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By Graham JW, Cullen GV

edicted increase in, Aluminium production and the possibility of a diminishing supply of petroleum coke for anode electrodes in alumina reduction cells makes it desirable to find alternative electrode materials. Brown coal char, with a lower ash content and with an elemental purity similar to petroleum coke, has been produced by leaching in hydrochloric acid, washing with water and charring at 115000. The cost of processing is estimated to be competitive with petroleum coke. Without further processing the bulk density and real density were undesirably low, but. by briquetting the coal before charring and crushing, the bulk density was improved to 92 per cent of the petroleum coke value and the Particle density was improved to 92 per cent of the density of petroleum coke by water-displacement or 75 per cent by mercury displacement. Pre-baked electrodes were prepared from the char alone, mixtures of petroleum coke and char and from petroleum coke alone, all bonded with coal tar pitch. The electrodes were tested for the usual physical properties and were, evaluated for performance in a laboratory size alumina reduction cell. Electrodes based on brown coal char alone were found to be inferior in physical properties, and performance, but mixtures of the char and petroleum coke, despite poorer density, electrical resistivity and carbon consumption on a theoretical basis, in performance tests gave up to 17 per cent better carbon consumption per weight of aluminium produced and 21 percent better electrical current efficiency than the electrodes based on petroleum coke alone. It is suggested that larger scale tests are warranted.

Jan 1, 1970

By Peter Beardmore, Michael B. Bever

The effects of the temperature of deformation and the degvee of deformation on the annealing spectrum of a Au-Ag alloy have been determined by vesistance measurements. Specimens were deformed in torsion at 4°, 78K and room temperature up to strains nd/l of about 1.0 and were isochronally annealed. Discrete annealing stages similar to those found for pure metals were observed. Stage A occurred below room temperature; the decrease in reszstance associated with this stage increased as the temperature of deformation was lowered or the strain was increased. Stage B manifested itself as an increase in resistance; this is attributed to the restoration of short-range order promoted by vacancy or vacancy aggregate migration. At temperatures above 48S0K, recrystallization or Stage C occurred. Stages A, B, and C in the annealzng curves of this alloy may be considered to correspond to Stages II, Ill, and V, respectively, in the terminology used to describe the annealing spectrum of pure metals. ThE annealing behavior after deformation below room temperature has been thoroughly investigated on pure metals, in particular gold and copper. The occurrence of several discrete stages in the annealing spectrum of these metals has been established, but the interpretation of some of these stages in terms of specific mechanisms is still controversial.' The annealing of alloys deformed below room temperature has been the subject of only a few investigations. In the investigation reported here, a Au-Ag alloy was annealed after deformation at and below room temperature. This continues a research program on the deformation and annealing behavior of Au-Ag alloys.2-8s EXPERIMENTAL PROCEDURE An alloy rod of composition 82.6 wt pct Au-17.4 pct Ag was reduced to wire, 0.0428 in. diam, by swaging and drawing. After a recrystallization treatment, the grain size was 0.031 mm, as obtained from the average linear intercept.7 The ends of wires about 6 in. long were flattened and sealed into short brass tubes with cold setting cement to form the grips of the torsion specimens. The equipment used for deformation has been described elsewhere.6 The specimens were deformed at room temperature, 78", and 4°K to various strains nd/l, where n is the number of turns, d the diameter of the specimen, and 1 its length between grips. The strain rate ?max was 0.1 min-' at the sur- face of the specimen except where noted otherwise. The specimens were annealed isochronally for 30 min at intervals of approximately 30°K from the temperature of deformation to approximately 800°K, except that after deformation at 4°K the lowest annealing temperature was 78°K. A potentiometric method was used to measure the resistance: all measurements were made at 78°K with the exception of some measurements at 4°K mentioned below. Data obtained with a single specimen yielded a complete annealing curve: in several cases duplicate specimens were used to confirm the reproducibility of the curves. Since the surfaces of the specimens were rough after deformation, their diameters could not be measured accurately. The resistance increments after deformation and annealing are therefore reported as percentages of the resistance of the same specimen measured after completion of the annealing, that is, after full recrystallization. The corresponding resistivity values can be calculated by obtaining the effective diameter of a deformed specimen from the ratio of its resistance after recrystallization to the true resistivity, which was determined with a smooth specimen of known dimensions. This method of calculation was used to obtain data shown in several of the figures. RESULTS AND DISCUSSION The isochronal annealing curves after deformation to various strains at 4", 78K, and room temperature are shown in Figs. 1, 2, and 3, respectively. The resistance increment of the as-deformed specimens as a function of strain is shown in Fig. 4. For the specimens deformed at 4°K. values measured at 78°K are plotted with the exception of those for the as-deformed

