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By O. R. Morris, G. L. Hawkes

A galvanic cell, using as electrolyte a fused salt solution of calcium carbide and as electrodes carbon and a Fe-C alloy of known composition, has been set up to study the thermodynamics of Fe-C alloys in the temperature rmzge 800" to 1000°C. Time independence and reproducibility of the cell electromotive force were taken as evidence of the reversible behavior of the cell. Carbon was believed to be present in the electrolyte as the so-called acetylide ion, C;-. The plots of the cell electromotive force us temperature for a specific alloy composition were straight lines within the limits of experimental error. The average Partial molar enthalpy of carbon in iron relative to pure carbon was found to be +10,610 i 93 cal per g-atom C. Thermodynamic analysis of the data has led to the following equation for the carbon activity, ac, based upon pure carbon as the standard state: In ac = In Zc + 10,560/RT + (10.02 + 77O/T)ZC - 2.350 where ZC is the lattice ratio [nC/(nF, - nc )] and T is the absolute temperature. This equalion gives carbon activity values generally slightly lower than those from gas equilibration studies reported in the literature. METAL LOGRAPHIC examination of a polished cross section of the steel anode used in the electrolysis studies of fused salt solutions of calcium carbide by Morris and Harry revealed extensive carburization of the steel by the electrodeposited carbon. This carburization was reflected in the variability, with time, of the applied potential to the electrolysis cell, necessary to maintain a constant current density at the electrodes. This observation suggested the setting up of a galvanic cell of the "alloy concentration" type to study the thermodynamics of some metal-carbon alloys. Cells of this general type have been widely used for the study of alloy systems.2 In view of the availability of published data in respect of the austenite phase of the Fe-C system, it was decided to carry out measurements upon these alloys before proceeding to studies of less well documented systems. The galvanic cell may be written: where [C] is carbon dissolved in iron. The electrolyte was a fused salt solution of calcium carbide, containing some 5 to 10 mol pct of carbide. The cell reaction is believed to be: C(s)-[CI [I1 Carbon forms an interstitial solid solution in iron, with the atoms located in the octahedral interstices. In the fcc crystal structure of austenite there is one octahedral interstice per iron atom. Thus, the lattice ratio, ZC, shown by Gurney3 to be the fundamental concentration parameter in the context of interstitial solutions, is given by: where nc and nFe are the number of carbon and iron atoms, respectively. chipman4 has recently shown empirically the advantages of using this concentration parameter instead of the more usual atom ratio or atom fraction. The cell electromotive force, E, assuming reversible behavior, is related to the carbon potential or the partial molar free energy of carbon in the solid solution relative to pure carbon at the same temperature and pressure, GP at the composition ZC, by the equation: where z is the carbide ion valency and F is the Faraday constant. An activity of carbon, ac, in the solution relative to the value of unity assigned to pure carbon, and an activity coefficient, qC , are defined such that: where R is the gas constant and T the absolute temperature. GF is further related to the relative partial molar enthalpy Hm, and the temperature coefficient of the cell electromotive force, (aE/aT)Zc, by the equations: Measurement of the cell electromotive force thus enables calculation of the relative partial molar thermodynamic properties of carbon in iron, if z is known. At E = 0, the solid solution is in equilibrium with pure carbon. More convenient for many purposes is the standard state based upon the infinitely dilute solution, Henry's law. The relationship between the activity coefficient of carbon based upon this standard state, and that based upon the pure carbon standard state, qC , may be obtained by considering the free energy of transfer of carbon from the latter standard state to the former. The relationship is: where +:H is the activity coefficient of carbon in the hypothetical standard state based on a reference of

