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By R. F. Steigerwald

The effects of heat transfer on the corrosion behavior of type 304 stainless steel in boiling water have been studied. Heat transfer conditions increase the tendencies of the stainless steel toward stress-corrosion mucking when the water is contaminated with Cl-. Surface preparation is the most important variable in determining the severity of the stress-corrosion problem in water with a given Cl- content. Heat treatment, chemical cleaning, and degree of wet film boiling also affect the corrosion of stainless steels used as heat transfer surfaces in boiling water. An up-paratus for corrosion testing under controlled heat transfer conditions is described. THE principal objective of this investigation was to study the corrosion behavior of AISI Type 304 stainless steel in boiling high-purity water under conditions of heat transfer. The principal variables in the study were: a) boiling conditions: limited boil, agitated boil; b) metallurgical structure: annealed or sensitized; c) surface condition: rolled, pickled, or ground. The results of the study should elucidate the role of heat transfer in the corrosion of stainless steel in boiling high-purity water and provide a base line from which to assess the severity of this type of corrosion. Although there has been an investigation of the effect of heat transfer on the corrosion behavior of stainless steels in alkaline waters,' work on the corrosion of stainless steels under heat transfer has been largely confined to various acid solutions.'-4 Furthermore, the study of the corrosion of stainless steels in high-purity water has been generally restricted to auto-clave and instream testing in superheated (e.g., 300°C) water and steam.5'6 Cooling water problems led to this study of the corrosion behavior of type 304 stainless steel in high-purity water at its atmospheric boiling point. In addition to the effects of heat transfer, this study also considered the influences of the type of boiling,7 metallurgical structure, and surface condition on the corrosion behavior of stainless steel in high-purity water. Two boiling conditions were investigated in this study: a) limiting boiling, i.e., when the heat-transfer surface had just reached the boiling point and boiling nucleated randomly over the specimen surface and b) agitated boiling, i.e., when a mild degree of superheat had been achieved on the specimen surface and boiling occurred generally over the specimen surface. Both boiling conditions are broadly classified as wet-film boiling. Originally, this program included the study of a third type of boiling, dry-film conditions. At dry-film boiling the temperature of the heat transfer surface is high enough so that it is covered with a continuous film of steam. Experimental difficulties made it impossible to study this kind of boiling with the available apparatus. Since surface condition affects heat transfer rates, three typical surfaces were chosen for study: a) as-rolled, the 2B finish received from the supplier, b) as-pickled, 30 min in 8 pct HNO3-1 pct HF, and c) as-ground on 120 grit paper. In order to evaluate the effect of improper heat treatment or welding on hot wall corrosion, both annealed and sensitized mi-crostructure were included in this study. EXPERIMENTAL Test Apparatus. The particular problems of interest in this investigation required a knowledge of the thermal gradient through the test specimen. From this gradient, the heat flux to the surface and the surface temperature could be determined. In order to satisfy this need, an apparatus similar to the boiling-disk apparatus of Fisher and whitney2 was designed. The solution is contained in a thermally-insulated, steel pipe lined with TEFLON resin. A stainless steel _______;________________________________________

Jan 1, 1970

By Peter N. Calder

The orientation of planes of inherent weakness (joints) with reference to an excavation in rock is the critical factor determining stability. The purely frictional 'residual' strength remaining following the breakdown of initial cohesion is the only strength which can be counted on to resist sliding for the long term. A simple method of resolving driving and resisting forces in three dimensions along joint intersections 'undercut' by the excavation is presented. Contrary to the case of slope failure in soils, it is shown how significant changes in the slope angle sometimes have no effect on the degree of stability pre-sent in rock slopes. Wall control by reorientation of the slope, the use of cable bolts and water diversion are briefly discussed.

Jan 1, 1970

By C. S. Barrett

WhEN a collimated beam of protons or other energetic particles is scattered by a single crystal, the emerging particles produce patterns that contain much crystallographic information. Calculations of the trajectories of individual particles can predict with reasonable accuracy the complete pattern (which is related reciprocally to channeling, now studied in detail6) but the task is a lengthy one which has been completed for very few cases. A many-beam dynamic diffraction calculation of the patterns would be even more difficult and in some cases may be invalid. Because of these complexities, simple methods that will predict to a rough approximation the relative intensities of the lines in films of the back-scattering patterns of a given crystal are wanted. I have found a method which, although it is not a valid computation of intensities or of film darkening by either dynamic or kinematic diffraction principles or by trajectory calculations, nevertheless is found to be useful in practice. It has been tested on several crystal types,7 and is here tested on additional ones. The method consists in first calculating the structure factor F(hk1) for the (hkl) plane, of spacing d, by the familiar equation: where the summation extends over the atoms in the unit cell and fj is the atom scattering factor of the jth atom (using tables computed for electron diffraction, preferably those computed without exchange). Then the F values are squared and summed over all the orders, n, for which F2 has an appreciable value, giving a quantity: Finally, I, is expressed as a percentage of Ic for the

Jan 1, 1970

By Galen G. Waddell

Several years of rock-burst research conducted by the Federal Bureau of Mines, in cooperation with the mining companies of the Coeur d?Alene Mining District, Idaho, in addition to progress made by others throughout the world, have led to a good understanding of the rock-burst problem. This paper describes conditions which have caused specific bursts, present capabilities of detecting stress buildup and bursts, control methods, and a suggested approach to analyzing any individual mine-burst problem.