Jan 1, 1970

"In response to needs created by intensive exploration and accelerating expansion of coal mining in the Western provinces, Canadian R & D on coal is progressively widening its scope. Principal interests continue to lie in coal geology, preparation and processing, carbonization, combustion and transportation, but much active work is also in progress with respect to mine environments, mined-land reclamation, and environmental consequences of coal mining, processing and use. Long-range 'basic' research, which characterized much of the R & D pattern in the fifties and early sixties and which was often no more than an attempt to prevent total extinction of a dying industry, has been somewhat de-emphasized, except insofar as it relates to 'safe' coal storage and to coal-based carbons (which are beginning to command attention as pollution control media).In this review, recent exploration, mine development and new preparation facilities are noted, and current R & D in transportation, processing, handling, carbonization and combustion is summarized. Reference is also made to investigations bearing on non-fuel uses of coal (notably as source-materials for carbons and agrobiological products)."

Jan 1, 1970

Jan 1, 1970

By David L. Holt, Walter A. Backofen, Anwar-uI Karim

Specimens of a hydrided Mg-0.5 Zr alloy were strained in tension at 500°C and constant rates of 2 x10-3 5 x 10-3, and 2 X 10" min-1. Hydride-denuded zones formed at grain boundaries normal to the tensile-stress direction as a result of magnesium transport during difusional flow. The width of the zones could be measured and the measurement used for calculating the diffusional component of the imposed tensile strain. The strain from diffusional flow was found to increase with imposed strain at a diminishing rate, tending to saturate at approximately 12 pct. Strain rate sensitivity of flow stress was low. The apparent non Newtonian character of the diffusional flow is attributed to a non Newtonian process acting in parallel with it which could be boundary shear. Fracture grows out of voids that form in the denuded zones. DEFORMATION of a grain by diffusion of atoms from boundaries stressed in compression to boundaries stressed in tension is Newtonian viscous,1-3 and evidence has accumulated in recent years that such a process may be responsible for the high strain-rate sensitivity of the flow stress of super-plastic alloys.4"7 One piece of evidence is that experimental stress: strain-rate relationships can be quantitatively explained.5-7 There is also metallo-graphic evidence of diffusional flow in superplas-ticity, but in a limited amount. The formation of striated bands on the surface of superplastically deformed specimens has been attributed to diffusional flow.5"7 The basis of that attribution came from experiments on a coarse-grained, nonsuperplastic and hydrided Mg-½ wt pct Zr alloy which formed hydride-denuded, light etching zones at tension-stressed boundaries when strained in tension at 270?C.6 The origin of these zones had already been traced to the diffusional flow of magnesium atoms to the boundaries.' The particular observations in the more recent work were of striated-band formation on the surface and denuded-zone formation internally, with both the bands and zones having the same width and appearing at tension-stressed boundaries. It was argued that the bands were a surface manifestation of the zones and hence of diffusional flow. Of course in superplastic alloys which do not contain internal metallographic "markers", the surface bands can be the only metallographic indication. In the present work, denuded-zone formation was utilized, as it has been by others,9-11 to extend the observations of diffusional flow and to measure the strain, ed, resulting from it. Grain size had to be large to measure ed with accuracy. The grain size chosen for this study was -30 , and with that a strain of 10 pct from diffusional flow produces a denuded zone only 3 µ in width. The large grain size naturally precludes superplasticity. The observations of diffusional flow were complemented by determining the strain from the other operative deformation modes: slip, e,, and grain boundary shear, egb. An incremental specimen extension is the sum of increments from slip, and grain boundary shear as well as diffusional flow. Division by a common length is required to convert to strain. If this length is taken as the initial specimen length, then imposed engineering strain, e, is given in terms of the component engineering strains by e = ed + es + egb [1] Stress:strain-rate relationships are determined by the way in which this "strain balance" is made up. EXPERIMENTAL Material. Zirconium hydride markers were introduced into the Mg-0.5Zr alloy by annealing in hydrogen at 450°C for 30 min. The hydride concentration was particularly high at zirconium rich stringers, which was fortunate in that the transverse boundaries at which denuded zones form lie perpendicular to the stringers. Grain size after annealing was 30 µ. Photomicrographs of unstrained and strained material are shown in Fig. 1. Procedure. Specimens were strained in tension with an Instron machine at crosshead velocities of either 2 x 10"3, 5 x X or 1 x 10-2 in. min-'. Specimen length and diameter were 1.0 and 0.2 in., respectively, so that initial strain rates in tests at constant crosshead speed were 2 x 10"3, 5 x X and 1 X l0-2 min-1. Tests were made at 500°C which is a compromise temperature at which diffusional flow is still measurable but grain growth is not active enough to interfere with metallographic measurements. The tests were made in a hydrogen atmosphere. Strain Balance. An equation additional to [I] is eg = ed + es [2] where eg is strain measured from grain elongation. Measurement was made of ed, eg, and, of course, e, which enabled all the strains in Eq. [I] to be determined. For this purpose, strained specimens were sectioned longitudinally, polished, and etched. The strain from diffusional flow, ed, was computed by measuring on photomicrographs the width in the tensile direction of denuded zones at either end of a grain XI, X2, adding them, and dividing by twice the initial longitudinal grain dimension L0, Fig. 2. Reported values are the results of measurements on seventy randomly selected grains; 95 pct confidence limits on ed were +1.5 pct strain. To measure eg, the maximum length, L, and the maximum width, W,