Jan 1, 1969

By G. L. F. Powell, L. M. Hogan

Large degrees of undercooling have been produced in bulk samples, 400 g, of copper and Cu-O alloys by melting in a slag of commercial soda-lime glass. The maximum degrees of undercooling obtained for copper, hypoeutectic and hypereutectic Cu-O alloy samples were 208°, 218°, and 97°C, respectively. No grain refinement as a function of undercooling was observed for the pure copper samples although in Cu-O alloys there was a marked decrease in grain size at degrees of undercooling greater than 150°C. The grain size change is the result of recrystallization during or immediately following the freezing process. THE first report of a large degree of undercooling in a bulk sample of metal was that by Bardenheuer and Bleckmann1 who produced 258°C undercooling in a 150-g sample of iron by melting in a glass slag. Garbeck2 extended this technique to nickel, cobalt, and copper and reported maximum undercoolings of 220°, 230°, and 60°C, respectively, while Fehling and schei13 undercooled a large number of metals as 2 to 20-g samples slagged in glass. Subsequently, one of the authors4 applied the glass slag technique to bulk samples, -500 g, of silver and obtained a maximum undercooling of 250°C. It was concluded that impurities which normally catalyze nucleation at small degrees of undercooling could be removed by oxidation and solution in a glass slag. Large undercooling of bulk samples of iron, nickel, cobalt, and their alloys has also been reported by other authors.8'10'11 Of the five metals mentioned above, copper was the only one which had not been undercooled by at least 200°C in the form of a large bulk sample. Since copper exhibits high liquid solubility for oxygen, as do iron, nickel, cobalt, and silver, it was considered that a much larger degree of undercooling than that observed by Garbeck for copper should be possible. This was obtained by modification of the technique applied previously to silver and the results of undercooling experiments with 400-g samples of copper form part of this paper. The undercooling behavior of Cu-O alloys was also studied, and the influence of a small oxygen content on the grain structure of undercooled copper was observed metallographically. 1) EXPERIMENTAL The copper was obtained as oxygen-free high-conductivity copper, the major impurities of which were Fe 0.01 pct, Zn 0.015 pct, and Si 0.02 pct. Melting was carried out in an open-ended vertical cylindrical fur- nace wound with Kanthal wire. A schematic diagram of the experimental setup is shown in Fig. 1. The undercooling technique previously used for silver4 involved preoxidation of the samples by melting the silver in contact with the atmosphere. The oxygen content was subsequently reduced by freezing the samples under a glass slag, whereby the oxygen was evolved as gas and the continuous glass cover over the surface prevented re-solution of oxygen when the sample was remelted. Since oxygen is not released as gas when a Cu-O alloy is frozen. the technique had to be modified for use with copper. Also, copper is oxidized during fire refining so that an in situ preoxidation treatment of the samples was not considered to be a prerequisite to large undercooling. Experimentation proved that this supposition was correct. Instead, it was found that care was necessary during melting of the copper under glass to minimize oxygen pickup. Samples of copper weighing 400 g were prepared by adding 50-g pieces of copper to a vitreous silica crucible partly filled with soda lime glass at a temperature of approximately 1000°C. Each piece was quickly immersed in the glass slag and held at this temperature until the oxide coating on the surface decomposed. This change was easily observed and coincided with the formation of gas bubbles in the glass

Jan 1, 1969

The only economically significant deposit of dolomite in New Zealand is at Mount Burnett, in north-west Nelson. The dolomite, associated with marbles and schists, is complexly deformed, and is of Paleozoic age.A very large quantity is present, although the recoverable amount is to some extent limited by the difficult terrain.Physically the quality of the dolomite is excellent. It is a tough, durable, fine grained rock. Chemically it is a little more variable. The range and frequency o~ the more important impurities are illustrated by hlstograms, as is the "dolomite factor"-a measure of the amount of the mineral dolomite in the rock. lbe dolomite factor averages 84 per cent, the remainder of the rock consisting largely of calcite. Quarrying, milling, production, and uses are described. In 1966 production reached 13,250 tons.

Jan 1, 1969

By Robert L. de Beauchamp

The Bureau of Mines reviewed aluminum chloride technology to determine the problems associated with its preparation from minerals, and to ascertain the best areas for research to solve these problems. Commercial AlC13 production processes are described and the ?state of the art? for the preparation of AlC13 from aluminous materials is evaluated. Areas for further research are indicated.

Jan 1, 1969

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,' Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.' In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,' employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,' i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,'' was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

By M. J. Kovalik

Lower Sunnyside seam coal from Utah was blended with various proportions of char and high-temperature coke to improve the quality of the coke obtained from carbonizing this coal. The Hanson 5-pound carbonizer was used as a "screening test" for the larger scale Bureau of Mines-American Gas Association (BM-AGA) tests, which were correlated with industrial production. Eighteen carbonization tests were made in the BM-AGA 13-inch retort, with a coal charge of about 90 pounds; the cokes were evaluated by the standard ASTM tumbler test. Carbonization of blends containing char and coke breeze yielded less fissured and blockier cokes of significantly higher ASTM I-inch tumbler indices as compared with the value for the straight Sunnyside coal. It was found that the simultaneous addition of char and coke breeze yielded stronger cokes than that obtained by the addition of either one of these additives. Addition of a small proportion of Pocahontas No. 3 or Sewell coal to an optimum blend improved the resulting coke strength further.

