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1. Mining to prevent and control underground acid formation should begin with education imparted through: (A) Course work at mining schools to teach prospective engineers. (B) Training of engineers presently employed in the mining industry through appropriate mining extension courses. 2. Considerable need exists to devote more attention to: (A) Hydrogeologic studies of mining areas to enhance the planning of new mines and the abatement program of existing mines. (B) Additional research to explore methods of dewatering the strata associated with mining areas. (C) Further effort to develop sealants for preventing contact between water or oxygen and the acid producing material associated with the coal seam.

Jan 1, 1970

By [Dipl. -Ing. ] Karl Angerer

The "New Austrian Tunneling Method" is one of the most significant developments in European tunneling in the last 15 years. I hope this report will show the significance of this tunneling method, which was developed in Austria exactly 18 years ago and which is now used in many European countries. In Austria from 1948 to 1953, the Moll tunnel with a length of 11.6 km (about 7.3 miles) was constructed as a part of the Kaprun power plant. Depth of overburden varied from 1000 to 1400 m, and there were many rock bursts in calcareous-schist formations. Here for the first time it was found that a thin concrete lining would help to prevent rock bursts if it was sprayed on the rock soon after blasting. During construction of the Prutz-Imst tunnel in Austria from 1953 to 1956, the shotcrete lining was sprayed on the phyllite surface a certain distance behind the blasting face to prevent rapid rock decomposition. This method was also tried in soft-rock sections of the tunnel where steel and wood supports usually were necessary. To prevent loosening of the rock, application of the sprayed concrete was tried immediately after blasting. This method made it possible to tunnel through very soft ground. Where necessary, the shotcrete was supplemented by steel arches and mesh reinforcement. At that time (1953-1956), the machines and equipment for guniting or spraying concrete were being improved rapidly and it became possible to spray aggregates up to 25 mm in diam. Hardening accelerators brought quicker strength and better adhesion of the shotcrete-this also made it possible to use the method in wet tunnels. If the tunnels are extremely wet or flowing with water, it is necessary to seal off the wet rock or drain the water, using, for instance, the Oberhasli method. After these first successful steps with the new Austrian method, large portions of the Schwarzach power plant in Austria were designed and built. At this operation, shotcrete was used almost exclusively for tunneling work. It was on this site where, for the first time, a tunnel 120 m long with a 45-sq- m section was driven through overburden without one piece of timber

