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By M. H. Yoo

Possible interactions of the perfect dislocations of six slip systems or the c dislocation with the (10i2f (ioii), {ioIi}(ioiZ), {1122}(1123), and {1121}(ii26) type twins in hcp metals have been analyzed from the crystallographic and the energetic points of view. Twenty-six distinct types of possible interactions were identified, and those selected based on crystallographic constraints were examined for their energetic feasibilities by use of the anisotropic energy factors. No long-range elastic interaction exists for a dislocation when its Burgers vector is parallel to the twin interface. Under a suitable applied stress, a screw dislocation can cross slip at the twin interface. For basal mixed dislocations in cadmium and zinc, the interaction with {1012} twins is found to be attractive, indicating that incorporation of these dislocations into the twins is energetically feasible and that twin growth will result. On the other hand, the interaction between both basal and Prism mixed dislocations and the {1012} and (1121) twins is found to be repulsive in Mg, Co, Re, Zr, Ti, Hf, and Be. This indicates that under an applied stress a local stress concentration will develop due to a dislocation pileup at the interface, which may result in a site for either the nucleation of other twins or the formation of a crack, depending on the cleavage strength. WHEN a metal undergoes plastic deformation, a certain configuration of slip dislocations will result in a state of dislocation pileup against an obstacle. The stress concentration thus developed may enhance the process of twin nucleation and also twin growth. Furthermore, once formed and dispersed in the crystal, twins can act as effective barriers against slip dislocations. The degree of such mutual influence or interrelation between slip and twinning is generally known to be pronounced in the case of hcp, metals. It is also known that deformation by twinning occurs more commonly in hexagonal metals than in cubic metals. In fact, under suitable stress states, all hexagonal metals exhibit {1012) <1011> type twinning.&apos; In addition to this common type, deformation by (1151) <1126> type twinning occurs in zirconium, titanium, and rhenium, which show remarkable ductility.&apos; The importance of twinning during general deformation to the ductility of hcp polycrystals has been briefly discussed in recent review works.2&apos;3 The purpose of this paper is to analyze the interaction between slip dislocations and twins in the hcp structure and to discuss the nucleation and growth processes of twinning and the role of twinning in the <"°" noil) o, 1/3[112O] (OOO2) 1/3[1123] Fig. l—-Slip systems in hcp structure. ductility of hexagonal metals. The problem will be discussed from the geometric and the energetic points of view in a manner similar to that of the previous work on zinc.4 Since hcp crystals deform by several slip and twin systems, numerous interactions result as possibilities. The Burgers vectors of six slip systems and the c dislocation shown in Fig. 1 and the four twin systems listed in Table I are considered here. A complete tabulation of the possible interactions is followed by discussion of those that are more likely to occur on the basis of crystallographic constraints and energetic considerations. 1) CRYSTALLOGRAPHY OF TWINNING The crystallographic elements, K1, K2, n1, and n2, for the four compound twin systems are now well established.= A unit cell with the base vectors n1, and n2 is shown in Fig. 2 for each twin system. The unit cell before twinning is shown in solid line, and the corresponding unit cell after twinning is shown in dashed line. Also shown in Fig. 2 are the following crystallographic parameters: S is the plane of shear, d the interspacing of the twin habit planes K1,Ø Iis the acute angle between n1, and n 2, e is a numerical factor, and q is the number of K, lattice planes intersected by 17&apos;. These parameters can be expressed in terms of the axial ratio, y = c/a, as listed in Table 11. The macroscopic shear strain of twinning, s, and the magnitude of a "unit twin dis-l~cation,"4 bt, are also expressed in terms of y and given in Table 11. In Table 11, K1 and q1 are given in both Miller-Bravais and Miller indices. In double lattice structures, shuffling of atoms in addition to a homogeneous shear of the lattice is generally required if the original crystal structure is to be restored after twinning. The extent of current understanding on this problem of atom shuffling is per- Table I. Four Twin Systems in Hcp Structure