Jan 1, 1969

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969

By Clarence O. Babcock

Model pillars of limestone, marble, sandstone, and granite with length-to-diameter (L/D) ratios of 3, 2, 1, 0.5, and 0.25 (0.286 for granite) were tested to failure in axial compression to determine to what extent an increase in end constraint increased compressive strength. Adjustable steel rings, mechanically tightened about the ends of test specimens to create a radial prestress of 3,000 or 5,000 psi prior to the application of axial load, increased end constraint more than was possible in previous tests using solid steel rings. (Solid rings, epoxy-bonded to the ends of dogbone specimens, increased compressive strength compared with that of straight specimens without ring constraint.) During the loading cycle, additional end constraint was produced by lateral expansion of the specimens against the rings. The effect of the end constraint was to increase the compressive strength 55 to 58 percent for the shorter pillars of dogbone shape compared with the compressive strength of straight pillars with the same L/D ratios without ring constraint. Most pillars with L/D ratios of less than 2 were made stronger by end constraint. Pillars with an L/D ratio of 3 did not benefit significantly from end constraint. When the results from compression testing of straight specimens of rock in the laboratory are used to design mine pillars in situ, the pillars will be larger than necessary if the horizontal compressive stress is several thousand pounds per square inch greater than that resulting from the weight of the overlying rock alone. The L/D ratio can be increased by a factor of 1.76 for ratios in the range 0.25 to 3 and still provide the same compressive strength. The safety factor applied with straight specimen test results should also be acceptable for use with constrained pillar test results.

Jan 1, 1969

By E. T. Turkdogan

The activity of sulfur was determined as a function of composition of ferrous sulfide by equilibrating with hydrogen sulfide-hydrogen gas mixtures at 670° , 800°, and 900". The present results supplement the available data over the composition range from 36.6 to 39.5 pct S. The X-ray lattice spacing measurements made are in accord with the available data and indicate that the limiting composition FeSl.008 may be taken for the iron-iron sulfide equilibrium. The growth rate of ferrous sulfide on iron was measured by reacting iron strips or blocks in hydrogen sulfide-hydrogen gas mixtures. Owing to the slow approach to equilibrium between the gas phase and the surface of the sulfide layer, The sulfidation experiments were carried out for several days. It is shown that the growth rate ullimately proceeds in accordance wilh the parabolic rate law. From the parabolic rate constants and the thermodynamic data on iron sulfide the self-difiusivity and chemical diffusivity of iron in ferrous bisulfide are evalualed. The self-diffusivity of iron thus derived zs found to increase with increasing sulfur content. THE ferrous sulfide known as "pyrrhotite" is a non-stoichiometric phase having a wide composition range from about 50 to about 58 or 60 at. pct, depending on the sulfur activity. RosenQvistl studied the thermodynamics of this phase over wide ranges of temperature and composition. Hauffe and Rahmel' and Meussner and ~irchenall~ studied the parabolic rate of sulfidation of iron in sulfur vapor. By using markers, these investigators showed that the iron cations were the predominant diffusing species in iron sulfide. This is confirmed decisively by the self-diffusivity measurements of condit4 who showed that the self-diffusivity of sulfur in ferrous sulfide is several orders of magnitude lower than the self-diffusivity of iron. Although much has been learned from these studies about the Fe-S system, further research on this subject was considered desirable for better understanding of the physical chemistry of iron sulfide. This work was confined to the study of the kinetics of sulfidation of iron in hydrogen sulfide-hydrogen gas mixtures. The results of this study are given in two consecutive parts. Part I, the present paper, is on the parabolic rate of sulfidation of iron and the diffusivity of iron in ferrous sulfide. The second paper, Part 11, is on the kinetics of the surface reaction between hydrogen sulfide and ferrous sulfide. EXPERIMENTAL Three types of experiments were carried out: i) equilibration of ferrous sulfide with gas of known E. T. TURKDOGAN, member AIME, is Manager,Chemical Metallurgy Division, Edgar C. Bain Laboratory for Fundamental Research, U. S. Steel Corp., Research Center, Monroeville, Pa. Manuscript submitted March 6. 1968. ISD sulfur potential; ii) X-ray studies of ferrous sulfide; and iii) measurements of the parabolic rate of sulfidation of iron. Equilibrium Studies. About 1 g of iron powder or foil. contained in a small recrystallized alumina crucible ind suspended from a calibrated silica spring, was reacted with a hydrogen sulfide-hydrogen mixture of known ratio until no further change in weight was observed. %hen the gas composition was changed and the new state of equilibrium was established after several hours of reaction time. The composition of the sulfide was obtained from the initial weight of the sample and the weight after equilibration. X-Ray Studies. The lattice parameters of some of the equilibrated samples were determined using the General Electric XRD-5 diffractometer with a cobalt tube (no filter) set at 40 kv apd 10 ma; the CoK, radiation was taken as 1.79020A. Observed 220 and 311 diffraction peaks of silicon served as an internal comparison standard to correct for possible misalignment of the goniometer. The lattice parameters of the sulfide phase were calculated from the corrected Bragg angles of the 110 and 102 peaks. Rate Studies. In the initial experiments attempts were made to measure the parabolic rate of sulfidation by measuring the gain in weight of a thin iron strip, -0.05 cm thick, suspended from a silica spring in the reacting atmosphere. The preliminary experiments showed that this technique was not reliable for the measurement of the parabolic growth rate of the iron sulfide layer. In the subsequent experiments the data on growth rate were obtained by measuring, on a microscope stage, change in the thickness of the sample after reaction for a specified time in a hydrogen sulfide-hydrogen mixture of known sulfur activity. For each reaction time a new sample was used. Precision-machined iron blocks, 0.5 by 2 by 5 cu cm, were de-greased and annealed in hydrogen for several hours prior to the sulfidation rate measurements. The experiments were carried out at 670°, 800°, and 900°C in gas mixtures having the ratios, and 1.0 for periods of times from a few hours up to 8 days. Apparatus and Materials. A vertical globar tube furnace with a 3-in.-long uniform temperature zone was used. The glass tube fittings were fused on the zircon reaction tube, 1.5 in. diam. The temperature was measured with a Pt-10 pct Rh/Pt thermocouple placed in the hot zone of the furnace inside the reaction tube (an alumina thermocouple sheath was used). A separate thermocouple was used for the temperature controller which maintained the furnace temperature constant within about 2°C. Anhydrous liquid hydrogen sulfide and oxygen-free dry hydrogen from gas tanks were used in preparing the gas mixtures by the constant head capillary flow-meters. In all cases volume flow rate was 1000 cu cm per min at stp, corresponding to a linear velocity of about 6 cm per sec at 800°C; under these conditions