Jan 1, 1970

Jan 1, 1970

By Y. C. Liu, G. A. Alers

The effect of rolling reduction on the textures of Cu-A1 alloys has been investigated both by pole figure and by modulus methods. In alloys which exhibit complete copper or brass types of rolling texture, the rolling reduction has little effect on the texture except to increase the degree of preferred orientation. In alloys which exhibit a transition texture, however, increased rolling reduction increases the amount of brass-type texture at the expense of the copper-type texture. The present experimental results show that there is no one-to-one correspondence between the SFE and the rolling texture of fcc metals. Additional data taken from the literature for fcc metals also support this conclusion. On the other hand, the present and previous experimental results are shown to be in good agreement with the suggestion that the texture transition occurs at a critical value for the separation distance between two partial dislocations—a consequence of the "dislocation interaction" hypothesis for texture. formation. This critical separation occurs when the parameter .r/ub is 3.75 x 10'3. From this, a value for the SFE of 39 ergs per sq cm may be deduced for a Cu-2.85 at. pct A1 alloy. ThE correlation between the rolling texture of fcc metals and the stacking fault energy, SFE, was one of the first attempts to relate atomistic properties with the type of rolling texture.' This correlation gives a qualitative explanation for the experimental observation that the addition of alloying elements, which generally lower the SFE, changes the copper-type texture to a brass-type texture. The simplicity of this correlation had led to its general acceptance and even its quantitative use.' However, it is only a correlation and is largely based on descriptive features of pole figures, and on the poorly known SFE values in dilute alloys. Quantitative verification of this phenomenologi-cal correlation is, in fact, completely lacking. One purpose of the present study is to test this correlation. Another atomistic description for the formation of rolling texture is the "dislocation interaction" hypothesis of texture formation.3 In this hypothesis, the factor controlling the type of rolling texture depends on whether or not the separation distance between two partial dislocations exceeds a critical value. Materials having a separation of less than the critical value are supposed to exhibit a copper-type texture while those with a separation above the critical value are supposed to have a brass-type texture. At the critical value, it is expected that the material should show equal amounts of copper- arid brass-type orientations in their textures, i.e., a 50 pct transition texture. The SFE appears in this hypothesis as only one of several factors which determine the separation distance between partial dislocations. It is possible to test the validity of these two concepts by studying the rolling texture as a function of rolling reduction. Since the SFE per se is an intrinsic property of the metal, it should not, by definition, be influenced by local irregularities, such as variable stress conditions. Thus, no change in texture-type is expected to occur with changes in rolling reduction. On the other hand, according to the "dislocation interaction" hypothesis, any factor that effectively influences the separation distance of partial dislocations would be expected to change the rolling texture. Since the separation distance between partial dislocations is known to depend upon local stresses,4-6 it is anticipated that there would be an effect of the degree of reduction on the texture-type. Also, since applied stresses are more likely to increase, rather than to decrease, the separation between partials,4'5 the overall effect would be to increase the amount of material in the brass-type orientations as rolling reduction is increased. Furthermore, this reduction dependence would be most prominent in alloys exhibiting the transition texture since the distance between partials in those alloys is thought to be close to the critical value. Experimental data in the literature is insufficient to distinguish between these two alternatives. Haessner studied the effect of rolling reduction on textures in a series of Ni-Co alloys by means of the X-ray intensity-ratio technique,' and found that while one texture parameter indicated no reduction dependence the other indicated a slight dependence of the rolling texture on reduction in the range of 96 to 99 pct. As has been noticed previously, the intensity-ratio technique is a convenient but controversial method7 because there is no a priori reason to suggest which intensity-ratio would describe the texture most meaningfully. A more quantitative method of describing textures is found in terms of the orientation dependence of Young's modulus. Here, the type of modulus aniso-tropy associated with the copper-type texture is sufficiently different from that observed for the brass-type texture to allow the two types to be easily distinguishable and a quantitative measure of the amount of each can be deduced from the numerical results. This ability to provide quantitative data is particularly valuable when the two textures occur simultaneously in one alloy as is the case for the transition textures. In this paper the modulus method, supplemented by pole figure data, is used to look for an effect of roll: ing reduction the texture. Also by combining the texture measurements with recent determinations of the SFE in Cu-A1 alloys'0'" it should be possible to test for a relationship between the SFE and textures.

Jan 1, 1970

By Alfred E. Schwaneke

The surface tension from 240° to 844° C and the density from 236° to 583° C of 99.999 percent purity liquid tin has been measured using the maximum-bubble-pressure method. Results for surface tension (y) show y (dynes/em) = 566.84 -4.76 X 10-2 T (° C) with a standard error of 1.9 dynes/cm. Results for density (p) show p (g/cm3) = 7.16 -6.3 X 10-4 T (° C) with a standard error of 0.012 g/cm3. Comparisons with other data found in the literature are discussed. The experimental results are considered to be as good as any data presently available.

Jan 1, 1970

"Quiet, please!" is the newest directive being thrust at industry by guardians of the environment-with good reason. In countless cases, industrial noise is literally deafening its listeners, and sooner or later the volume must be turned down. Noise control is already mandatory for many companies under a Federal regulation that went on the books when the Walsh-Healey Act was revised last May 20. The new rules impose specific noise limits on any plants supplying the Government with goods under a contract valued at more than $10,000.

Jan 1, 1970

By Donald R. Johnson

Apparatus providing simultaneous differential thermal analysis, thermo-gravimetry, and evolved gas analysis, has been developed by the Bureau of Mines specifically for thermal study of oil shale and other solid, natural fuels. The apparatus is described in detail, and simultaneous analyses on a single sample of an oil shale mineral, nahcolite, and a thermal analysis demonstration compound, calcium oxalate monohydrate, are presented to demonstrate the instrument's capabilities.