Jan 1, 1970

By Richard F. Down

The Tynagh mine of Irish Base Metals Ltd., a subsidiary of Northgate Exploration Ltd., of Toronto, Canada, is situated one mile from the village of Tynagh in County Galway, one of the western counties of the Republic of Ireland. Mining has been carried on in Ireland since the Bronze Ages, but, apart from a reference in the 1859 Geological Survey records to much earlier mining attempts, mining has not been a feature of the Tynagh area in recent times. The present ore body was discovered by geochemical techniques in 1961. Following a diamond drilling programme to delimit the orebody, a pilot plant was operated at the property in late 1963 and early 1964. Construction of the 2000 tons per day treatment plant began later in 1964 and production commenced in December, 1965. The orebody contains both sulphide and &apos;oxide&apos; ores and these are treated to produce, by flotation, a variety of lead concentrates, a zinc concentrate, and a bulk lead-zinc concentrate, which are shipped to several European smelters. The term "oxide ores" is used here to mean all ores which contain economically important amounts of the oxidised minerals of lead, zinc or copper. THE ORE The ore body lies on the northern side of a major east west fault between sandstone and limestone; it is a boat shaped mass of residual or secondary ore lying over primary sulphide in limestone. (1) (2) The secondary ore consists of both residual sulphides and

Jan 1, 1970

By T. Suganuma

Mitsubishi-Cominco Smelting Co. is a joint venture of Mitsubishi Metal Mining Co. Ltd. (M.M.M.) of Japan and Cominco Ltd. of Canada. The smelter, which is located alongside M.M.M.&apos;s Naoshima copper smelter, was completed in May, 1966 and has a capacity of 36 000 metric tons per year of refined lead. The concentrate feed for the smelter from Pine Point Mines Ltd. is high grade with low impurities; particularly silver, bismuth, antimony, and arsenic, which facilitated a simple plant layout and operation. Concentrate, fluxes, recycle granulated slag and return sinter are drawn from bins by automatic control over weigh belt feeders, sintering is carried out on a 20 m2 Lurgi updraught sintering machine, furnacing in a 3.0 m x 1 ½ m water jacketed blast furnace equipped with an Asarco continuous tapper, refining in four 120 metric ton kettles and casting on a 25 metric ton/hour automatic casting machine. The S@ gas from sintering is cleaned in a high temperature baghouse utilizing glass bags and is then delivered to the M.M.M. copper smelter acid plants. The furnace gases after cleaning in a low temperature baghouse are vented to atmosphere.

Jan 1, 1970

By Erwin Pink

It has been pointed out in a previous publication&apos; that, for a given strain rate, serrated yielding can be observed only at certain test temperatures. Fig. 1 shows the results obtained for polycrystalline and re-crystallized tantalum, Va group in the periodic table of elements, where serrations in the course of deformation match the decrease of total elongation. However, there was no evidence of repeated yielding when testing molybdenum or tungsten, VIa group, at similar conditions, i.e., annealed and air-cooled samples (serrations have been found in quenched tungsten2). The reason for the observed serrations in the stress-strain curve are dissolved impurities on interstitial sites of the lattice. Of importance is the concentration of oxygen, carbon, and nitrogen, which are in random solution. Two methods to calculate the limiting concentrations for serrated yielding have been evaluated and applied with more or less success in estimating the role of carbon and nitrogen in mild steel.3 J. Friedel4 has given two equations, which determine the upper and lower strain rates i for the appearance of serrations at a certain test temperature: W denotes the binding energy of the interstitial atom, -1 ev for refractory metals;5 e&apos; the portion of continuous strain in the discontinuous stress-strain curve, measured as -3x10-3; b the Burgers vector, c the concentration, see Table 11, in atom fractions; p the dislocation density, -2 X l09 per cm2 at an average stress ?, -15 kp per mm2 at medium strain. k stands for the Boltzmann constant, T for the absolute temperature, and D for the diffusion coefficient. Table I. Eq. [1], for a given strain rate, determines the minimum temperature, and [2] the maximum temperature, below or above which no "dynamic strain-aging" can occur. According to the calculation, which uses the given quantities, serrations should only be observed within the cross-hatched temperature regions in Fig. 1, and this is in good agreement with the experiment. The effect of varying impurity concentrations is indicated schematically in Fig. 2: only Eq. [I] is affected. Setting Eq. [I] equal to [2], one can calculate the limiting concentration cmin which first causes serrations. The second method uses the aging condition by Cottrell and Bilby6,7 \£i/ \ n. a / where n(t) is the number of impurity atoms, which segregate at a dislocation line of 1 cm length after the time t (t in our case is the time between "repeated yield drops" in the serrated curve, or, the time until the above mentioned strain E&apos; is obtained, i.e., -1 sec for medium intensity or serrations). no is the number of impurity atoms in 1 cm3 and A = Qb4ep[(1 + v)/(l - v)], derived from equations given in Ref. 7. p is the shear modulus, 18,800 kp per mm2 for tantalum, 12,200 for molybdenum, AE the tetragonal distortion caused by interstitial impurities in a bcc lattice (approximately 0.4 for both tantalum and molybdenum) and v Poisson&apos;s ratio (0.35 for tantalum, 0.30 for molybdenum). From Eq. [3], combined with the condition for a pronounced yield drop as formulated by cottrel16 (at least one impurity atom segregated at the unit length of a dislocation), again a no min, and hence the concentration Cmin can be calculated.

