4 used for this study was obtained from the P1utoniu:m Metal Production Department at Rocky Flats. The PuF4 was prepared in a con- tinuous hydrofluorinator by reacting Pu02 with HF at 650°C. The isotopic composition of the plutonium was approximately 93 pct 239PU, 6 pct 240PU, and 0.5 pct 241PU. Some of this PuF, contained less than 1 pct Pu02 (Batch No. 6 and 7), while other batches contained up to 15 pct Pu02 (Batch No. 3). The chemical analyses of all the PuF4 used for this study is given in Table I. The calcium was 99 pct pure, AEC grade, and only that fraction which would pass through a 20 mesh screen was used. The I2 was USP grade re-sublimed I2 which was ground before being used. Procedure. Various charge compositions and methods for loading the double crucible system were tested. The optimum conditions for 1-g scale reductions are described below. The double crucible system was loaded as shown in Fig. 1. The outer crucible was placed in the pressure vessel and the annulus between them was filled with MgO sand. The inner crucible was placed in the outer crucible, supported by a layer of MgO sand in the bottom of the outer crucible. A mixture of 5.2 g of Ca and 25 g of I2 was placed in the annulas between the two crucibles. The upper portion of the annulas was filled with MgO sand. Next, a layer of a mixture of calcium and I, equal to 20 wt pct of the calcium and I2 used in the main charge was placed in the bottom of the inner crucible. The PuF, to be reduced was mixed with a 30 pct excess of calcium and 1 mole of I2 per mole of Pu and this mixture was placed in the inner crucible. The charge was topped with a layer of a mixture of calcium and I2 equal to 20 wt pct of the calcium and I2 used in the main charge. The pressure vessel was sealed with a flat copper gasket and was purged by alternately evacuating and filling with argon. The purge valve was closed and the vessel was placed in a vertical crucible furnace which was preheated to 950°C. The furnace was turned off after 20 min of heating and the vessel allowed to cool. Experience has shown that. this amount of heating is sufficient to assure complete reaction of the charge. RESULTS AND DISCUSSION The double crucible system has been used to produce plutonium metal on a 0.1- to 1-g scale. Reduction

Jan 1, 1970

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was (&apos;Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By S. N. Singh, M. C. Flemings

