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By B. D. Lichter

In a previous paper, Oelsen, Schuermann, and Hey-nertl pointed out the possibility of obtaining complete thermodynamic functions for alloy systems from calorimetric measurements alone. Specifically, if the heat content of a heterogeneous, multicomponent system is known as a function of temperature and composition, then it is possible to derive the heats, entropies, and free energies of formation of liquid phases and of solid intermediate phases of fixed composition. The authors present equations and graphical techniques applicable to eutectic systems and systems with intermediate phases without solid solubility at lower temperatures. eijering has considered possible extension of the treatment to systems with complete solid-state miscibility at lower temperatures; however, experimental difficulties practically restrict the method to systems with very limited miscibility in the solid state. The purpose of this note is to present an alternative derivation of the heats and entropies of formation of liquid phases and of solid intermediate phases from heat-content measurements alone. Fig. 1 shows three types of phase diagram to which the analysis may be applied. If the heat content is determined as a function of composition x, at temperature T, we have quite generally and the heat of mixing of the liquid is obtained directly from heat-content measurements. If the temperature T lies in a two-phase region (solid-liquid) then

Jan 1, 1967

By T. Estelle Gardner

Heat-capacity measurements were made over the range 8° to 350° K on beryllium sulfate dihydrate and beryllium sulfate tetrahydrate using an adiabatic calorimeter. No anomalies were noted in the curve for either compound. Smooth values of heat capacity, entropy, enthalpy function, and free-energy function were calculated from the heat-capacity data at 10° K intervals and at 273.15° and 298.15° K. The entropy values calculated at 298.15° K were 39.01 ± 0.12 entropy units (eu) for the dihydrate and 55.68 ± 0.17 eu for the tetrahydrate.

Jan 1, 1967

By Gordon W. Hines

This paper, dealing with network planning in an industrial complex, discusses the type and size of project that can be handled on a manual basis. After a review of the fundamentals of network planning, and specifically of the Critical Path Method, the author analyses several different types of projects, each with its own characteristics. Some can be handled in conjunction with a computer, but others can be dealt with equally well without one. Among the projects discussed are a blast furnace reline, the installation of a billet mill flying shear, and routine maintenance-type operations.

Jan 1, 1967

By F. V. Shallcross

Physical properties of thin films of CdS and CdSe formed by vacuum deposition onto glass sibstrates have been studied as a function of deposition and processing conditions. The crystallinity and surface features of CdS films were examined using electron microscopy and electron and X-ray diffraction techniques. The films were poly crystalline; the preferred orientation and crystallite size increased with film thickness, substrate temperature, and deposition time. The CdS films consisted primarily of hexagonal-phase material, in contrast to similarly prepared CdSe films which have previously been observed to contain mixtures of cubic and hexagonal phases. As-deposited CdS films showed no major dependence of Hall mobility on crystallite size or degree of preferred orientation. Hall mobility and carrier concentration in CdS and CdSe .films were measured at various temperatures; both parameters increased with temperature and yielded activation energies which depended on fabrication conditions. Surface-desorption phenomena and overcoating of the semiconductor with SiO affected the observed electrical properties significantly. THIN films of cadmium sulfide1,2 and cadmium sele-nide3,4 have been employed by various workers as semiconductors in the insulated-gate thin-film field-effect transistor, known as the TFT. These devices are most commonly made by vacuum deposition of all materials onto an amorphous substrate such as glass. A knowledge of the microstructure and electrical properties of semiconductor layers used in the thin-film transistor is essential in order to form a realistic model for the device and to improve its performance, reproducibility, and reliability. This paper will describe studies of the physical properties of vacuum-deposited CdS and CdSe films prepared under various conditions. Structural characteristics examined in- cluded phases present, crystallite size, nature of preferred orientation of crystallites, surface roughness, and structural homogeneity throughout the film thickness. Electrical properties measured were Hall mobility and conductivity and their dependence on temperature and ambient. Thin-film properties are affected by many fabrication parameters including purity and physical form of evaporant, deposition rate, film thickness, design and temperature of the evaporation crucible, geometry of the deposition chamber, nature of the residual atmosphere, composition and temperature of the substrate, and details of postdeposition processing. PREPARATION OF FILMS In this work the semiconductor films were deposited in a conventional oil-diffusion-pumped system with pressures in the 10-8 torr range. The CdS evaporant was obtained from the Eagle-Picher Co. as a high-purity coarse-grained crystalline powder; the CdSe was a high-purity sintered powder supplied by the Harshaw Chemical Co. The evaporation crucible was a resistance-heated molybdenum-wire basket coated with aluminum oxide and filled with a quartz wool plug at the top. The source to substrate distance was usually 10 cm. This region was enclosed by a Pyrex inner cylinder. The substrate was heated with an overlying Pyrex plate coated with tin oxide. The substrate temperature was controlled using a thermocouple attached to the lower side of the heater. This thermocouple was calibrated against another thermocouple attached to a dummy substrate and by observation of melting points of various metal films deposited in the system. The substrates were polished borosilicate glass plates and conventional glass microscope slides. Substrate preparation included cleaning with an ultrasonically agitated detergent bath followed by isopropanol-vapor de-greasing. Film thickness was measured interferomet-rically during and after deposition. STRUCTURE OF CdS FILMS Structural studies were performed on CdS films using electron diffraction, electron microscopy, and