Jan 1, 1970

By J. Szekely, V. Stanek

Steady state heat transfer and fluid flow rates are predicted for the counter-current contacting of gas and solid streams. For a .fixed pressure drop across the bed the convective heat transfer rate is affected by the gas flow rate, which in turn is affected by the temperature distribution in the system. Variations in bed voidage and in particle size were found to change the predicted temperature profiles quite markedly, in particular when the thermal capacities of the gas and solid streams were equal. IN Part I we examined the effect of step and pulse changes in the inlet gas temperature on transients in the flow of gases through fixed packed beds. Here we shall discuss heat flow and fluid flow interactions in the counter-current heat exchange between packed solids and a gas stream. Counter-current heat exchange in packed beds has been extensively studied. In his now classical paper, Furnas&apos; assumed constant property values and developed a simple analytical. expression for the temperature profiles in the gas and in the solid stream. A highly sophisticated analysis of counterflow systems, allowing for transients and interparticle conduction was developed by Amundsen. In preparing a very readable review of this topic Elliott&apos; also presented a number of elegant solutions, including the case involving heat generation. A great deal of work has been done on the application of these concepts to the modelling of the blast furnace. However, in all this previous work the mass flow of the gas was regarded as a quantity independent of the gas-solid heat exchange process. In the following we shall consider counter-current heat exchange between a gas stream and a packed bed of solids, under conditions where the pressure drop across the bed is specified, rather than the mass flow of the gas. FORMULATION Consider a packed bed, extending from y&apos; = 0 to y&apos; = L, in which moving solids and a moving gas are contacted in a counterflow arrangement. Let cold solids, with an initial temperature Tsi and mass flow GA, enter at y&apos; = L, and hot gas with an initial temperature of Tgi and mass flow Gg enter at y&apos; = 0. In contrast to the problems considered in Part I this system has a nontrivial steady state and we shall restrict our attention to the study of the pressure drop flow relationships and the resultant temperature distributions for steady state conditions. Under these conditions the formulation of the problem requires the statement of the following: 1) heat balance on the gas 2) heat balance on the solids 3) the mechanical energy balance equation and in addition the knowledge of the equation of state, and a functional relationship between viscosity and temperature and an expression for the heat transfer coefficient in terms of the other parameters. On neglecting temperature gradients within the solids and for a constant mass flow of the gas, the solution to this problem is well known.&apos;" The expressions for the temperature profiles of the gas and solid streams may be put in the following form: where Tg and T, denote the dimensionless gas and solid temperatures respectively, y is a dimensionless distance, and R is the ratio of the thermal masses. These quantities are defined as follows: For the particular case of equal thermal mass capacities by the gas and the solid, that is R = 1, the Eqs. [1]and[2] simplify to Eqs. (71 and[8], respectively: i.e., the resultant profiles are linear. As for most practical cases , solutions given by Eqs. [7] and [8] will contain only the inlet temperatures as parameters. For a fixed, predetermined value of C;b the above