Results are presented of a detailed study on the combined influences of ingot dendrite am spacing and thermomechanical treatments on the structure and solution kinetics of high --purity cast and worked 7075 alloy. Solution kinetics were found to depend sensitively on ingot dendrite am spacing and on details of therrnomechanical processing, including amount of reduction and extent of&apos; solution treatment before reduction. An approximate analysis is given for rate of solution of nonequilibrium second phase in the cast and worked structres; results of the analysis are compared with experiment. MICROSEGREGATION in high strength aluminum alloys manifests itself as "coring" (composition differences within the primary aluminum-rich phase), and as interdendritic second phase. The mechanism of formation of the microsegregation is understood, and approximate prediction of the amount of second phase is possible for simple binary systems.1,2 When alloy elements or impurities are present in amounts less than their solid solubility at solution temperature, any phases forming from these elements are termed "nonequilibrium" and can be dissolved by appropriate solution treatment. The rate at which the nonequilibrium phases are removed depends sensitively on their spacing (dendrite arm spacing in the cast material, or band spacing in wrought material). When alloy elements or impurities are present in amounts in excess of their solubility at the solution temperature, second phase particles form an "equilibrium" second phase that does not dissolve in heat treatment and may, in fact, coarsen in such treatment. Usual commercial, high strength, wrought aluminum alloys contain nonequilibrium second phases that were not fully dissolved during ingot processing. They also contain equilibrium second phases resulting from impurities present in amounts greater than their solubility. As has been shown by Antes, Lipson, and Rosenthal,3 and will be demonstrated further in a subsequent paper by the authors,4 significant improvements in mechanical properties of high strength alloys can be achieved by reduction or elimination of these second phases. Methods of elimination are 1) to employ high purity materials to minimize amounts of equilibrium second phase, and 2) to employ suitable thermomechanical processing techniques to fully eliminate nonequilibrium second phases. Work reported herein comprises a study of selected thermomechani- cal processing treatments, and of their influence on solution kinetics of wrought high purity 7075 alloy. EXPERIMENTAL PROCEDURE Melting and Casting. The bulk of the work reported was performed on a single ingot of high purity 7075 alloy. The ingot was 4 in. by 4 in. by 8 in. high, uni-directionally solidified following a procedure previously described.5 The mold was heated to 1350°F before pouring the melt. The bottom chill was carbon coated stainless steel. Water was circulated through the chill after the melt was poured. The 7075 alloy was prepared from high purity virgin material (aluminum, zinc, magnesium) and from master alloys (Al-50 pct Cu, A1-15 pct Cr, A1-5 pct Ti). Final measured melt composition (wt pct) was: Zn Mg Cu Cr Ti Fe Si Al 5.70 2.28 1.35 0.18 0.15 <0.002 <0.012 bal Melting was done in a silicon carbide crucible; all tools were coated with zircon wash to minimize iron contamination; degassing was by bubbling chlorine through the melt. che-rmomechanical Treatments. Detailed studies were made on material taken from a location approximately 13 in. from the chill and 51/2 in. from the chill (i.e., from 1 in. thick slices taken between 1 and 2 in. from the chill and between 5 and 6 in. from the chill). Solution treatment was done at 860°F in an air-circulating furnace with a "bottom drop" arrangement to achieve minimum delay time between solution treatment and quench. Samples solution treated in this way were 2 in. by 2 in. by 1 in. Temperature of the quench water was approximately 10°C. Mechanical reduction was by cold rolling. Samples 11/2 and 51/2 in. from the chill were treated for 12 and 24 hr, respectively, before cold rolling. Reduction by cold rolling was then 4/1, 16/1, and 35/1. In each case, several intermediate anneals (1/2 hr at 860°F) were used to permit reaching the final thickness without cracking; two such anneals were used for the 4/1 reduction, five for 16/1, and six for 35/1. After working, materials were again solution treated for various lengths of time from 0 to 48 hr and quenched in water. Structural Measurements. Secondary dendrite arm spacings were measured using procedures previously described.&apos; For each measurement reported, five photomicrographs were first made at X75. Measurements were made of dendrite arm spacings in at least 20 different grains (grain structure was equiaxed). Grain size measurements were made by running a number of random traverses across photomicrographs of the samples and obtaining the mean lineal intercept. Measurement of the volume percent of second phase and porosity was done by quantitative metallography. A two-dimensional systematic point count was used