Jan 1, 1969

By G. W. Weems

The Bureau of Mines used the Burnett method and apparatus to determine the compressibility factors for helium and carbon dioxide mixtures at 0°, 10°, 20°, 23°, and 35° C and to pressures of 900 psia. Tables of compressibility factors and approximations of the virial coefficients are presented for seven binary mixtures as well as for helium and carbon dioxide. The results compare favorably with existing data.

Jan 1, 1969

By R. E. Siemens

The Bureau of Mines sought to correlate the variation of structure-sensitive superconducting properties with microstructure in selected Cb-Hf alloys and to compare the experimental results with those predicted by the GLAG theory. Alloys in wire and rod form were evaluated by critical temperature, critical current, magnetization, resistivity measurements, and optical and electron microscopy. In the absence of an external magnetic field, the current carrying capacity of columbium was greatly reduced with addition of up to 85 wt pct Hf, but a large increase in Ic occurred for Cb-90 wt pct Hf. Favorable Ic-H behavior was observed in cold-drawn alloys containing 25 and 57 wt pct Hf. Correspondingly, a maximum in Tc occurred at 10-25 and 90 wt pct Hf. Four- or five-hour heat treatment at 600° C resulted in maximum Ic values and maximum hysteresis in magnetization. Dislocation pileup, polygonization, and fine precipitates, responsible for flux pinning, are listed in order of their effectiveness as pinning sites. Sites having an average separation of 1,500 to 3,000 A and a diameter of 1,000 A or less were most effective in influencing Ic-H and M-H behavior. The resistive critical fields increased smoothly to a maximum of 80 k0e between 60 and 65 wt pct Hf. Highfield, mixed state, reversible paramagnetism was observed in some alloys; however, the GLAG theory was in good agreement with experimental results for the majority of the composition range studied.