Jan 1, 1970

By A. A. Mathews

During the past year (1967-68), there have been many instances of either partial or complete failure of a tunnel-support system. It looks like the art is in a pretty sad state, but as long as we permit the field of tunnel design to remain basically an art, that&apos;s about what we can expect. The application of scientific principles to tunnel design involves much more than assigning values to a series of factors in an equation. I am reminded of the case where the engineer calculated that steel ribs with struts were required to support a horseshoe-shaped tunnel in firm ground. The contractor had driven several hundred feet without installing the struts when the engineer visited the job. When he was informed that the struts had been left out, he fled the tunnel in alarm. As one authority has so aptly put it, "There is far too much calculating and too little observing." Initially, one might think of a tunnel support as a structural member, such as a strut or arch which is installed in order to support some definite load. Similarly, a tunnel lining might be considered as a treatment of the interior surface of the tunnel in order to produce desired aesthetic, hydraulic, or architectural results, or to serve a protective function. Actually, many linings, such as a concrete lining, serve a dual purpose and support a load as well as satisfy other requirements. Not too many years ago a tunnel, during the driving or excavating stage, was considered to be either supported or unsupported. In recent years, however, several techniques have been developed, which by helping the tunnel to support itself, permit the elimination of separate structural support. Since these techniques in many cases actually become a substitute for the conventional types of supports and linings, a state-of-the-art review would hardly be complete without including them for consideration. Thus, for the purpose of this discussion, we shall define tunnel supports as any system or technique which effectively maintains the integrity of the tunnel opening. In their chapters, both Jacobs (No. 6) and Lippold (No. 7) pointed out how support systems have advanced from timber supports to steel supports

Jan 1, 1970

By W. D. Bachman

A study has been made of wet, autogenous grinding of disseminated copper ores, including testing of a large number of samples from Kennecott Copper Corporation&apos;s Chino mine. The efficiency with which the various samples could be ground was found to vary over an extremely wide range, even among samples taken from different locations within the same ore body. These variations in grindability can be qualitatively correlated with the composition of the rock and the fracturing and alteration that had occurred. Because of the large-scale non-homogeneity of disseminated copper ore bodies, extensive and careful testing of autogenous grinding is needed. An accurate correlation of the grinding data from various samples with the geology of the ore body and with mining plans will indicate if variations in grinding mill throughput can be avoided in practice by mixing or blending of mill feed and if, therefore, autogenous grinding can be applied successfully.

Jan 1, 1970

Builders have been very familiar with iron since ancient times, but because of its weathering characteristics it was relegated to use as a fastening material in unexposed places and bronze became the popular metal for exposed applications. It is of interest that iron nails buried deeply about A.D. 87 at a Roman fortress and carefully covered with clean beaten earth under conditions practically excluding oxygen were found to be almost unrusted 1870 years later. (1) Today, weathering steels, which contain less than 2% of alloying additions, can be used in exposed situations without protection and without experiencing continuous wastage. As we all know the steady access of atmospheric oxygen to the surface of plain steel causes continuous corrosion. Weathering steels, on the other hand, due to their alloying additions develop their own impervious surface layer which limits the access of atmospheric oxygen and effectively limits corrosion. Table 1 shows the chemical composition of a plain carbon steel and a typical weathering steel. Fig. 1 shows what we refer to as direct corrosion - time curves in which corrosion loss is plotted against time of exposure in an strial environment. The weathering steel has a high rate initially which then decreases steadily for about three years, as the stable rust film builds up. This is followed by a practically linear relation where the very low corrosion rate, according to one school (2), is due to a blocking of the rust pores by insoluble complex salts formed from interaction of the oxidation products of the separate alloying elements. The start of the linear region represents a total corrosion loss of only about 2 thousandths of an inch.

Jan 1, 1970

By S. P. Ray, B. D. Sharma

THE activation energy values for self-diffusion in pure metals have been correlated with a number of physical properties such as melting points,1 valences,&apos; Debye temperatures,3 and cohesive energy densities.4 Extending the melting point correlation, the self-diffusion activation energy values for the alloys can be similarly correlated with the solidus temperatures. For metals and alloys which exhibit phase transformations, such a correlation is not feasible because of the uncertainty of various physical properties of the corresponding phases. Using thermodynamical approach, Ardell5 calculated the hypothetical melting points of the low melting phases of the polymorphic metals. However, these calculated melting points do not show reasonable correspondence with the activation energy of self-diffusion. Recently, a new approach treating metals and alloys as electron concentration phases has been developed by Engel6 and Brewer.7 These workers have attempted to correlate the crystal structures with the electron configurations of the atoms existing either in ground state or in an excited state of low promotion energy. The basic postulate of this theory is that whereas the contribution to the bonding of the metal comes from the interaction of both d and (s-p) electrons existing either independently or in hybridized states, the existing crystal structure is controlled by the (s-p) electrons alone. Specifically, a metal is supposed to crystallize in bcc, hcp, or fcc phase provided the metal has one, two, or three valence electrons per atom in the (s-p) configurations. The diamond, or ZnO and ZnS structures, occur with four (s-p) electrons per atom. Secondly, the contribution of d electrons to bonding is supposed to increase with atomic number