Jan 1, 1970

By A. A. Rauth

In this paper, the author derives a series of formulas from basic principles and illustrates the application of these formulas to practical grinding charge problems. The paper establishes the nearly proportional relationship of mill power to charge level and shows how this relationship can be used to advantage in the design, manufacture and operation of grinding mills. The procedures outlined offer a rapid means of anticipating the power requirements for a given charge or determining makeup charges for a given power reading. The theories which have been developed concerning the dynamics of grinding have been motivated largely by the desire to derive workable formulas for the accurate determination of grinding mill power. This accurate determination has always been handicapped by the large number of variables to be considered, some of which are mill diameter, length, speed, liner design, grinding charge and material density, volumetric mill loading, internal friction, and charge size and gradation. In efforts to determine mill power, attempts have been made to utilize torque concepts. The formulas derived consider the grinding mass as a rigid body and utilize factors that are based on empirical data so that the movement of the charge within the mill is compensated for. These formulas are of principal interest to the mill designer since he is charged with the responsibility of analyzing all of the variables and from them predicting a mill size and a motor size which are compatible both with each other and with the grinding job for which they were intended. The mill operator, on the other hand, has an entirely different problem. The mill dimensions are already established and so is the driving motor. The operator's main concern is to obtain maximum performance from the mill he already has. For him, the many variables which perplex the mill designer are fixed values. Mill diameter, length and speed are set and, to a large extent, so are the conditions inside the mill from which the torque formula advocates derive their empirical data. It is conceivable that if the major mill dimensions which affect power demand are held constant, and if the variables influencing empirical factors are held fairly constant, as they are in an operating mill, then the only major variable remaining which affects power is the level of the charge itself. Under this condition.

Jan 1, 1970

By H. J. Heinen

Malononitrile [CH2(CN)2J, which forms a carbanion in basic solutions, was investigated as a potential leachant for gold and was shown to be an effective extractant in alkaline pulps. Malononitrile was comparable to equal molar quantities of sodium cyanide (NaCN) in leaching gold from an oxide ore and yielded 10 to 20 percent higher recovery in leaching a refractory carbonaceous ore, although dissolution was slower with malononitrile than with cyanide. Complete recovery of the gold from the pregnant solutions was achieved by coprecipitation with a lead salt on zinc dust; the leachant was shown to be capable of regeneration and recycling a limited number of times. Addition of an anion-exchange resin to the carbonaceous pulp containing malononitri1e increased gold recovery from 67 to 95 percent. Some malononitrile derivatives were also shown to be gold solvents.