Jan 1, 1970

By R. Cohen-Alloro

Classical apparatus for granulometric separation generally have limited applications which are found either in the level of the size of separation or in that of the accuracy and the efficiency of the separation or in that of the rate of feed. In industrial practice, the classification of the products of coarse dimensions generally poses no problems. On the contrary, the separation of fine particles presents some difficulties, however the apparatus is used (mechanical classifiers, curved screens and sieves, hydrocyclones, etc...). These difficulties are due to hprfections of separation, rather high cost prices, and sometimes large amounts of recycled materials.

Jan 1, 1970

By J. Szekely, P. Tarassoff, N. J. Themelis

In a copper converter air enters the bath in the form of turbulent jets. The interaction of these jets with the molten matte is fundamental to the converting process. In the present study, an equation is derived to describe the trajectory of a gas jet in a liquid. Calculated and experimental results for air jets injected into water are in good agreement. The trajectories of air jets in copper matte are predicted. THE air injected through the tuyeres of a Peirce-Smith copper converter emerges into the bath of molten matte in the form of a highly turbulent jet. The air jets affect a number of chemical and physical processes occurring in the converter: i) Converting Rate. It is generally recognized that the production capacity of a converter is limited by the flow of air which can be injected through the tuyeres and by the oxygen efficiency. In turn, the air flow is limited by pressure drop considerations or by the amount of splashing within the converter. ii) Oxygen Efficiency. This depends on the dispersion of the air jet in the liquid bath, and its trajectory through the bath. iii) Mixing. The jets act as mixing devices by transferring momentum energy to the bath; in this way the heat generated by the converting reactions occurring in the jets is distributed through the bath. iv) Refractory Wear. The proximity of the jets, which are centers of heat generation, to the refractories in the tuyere zone may have an important effect on refractory life. Mixing conditions in the bath will also influence refractory erosion. v) Splashing, and Accretion Build-Up. The energy of the jets is not dissipated entirely in mixing the bath. particles of liquid are carried out kith the gas above the surface of the bath in the form of liquid spouts and droplets. These result in the undesirable build-up of accretions on the converter mouth, and dust losses in the flue gas. Despite the importance of the interaction of the air jets and the matte in a converter, very few studies of the fluid dynamics of converting have been reported in the literature. Metallurgists in the USSR appear to have been more concerned with the subject than their Western counterparts. Deev et al.1 studied the interaction of an air jet with aqueous solutions in a converter model and qualitatively determined the tuyere air velocity and tuyere inclination which produced the most favorable results with respect to good mixing in the bath, and minimum splashing. Shalygin and Meyer-ovich2 also examined the air-matte physical interaction both in models and in industrial converters; they concluded that in conventional converting practice, there was no significant penetration of the air jets into the matte layer, and consequently the converting reactions occurred mainly in a zone adjacent to the tuyeres. The behavior of air jets in a converter bath, and the aerodynamic characteristics of tuyeres are discussed at length in a monograph on converting by Shalygin.3 However, the description of the phenomena occurring in the converter bath is largely qualitative. The side-blown Bessemer converter for steelmak-ing is very similar to the Peirce-Smith copper converter. Among the few investigations of the behavior of air jets in the bath of a Bessemer converter are those of Kootz and Gille4 who studied splashing in the course of an investigation on the effect of blowing conditions and converter shape on nitrogen pick-up in Bessemer steel. They found that during blowing standing waves were formed on the surface of the bath; the amplitude of the waves increased with the depth and angle of tuyere immersion until the whole bath moved backwards and forwards causing heavy splashing. Kazanstev5 used a model of a Bessemer converter to obtain correlations between the axial velocity of a gas jet and distance from the tuyere orifice and the Froude number of the jet. shalygin3 used these results to calculate the horizontal penetration of an air jet in a copper converter; the penetration was defined as the distance in which the axial jet velocity decreased to 10 pct of its initial value. However, the rising trajectory of the jet was not taken into account. In the absence of quantitative information on the fluid dynamics of converting, the design of copper converters has been based mainly on operating experience. Such experience tends to vary widely from smelter to smelter., This is reflected in Table I which is based on data compiled by Lathe and Hodnett.6 Aside from a rough, and perhaps obvious correlation between the total air flow and converter volume, Fig. 1, no pattern emerges from the data. For example, tuyere throat air velocities vary from 215 to 465 ft per sec in converters of the same size, for little apparent reason. The air jet energy input per cubic foot of converter volume, which may be taken as a measure of the amount of mixing in the converter bath, also varies greatly. A recent analysis of converter data by Milliken and Hofinger7 has also revealed unexplained variations in operating parameters. It is believed that by gaining a better understanding of the fluid dynamics of converting a more rational basis may be provided for the design of converters. In particular, it is proposed that if one takes into account the desirable criteria of a high converting rate, high oxygen efficiency and long refractory life, there should be an optimum configuration of tuyere air flow for a converter of a given diameter. The present investigation is concerned with the form and trajectory of an air jet in a converter bath. The general theory of turbulent jets has been expounded by Schlichting8 and Abramovich.9 However, most experi-