Jan 1, 1967

By G. J. Biefer

"Fatigue and corrosion fatigue measurements were carried out on five commercially available metals -four steels and an aluminum alloy -which are used as structural materials in mine shaft conveyances. In the corrosion fatigue measurements, drain waters collected in the shafts of three different Canadian mines were used as corrodents. The mine waters had been selected on the basis of their relatively large differences in acidity and/ or composition.It was found that the corrosion fatigue strengths of the four steels were similar, despite their differences in tensile properties, and that the type of water used in the tests had little effect on the results. Mild steel showed the highest and most consistent values of the damage ratio (ratio between the corrosion fatigue and the plain fatigue strengths at 107 cycles). The corrosion fatigue behaviour of the aluminum alloy (ASTM Type 6061-T6) was found to differ markedly in the three mine waters. A high damage ratio (i.e., superior performance) was shown in a mine water in which the corrosion attack was uniform; much lower damage ratios were shown in waters which produced localized corrosion attack. Corrosion rates were too low to be deter-mined conveniently by conventional weight-loss methods, but calculations from polarization curves provided a rapid demonstration that corrosion rates were distinctly lower in the mine water which produced high damage ratios."

Jan 1, 1967

By Rogers F. Davis

This publication has been prepared to supply manufacturers and industrial users a listing of mobile diesel-powered transportation equipment approved or certified by the Bureau of Mines f r use in gassy noncoal mines and tunnels. Testing of diesel-powered equipment is one phase of the Bureau's health and safety program of approval of electrical and diesel equipment designed to prevent explosions, fires, shocks, and toxic hazards in underground mines. In mines such equipment must be used and maintained properly. Manufacturers submit machinery and component parts to the Bureau for study f their design and safety features. Equipment must pass exacting tests and meet strict requirements established through research, development, and experience before the Bureau approves it as permissible for safe use in mines.

Jan 1, 1967

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By Robert E. Barieau

This report describes a method for treating pressure-volume-temperature (PVT) data obtained with a Burnett compressibility apparatus. The method makes use of a general nonlinear least-squares technique developed at the Bureau of Mines Helium Research Center. It is assumed that an adequate functional form is available for the expression of the compressibility factor as a function of either the molal density or the pressure. The functional form of the compressibility factor can be either linear or nonlinear in the parameters to be evaluated. Formulas are given for calculating variances and covariances of all parameters evaluated and for calculating the variance of calculated quantities of interest.

Jan 1, 1967

By the use of flotation tests it was confirmed that there are two functions of oxygen in sulphide mineral flotation. Sized samples of galena and chalcopyrite were sulphidized, washed free of excess sulphide ion, and then contacted with air-saturated water for certain lengths of time. The mineral was then transferred to a sealed laboratory flotation cell containing water with a known concentration of dissolved oxygen. Xanthate and frother were added and flotation continued for 1 min.Both the extent of mineral oxidation and the concentration of dissolved oxygen markedly affected the flotation of galena and chalcopyrite. The response to a change in either variable is dependent on the level of the other, but generally best flotation occurs with the maximum degree of air saturation of the pulp. Galena flotation is hindered by oxidation of the mineral beyond a small threshold amount but a similar effect for chalcopyrite was not observed...