Jan 1, 1970

By S. H. McFarlane, K. H. Zaininger, G. W. Cullen, C. C. Wang, G. E. Gottlieb

Heteroepitaxy of silicon on stoichiometric spinel has been studied. Both boron-doped (p-type) and arsenic-doped (n-type) single-crystal silicon films have been grown by the pyrolysis of silane on sioichiometric spinel (MgAl2O4) substrates prepared by a flux technique. The spinel crystals are free from strain and subgrains, and exhibit no thermal instability at temperatures employed for silicon deposition. The growth parameters of epitaxial silicon have been studied. Effects of substrate orientation, surface preparation, and growth conditions on the silicon Properties have been determined. The silicon-spinel composite was characterized by X-ray diffraction, electron diffraction, electron microscopy, and optical techniques. Information on epitaxial orientation relationship, defect structures and film-substrate interface has been obtained. A parallel orientation relationship was found between silicon and spinel. The silicon films exhibit no subgrain structures. However, growth pyramids, microtwins, stacking faults, and dislocations are the prevalent defects. The deformation of epitaxial silicon was measured by an X-ray technique. It was found that the epitaxial silicon is strained under compres-sive stress due to the thermal expansion difference between the film and substrate. The stress was estimated using the classical plate theory and beam equation. Electrical properties of the epitaxial silicon have been measured, including resistivity, carrier concentration, and Hall mobility. MIS and vertical through diffused junction structures have been fabricated wing silicon-spinel composite. Information on MIS characteristics, minority carrier life time, and junction properties has been obtained. THE achievement of single-crystal growth of large area silicon semiconductor films on oxide insulating substrates is of technical importance to many solid state electronic devices. The semiconductor-insulator composite structure is also of scientific interest because the heteroepitaxy is determined by the spatial relationship between the atomic arrangement in the substrate and that of the atoms in the appropriate crystallographic plane of silicon. The degree of crystalline perfection of the silicon deposits depends also on the physical condition of substrate surface. Epitaxial growth of silicon on commercial flame fusion Al-rich spinel (MgO:3.3A12O3) has been reported by several investigators.'-4 The lattice of spinel of this composition is distorted. The material cracks and exsolves the excess alumina in the lattice at temperatures (-1200°C) used in fabricating silicon devices. Stoichiometric MgA12O4 spinel exhibits neither lattice distortion nor thermal instability. Results are given on the epitaxial growth and characterization of silicon on stoichiometric spinel. EXPERIMENTAL Fabrication of Silicon-Spinel Composite Structures. The MgA12O4 spinel substrate wafers were prepared from bulk single crystals grown at about 1200°C by a flux technique5 using a PbF2 flux. The crystals are free from strain and subgrains, and exhibit a typical dislocation density of less than 50 lines per sq cm. The crystals are thermally stable without cracking and exsolution of alumina to at least 1500°C. The spinel crystals were oriented for cutting by the Laue X-ray back-reflection method.6 Substrate wafers (about 25 mil thick) of (Ill), (loo), and (110) orientations have been obtained bu cutting the X-ray oriented crystals using a standard type diamond wheel. An accuracy of better than 1/2 deg is maintained throughout the operation. The spinel substrate wafers were mechanically lapped and polished to produce the flat and smooth surface which is required for silicon epitaxy. Lapping was carried out with about 30-µ boron carbide abrasives to obtain a flat coplanar surface. The lapped surface was further polished using successively finer grades of alumina, ending with the 0.3-µ grade. After polishing the wafers generally have a flatness of ±0.4 µ per cm, as revealed by interferometry. Fig. 1 shows (111) oriented MgA12O4 spinel wafers of various shapes.