Jan 1, 1970

The principal activities of the Bureau of Mines Explosives Research Center during fiscal year 1969 (July 1: 1968, to June 30, 1969) are reviewed in part 1. Part 2 presents short abstracts of the publications issued during this period in the Bureau series and in the outside press. These publications are referenced in part 1 by underlined numbers in parentheses. Other publications, which are not abstracted, are cited in footnotes throughout the paper. ACKNOWLEDGEMENTS The Bureau acknowledges the support received through cooperative agreement in fiscal year 1969 from the Manufacturing Chemists Association. It also acknowledges the sponsorship by the following Government agencies of research conducted during that period: Department of the Air Force, Department of the Army, Department of Health, Education, and Welfare, Department of the Navy, Federal Aviation Administration, National Aeronautics and Space Administration, Space Nuclear Propulsion Office, and United States Coast Guard.

Jan 1, 1970

By F. S. Karn

Conditions necessary to obtain optimum yield of useful products when coal is rapidly heated to extreme temperatures by laser irradiation were determined by the Bureau of Mines. Product distribution and yield were investigated as functions of several variables. Low-rank coals with high-volatile matter gave highest total gas yields. Medium-rank coals gave the highest yields of H2 and CA and low-rank coals gave highest yields of CO and C02. Macerals gave gases of approximately the same composition, but the total gas yield increased in the order fusinite, micrinite, vitrinite, and exinite. Total gas and C2H2 yields varied inversely with particle size. The addition of nominally inert gases such as Ar, He, N2 increased yields of H2, C2H2, and total gas. Metals such as nickel and platinum had little influence on the rate of coal decomposition. Total gas yield increased with total energy of irradiation, and the ratio of C2H2-CH4 increased with concentration of energy. A study was also made of the irradiation temperature, and a material balance was calculated.

Jan 1, 1970

By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By A. Blake Caldwell

The Anaconda Company, an organization of mining people, enters a new world of copper production as it brings on stream its recently constructed Twin Buttes operation some 25 miles south of Tucson, Ariz. Twin Buttes comprises the largest earth-moving task performed in the history of mining. Some people liken this job to moving enough earth and rock to complete the famed Aswan High Dam in Egypt. In all, some 236 million tons of overburden and rock were removed from over the ore deposit.