Jan 1, 1970

By George Simkovich

It was hypothesized that solid-state point defects should alter the flotation properties of solids. Tests conducted on pure AgCl and AgCl doped with CdC12 show that atomic point defects exhibit an important role in the floatability of AgC1. Tests conducted on PbS doped with Ag2s or Bi2S3, also show that the defect structures resulting from these dope additions, i.e., a combination of electronic and atomic point defects, contribute significantly to the flotation of PbS. IT has been established that flotation occurs only when a finite contact angle exists between a solid and a gaseous bubble.&apos; This angle, measured through the liquid phase, is expressed by the equation where the are inter facial free energies and the subscripts S, G, and L represent solid, gas, and liquid phases, respectively. As is seen in Eq. [I] three interface free energies, sG, sl, and GL, enter into the contact angle equation. Therefore, any variation in these energies which sufficiently varies the contact angle will, in turn, vary flotation processes. Changes made in any of the phases concerned, i.e., gas, liquid, or solid phase, are reflected through the changes occurring in two of the surface energy terms. Thus, a change in the liquid composition would be noted in sL and GL, and it is this phase, the liquid, which is most frequently altered in flotation studies., Changes in the solid phase must be reflected through the changes occurring in the sG and sL terms. In particular, it is hypothesized that changes in the surface concentrations of point defects in the solid-phase will alter the sG and sL terms which, in turn, will be reflected by flotation results. As an illustration of this hypothesis one may consider the defect structure and the flotation of AgC1. The bulk defect structure of AgCl is essentially one involving equal number of cation vacancies and interstitial cations.3 Upon adding CdC1, to AgC1, a greater number of silver ion vacancies are created in the bulk of the crystal.4 On the surface of the crystal the smaller binding forces and the free space accomodations may also allow for the creation of "surface interstitial anions", which will be designated as ad-anions. Thus, the point defect structure of the surface of AgCl doped with CdCl, will consist of cation vacancies and/or adanions. If the molecular forces responsible for the surface energies, ?SG and ?sL, are significantly altered by the presence of these surface point defects, then differences in flotation results will be noted as the concentration of these defects is varied. The defects present in AgCl are predominantly atomic in nature. In the case of PbS both electronic and atomic defects are present.5 This compound conducts electrically by either electrons or electron holes depending upon whether excess lead or excess sulfur is present. Upon disolving BiS3 in stoichio-metric PbS, one increases the concentration of cation vacancies and the number of electron carriers in the bulk of the crystal.5" At the surface, the possibility of ad-anions must also be considered. Conversely, upon dissolving AgS in stoichiometric PbS one increases the concentration of interstitial cations and the number of electronhole carriers in the bulk of the crystal.5,6&apos; At the surface the interstitial cations will be designated as ad-cations. Thus, the point defect structure of the surface of a PbS crystal doped with Bi2S3 will consist of a number of cation vacancies and/or ad-anions and an excess of electrons. Conversely the point defects on the surface of a PbS crystal doped with Ag2S will consist of a number of ad-cations and an excess of electron holes. Again, as in the case of AgC1, should the molecular forces responsible for the magnitude of the interface free energies, ?sG and ?sL, be significantly altered by the presence of these surface defects then significant differences in flotation results will be noted as the concentration of these defects is varied. EXPERIMENTAL To test this hypothesis flotation tests were conducted on pure and doped AgCl and on PbS doped with either Bi2S3 or Ag2S. Preparation of the AgCl samples was performed as follows: AgCl and weighed amounts of CdC1, were melted in a porcelain crucible. The melt was then forced through a capillary tube and the particles emitted solidified in air as they fell about 1.5 meters. Spherical particles, -0.50 + 0.25 mm, were separated from the remaining solidified material