Jan 1, 1970

By James D. Cooper

Technologic advances in materials utilization during the past two decades have brought is a long way toward the point where we can make the products we need from the materials we have readily available. Notable examples are the synthesis of diamond, zeolites, quartz crystal, mullite, and mica, and the development of phosphate bonded tale. Two of these--zeolites and mullite--involve the use of clays. There is little reason to doubt that equally important advances will be realized in the next decade, and that clays will play an important role in the developing materials technology. Indeed, the stage is already set for many of them. This discussion is concerned primarily with the high quality, relatively high priced clays, kaolin, bentonite, fuller's earth and ball clay. The first three have enjoyed demand growth rates over the past two decades which on the average exceeded the growth rate for the economy as a whole. There are indications that demand for ball clay will be growing at a faster rate in the future.

Jan 1, 1970

By Richard H. Olson

The following discussion will deal with the domestic talc industry only, inasmuch as the writer has had no experience in this field outside of the U. S. This is strictly a geological-mining approach; no attempt is made to assess in depth the effects which milling technology and marketing capability might have in determining the potential of any given talc deposit.

Jan 1, 1970

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 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

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

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 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. 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

By C. F. Weinaug, P. M. Blair

Many difference equations used to approximate reservoir flow problems treat the phase pressures implicitly but not the mobility-density coefficients. Such difference equations are neither wholly explicit nor implicit, but might be described as mixed. Mixed equations are relatively easy to apply. But the associated time truncation error is relatively large, and when used to solve problems characterized by high flow rates, these equations may be unstable for practical size time steps. This paper outlines the development of a completely implicit difference analogue for reservoir simulation, along with a Newtonian iterative method for solving the resulting nonlinear set of algebraic equations that arise at each time step. While this implicit equation requires two to three times more work than does the mixed equation, it is shown to markedly decrease the time truncation error and to yield a stable solution for much larger time steps than does the mixed equation. INTRODUCTION Calculation of multiphase, multidimensional flow in porous media is generally accomplished by numerical methods that involve approximating systems of partial differential equations by systems of partial difference equations. The early development of difference equation techniques was directed toward the solution of linear differential systems. However, the equations of multiphase fluid flow through porous media are highly nonlinear in that mobility and density often are strong functions of pressure and saturation. Thus, solution of the flow problems by difference equations involves solving sets of algebraic equations whose coefficients change from step to step of the calculations. Current practice is to evaluate most coefficients at the beginning of a time step and then to apply difference methods well suited for solving linear problems. At least two major difficulties arise from the use of this practice. First, evaluation of coefficients at the old time level and evaluation of pressures at the new time level results in larger time truncation errors near displacement fronts than if all quantities in the distance derivative were evaluated at the same time level. Second, evaluation of mobility coefficients at old time levels results in an unstable difference equation in regions of high flow rate. The first of these difficulties often results in optimistic recovery behind the displacement front, and the second requires the use of small time steps or special techniques in solving coning problems1 or problems of gas percolation.2 Evaluation of all quantities in the distance differences at the new time level results in a completely implicit difference system. Such a difference system has a lower time truncation error than equations in which mobilities are evaluated at the old level and pressures evaluated at the new level. The algebraic equations resulting from the fully implicit difference equation are, in this case, nonlinear and require some iterative method for their solution. This paper develops fully implicit difference equations for two-phase flow in porous media, describes their solution by Newtonian iteration, and gives examples of problems more easily solved by the new method than by previous methods. EVOLUTION OF DIFFERENCE EQUATIONS FOR NONLINEAR PROCESSES The completely implicit difference equation used in these calculations results from evolution beginning with explicit difference equations, proceeding through what we will call "mixed" equations, and arriving now at a completely implicit equation. Let us illustrate the evolution by considering different analogs of the nonlinear equation

Jan 1, 1970

By John E. Young

United States Steel Corporation&apos;s Winifrede Mine is operated by Lynch District in the mountainous region of Eastern Kentucky. This region is characterized by narrow mountain ridges and precipitous slows which present both an opportunity and challenge in the design and selection of coal handling facilities for the movement of coal from the section belts to the railroad cars. The narrow finger ridges precluded use of underground haulage and, thereby, presented the opportunity to use high capacity equipment on the outside bench. The precipitous mountain slopes, steepest at the Winifrede seam horizon, presented a challenge to select a solution for lowering the coal approximately 1000 feet from the seam level to the valley floor railroad load-out point. It was evident from the start of planning that these two factors predominated; namely, rail haulage and coal lowering, and solutions to these would determine the final design of the Winifrede Mine coal handling facilities.

Jan 1, 1970

By William F. Lawrence

Within ten to fifteen years, coal-fired power generating stations will be producing over 40 million tons of coal-ash annually in the United States. The largest part of this ash will be emitted from the boilers, entrained in the off-gas stream and trapped as flyash. However, about 15 percent (six million tons) will he removed from furnace bottoms as bottom ash or molten coal-ash slag. In current practice, the molten coal-ash slap is generally water quenched and then transported either as a slurry or in granular form to storage or disposal areas. Although a small amount of this slag is marketed as abrasive grit or as roofing granules, most of it is considered a waste material which must be disposed of at considerable cost to the power companies and therefore to the public. The accom¬panying economic loss in terms of unused raw materials and displaced land is not as obvious but is just as real. The Coal Research Bureau at West Virginia University under the sponsorship of the U. S. Bureau of Mines has been examining the possible utilization of both coal-ash slag and flyash in the mineral wool industry as a method of partially alleviating the growing national problem of solid waste disposal. The potential marketing situation for mineral wool manufactured from coal-ash is illustrated in Figure 1. This bar graph depicts the growth in value of mineral wool shipments1 from 1949 through 1966. In this 17-year period, the value in¬creased by over 350 percent, more than 20 percent per year, despite a decrease in unit cost of mineral wool. It therefore appears likely that coal-ash could find a steady market as a supplement to existing sources of raw materials for mineral wool production.

Jan 1, 1970