Jan 1, 1967

By Jr. Hill

Laboratory metallurgical treatments of three high-iron bauxite ores from Arkansas were conducted to determine the relative effectiveness of experimental methods for recovering alumina and a commercially acceptable iron concentrate. The standard for evaluating recoveries from experimental processes was the Al2O3 recovery from Bayer digests of the crude ores; recoveries from digestion of the three ores were 74.1, 87.4, and 88.7 percent. Flotation, magnetic separation, or various combinations of digestion, calcination, and reduction-sintering, leaching, and magnetic separation of leach residues failed to produce Al2O3 recoveries as high as the standard. A high-iron-bearing fraction, containing between 68 and 78 percent of the total iron, was produced in a three-phase treatment involving a caustic, lime reduction-sinter of the crude ore, water extraction of Al2O3 from the sinter, and magnetic separation of the leach residue.

Jan 1, 1967

By J. M. Stuve

Standard heats of formation (AH°p) of YbCl3 (c) and TmCl3 (c) were measured by solution calorimetry. Heat of solution data are given for ytterbium and thulium metals and corresponding anhydrous trichlorides in 4.360 molal hydrochloric acid. The derived standard heats of formation of YbCl3 (c) and TmCl3 (c) were -229,370 ±720 and -235,820 ±400 cal/mole, respectively, at 298.15° K. The resulting heats of formation for YbC13 and TmCl3 are about 1 kcal and 6.3 kcal more negative than previously published values.

Jan 1, 1967

By Heinz W. Sternberg

A method for the electrochemical reduction of the benzene ring was developed and applied to the electrochemical reduction of coal. Successive electrochemical reductions of a vitrain from low-volatile bituminous coal in ethylenediamine saturated with lithium chloride resulted in the addition of 53 hydrogens per 100 carbon atoms. Ultimate analyses and pyridine solubility of the vitrain recovered after each reduction showed that hydrogen added at the beginning has a much greater effect on solubility than hydrogen added at a later stage. Surprisingly, the removal of sulfur from the vitrain takes place only after the more reactive aromatic rings are reduced. Nuclear magnetic resonance analysis and average molecular weight determination of the extracts of the reduced vitrain samples, representing about 18 percent of the vitrain, showed that these fractions had 95 percent of their hydrogen content on saturated carbon atoms and an average molecular weight of 800 to 900. A study of the effect of operating variables on current efficiency showed that current efficiency is highest with aluminum as cathode material and with lithium chloride as electrolyte. A substantial increase in current efficiency of difficulty reducible olefinic double bonds was achieved by adding a proton donor. This result is significant in connection with the electrochemical reduction of coal which proceeds from readily reducible aromatic double bonds to difficultly reducible isolated double bonds. It is proposed that reduction is achieved by electrolytically generated and subsequently solvated electrons and hence does not require prior adsorption of the substrate at the electrode surface. This offers a distinct advantage for electrolytic reduction of sparingly or insoluble substrates such as coal.

Jan 1, 1967

By K. S. Lane

The problem of stability of slopes in reservoirs is one of real interest in civil engineering. The problem is whether the valley walls will remain stable or whether they are likely to slide as conditions are changed by storage of water in the reservoir. If major slides are indicated, as on the walls of relatively steep canyons, one must estimate whether they will be so located and of sufficient size as to interfere with operation of the reservoir-as by blocking the outlets, or by displacing sufficient water to over-top the dam in a huge wave. Some cases involve problems in soil mechanics for slides in earth or weaker rock; other locations need the assistance of rock mechanics for slides in harder rock. While this is not a new problem, attention has recently been focused on its importance by the hugh landslide into the Vaiont reservoir in 1963, which claimed the lives of over 2000 people and forced abandonment of the dam and powerhouse. VAIONT RESERVOIR SLIDE Fig. 1 shows Vaiont Dam in Italy which is a double curvature arch, 875 ft high, located on a tributary of the Piave River, north and west of Venice. When completed in 1960 it was the highest arch dam in the world. In 1960 a sizable landslide (some 700,000 cu yd) occurred on the left abutment a short distance above the dam. Following this, the reservoir was held down for construction of a by-pass tunnel through the right valley wall to insure connection with the upper end of the reservoir in event of further slides. In October 1963 a giant landslide occurred on the left valley wall, over a width of some 14 miles (see Fig. 2). Over 300 million cu yd slid into the reservoir, displacing the water and forming a hige wave 700 ft above the top of the dam as it hit the opposite, or right, wall of the valley. The wave then passed some 500 ft over top of the dam, followed down the tortuous winding canyon and debouched into the