Jan 1, 1963

By John D. Roach

DURING an investigation of the yttrium-hydrogen system aimed at producing solid yttrium hydride specimens containing various amounts of hydrogen, it was observed that yttrium containing approximately 2 wt pct H exhibited a tendency to crack and crumble to a powder on standing in air at room temperature. It was also observed that longer hydriding times, at a given temperature, increased this susceptibility to powdering without an increase in hydrogen content, also that moisture in the air is necessary for the observed effects to occur. Even if cracking did not occur, there was a continual formation of a light gray powder on the as-treated surface of the hydrided yttrium and this reaction continues until the entire hydrided piece has been reduced to a powder. Storing the hydrided specimens in the absence of air or removing the surface either by machining or grinding were effective means of preventing this disintegration of hydrided yttrium. In an attempt to determine the reason for this powdering phenomenon, the surfaces of a number of as-hydrided yttrium specimens were examined by X-ray techniques. In all cases the X-ray pattern obtained showed the major phase to be yttrium hydride (YH2) as would be expected since the specimens contained 2 to 2.2 wt pct H. In some cases a trace of yttrium oxide was observed. There was also a third phase present on the surface of these hydrided specimens which could not immediately be identified. This unknown phase was a face-centered cubic material, NaC1-type structure, with a lattice parameter of 4.855 and a calculated density of 5.914 g per cc. Very slight hand polishing of the surface of the hydrided yttrium specimens completely removed both the unknown phase and the traces of oxide so that only the yttrium hydride pattern remained. Based on the X-ray patterns the quantity of the unknown phase on the surface of the hydrided yttrium appeared to be directly related to the susceptibility of the material to powdering. Work at the Denver Research Institute on the yttrium-nitrogen binary system showed that yttrium nitride (YN) is a face-centered cubic material with a lattice parameter of 4.878A and a density of 5.890 g per cc. They also noted that this compound rapidly disintegrated to a powder on standing in air. The unknown pattern observed in the above specimens corresponds very closely to that of the nitride—fcc structure, 4.885 parameter, and density of 5.914 g per cc. The presence of this thin film of nitride on the surface of the hydrided specimens probably accounts for the observed powder formation and crumbling. The nitride reacts with the water vapor in the air (verified by private communication from Dr. C. Huffine, General Electric Co.) to yield yttrium oxide and ammonia. Ammonia is readily detected when hydrided yttrium specimens were allowed to stand in bottled moist air. The powder formed on the surface of the hydrided specimens was shown by X-ray analysis to be yttrium oxide. This reaction appears to occur primarily at the grain boundaries since discrete particles of yttrium hydride separate from the specimens during this powdering process. The reaction of yttrium nitride with water vapor is believed to be as follows: 2YN + 3H2O - Y203 + 2NH3. Despite the fact that this nitride is present only as an extremely thin surface film, if the above reaction is not prevented by removing this film from the surface either by machining or grinding, the reaction continues until the entire hydrided piece has been reduced to a powder. To account for this continuation of the reaction, it is believed that the following reactionalsooccurs: 2YH2 + 2NH3 -2YN + 5H2. The nitride produced by the latter reaction reacts in turn with water vapor. The reaction therefore becomes autocatalytic and continues until the hydride has been consumed and the entire piece reduced to oxide powder. The amount of nitride required to initiate this reaction is quite small and this nitrogen contamination can occur from a number of sources—hydrogen gas employed, minute leak in the hydriding apparatus or even from degassing of the reaction vessel itself. Longer hydriding times increase the possibility of nitrogen contamination and this is especially true when a dynamic gas system is employed in the hydriding process. The production of stable, solid hydrided yttrium is dependent on the complete absence of nitrogen contamination during processing. If such contamination does occur, powdering of the hydrided product can be prevented by removing the nitride from the surface e.g. grinding or by preventing access of air to the pieces e.g. sealing in wax or plastic. The author wishes to express his appreciation to General Electric Co. for sponsoring this research and for permission to publish the results of work under Subcontract AT-93.