Jan 1, 1970

By John T. Awald

The Bradshaw Mountains of west-central Arizona cover an area of 1600 square miles and contain numerous old mines and prospects. The area has been geochemically sampled on a reconnaissance basis to relate mineralized areas to regional structure and rock types. Copper analyses of stream sediments have been classified and contoured to show the distribution of low background, high background, and low, intermediate and highly anomalous areas. Contoured results are compared to geology and known mines. Several prospecting areas are indicated.

Jan 1, 1970

By L. W. Sink, B. H. Kear, S. M. Copley, M. F. Hornbecker

IT is well known that under appropriate conditions of chill casting, many metals and alloys develop a columnar grain structure having a high degree of preferred orientation.&apos; In cubic materials, this principle has been employed to produce shaped castings with a unidirectional cube oriented columnar grain structure as well as shaped single crystals with a cube axis parallel to the growth ais.&apos; "he purpose of this note is to describe how this same principle can be enlployed to produce wires, rods, or more complex crystal Shapes with a variety of conlpositions in cube or random orientations by a single casting operation. The procedure for directional solidification of in Fig. 2. Examination under crossed polarizers indicated that the striations were a second phase (presumably the B19 phase) which frequently forms initially at primary grain boundaries and then grows toward the interior as thin ribbons. X-ray studies on filings of this alloy reannealed at 1300°C for 15 min indicated a strong pattern of the fcc phase together with a substantial pattern of the B19 phase. The un-annealed filings, however, showed only the pattern of a cold-worked, fcc structure. In these two-phase alloys it appears, therefore, that the B19 phase is transformed into a disordered fcc structure by cold-working. The mechanical properties of these alloys would be of some interest since a fcc structure might be expected to possess greater ductility than the or-thorhombic B19 structure from which it forms. The author wishes to thank Mr. Harvey Yakowitz and Mr. Richard Manuszewski for obtaining the photomicrograph in Fig. 2. This research was partially supported by Research Grant DE-02455 from the National Institute of Dental Research. columnar grained ingots involves pouring a melt into a preheated mold having a water-cooled copper chill at its base? and controlling the temperature gradient in the mold so as to maintain columnar grain growth from end to end of the ingot.4 This is illustrated schematically in Fig. l(a). It should be noted that the longitudinal temperature gradient promoting unidirectional columnar grain growth is maintained by heat loss primarily through the solidifying ingot to the chill, so that both the temperature gradient and the growth rate diminish with increasing distance from the chill. As the distance from the chill increases? the columnar structure coarsens, and the perfection in preferred orientation tends to increase progressively. Using this same procedure of gradient solidification, Fig. l(b) shows a simple scheme for producing a batch of crystals having the same cube orientation rather than an assemblage of columnar grains. Wires and rods are produced by cementing ceramic tubes to the wall of the mold. The steep temperature gradient produced in the central chamber is controlled by the mold heater to produce favorable conditions for crystal growth. Clearly the success of the operation lies in the selection of individual growing columnar grains by some kind of orifice at the base of each channel in the mold. Using simple constrictions, experience with nickel-base alloys has shown that 4 -in.-diam holes at a distance of -1 in. from the chill yield crystals within 7 deg of (100); closer control of orientation is possible by placing the crystal selector farther away from the chill.

Jan 1, 1970

By Horst Huettenhain

The Rowland Coal Preparation Plant is located on Workman&apos;s Creek in Raleigh County, West Virginia, approximately 20 miles Northwest of Beckley and 10 miles Southeast of Ameagle. It is owned and operated by the Rowland Division of Consolidation Coal Company. This paper describes the plant flowsheet, process considerations that were evaluated in its development, and observations made during and since the plant was constructed. The final flowsheet was developed specifically to wash the coal from the Rowland Mine and contains several equipment combinations and applications heretofore never placed in a single, commercial operation. The major process equipment is presented in a functional description of the flowsheet. The coal reserves are leased from the Rowland Land Company and consist primarily of #2 Gas and Middle Eagle coals and various major splits of the Middle Eagle seam. The Rowland Coal Preparation Plant was designed to process 560 TPH of raw coal consisting of 50 percent #2 Gas coal intimately mixed with 50 percent Middle Eagle coal and containing lumps no larger than a 12-inch cube.