Jan 1, 1967

By J. D. Prater, H. R. Spedden, E. E. Malouf

With the expansion of copper leaching of the various mine wastes at the Kennecott properties, additional copper recovery facilities have been required. A research and development program has been pursued to determine a suitable economic approach to the processing of the additional leach solutions contemplated. lnvestigations on laboratory and pilot plant scales covered electrowinning, solvent extraction, launder and vat type cells, activated launders, precipitation drums, and precipitation cones. This paper contains information on the development and use of a new precipitation-cone-type copper recovery plant, which provides many advantages over older systems. The application of research findings to the old art of leaching copper from copper-bearing mine waste has resulted in a significant contribution of copper to over-all copper production. For example, at the completion of the current expansion program at the Kennecott properties in the United States, copper produced from waste dump leaching will amount to about 25% of the total production. Formerly only 2% was derived from this source. This planned expansion of copper leaching focused attention on the problem of developing more efficient methods for the recovery of copper from greatly increased volumes of copper-bearing solutions.1 The detailed investigations which have been made in laboratory pilot plant and plant tests for the recovery of copper from copper-bearing solutions have included electrowinning, solvent extraction, ion exchange and cementation with iron in launders, precipitation drums, activated launders, and precipitation cones. The results of these investigations have led to the development of a new precipitation cone-type copper recovery system providing many advantages over older methods. ELECTROWINNING OF COPPER FROM COPPER-BEARING SOLUTIONS The direct electrowinning of copper from relatively dilute solutions of copper-bearing mine water, namely solutions containing 10 to 20 lbs of copper per 1000 gal, has always been an attractive possibility.2,3 By this method, high-purity copper powder can be recovered with a power consumption of 3.5 kwh per Ib of copper. However, once the solution strength de-

Jan 1, 1967

By J. F. Shultz

The Bureau of Mines investigated the hydrogenation of carbon monoxide and carbon dioxide over Raney nickel catalyst and nitrided fused-iron catalyst using both a single-pass and a recycle system. Activation energy over Raney nickel catalyst is 29 to 32 kcal/mole for synthesis from either CO or CO2, Pressure dependence of the gas conversion is to the 0.3 power for synthesis from CO and to the 0.5 power for synthesis from CO2. Nitrided fused-iron catalysts were tested using high recycle rates and 3H2+lCO, 2H2+lCO, and 1H2+lCO feed gas at 21.4 atmospheres absolute pressure. The relative usage of hydrogen (moles H2 consumed per moles Ha+CO consumed) was larger than in corresponding single-pass tests, and the relative usage of hydrogen approached the feed gas ratio monotonically as conversion increased. Activation energy was found to be 12 or 13 kcal/mole fresh feed gases of 3H2+lCO or 2H2+lCO. For single-pass operation the activation energy under the same conditions was 19 to 21 kcal/mole.

Jan 1, 1967

"Far from being eclipsed by petroleum and natural gas, Canadian coal continues to command wide (and apparently growing) interest.Major R & D investigations are currently heavily oriented toward coal beneficiation (e.g., cleaning and utilization of fines) and toward a broad range of studies on metallurgical coals and cokes. However, active work is also being carried out in the areas of coal geology, mining, transportation and combustion; and, in some laboratories, increasing stress has been laid on developing a number of new, essentially non-fuel uses for coal and coal products.This review summarizes the work of Canadian coal research agencies during 1966 and indicates some of the more important advances made by them."