Jan 1, 1970

By F. W. Gibson

A detailed description of the smelting and refining operations of the Amax-Homestake Lead Toller's smelter at Buick, Missouri. This is one of two completely new lead smelting and refining operations to go into operation in the United States in over forty years. Incorporated into the operation are the new methods and equipment which have been developed and lend themselves to the particular metallurgy of this plant. The text, as well as the statistical data presented, represent actual current practice after 22 months of operation, and although the metallurgy is considered to be relatively simple, several metallurgical problems unique to Missouri concentrates are discussed.

Jan 1, 1970

By H. B. Huntington

Some of the basic problems in understanding elec-tromigration in metals are discussed, along with the attempts that are being made to handle them. One such problem is the effect of the electrostatic forces. It is now acknowledged that the momentum exchange with charge carriers plays generally a dominant role in the driving force but the question remains to what extent the electrostatic force may still be effective. The electromigration of interstitial impurities is also an area which presents some intriguing questions. For the substitutional impurity, moving by the vacancy mechanism under the influence of an electric field, the correlation considerations are somewhat more complex than have been previously recognized. Another problem of basic importance in the calculution from first principles is the strength of the "electron friction" force, say for a simple one-band metal. A related problem growing out of the preceding is the prediction of the direction of the "electron wind" force for metals with band structure involving both holes and electrons. THE term electromigration has come to be used to describe the flow of matter in condensed phases carrying high electronic currents such as metals and alloys, whereas one usually reserves the term electrolysis for situations where the current is largely ionic, particularly in the liquid state such as molten salts. It follows that the mass transport number in electromigration is always very small, of the order of 10-7. Studies of electromigration date back some 30 years but the modern period would appear to date from the work of Seith and Wever1 who in the mid 1950's first incorporated markers to display mass motion relative to the lattice and first suggested that the direction of the mass flow was primarily determined by the sign of the charge carriers. Since that time interest in the field has grown steadily and more rapidly recently as certain technological applications became apparent. Chief of these is certainly the deleterious effects that electromigration can cause, even at relatively low temperature, to current-carrying elements in integrated circuitry.2 These phenomena have been the subject of intense study and considerable ingenuity. On the constructive side electromigration has proved a useful tool in the purification of certain metals.3 The interest of this paper is, however, centered more on the basic aspects of the subject than on its technological applications. That high electric currents should give rise to mass flow in metals and that the driving force should be more directly associated with momentum exchange with the charge carriers than with the electrostatic field are ideas that no longer cause surprise or particular interest. The field has matured to the point where the general concepts are widely accepted and continued progress in basic understanding rests on more detailed and quantitative exploration. It is the purpose of this paper to point out what are some of the current problems. As a result, we expect to raise more questions than we answer. The first of these will be the role of electrostatic forces, if any, in electromigration. A second section will deal with the electromigration of interstitials. A third and final section treats with electromigration of substitutional impurities or of the matrix atoms themselves. ELECTROSTATIC DRIVING FORCE In the conceptual treatments of electromigration it has been customary to write the driving force in terms of an effective charge number Z* and to divide it into two terms F = e£Z* = e£[Zel- z(pd/Nd)(N/p)(m*\m*\)] [1] The first of these represents the electrostatic force under immediate consideration in this section and the second and usually dominating term for metals arises from momentum exchange with charge carriers, commonly called the "electron drag" term. As can be seen it is set proportional to the electrons per atom, z, and the ratio of the specific resistivity of the moving entity to the corresponding resistivity per matrix atom. The (m*/Im*I) factor takes into account the fact that the sign of the charge carrier determines the sign of the driving force. The specific resistivity of the moving entity is averaged over its path. In the case of motion of the matrix atoms by vacancies this gives rise to approximately one-half the resistivity at the saddle point since the scattering power of the atom at its equilibrium position bordering the vacancy differs only slightly from that of a normal matrix atom. Although the formulation of the "electron drag" term in Eq. [I] is based on a highly simplified model for electron defect scattering, the essential features implicit in the expression are common to all the theoretical approaches that have so far appeared in the literature.4-6 As for Zel, most treatments of electromigration have included the quantity as the parameter which measures the direct interaction of the electrostatic field with the ion and equated it to the nominal valence of the latter. However, there has been considerable discussion whether this interaction may not be 0 in many cases.6 If the moving ion is always enveloped by the same distribution of shielding charge, then clearly its motion will not involve any work done by the electric field and one can expect there will be no electrostatic force exerted on such a neutral composite. From this point of view the shielding charge around the ion would be said to be complete and hence the entity within the Debye shielding sphere would be unaffected by the electrostatic field per se. There is, however, the prospect that, as the moving ion progresses, new charge comes in to participate in the shielding action