Jan 1, 1970

A mechanised sub-level overhead benching method is used at Cleveland, to produce 22,000 tons per month of ore assaying 0.92% Sn and 0.40% Cu. The ore occurs in a series of vertical lenses which can be mined by open stoping. Levels are developed at 60ft., vertical intervals by jumbos. The ore is silled out and the stope block formed between levels drilled out by long hole drilling. Each row of holes is fired and broken ore within safe reach from the stope brow is mucked out by Wagner ST-5A Scoop Trams. The remaining broken ore is recovered on extraction of the next lower level. Ore is hauled by road to the crusher station from the mine. As mining proceeds below the lowest surface portal a spiral decline will be used for ore haulage and mine servicing.

Jan 1, 1970

By G. H. K. Schenck

Weather changes of a daily, weekly, or seasonal period affect mineral production and cause significant losses that are considered unavoidable. Private weather forecasting services are available on a contract basis that can significantly reduce the uncertainty associated with weather-induced changes in the production of and demand for minerals. This paper provides examples of current practice and reviews the opportunities that await those producers who incorporate weather services as an integral part of their operating, scheduling, and planning procedures. Private weather forecasts can be highly accurate because atmospheric trends such as conditions and movement tend to persist and are related to previous meteorological events. Commercial meteorological services are prepared to deal specifically with a mineral producer&apos;s special problems (Table 1). Tactical use of private forecasts is a major advance over the severely restricted value of public forecasts which, of necessity, are general in nature and cover a dispersed geographic territory. Private weather services provided on a consulting fee basis offer the mineral producer the opportunity for tactical and strategic response to weather conditions at an acceptable cost. This contrasts with the too-frequent current tendency to view weather as a random variable the costs of which are unknown and about which nothing can be done.

Jan 1, 1970

By William G. Gates

INTRODUCTION The Heath Steele mine is located in the Bathurst-Newcastle area of northern New Brunswick. It is jointly owned by American Metal Climax, Inc. and the International Nickel Company of Canada who hold a 75% and 25% interest, respectively. The ore deposits of lead, zinc and copper sulphide occur in very fine grained pyrite and/or pyrrhotite masses. A consistent spatial relationship with a quartz feldspar porphyry is characteristic of these deposits and the many other similar sulphide deposits in the district. The two principal mineral assemblages of pyrite-sphalerite-galena, and pyrrhotite-chalcopyrite-pyrite, occupy characteristic positions relative to the enclosing rocks. This feature and the nature of the sulphide mineralization are described and the variations in metal content are noted .with special emphasis on the lead-zinc ore zones. The mine product ion rate is 3,000 tons per day of a mixed lead- zinc and copper ore which is extracted from the B-1 zone. The complex nature of the ores presents many metallurgical problems. Optimum metal recoveries are achieved when milll feed grades are relatively consistent and proportions of the contained metals are with in acceptable limits. Ore outlines and stoping blocks are delimited by close spaced diamond drilling. From this information it is possible to forecast the grade of any portion of a stoping block. Production from the various stopes may then be scheduled so as to achieve an acceptable mill feed grade.

Jan 1, 1970

By Martin E. Chenevert

The early work of Terzaghi1 showed that the true stress state of a rock can be expressed by the principle of effective stress. This principle states that effective stress is equal to total applied stress minus the pore pressure. Since the introduction of this principle, a great effort has been made to measure the pore pressure of rocks so that the true stress state can be determined. For clean, permeable sandstones, it is usually found that the effective stress principle can easily be applied. Direct measurement of the pore pressure is achieved with a hydraulic pressure device and the effective stress state thereby computed. However, for fine-grained rocks which contain large amounts of clay (referred to herein as shales), pore pressure measurements are usually quite difficult because of the adsorptive forces of the clay platelets, which produce negative internal pressures. No suitable device is known for measuring internal pressures of dry shales; the effective stress approach is therefore not feasible and data are usually presented in another form. As an example, data from compressive strength tests are presented as a function of rock wetness, rather than effective confining stress. The work of Belopoloskii2 and Colback and Wiid3 are examples of such data. It was pointed out by Lambe and Whitman4 that a better way must be found to express the effective stress of argillaceous rocks. The information presented herein is an attempt to fill that need. Various authors have been able to measure moderate negative pore pressures (0-240 psi) within rather wet, argillaceous rocks by means of various pore pressure devices. In 1961 Lambe5 resented information which shows that pore pressures in argillaceous rocks are indeed negative ; he presented values of suction pressure as low as - 14 psi. Likewise,