Jan 1, 1970

By Lennart Wellenius

LAISVALL - ONE OF THE BOLIDEN MINES Until the Aitik Mine (2,000,000 mtpy) started in 1968 the Laisvall Mine (1,200,000 mtpy) was the biggest unit of about 20 producing mines, belonging to the Boliden Company Ltd. As shown in Fig. 1 the mines are spread over a wide area. Most of them are small complex ore mines (50,000 - 300,000 mtpy), for which reason the total mine production does not exceed 5,500,000 mtpy. When our company was invited to present a paper, Laisvall was chosen because it is the biggest European galena-mine in production today. The Laisvall Mine is situated in the county of Norrbotten, Sweden, at the eastern border of the Caledonian mountain-chain. The road distance to Slagnäs, the nearest railway station, is 60 miles. The railway between Slagnäs and BOLIDEN's smelting plant, the Rönnskär Works, is 140 miles long. PRODUCTION STARTED IN 1943 In the Autumn of 1938 a boulder was discovered, consisting of sandstone with galena, on the shore of the Lake Stor-Laisan. The boulder came from an Eocambrian sandstone formation, which is overlain by Cambrian-Silurian rock.

Jan 1, 1970

By Robert H. Merrill, David W. Wisecarver, Raymond M. Stateham

The US. Bureau of Mines, in cooperation with US. Borax and Chemical Corp. and Kennecott Copper Corp., has investigated the use of the microseismic method to evaluate the stability of large, open-pit slope walls. The method is based on the phenomenon that stressed rock normally emits subaudible rock noises, and the number of rock noises per unit time (noise rate) and the magnitude of the rock noises (amplitude) increase as the stresses in the rock approach the failure stress of the rock. Therefore, the detection and recording of those rock noises serve as a semiquantitative method of predicting the incipient failure of rock. This report briefly describes the three different types of micro-seismic apparatus, the procedures, and the results of microseismic investigations in the slope walls of the Boron mine near Boron, CaL, and the Kimbley, Liberty, and Tripp-Veteran open-pit mines near Ely, Nev. Microseismic monitoring within a frequency band of SO to 5000 Hz indicates noise rates in stable, inactive mining areas are between 0 and 10 noises per hour; the rates in stable, active mining areas are between 10 and 50 noises per hour; and the rate in unstable areas is as high as 2500 noises per hour. High microseismic noise rates in the Liberty pit correlate with the time of nearby earthquakes, indicating that the earthquakes affected the slope wall. The results provide evidence that the microseismic technique is applicable to large pit walls, and that the wide-band, wide-range microseismic equipment appears to be suitable for open-pit investigations. The microseismic method is based on the phenomenon that stressed rock normally emits subaudible rock noises, and the number of rock noises per unit time (noise rate) and the magnitude of the rock noises (amplitude) increase as the stresses in the rock approach the failure stress of the rock. Therefore, the detection and recording of those rock noises serve as a semiquantitative method of predicting the incipient failure of rock. The method has been used for many years to detect incipient failure in roofs or pillars in underground mines. In 1963 the U.S. Bureau of Mines (USBM) started an investigation of the microseismic method in large, open-pit slope walls. The purpose of this investigation was to evaluate the method in open-pit slopes where the rock may be fractured and broken and where the size of the rock mass under investigation is much larger than normally encountered underground. In addition, both the stresses in the rock and the strength of rock near pits are lower than usually found underground. Consequently, there was some doubt concerning the feasibility of the method for open pits, and the economics of such an investigation may have been prohibitive especially if large walls had to be monitored with closely spaced geophones. The successful application of the microseismic method to underground operations has improved safety at little, or no sacrifice, to production or extraction ratios. The anticipated reward in open-pit mining would be the improvement of safety with a minimum sacrifice to mining operations. There is also a possibility that the method could be used to optimize the unloading (stripping) of potential failure areas by the removal of intact rock from the slope wall rather than the cleanup of a slide from the bottom of the pit. This report contains a brief description of three types of microseismic apparatus used in four different pit walls, each of which is different in height, slope, rock types, or has different planes of weaknesses, such as faults, fractures, or joints. Because the geologic features of the pit walls are varied and complex, for brevity, this report dwells mostly on the microseismic apparatus, techniques, the rock noise rates, and the slope movements measured at the various sites. PROGRESS AND DEVELOPMENT The microseismic method was developed over 20 years ago; and the method and examples of investigations in underground mines are summarized by Obert and Duvall. 1 In more recent years, the method has been applied in several underground mines, and an in-situ test under controlled stress conditions is described by Morgan and Merrill. 2 Experience has shown that, on occasions, the microseismic noise rate and amplitude reach a peak value and then start to decrease before a failure occurs in an underground mine; on other occasions, the noise rate steadily increases to a maximum at failure. The method has been applied to slopes by Goodman and Blake,3 and by Paulsen. 4 Goodman and Blake found that the noises corresponded with failures in the slope