Jan 1, 1970

By Freeman Bishop

The first session of the 91st term of Congress became so completely snarled up in economics and politics that no one knows how things will go in 1970 including the White House. Everything from mineral depletion allowances to tax deferments kept the Republican President and the Democratic Congress from settling their differences. But as these reconcilements approach definition, a new battleground develops around the President's authority to make trade and tariff adjustments.

Jan 1, 1970

By F. Daniel Rosenkranz, Peter L. Silveston

Experiments investigating the treatment of a ground wood white water waste from an Ontario pulp and paper mill by an HVCB coal are reported. Adsorption capacity for the waste, with a soluble COD contribution of 2,100 mg/I, amounted to 0.17 per cent, by weight, of the Nova Scotia coal used. Percolation of the white water waste through a coal bed indicated that soluble COD is removed. For finely ground coals, over 90 per cent of the suspended solids in the waste are retained on the coal. Plugging of the coal bed is rapid, so that any treating process using filtration would have to renew the surface of the bed frequently.

Jan 1, 1970

By R. L. Skaggs, R. A. Molsberger

DARKEN1 has pointed out that in most binary liquid metal systems the thermodynamic behavior is relatively simple in the terminal regions. Between the terminal regions. the thermodynamic behavior is more complex. To describe this behavior. he has defined the stability and the excess stability as shown: Qualitatively, an inflection in the free energy of mixing curve results in a change in sign, from positive to negative, of the stability function and is associated with a phase separation. Conversely, a large, positive stability over a narrow composition range is indicative of compound formation. Darken has shown a number of binary systems where the excess stability is constant in the terminal regions and varies sharply in between. The work described in this communication was undertaken to study the variation of stability and excess stability in a binary system as a function of temperature. In addition, this work provides means for the direct comparison of previously existing equilibrium (activity) and calorimetric (molar heat of mixing) data on the Hg-Sn system. Hildebrand2 measured the vapor pressure of mercury over Hg-Sn alloys at 595°K. Calorimetric studies were made by Kawakami3 at 523°K and by Kleppa4 at 423°K. In this work, the equilibrium vapor pressure of mercury was measured over a series of Hg-Sn alloys at 453" and 503°K by use of fused salt manometer with one arm exposed to mercury vapor. Deflections of the fused salt manometer were balanced by argon pressure on the other arm. Argon pressure was subsequently measured with a dibutyl phthalate manometer. Tin activities were determined by graphical integration of the Gibbs-Duhem equation making use of the familiar Darken5 a function. The activities of mercury and tin showed positive deviation from Raoult's law at 453 and 503°K as Hildebrand observed at 595 K. In Fig. 1 are plotted log activity of mercury and tin vs reciprocal temperature. The plot contains activities obtained from calorimetric studies. Hult-gren6 has calculated activities from Kleppa's4 data, and Kubaschewski7 has similarly treated Kawakami's7 data. Presumably. in each case a regular solution was assumed. For regions where a two-phase field

Jan 1, 1970

By J. B. Scott, J. S. Nelson, G. H. Kruse, W. S. Johnson, K. L. Zerneke

The economics of pressure tunnel design emphasize the utmost utilization of the least expensive pressure-resisting material available, namely, the rock surrounding the tunnel. A major difficulty in the design is the problem of transferring internal hydraulic pressure to the rock through a tunnel lining or membrane provided to maintain watertight conditions. The lining is necessary not only to prevent water loss, but to prevent the diffusion of water at high pressure through joints and fractures beyond the confines of the tunnel, an occurrence which could ultimately affect the stability of the rock mass through which the tunnel passes. Because of its toughness and ability to bridge localized areas of weakness, steel is used for a lining material whenever high internal pressures are involved. The steel lining is coupled to the surrounding rock mass through an annular ring of concrete backfill. It is paradoxical that the steel lining, needed primarily to assure water tightness, must of necessity be incorporated into the structure as a major pressure-resisting component, not to augment the bearing capacity of the concrete and rock, but to limit the strain for the safety and preservation of the steel lining itself. With the deformation modulus of the steel so much greater than that of the rock, the liner approaches its yield strength before the load capacity of the rock can be fully mobilized. An economical determination of plate thickness for steel liners is therefore dependent upon measurement of the properties of the surround-