Jan 1, 1969

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid iron alloys containing chromium and nickel has been measured in the temperature range 1550° to 1700°C at nitrogen pressures to 1 ah. The solubility surface has been determined for the iron corner of the liquid metallic ternary to 21 pct Cr and 11 pct Ni. The nitrogen solubility increases markedly with increasing chromium concentration. The effect of nickel and the bilinear effect of chromium and nickel are less pronounced. The solubility data are presented, and interaction coefficients are determined from them. THE solubility of nitrogen has been determined in liquid Fe-Cr-Ni binary and ternary alloys. The work in this laboratory has been directed toward a relatively limited composition range, that is to 20 pct Cr and 10 pct Ni. Humbert and Elliott1 studied the entire ternary; but their investigation was, understandably, limited in this region. The region considered here is of the greatest commercial interest. Knowledge of the solubility in these alloys is important for accurate control of the nitrogen levels in various stainless alloys. Also, the solution behavior is of theoretical interest because of its deviations from ideal dilute solution rules at moderate chromium levels. The nitrogen solubility in the iron binaries has been reviewed extensively by Pehlke and Elliott,2 particularly with respect to the dilute solution interaction parameters. More recently, there has been some interest in accurate descriptions of solute interactions in non-dilute solutions. Most of the investigators have adopted a power series fit to accommodate any non-linearity of the data. The Taylor series expansion is adopted here, using Scimar's notation3 for the interaction coefficients. An alternate method, instead of requiring higher-order expansions, is to restrict the range of the composition variables. A planar solubility surface may be fitted to the data and its range of validity determined. If the axes of this region are displaced from the usual origin—the solvent pure iron—a change in standard state is required for the solution reaction. The standard state for nitrogen in iron is commonly taken as the hypothetical 1 wt pct solution of nitrogen in pure iron. However, for an alloy of appreciable solute concentration, e.g., 13 pct Cr or 18 pct Cr-8 pct Ni, it would be convenient to use that base composition as the solvent and redefine the solution reaction in terms of that particular solvent. A brief derivation follows, defining the free energy of solution in an alloy solvent. Following the treatment by Darken and Gurry,4 for a nitrogen pressure of 1 atm: N (pure component) = N (1 wt pct in solvent) [l] AG=RT ln100/ wt pct N in solvent Taking this reaction for an alloy solvent less the same reaction for a pure iron solvent the relation between nitrogen in pure iron and an alloy is: N (1 wt pct in Fe) = N (1 wt pct in alloy) [2] AG = RT[ln(wt pct N in Fe) - ln(wt pct N in alloy)] Adding ½ N2(g) to each side and subtracting N (1 wt pct in Fe) = ½N2(g), the total free energy for solution of nitrogen in an alloy, referred to nitrogen at infinite dilution, is given by: ½N2 (g) = N (wt pct in alloy) L3] AG°3 = -RT ln(wt pct N in alloy )PN =1 atm Interaction parameters have their usual meaning when ?G°/RT is differentiated with respect to the proper composition coordinate. If desired, the dilute alloy treatment may be utilized with the new reference composition as the solvent. This has. indeed, been done by Small and pehlke5 in their analysis of nitrogen solution in liquid 18-8 alloys. The Sieverts' technique was used for this investigation on an apparatus previously described.6 The materials used in this program were: Ferrovac-E iron, 99.95 pct, Crucible Steel Co.: chromium, 99.95 pct, Union Carbide Metals Co.; nickel, 99.9 pct, International Nickel Co. Recrystallized alumina crucibles were used with no evidence of crucible-melt reaction. RESULTS The locations of the ternary compositions investigated are shown in Fig. 1. The data of Turnock7 and small8 have been alluded to in other papers.5'6 There were no departures from Sieverts' law observed for

Jan 1, 1969

By G. H. Keith

The Bureau of Mines determined the mechanism(s) involved in observed anomalous changes in mechanical properties of vanadium-base alloys. Tensile properties of electrorefined and commercial-purity vanadium-base alloys containing up to 5 atomic percent molybdenum or titanium were measured between 77° and 673° K. Snoek oxygen and nitrogen peak heights were measured to determine the changes in dissolved interstitial content caused by increasing quantities of solute. In addition, changes in lattice parameter were followed wit: precision X-ray techniques. Softening, observed in alloys containing titanium, is explained by the formation of a second-phase titanium compound with oxygen or nitrogen. However, because of partitioning of titanium between compound formation and solid solution formation, about five times the stoichiometric amount was required for complete reaction. Addition of 1 percent titanium drastically lowered the strengthening due to strain aging, at 673° K, and 2 percent titanium essentially eliminated it. All alloys were ductile at 77° K. Variations in the tensile properties of the molybdenum-containing alloys are explained by variations in the amounts of interstitial impurities present. The molybdenum did not react with these impurities and had no effect on strengthening due to strain aging. Commercial-purity vanadium alloys containing more than 2 percent molybdenum were brittle at 77° K.