Jan 1, 1970

By Horst Konig

This paper illustrates that, with the application of new processes, smaller steel plants using local raw materials can be economical and advisable. It also introduces the problems connected with the direct reduction processes, which use non-coking coal or gas as reducing agents, and which are employed in connection with conventional reduction to produce excellent results. Electric smelting is also discussed, and some practical examples of operating plants are given.

Jan 1, 1970

By A. C. Fraker, H. H. Stadelmaier

In the systems Mo-Fe-C, Mo-Co-C, and Mo-Ni-C the phase boumdaries of the cubic Ij carbides were determined at 1000°C and the variation of the lattice parameter with composition was measured. In the system Mo-Fe-C a single ternary carbide, Mo3Fe3C, was observed. In Mo-Co-C and Mo-Ni-C two new n phases of the type M12C were found: Mo6C06C and Mo6Ni6C. At 1000°C they coexist with the M6C phases MO3-4,CO3-2C and Mo3-4Ni3-2C, respectively. Mo3C03C and Mo4C02C are not separate phases but parts of a single M6C phase region, and the same is true of Mo3Ni3C and Mo4Ni2C. THE n carbide structure type has been known since it was determined by westgren' in 1933, yet reliable information on phase compositions of this type is ap-parently scarce. The following selection of suggested formulas illustrates the extent of the confusion con-cerning compositions: W2-3Fe4-3C,1W6Fe6C,2 W2_4Fe4-2C,3 (W,Fe)6C,4 Tj.-W4Co2C and nz-W6Co6C,5 n1-W3Co3C and n2-w4Co2C,5 W3C03C and w6Co3C2,7 MO3Fe3C,8n2-M04Fe2C,9 (MO,Fe)6C,4 MO3CO3C,8 n2-MO4CO2C.9 Many of these compositions obviously overlap, some disagree in carbon content. The use of the designations 77, and n2 is not consistent. There is uncertainty whether two carbides M6C coexist or whether there is only one M6C with a wide range of substitution of one metal for the other. The existence of M12C seems questionable altogether if one ignores the results of a neutron diffraction study of W6Fe6C supporting that particular metal to carbon ratio.'' More reliable information is available for the iso-typic oxides studied by Nevitt,11 Nevitt, Downey, and orris," and Meussner and carpenter.l3 That n car-bides and oxides are structurally identical, particularly with respect to the location of the metalloid atom, has been demonstrated clearly by Stadelmaier and Meussner14 and also by Parthe, Jeitschko, and sadagopan.15 Therefore the present paper, which attempts to establish the phase boundaries of n defini-tively for three carbon systems, has implications for the whole family of filled Ti2Ni types. EXPERIMENTAL PROCEDURE The samples were prepared in two stages. Pellets weighing 3 g were compacted from powders of the elements and presintered in a closed tube of fused silica that had been evacuated to lO-4 mm Hg. This was fol- lowed by arc melting the sintered samples under argon. Remelting the button once was sufficient to produce homogeneous specimens. The metal powders had the following minimum purities in wt pct: molybdenum 99.5, iron 99.0, cobalt 99.7, nickel 99.9, graphite 99.94. Carbon determinations by the gas volumetric method were obtained from thirty-one of the one hundred samples in the annealed condition. They were limited to compositions that were critical to placing a boundary line in the isothermal sections. The carbon losses were comparatively low and averaged less than 1.5 at. pct. For annealing, the samples were sealed in tubes of fused silica evacuated to 10-4 mm Hg. The annealing schedule was 20 hr at 1250°C followed by 150 hr at 1000" ±10°C. For the water quench the silica glass tubes were broken mechanically to speed the quench. The specimens were examined in the as-cast and annealed condition by standard metallographic techniques. Some of the as-cast and all annealed samples were studied by X-ray diffraction using a 114.6-mm powder camera with filtered Co radiation. The lattice parameters of the n phases were determined by graphic extrapolation to 8 = 90 deg on a plot against sin2 8. It is estimated that the maximum error in the lattice parameters is ±0.002A.. The phase fields were determined by the disappearing phase method, relying on X-rays for phase identification and on microscopy to detect small amounts of a phase. RESULTS Pertinent information on the binary side diagrams has been summarized by Hansen and Anderko16 and Elliott17 and will not be discussed further. Photomicrographs documenting the equilibria at 1000°C have been selected to avoid redundancy due to the similarity of the three systems. Thus there will be only one picture showing an equilibrium with Mo2C, and so forth. Molybdenum-Iron-Carbon. An isothermal section of most of the Mo-Fe-C system at 1000°C is shown in Fig. 1. No attempt has been made to distinguish between a and y iron or to determine their phase boundaries. A conspicuous absence is the phase Fe2 1Mo2C6 with the Cr23C6 structure, supporting the suggestion by Krainer4 that it decomposes by annealing at high temperatures. The only ternary phase is found in a narrow range around Mo3Fe3C (MO43Fe43C14). A microstructure with a two-phase mixture of Mo + n is seen in Fig. 2. The variation of the lattice parameter of n with the estimated composition is shown in in Table IA. The phase diagram does not agree with the results of Kuo9 who reported n2-Mo4Fe2C. Our lattice parameter Varies from 11.095A at the iron-rich end to 11.140Å at the molybdenum-richoend of the phase field whereas Kuo9reported 11.26Å for Mo4Fe2C. We are in agreement with the older work