Jan 1, 1962

By R. L. Bell, T. G. Langdon

A technique was developed- for determining the grain strain, and hence the grain boundary sliding contribution, occurring during the high- temperature creep of a magnesium alloy, from the distortion of a grid photographically printed on the specimen surface. The results were compared with those obtained from measurements of grain shape, both at the surface and interrwlly, and it was concluded that the grain shape technique may substantially underestimate the grain strain and overestimate the sliding contribution due to the tendency for migration to spheroidize the grains. ALTHOUGH a considerable volume of work has been published on the role of grain boundary sliding in high-temperature creep, many of the estimates of Egb (the contribution of grain boundary sliding to the total strain) have been in error due to the use of incorrect formulas or inadequate averaging procedures.&apos; One of the most easy and convenient measurements from which to compute Egb is that of v, the step normal to the surface where a grain boundary is incident. Unfortunately, this parameter is also the one associated with the treatest number of pitfalls. Values of v have been used to calculate Egb from the equation: egb =knrVr [1] where k is a geometrical averaging factor, n is the number of grains per unit length before deformation, v is the average value of v, and the subscript ,r denotes the procedure of averaging along a number of randomly directed lines. If the dependence of sliding on stress were assumed, it would be possible, in principle, to calculate k from the known distribution of angles between boundaries and the surface. This in itself is difficult because the distribution depends on the history of the surface,&apos; but the problem is even further complicated by the fact that v depends on other factors such as the unbalanced pressure from subsurface grains.3 However, the great simplicity of the measurement procedure for v makes it highly desirable that this problem of k determination should be overcome. In the present experiments, this was achieved by the use of an indirect empirical method in which the grain strain, eg, at the surface was determined by the use of a photographically printed grid. The assumption here is that the total strain, et, is simply the sum of that due to grain boundary sliding, egb, and that due to slip or other processes within the grains, eg. SO that: Et = Eg + Egb [2] Thus k is given by: In practice, it is customary to indicate the importance of sliding by expressing it as a percentage of the total creep strain; this quantity is termed y (= 100Egb/Et). The determination of Eg from a printed grid within the grains avoids the difficulties due to boundary migration which should be considered when the grain strain is calculated from measurements of the average grain shape before and after deformation. As first pointed out by Rachinger,4,5 however, this latter technique has the particular advantage that it can also be applied in the interior of a polycrystal. Recently, several workers have produced evidence on a variety of materials6-&apos;&apos; to support the observation, first made by Rachinger on aluminum,4,5 that 7 can be very high, 70 to 100 pct, in the interior, even when the surface value, determined from boundary offsets, is very much lower.10&apos;11 Although there have been criticisms both of the shortcomings of the grain shape technique&apos;&apos; and of the different procedures used to determine y at the surface,&apos; it seemed important to check whether measurements of sliding by grain shape gave values of y which were truly representative of the material. In the present experiments, grain shape measurements were therefore made both at the surface and in the interior for comparison with one another and with the independent measurements of grain strain using the surface grid technique. EXPERIMENTAL TECHNIQUES The material used in this investigation was Magnox AL80, a Mg-0.78 wt pct A1 alloy supplied by Magnesium Elektron Ltd., Manchester. Tensile specimens, about 7 cm in length, were prepared from a 1.27-cm-diam rod, with two parallel longitudinal flat faces each approximately 3 cm in length. The specimens were annealed for 2 hr in an oxygen-free capsule, at temperatures in the range 430° to 540°C, to give varying grain sizes, and, prior to testing, the grain size of each was carefully determined using the linear intercept method. This revealed that the grains were elongated -0.5 to 5 pct in the longitudinal direction. Testing was carried out in Dennison Model T47E machines under constant load at temperatures in the range 150" to 300°C. At temperatures of 200°C and below, tests were conducted in air with the polished flat faces coated with a thin film of silicone oil to prevent oxidation; at higher temperatures, an argon atmosphere was used. To determine v,, each test was interrupted at regular increments of strain and the specimen removed from the machine. At the lower strains, when v, was less than about 1 pm, measurements were taken on a Zeiss Linnik interference microscope;

Jan 1, 1969

By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p&apos;robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI&apos;U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts&apos; wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.&apos; This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d&apos;~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU&apos;~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968