Jan 1, 1969

By M. J. Pool, P. J. Spencer, R. V. Miner

The partial molar heat of solution of rhodiunz in liquid lin and Rh-Sn alloys has been measured as a function of rhodium concentration at 700" , 725" , 750" , and 775°K. The values at infinite dilution are very exo thermic, ranging from -29,950 to -28,260 cal per g-atom Rh at 700" and 775"K, respectively. At the solubility limit the heat of solution becomes sharply nzore exothermic and has permitted the liquidus boundary to be accurately established at each temperature. From the measurements in the two-phase region of liquid Plus RhSn, the heat of formation of RhSn,has been determined. A large increase in the heat of formation between 725" and 750°K suggests the possibility of a phase transformation in this compound. V ERY few measurements have been made of the heats of solution of transition metals in liquid tin; yet those values that are available are of great interest because of their very large exothermic nature. For example, the heat of solution at infinite dilution of palladium in tin has been measured as about -26,000 cal per g-atom (625" to 800°~),' while the heat of solution at infinite dilution of platinum is even more exothermic at -28,591 cal per g-atom (914°K).' These values are of the same order of magnitude as the heat of formation of many intermetallic compounds and as such clearly indicate that very strong bonding must exist between the solute and tin atoms in the liquid solutions. Rhodium might be expected to display similar solution characteristics in tin in view of its close electronic resemblance to palladium and platinum. Since no thermodynamic data are available for Rh-Sn alloys, rhodium was chosen as an appropriate solute for further investigation of transition-metal systems with highly exothermic heats of solution at infinite dilution. EXPERIMENTAL The heat of solution of rhodium in dilute Rh-Sn liquid solutions was measured as a functlon of rhodium concentration at 700°, 725", 750°, and 775°K. The liquid-metal solution calorimeter used in this work has been fully described elsewhere. At the start of each series of measurements, the solvent bath consisted of about 0.5 g-atoms of 99.9+ pct pure tin. To this was made a number of small rhodium additions, about 0.0005 g-atoms each, and the heat of solution was measured for each. Rhodium of 99.9+ pct purity in powder form was used in order to promote rapid dissolution in the liquid tin. The powder specimens were contained in tin foil stated to be purified (lead-free). This foil was found to have no measurable heat of solution in pure tin so the effect of any impurities could be neglected. The energy equivalent of the calorimeter was experi- mentally determined by dropping tungsten and/or tin specimens at intervals during each series of rhodium drops. The tungsten and tin used were 99.95 and 99.999+ pct pure, respectively. The only heat effect due to a tungsten drop, or a tin drop at low rhodium concentrations in the bath, is the sensible heat of the specimen. The heat content of these materials is well-established and is presented in the compilation of Hultgren et al. 4 As the rhodium concentration in the tin bath increases a small heat effect arises from the reaction: Sn (liquid, T) — & (soln, T) where T is the temperature of the tin bath. Where necessary, this heat of solution of tin was determined by Gibbs-Duhem integration, and corrections were made to the heat effect of the tin calibration specimens and the tin foil containing the rhodium specimens. RESULTS AND DISCUSSION The calculated values of the heat of solution of rhodium in dilute Rh-Sn alloys as a function of composition are shown graphically in Fig. 1. The values have been corrected for the sensible heat of the specimens, initially at 273"K, and apply to the reaction:

Jan 1, 1969

By R. M. Douthwaite, G. Birkbeck

The effect of grain size and specimen dimensions on the occurrence and magnitude of a yield point drop in pure iron has been examined. The tests were done at room temperature. The results indicate that gain size is the critical factor determining whether a yield drop occurs. The specimen diameter:gain size ratio does not influence the magnitude of the yield drop for the range of gain size and specimen diameters investigated. HUTCHINSON,' petchY2 and worthington3 have investigated the grain size dependence of the upper yield stress (uUYP) and the yield point drop, ouyp - aLYP, in Armco iron, mild steel, and Si-Fe, respectively. These authors used center-annealed wires to avoid stress concentration from specimen shoulders and to ensure uniformity of the applied stress. Coarsegrained specimens show no yield point drop; the yield point drop then increases as d-'I2 increases (where d is the grain diameter). These results can be understood in terms of Petch's analysis2 in which the magnitude of amp depends on the strain rate in the (limited) number of grains deforming plastically at the upper yield point. If N grains per unit volume are undergoing plastic deformation, the strain rate in the deforming grains is l/Nd3 times higher at the upper yield stress than when the whole specimen deforms homogeneously. If N is constant and independent of grain size at uUyp, then all the grains are deforming when ~d~ = 1, so there is no yield point drop. At finer grain sizes, the yield point drop is given by: where AU, is the friction stress increase corresponding to a tenfold strain rate increase. Christ, Smith, and Burton studied the upper yield point in 0.050-in.-diam wire specimens prepared from zone-refined iron. Each end of the 2; -in. specimens was soldered to a & -in. diam steel ball and the load applied through the two balls. There was a yield point drop in specimens with grain diameters less than 0.1 mm; no drop was observed in specimens of grain diameter greater than 0.1 mm that were free from veining substructure, but specimens of grain diameter 0.129 mm, annealed in the y range, showed an upper yield point. and this was associated with the presence of a veining substructure in these specimens. Christ et al. suggested the upper yield point occurs when more than a specific number of grains fill the specimen cross section so a multiplicity of slip is required to initiate plastic deformation. Table I summarizes the published data on the grain size at which the yield drop disappears. On the basis of this data the ratio of specimen diameter:grain diameter = 5 to 27 appears to be the critical value for the occurrence of a yield point drop. Thus, petch2 interprets the appearance and magnitude of the yield point drop in terms of the limited number of grains deforming plastically at uuyp, whereas Christ et a1. consider that the occurrence of the yield drop depends on the ratio specimen diame-ter:grain diameter. The published data cover a wide variety of materials so some variation between the results is to be expected, but the size range covered in the data of Table I is rather limited. In an attempt to discover whether the specimen diameter:grain size ratio or the grain diameter is critical in determining