Jan 1, 1970

Jan 1, 1970

By K. Tangri, M. Chaturvedi

On water-quenching from within the (a + ß) phase region Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys can undergo w transfirmation. This transformation has been attributed to the enrichment of ß Zr phase, at the solution-treatment temperature, by the solute atoms. The ß—w transformation is accompanied by a hardening 01 the alloys and in the optimum condition w-bearing specimens of the ternary alloy are about 14 pct harder than those bearing only a' phase. On aging crl reverls thermally to more stable phases, which results in a considerable softening of the specirnens, as follows: w quenched -waged + ß Zr (enriched) waged - a + ß Nb The high-temperature bcc ß Zr in certain zirconium alloys can transform to a metastable w phase which has a primitive hexagonal structure. In the Zr-Nb alloy system w phase has been observed in the composition range of 7 to 15 wt pct Nb by a number of investigators.'-' In this composition range w can form by water-quenching ß Zr or by aging. known as athermal and thermal w, respectively. Hatt and Roberts' have found that thermal w has a constant c/a ratio of 0.622 +0.002 regardless of the composition and tha: the lattice parameters are of the order of a = 5.02A and c = 3.0 ?. The actual lattice parameters depend upon composition and the temperature of aging. The lattice constants of athermal w. however, depend upon alloy composition.3 The presence of w phase in zirconium alloys can cause substantial strengthening which has been attributed as probably due to the coherency between w and parent ß Zr phase. Robinson et al.' found that the presence of w can raise the strength of Zr-5.0 Nb-2.0 Sn and Zr-5.0 Mo-2.0 Sn alloys to about 170.000 psi: however. the ductility is considerably reduced. With the growing use of Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys in the nuclear reactors, and the significant effect of w transformation on the mechanical properties of zirconium alloys studies were undertaken to study the w transformation in Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys. This paper is concerned with the formation and reversion of w phase in these alloys. 1) MATERIALS AND EXPERIMENTAL TECHNIQUES The following two alloys were studied: 1) Zr-2.5 Nb-0.5 Cu (referred to as the ternary alloy): 2) Zr-2.5 Nb (referred to as the binary alloy). The chemical analysis of the alloys is given in Table I. The alloys, in the form of 3/8-in.-diam rods and 1/8-in.-thick sheets, were supplied by the Chalk River Nuclear Laboratories of the A.E.C.L. Initial fabrication for preparation of various specimens was carried out by cold rolling and swaging with intermediate anneals at 1000°C. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-% m of Hg. For optical metallography and hardness measurements disc specimens + in. diam by + in. thick were used. After the required heat treatments the specimens were mechanically and then chemically polished in a 45 pct HNO3, 45 pct H20. and 10 pct HF solution. The hardness measurements on the chemically polished specimens were carried out on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative hardness value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using copper K-a radiations in 114.6-mm-diam camera. Thin films for transmission electron microscopy were prepared by electropolishing heat-treated a by 7 by 0.005-in.-thick strips using a modified Bollmann-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol electropolishing bath was kepl at -5OCC and polishing was done at 5 to 10 v. The thinned specimens were washed in ethyl alcohol at -30" to -40°C and dried between filter papers. The thin films