Jan 1, 1970

By William I. Gardner

Optimum design of a structure obviously requires a thorough knowledge of the materials to be utilized in its construction. When the structure is a tunnel, a most important element in its design and construction is the geology. As a tunnel may be many miles in length and at depths of hundreds or thousands of feet, we face a real problem to meet the needs of the designer and builder. How can we determine the properties of our construction materials in this situation? Engineering geology has had a formidable challenge to meet the requirements of conventional excavation methods; the advent of machine methods for rapid excavation compounds the requirements for more detailed and more precise geological knowledge of the tunnel site. This chapter will discuss the means now at our disposal to meet the challenge to produce the required data on the tunnel site in the preconstruction stage. Our considerations will be directed towards construction of a free-flow tunnel, primarily in fractured rock formations, without any requirements for the rock mechanics type of in-situ tests that might be made for a pressure tunnel or for a large opening for an underground power plant. In essence the investigation must determine: (1) The geologic conditions affecting the type of construction equipment and excavation method of the rock to be broken and removed. (2) The quantities of water and gas to be encountered. (3) The strength and stability of the material surrounding the bore and its need for support and lining. GEOLOGICAL FACTORS AFFECTING TUNNEL DESIGN AND CONSTRUCTION The engineer or contractor may classify the rock as either competent or incompetent or more pointedly as "good" or "bad" ground. The geologist may bestow a precise petrographic name upon the rock, such as granodiorite or indurated tuff breccia or name the formation, as Mancos shale, for

Jan 1, 1970

By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.' In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.' This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,' electrochemical potential,8 time lag,' and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda's result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.' MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By R. E. Maringer, B. A. Wilcox, A. H. Clauer, J. H. Sovik

Internal friction measurements from 25° to 1100°C have been made on specimens machined from TD nickel bar. The use of miniature torsional pendulum specimens alloived damping measurements to be made on specimens whose axes were parallel to the original bar axis, at 45 deg to the bar axis, and at 90 deg to the bar axis. There was a marked difference in damping with varying specimen orientation, and this was related to the pronounced micro structural anisotropy of this material. Varying the microstructure by cold working plus re crystallization annealing also greatly affected the damping behavior. Recrystallization essentially removed the broad peak found at 400° to 650°C in as-received TD nickel, and in addition greatly lowered the background damping. DlSPERSION hardened metals such as SAP-type alloys (Al + AI2O3) and TD nickel (Ni + 2 pet ThO2) have been developed primarily to improve high temperature strength properties. There have been numerous damping studies on SAP-type alloys,1"9 and one of these6 showed that the damping capacity was greater than that of 99.5 pet pure Al from 25° to 600°C. Several preliminary observations on TD nickel10 and an experimental Ni-ThO2 alloy11 indicated that here, too, the damping capacity was quite high. A high damping capacity in TD nickel, combined with its relatively good high temperature creep strength, could provide an additional benefit for some high temperature structural applications. This work was undertaken to study the internal friction behavior of TD nickel bar over the temperature range 25° to 1100°C. In Ni-ThO2 and Ni-Cr-ThOz alloys, other properties such as steady-state creep rate,12 creep rupture life,12'13 modulus of elasticity,14 and ultimate tensile strength,14 are sensitive to orientation with respect to the primary working direction. Thus, in order to examine anisotropy effects in damping, studies were made on specimens machined with their axes parallel, at 45 deg, and transverse to the original bar axis. MATERIAL DESCRIPTION AND EXPERIMENTAL PROCEDURES The material used in this investigation was from the same £ in. diam TD nickel bar that has been studied previously.13'15 The structure typical of the as-received TD nickel is shown in Fig. 1, and additional details of the structure can be found in Refs. 13 and 15. Elongated grains are parallel to the bar axis and are about 10 to 15 u long and about 1 u in diam. This structure is very stable, since no recrys-tallization or grain growth occurred after annealing for 3 hr at 1300°C.13 The total ThO2 content was 2.3 vol pct and the particles ranged in diameter from 100 to 1000. The average particle diameter was 370Å and the mean planar center-to-center particle spacing was 2340Å. To examine the influence of grain and subgrain structure on damping, a section of TD nickel bar was swaged and drawn at room temperature from 1/2 in. diam bar to 0.040 in. diam wire (99.3 pct re-duction in area). The structure in Fig. 2 resulted after the wire was annealed for 3 hr at 1250°C. The recrystallized grains were much larger than the grains in as-received bar, but still showed considerable elongation in the direction of working. A high