Jan 1, 1969

By D. H. Desy

The Bureau of Mines studied the properties of copper that had been oxide dispersion-strengthened with 2 vol pct of either yttria or alumina. Compounds of copper and aluminum or yttrium, coprecipitated from aqueous solution, were converted to oxides; the copper was reduced, compacted, sintered, and extruded. For the resulting copper-dispersoid composites, room temperature tensile properties after annealing in hydrogen, elevated temperature tensile and stress-rupture properties, and electrical conductivity were determined. Compared with oxygen-free copper, copper-2 vol pct alumina or yttria had improved strength after annealing between 400° and 1,000° C, and improved elevated temperature strength, with little loss in electrical conductivity.

Jan 1, 1969

By Andrew J. Freyman, Graham T. Armstrong

"In September, 1968, a survey of operating mines in the Yukon and the Northwest Territories was undertaken to determine the role of Indigenes (Indian, Metis, Eskimo) on the mines, and the attitude of mine management to these employees. The operating mines in the Territories had (at that date) a total employment of 2,002 men, of which 91 (4.5 per cent) were Indigenes. Indigenes make up 45 per cent of the Territorial population (18 per cent in the Yukon and 63 percent in the Northwest Territories). The paper documents some of the problems associated with indigenous employment in mines. A study was undertaken to determine the role of Indigenes (Indians, Metis, Eskimos) in operating mines in the Yukon and in the North-west Territories. In addition to the mines north of the 60th parallel, the experience of several other Canadian mines was examined. The general picture obtained is considered to be representative of the Canadian mining industry."

Jan 1, 1969

By A. J. Mortlock

Cobalt and nickel have been diffused at tracer concentrations in gold at several temperatures in the range from approximately 700° to 950°C. The diffusion penetration profiles were determined by a serial sectioning technique in which the gold is first anodized and then the anodic layer is dissolved in acid. In this ulay sections as thin as 250A could be removed reproduci-bly. In all cases, the region close to the specimen surface was characterized by irregular behavior in the sense that the logarithm of concentration was not linear in the square of the penetration distance. In sotne cases, there zuas an indication of the operation of very slow dijfusion in this region, while in others the apparent diffusion coejj'icient was negative. Possible reasons for this anomalous behavior are briefly discussed. In recent years it has been found that the region close to the surface of a metal can sometimes exhibit anomalously slow diffusion characteristics relative to the interior of the metal. One of the best examples of this fact is the work of Styris and omizuka,' who showed that the apparent diffusion coefficient for zinc in the region withi: about 1 p of the free surface of copper was about ,,,, that at deeper penetrations. This result is particularly interesting, because it is free from the possibly complicating effects of low solubility of the diffusing tracer in the solvent metal. In the case of diffusion under conditions of low solubilitjr, interpretaticn of the results in terms of lattice diffusion is difficult because of the enhanced short-circuiting produced by segregation to dislocations.2'3 Measurements by Duhl et 1. suggest that cobalt diffusing in gold may also show a near-surface effect of this type. Once again the solubility is high, so that this result could be of great interest. However, the technique used for analyzing the diffusion penetration zones by Duhl, viz. the counting of residual gamma activity in the specimen following sectioning, appears to have indicated a near-surface effect in a parallel experiment on the self-diffusion of gold reported at the same time. The latter result is known to be spurious, since Kidson5 has demonstrated that self-diffusion in gold does not show this effect. Duhl et 01. also reported some measurements on the diffusion of nickel in gold, but failed to give any data for the near-surface region. As the solubility of nickel in gold is high, such data would also be of special interest. We, therefore, decided to conduct another set of experiments on the diffusion of nickel and cobalt in gold, using a sectioning technique that allows the individual sections to be assayed for solute content and thus gives direct determinations of penetration profiles. Also, by sectioning with an anodizing/stripping tech- nique, very thin layers can be removed and the region close to the surface studied in detail. MATERIALS The gold specimens were supplied as single crystal disks $ in. in diam by a in. high by Monocrystals Co. of Cleveland, Ohio. The gold itself was of spectro-scopic purity, i.e., better than 99.99 pct pure. METHOD Specimen Preparation. One flat end face of each gold crystal was spark planed with a Servomet spark erosion machine set for minimum spark energy. Following this treatment the crystals were preannealed for 2 to 4 days at temperatures of either 400" or 700°C. The three crystals preannealed at 700°C showed signs of recrystallization. The spark-planed end face of each crystal was then coated with the appropriate amount of 63i or 60 radioactive tracer. This deposit was laid down in a simple plating bath containing the as-supplied solution of the radioactive isotope as well as sufficient ammonium oxalate to saturate the solution. Some ammonium oxalate remained undissolved on the floor of the bath for this purpose. During plating further additions of ammonium oxalate were sometimes required to allow the plating to continue satisfactorily, perhaps due to passivation of the undissolved oxalate already present. The thickness of the deposited layer was determined by comparison of the apparent surface activity of the plated specimen with that of a similar specimen having a weighable deposit of the isotope on its end face. Correction for self-absorption of the radiation was made in this calculation. Annealing. The deposited crystals were annealed in a hydrogen atmosphere in sealed silica tubes. During this heat treatment they were supported, active face down, on optically flat silica plates. The temperature was measured with calibrated Pt vs Pt-10 pct Rh thermocouples, and the tabulated values can be taken to be correct to Z°C. All the crystals showed evidence of recrystallization following these heat treatments, suggesting that initially they may not have been good single crystals or had suffered strain during delivery. Concentration Profile Analysis. After annealing, the crystals were sectioned by the anodizing-stripping technique.6 The anodizing involved suspension of the specimen with its cylindrical axis horiz6ntal by a gold wire in a 200-ml beaker containing 1 M Hg304. A cathode in the form of a strip of gold sheet, 2 in. wide and positioned to be in contact with the curved side of the beaker, completely encircled the specimen. An anodizing current of 30 ma, corresponding to a current density of 5 ma per sq cm on the surface of the specimen, was passed for times ranging from 5 to 150 min depending on the thickness of gold to be removed; the solution was stirred continuously during this process. Following this treatment, the specimen