Jan 1, 1970

By Arnulf Muan, Carlos Landolt

Equilibria involving Cu-Pt alloys, copper oxides, and atmospheres of known ox2gen pressures have been determined at 1000' and 1200 C. The data obtained have been used to calculate activity-composition relations in the alloys. A moderate negative deviation from ideality is found. At high copper concentrations, the results of the present study are in good agreement with those of previous investigators, whereas at low copper concentrations the activities obtained in this investigation are slightly higher than those reported previously. The present study is part of a research program dealing with the determination of phase relations and thermodynamic properties of copper-containing systems at high temperatures. The information available for such systems is very scanty, particularly for copper oxides and their combinations with other oxide components. Platinum is commonly used as a container in studies of oxide equilibria. To evaluate quantitatively the extent of reaction between the oxide and the container, a knowledge of activity-composition relations in Cu-Pt alloys is necessary. Such data are not available for Cu-Pt alloys in the temperature range of particular interest in the present research program, and particularly for alloys low in copper. Studies of various aspects of the systems Cu-Pt and Cu-0 have been reported in previous literature. The system Cu-Pt is known1 to form a continuous solid-solution series above 812.C, whereas ordered phases are present in certain composition ranges at lower temperatures. Thermodynamic data for the system have been reviewed by Hultgren et al.,' who presented free energies of mixing at 65Oo C, mainly derived from electromotive force cell measurements by Weibke and Matthes.3 Enthalpies of mixing at 640°C have been obtained by Oriani and Murphy4 with liquid tin calorime-try. Their results differ considerably from those derived from the temperature dependence of the data of Weibke and Matthes. Thermodynamic data for the disordered alloys have been obtained by Assayag,5 and more recently by Schmahl and Minzl,6 by Myles and Darby,7 and by McCormack, Myers, and Saxer.8 The two latter sets of data7'' became available after the present study was completed. In the system Cu-0+ two oxides are stable at high temperatures, CuO and CuzO+ each having only minor deviations from stoichiometry. Equilibria in the liquidus temperature region of the system Cu2O-CuO have been studied by Roberts and systemsmyth,9'10CuzO-CuO by Vogel and ocher,I1 by Osterwald,12 and recently the the present authors.13 The system is of the eutectic type with a eutectic temperature of 1083.C The composition of the eutectic liquid corresponds to Xcu0 = °.44, and the oxygen pressure of the coexisting gas phase is Po2 = 0.55 atm.13 Equilibrium oxygen pressures for coexistence of solid CuO and solid Cu2O have been determined by Schmahl and Muller,l4 by Gadalla, Ford, and white,l5 by Bidwell,16 and recently by the present authors.13 There is reasonably good agreement among the various sets of data. Free energies of formation of Cu2O(s) from the elements have been derived by Tretyakov,17 by Bidwell,16 by Kiukkola and wagner,18 by Pal'guev and Neuimin," and by Steele and Alcock,20 There is particularly good agreement among the latter three1'-20 sets of data. THEORETICAL BASIS Consider a subsolidus isothermal section of the system Cu-Pt-0, as shown in Fig. 1. Two phase as-

Jan 1, 1970