Jan 1, 1970

By H. Biloni, H. R. Bertorello

GruZLESKI and winegard1 have recently reported on the origin and development of the cellular substructure in Sn-Cd eutectic unidirectionally grown with different amounts of constitutional supercooling (CS). This communication deals with the results obtained in a parallel study on the instability of a plane interface in Al-Cu eutectic unidirectionally grown. Similarities as well as differences with the results of these authors1 will be presented. A1-Cu eutectic alloy ingots of 99.999 pct purity were grown unidirectionally under different G/R ratios where G = thermal gradient in the liquid, R = solidification rate. The ingots were cut in slices perpendicular to the solidification axes and the substructure studied on parallel sections following the sense of growth. It was generally found that the last part of the ingot to solidify presented a well developed colony substructure as a result of impurity build up and constitutional supercooling. The results obtained were: 1) When the structure was observed with low niagnification (of the order of 150 to 300 times) the first instabilities were observed at the grain boundaries and node-like structures formed at the junctions of the growth-induced boundaries, as reported by Gruz-leski and Winegard.1 Inside the grains the first signs of instability appear later and correspond to the type shown in Fig. 1; this is a two dimensional cell substructure. ' 2) Figs. 2 and 3 correspond to the evolution from a two dimensional substructure to a cellular type. In the A1-Cu eutectic the boundaries of the two dimensional cell are always perpendicular to the laniellaes instead of parallel as in the Sn-Cd eutectic. 1

Jan 1, 1970

The main orebody of the Bodangora mine is a metalliferous quartz reef within a major fault plane in the strongly folded and faulted volcanic rocks of the Ordovician-Silurian Oakdale Formation. The similarity of the type of mineralization to that of other pyrometasomatic deposits in this area suggests that the mineralizing fluids originated in the nearby Wuuluman Granite.The associated Mitchell's Creek West or Dick's reef is discussed briefly.

Jan 1, 1970

By H. R. Wuthrich

The Metallgesellschaft AG decided in late 1965 to build an Electrolytic Zinc Plant at Datteln (W. Germany). Lurgi-Chemie was entrusted with the engineering and erection of the entire plant. Ground was broken in February 1967 and the operation was started on August 1st, 1968. The new Electrolytic Zinc Plant was designed to produce a minimum of 100,000 metric tons of special high grade zinc and 200,000 metric tons of sulphuric acid. Concentrates from Meggen (W. Germany) and mainly Timmins (Canada) are roasted in two turbulent layer roasters. The sulfur dioxide containing gases are converted in a "Bayer double catalysis unit" to sulfuric acid. The calcine is leached batch wise, the leach residue separated from the pregnant solution by counter-current thickeners and drum filters. For maintaining the sulfate balance a modified jarosite leach is being used. After a two step purification the neutral solution is mixed with spent electrolyte and cooled in unpacked atmospheric cooling towers. Three electrical circuits are supplying the power to the tankhouse, each rated at 30,000 amperes. With a maximum current density of 750 amperes per square meter and a stripping cycle of 24 hours, an average current efficiency of 90 percent is obtained. Cathodes are melted in one induction furnace and cast into shapes, or alloyed with aluminum and copper for die-cast metal.

Jan 1, 1970