Jan 1, 1967

By Robert M. Doerr

The purpose of the investigation was to determine the oxidation behavior of selected tungsten-cobalt alloys. Specimens of Wand W-Co containing 0.7, 1.7, 3.4, and 9.7 weight-percent Co were subjected to pure 02 at 1,000° and 1,100° K, and specimens of W-Co containing 29.8 weight-percent Co, at 1,100° K. Reaction kinetics were determined volumetrically. For specimens other than those containing 29.8 percent Co, the reactions proceeded at about a constant rate at either temperature, indicating the formation of a scale of constant protectivity; the reaction rates were essentially independent of the Co concentration. The scales on these alloy specimens consisted principally of WO3 and CoWO4. Specimens of a 29.8 weight-percent Co alloy, consisting primarily of the W6CO7 phase, oxidized with only slight deviations from the parabolic rate law at 1,100° K. The protective scale on these specimens consisted chiefly of Co3O4, CoW04, and W1 8°49; Co3O4 was outermost, and the W18O49 was adjacent to the alloy. The results suggest that the Co-rich outer scale inhibited the inward transport of 0 to an extent sufficient to greatly limit the amount of the nonprotective WO3 formed, so that protective W18O49 formed instead.

Jan 1, 1967

By S. J. Aresco

The Bureau of Mines has been active in promoting the purchase of coal for Government use under specifications that define the requirements in terms of heating value of the coal, expressed in British thermal units, and the composition as shown by proximate analyses. To these, when required, are added the ash-softening temperature, the free-swelling index, and the Hardgrove grindablity index. Under most of these specification contracts the bidders guarantee the quality of the coal, and that guaranteed by the successful bidder becomes the standard of his contract. The deliveries are sampled in accordance with instructions3 issued by the Bureau of Mines; the samples are analyzed in the Bureau laboratory to determine whether the coal is of the quality guaranteed by the contractor; if it is not, a price adjustment is made. Analyses of the delivered coal and tipple samples (samples collected at mine tipples as coal is being loaded into railroad cars or trucks) provide valuable data for use in evaluating future bids. In addition, the continuous of coal as delivered is a check on the practical results obtained in the coal.

Jan 1, 1967

By D. A. Elkins

This report is the second of a series of three that will evaluate, in order, the metallothermic, carbothermic, and electrolytic methods of magnesium production. The historical development of the carbothermic process is outlined. Production costs varying from 38.9 to 21.8 cents per pound of magnesium are estimated for different versions of the process. Additional suggested process modifications are listed. The technical and economic potential of the different versions are compared. Areas deemed most promising for future research on the process are delineated.

Jan 1, 1967

By H. G. Iverson

Solid state reactions of manganese with silica were investigated in high-temperature tests. Reactions of 0.5 to 4.0 moles manganese (Mn) with 1 mole silica (SiO2) at 1,100° C and of 2.0 Mn:SiO2 mole-ratio mixtures at 1,000° to 1,150° C yielded products consisting of a slag phase and a metallic phase. At 1,100° C, the slag phase from reactions of the low Mn:SiO2 mole-ratio mixtures was composed of SiO2 and rhodonite (MnSiO3), and the slag phase from the high Mn:SiO2 mixtures was composed of MnSiOs and tephroite (Mn2SiO4). The metallic phase from the corresponding low Mn:SiO2 mole-ratio reactants consisted of two manganese silicides, Mn5Si3 and Mn3Si; from the high Mn:SiOg mixtures, it was Mn and the manganese silicide (Mn5Si). For the higher mole ratios of MnSiO2 the manganese content in the metallic phase increased, while the manganese and silica contents of the slag phase remained nearly constant. The slags did not contain free or uncombined manganese oxide (MuO). For the 2.5 to 4.0 Mn:SiO2 mole-ratio mixtures reacted at 1,100° C, the maximum quantities of silica reduced and of the manganese in the slag appeared to become asymptotical at about 41 and 48 percent, respectively. A brominating procedure was developed that was highly selective in removing the metallic constituents from the reaction product, leaving the slag phase as residue. X-ray diffraction patterns were obtained on prepared silicides Mn5Si, Mn3Si, and MnSi.

Jan 1, 1967