Jan 1, 1970

By Edward J. Felten

Binary Cr-A1 alloys containing from 2.5 to 30 wt pct Al and 0.7 wt pct Y were heated in oxygen, air, and nitrogen between 1000" and 1200°C. The reacLivity of the alloys was found to be dependent both on the alloy composition nnd the nature of t he atmosphere. In oxygen, nllojs containing up to 15 to 20 wt pct A1 reacted to produce an external scale of Crz03 and a subscale consisting Predominently of Al203. Alloys contazning 20 to 30 wt pct A1 react in oxygen to produce an A1203 external scale and little m no subscale. The latter alloys were markedly more oxidation resistant than those of low alurninum content. In air, the alloys on which an external Crz03 scale was formed were found to be permeable to nitrogen ns evidenced by the copious amomts of chromium and aluminum nilrides observed ns part of the subscale. The reactizities in nir (or nitrogen) of these alloys increase <m their aluminurn contents increase. However, alloys on which Al,O, us an external scale is formed were nol culnerable to nccelerated attack in air, and no eltldence of nitvide subscnles were observed. For all alloys, yttrium serwed pYimarily to improve oxide adhrence. THE role of chromium in the oxidation resistance of Fe-Cr alloys &apos;-&apos; and that of aluminum in Fe-Cr-A1 al10s&apos; has received considerable attention in recent years. This is understandable since many of these alloys have excellent oxidation resistance due to the formation of either a Cr203 or a-Ala03 film between the metal and the oxidizing atmosphere. Small additions of yttrium or other rare earth metals are effective in preventing spalling of the protective oxide from the metal substrate."" In contrast, little is known regarding the oxidation resistance of Cr-A1 alloys, although some work has been done by Tumarov et a1.&apos; The poor niechanical properties exhibited by Cr-A1 alloys make them undesirable for use as structural components, but their use as coatings cannot be disregarded. The use of chromium-rich aluminide coatings for refractory metal alloys is an example of the potential use of this type of sytem. The purpose of this work is to examine the oxidation behavior of Cr-A1 alloys containing 2.5 to 30 wt pct A1 and 0.7 wt pct Y. The effects of temperature, atmosphere, and thermal cycling have been determined. EXPERIMENTAL PROCEDURE The alloys used in this investigation can be divided into two groups. Those containing 2.5, 5, 7.5, and 10 wt pct A1 and 0.7 wt pct Y were extensively evaluated in the temperature range from 1000" to 1200°C. Alloys containing 15, 20, 25, and 30 wt pct A1 and 0.7 wt pct Y were tested only at 1200°C. All of the alloys were prepared by standard arc-melting techniques in the form of cylinders approximately 4 in. long and 19 in. in diam. Wafers were cut from the cylinders and subsequently subdivided into rectangular coupons. The alloys were brittle and therefore some cracks were found in almost all specimens. The coupons were prepared for oxidation by mechanically polishing through 600 grit Sic paper, and were thoroughly degreased just prior to testing. Two types of oxidation experiments were conducted, namely; cyclic tests in which the specimens were examined and weighed after each 2 hr exposure, and continuous thermal balance tests run in a controlled atmosphere (oxygen, air, or nitrogen) for 20 hr. In the former test the spalled oxide was not included when the specimens were weighed. The physical condition of a specimen was noted visually after each cycle and testing was continued either to failure or until the performance of the specimen was well characterized. Both Micro and Semi-Micro Thermal Balances (Ains-worth) were used in the continuous tests. The oxidized specimens were sectioned and prepared for metal log raphic examination. The specimens were polished through 600 grit Sic paper. After polishing through 6 and l p diamond, a final mechanical polish with Linde B-Alz03 was used. Specimens containing 2.5 pct A1 were etched electrolytically using a 10 pct oxalic acid solution at 4 v for about 2 sec. Selected specimens were examined in the electron microprobe analyzer. Oxide specimens were examined by standard X-ray diffraction techniques. EXPERIMENTAL RESULTS For convenience, the test results have been broken down according to the exposure temperature, and further subdivided according to the type of test and atmosphere employed. Because of the poor quality of the specimens a larger than normal amount of scatter was observed in the measured rate constants. Also, the evaluation of the weight gain data was done on a somewhat arbitrary basis and may not be truly representative. However, the results obtained do show a significant trend in behavior regarding both alloy composition and the nature of the oxidizing atmosphere. I) Oxidation Behavior at 1000°C. A) Continuous Oxidation estsin Oxygen. This series of experiments was run in the Ainsworth Micro-Thermal Balance using pure oxygen at a pressure of 76 mm Hg. Under these conditions all specimens oxidized in accordance with the parabolic rate law over a major portion of the exposure time; the rate constants appear in Table I. The oxide formed externally on all specimens was predominantly Cr,O,, which was generally adherent. In some cases a slight amount of spalling in the form of a fine powder was noted. a-A1203 was observed as a subscale, along with Yz03 in all alloys. Alloys containing up to 7.5 wt pct A1 oxidize more rapidly than the Cr-0.7Y alloy.