By R. K. McGeary, B. Lustman

The textures produced in zirconium by cold and hot rolling, and by recrystallization above and below the transformation temperature were determined. Thermal expansivities were measured in the thickness, transverse, and rolling directions of preferentially oriented zirconium and were correlated with the texture scatter in these directions. REVIOUS investigations have indicated that minor differences between hexagonal close-packed metals of similar axial ratio may appear with respect to the textures produced both on cold rolling and on subsequent recrystallization. In the case of magnesium, beryllium, and titanium, metals of axial ratio similar to that of zirconium, the ideal orientations produced by rolling are fundamentally the same, although marked variance is reported in the degree and type of scatter about the mean orientation; in those instances where recrystallization textures were observed, they were reported to be similar to the rolling textures. Measurement of the anisot-ropy of thermal expansion of both rolled and re-crystallized zirconium could not be correlated satisfactorily with the textures reported for the above metals, and therefore a study was made of the preferred orientations produced in zirconium. Reported below are the textures produced in zirconium by cold and hot rolling, and recrystallization above and below the transformation temperature, together with the results of thermal expansion measurements. Determination of Preferred Orientation Two types of zirconium were investigated: 1— "crystal bar" zirconium obtained from the Foote Mineral Co., produced by the thermal decomposition of zirconium tetraiodide, and 2—zirconium ingot obtained from the Bureau of Mines prepared by melting sponge zirconium in a graphite resistor vacuum furnace in a graphite crucible. The major impurities present in the two materials used are listed in Table I. Several of the pole figures were later checked with 0.03 pct hafnium crystal bar material and the results were identical with those to be shown for the 1.5 pct hafnium material. The materials were cold rolled to 0.014 in. in thickness as shown in Table 11. Specimens were cut from the 0.014 in. thick rolled sheets and etched to thicknesses of 0.002 to 0.010 in. Such specimens were used for exposures up to a 50&apos; to 60" angle between the beam and plane of the specimen; for higher angles a wire shape, similar to that described by Bakarian,&apos; was formed on an end of the original 0.014 in. sheet. A fine-bladed abrasive cut-off wheel was used to slot the sheet and to form the cylindrical cross-section. The wire shaped ends were then etched to 0.006 to 0.010 in. in diam. Although absorption of X-rays in the wire-shaped specimens does not vary with angle of rotation, the line width around the diffraction rings was not uniform, because the wire was narrower than the X-ray beam, and this condition caused some uncertainty in the estimation of azimuthal intensities. Furthermore, scanning was not practicable with this type of specimen so that spottiness of the rings due to large grain size was excessive for specimens which had been heated above about 650°C. Nevertheless, satisfactory information could be obtained for high angle exposures from the negatives by the use of both types of specimens. Transmission Laue photograms were taken using unfiltered molybdenum radiation (47.5 kv, 18 ma) and a 0.025 in. pinhole. With the film 8 cm from a 0.005 in. thick specimen exposures of about 30 min were adequate. For specimens with a coarse grain size, a device that scanned about 0.15 sq in. of sheet surface was used. An attempt was made to plot the pole figures by use of an X-ray spectrometer as described by Norton.&apos; However, for the particular technique used, the intensity variations obtained were not considered definite enough to give reliable results, especially for the large grained recrystallized and transformed specimens. This method was therefore abandoned in favor of the standard photographic method. Nine exposures were taken of each specimen: seven exposures with the beam perpendicular to the rolling direction and at 0°, 10°, 20°, 35", 50°, 65", and 80" to the transverse direction, and two exposures with the beam perpendicular to the transverse direction and at 60" and 80" to the rolling direction. Additional exposures were then made where necessary. The intensity variations of the diffraction rings were estimated by eye. It was usually possible to estimate 3 degrees of intensity from the photograms but in some cases 2, 4, or 5 degrees were estimated. Experimental Results The preferred orientation was determined for the following treatments: 1—cold-rolled, 2—low temperature rolled, 3—cold-rolled surface layer, 4— cross-rolled, 5—hot-rolled, 6—recrystallized below the transformation temperature, and 7-—recrystallized above the transformation temperature. I—Cold-Rolled Textures: The slip plane in hexag-

Jan 1, 1952

By B. D. Harden

FOR over fifty years the Spanish mine, 21 miles northeast of Nevada City, in Nevada County, California, has been one of the Bradley properties. Between 1883 and 1889 it was operated by the late Frederick W. Bradley and P. R. Bradley. The ore averaged only about $1 a ton at that time but the mine was credited with a production of about $900,000 in that period. The property was then closed down until 1922, when the Bradley interests reopened it and continued development for the next nine years, when a 50-ton mill was built. This began operation in April, 1931. This was a selective flotation plant, with the tailing treated on Wilfley tables, and operated on ore from the No. 4 and No. 16 tunnel stopes. This ran from $3 to $6 in gold, 2 to 3 oz. of silver, copper 0.6 per cent, lead 1.5,

Jan 1, 1935

By Thomas A. Simpson, Tunstall R. Gray

The Birmingham district first produced steel from Alabama hematite ores in 1899. Since then, the district generally produced more than 6.0 million gross tons of ore a year to the late 1950's. Production has declined since then to an annual rate of about 1.5 million gross tons. Reserves calculated for the district are sufficient to last many years. Mining in the district is now confined to Woodward Iron Company's Vance and Pyne mines. The rocks exposed consist of about 15,000 feet of consolidated Paleozoic sediments with a thin veneer of unconsolidated Cretaceous sediments in the Vance area. The district is characterized by a distinctively parallel and subparallel, slightly arcuate series of faults and joint systems. In view of available information, it seems reasonable to conclude that the Birmingham red ores are of sedimentary origin, modified to a small extent by diagenetic replacement after original deposition.

Jan 1, 1968