Jan 1, 1969

By G. W. Neumann

"In order to avoid pollution of water in Flemming Brook and Little River, which drain the area in which the Brunswick No. 12 Mine and Concentrator are located, the company has gone to considerable expense in preparing tailings storage and effluent setting ponds. The attached drawing gives a plan of the six settling ponds together with elevations of the dikes and the effluent weirs.All original dikes for the six ponds were constructed from humus-free clay and rock material, which was obtained, preferentially, by excavating from within the dike area. Run-off water, precipitated on the outside slopes of the dams will drain off without contacting the tailing material. A ditch was made north of the dam site to deflect surface run-off to the east into a branch of Flemming Brook.A secondary dike, made from tailings, has recently been erected on No. 1 and No. 2 tailings pond inside and above the earth-filled dike which serves as a roadway. Run-off from the tailings dikes will be retained inside the ponds by ditching between the roadway and tailings dike into ponds 4 and 6."

Jan 1, 1969

By A. Karim, T. G. Langdon, C. Y. Cheng, J. E. Dorn

The effect of changes in temperature and stress on the creep behavior of Fe-4 pct Si was investigated over the temperature range from 650° to 1175K Over the temperature range of 799° to 110l°K, the shear strain rate, ?', obeys the relationship: where K is a constant, 7 the applied shear stress, G the shear modulus, g the free activation energy for diflusion, R the gas constant, and T the absolute temperature. The results strongly suggest that the creep in this alloy is controlled by a dislocation climb mechanism. In a recent investigation, Ishida, Cheng, and Dorn1 observed that the apparent activation energy for creep of a! Fe from 480" to 775°K corresponded to that for self-diffusion. Over the magnetic transformation range (775" to 1045"K), the apparent activation energy for creep increased steeply with increasing temperature in agreement with the known decrease in the free activation energy for self-diffusion. Passing through the Curie temperature, the apparent activation energy decreased abruptly following which it then increased mildly as the temperature further increased. Inasmuch as the apparent activation energy for creep of a! Fe below the Curie transformation range of temperatures appeared to decrease with increasing values of the stress, the data were analyzed in terms of a model based on the nonconservative motion of jogged screw dislocations. But since the observed creep rate was much higher than that which could be accounted for on the basis of usual models, the authors found it necessary to assume that pipe diffusion became significant over the lower temperature range. Furthermore, the abnormally high activation energy for creep above the Curie temperature was attributed to grain boundary migration which became prevalent in this temperature range. It was thought that a number of the interesting issues that arose in the creep of a Fe might be resolved by investigating the creep of Fe-4 pct Si alloy: This alloy has about the same Curie range and therefore should give creep results that closely parallel those for a Fe and in this way provide comparable data for analysis of creep mechanisms. Furthermore, it can be annealed at higher temperatures which could provide some stabilization against grain boundary migration. In addition, it might serve to illustrate the possible effects of short-range ordering on creep.

Jan 1, 1969