Jan 1, 1970

By R. T. Erskine

"IntroductionIn this paper it will not be possible to cover all details of the reagent systems at Brunswick Mining and Smelting but it is hoped that a description of the evolution of these systems will be of some benefit. The concentrator of Brunswick Mining and Smelting located near Bathurst, New Brunswick was originally designed as a 3,000 ton per day operation but before construction commenced was uprated, with 4,500 tons per day being treated by the summer of 1964. Development of the open pit at another ore body five miles away was initiated in 1965 and additional concentrator and crusher facilities went into operation in September, 1966. Present total daily throughput is over 8,000 tons per day. The ore at Brunswick is very high grade but mineralization is very fine grained and requires grinds generally over 75% minus 400 mesh for liberation. The amount of surface exposed using grinds of this order understandably requires great quantities of reagents, Reagent mixing systems for the original concentrator allowed only for batch mixing and were very expensive in labour cost especially.During the first three years of operation total number of men employed in reagent handling reached a peak of four men per shift and six men on dayshift unloading cars for a total of 22 men. At present only one man is employed on shift, and four men on dayshift take care of unloading and mixing reagents, a total of 8 men. The man on shift is almost entirely occupied with checking feeder operation, flow rates, and head tank levels. Most commonly used reagents are tabulated in Fig. 1 showing average monthly and daily requirements in the Brunswick operation as well as pounds per ton of mill feed as found in 1969. It is very obvious that with over seventeen tons each of lime and soda ash and six tons of copper sulphate used each day, opening of bags and mixing batches of solution is an inefficient undertaking."

Jan 1, 1970

By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.&apos; and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By E. J. Harvey

The Ozarks has been called "a diamond in the rough". In this region streams have steep gradients, sparkling clear flows of cold water fed by many springs, and a wildness that is almost unique in the central part of the United States today. The Current River and its tributary, Jacks Fork, have been set aside for preservation by the National Park Service as a "Wild River" in the first park of its kind in the country. It is called the Ozark National Scenic Riverway. Similarly, responsibility for the preservation of the Eleven Point River has been assigned to the U. S. Forest Service. Protection of other streams in the Ozarks has been considered by State agencies. The hydrologic system of the Ozarks is a complex network of gaining and losing streams, caves, conduits, and large springs. Increased sewage loads derived from the growing towns and expanding tourist trade are a potential hazard; effluents may flow underground for long distances, polluting springs and wells. To add another dimension to the hydrologic picture a new lead industry is also flourishing in the Ozarks. Although the history of lead mining in the area goes back to 1701 (U. S. G. S., p. 43), the area has not seen a revitalization like the one that has been developing in the last 10 years; and the economic growth promises to continue indefinitely. Although this brings capital expenditures and wages into the area, it also brings potential hydrologic problems. Chemicals, wastes and other substances either stored on the surface or transported across it are subject to accidental spillage. In an area where these substances remain on the surface their effects are subject to surveillance. In the Ozarks, however, this may not be possible.

Jan 1, 1970