Search Documents

By G. A. Vissac, R. G. Minet, N. E. Sylvander

R. G. Minet—The authors' description of the remarkable progress made in the last few years in applying the fluidized solids technique to the problem of lignite drying and carbonization clearly demonstrates that engineering techniques available today may make many processes practical and profitable which a few years ago were considered otherwise. As pointed out in the article, the future of the carbonization step hinges on the value and utilization of low temperature tar. On paper, at any rate, this tar looks like a valuable raw material for the chemical industry to use. Some 50 to 60 pct may be converted to pitch for electrodes, roofing, road tars, and other valuable products; the 25 to 30 pct tar acids could conceivably form a basis for a new low cost resin or plastic of the phenolformalde-hyde type. Yet these materials are so new and dissimilar from available sources that much work must be undertaken by the chemical industry before they will be accepted. Now that the work of Dr. Perry and his colleagues has made a large supply of low temperature tar a real possibility, I would expect the chemical industry to accelerate its work in this field. On the basis of certain data available in the literature it appears possible to produce a more aromatic tar, although in smaller yield, by operating at temperatures in the range of 1300" to 1500°F. Operating a fluidized bed process for lignite at these conditions should be technically possible, at least, and could produce a tar having more familiar characteristics. I wonder if Dr. Parry would care to comment on such a possibility. Incidentally, in our own work on carbonizing coking coals in fluidized beds, using Ohio, Pennsylvania, and West Virginia high volatile bituminous coals, we have obtained yields which agree with the correlation given for tar yields vs moisture and ash-free volatile Btu. Our data are slightly under the line, but certainly in the range of the correlation. We have also obtained evidence in support of the authors' statement as to the effect of air on the process. In our pilot plant all the heat required for carbonizing is released by internal combustion of char in the fluidized bed in normal operation. We are also equipped to obtain all carbonization heat by external electric heaters on the shell of the carbonizer while introducing only an inert gas to the process. We note no difference in tar yield or characteristics between the two operations. In the case of the gas, however, it appears that some hydrogen is consumed by the air combustion. We would be interested in hearing in a little more detail about the hot dust and char handling problems at Sandow. Have the authors found char subject to spontaneous combustion? Have they ever tried a coking coal in their pilot plant? V. F. Parry (author's reply)—Production of a more aromatic tar by operation of the carbonizer at 1300" to 1500°F does not appear to be economical. 1) The capacity of a reactor operating at 1500°F would be 30 to 50 pct less than the capacity at 932 °F and the cost of processing would increase materially. 2) The cracking of tar vapors in a reactor requires appreciable time to complete the reactions and it is doubtful that considering the very short time of residence of tar vapors within the reactor (4 to 10 sec after evolution) the basic character of the tar would be changed significantly. This is indicated from the data reported in Table XIV. 3) General studies have shown that it is advisable to operate at the minimum temperature to produce the maximum tar and minimum gas. 4) Operating problems and the maintenance of vessels and reactors, and the hazards of handling hot char, increase with the temperature of carbonization. It is technically possible to operate at temperatures as high as 1500°F, but in my opinion it is not economical or desirable. We believe that the primary tar must be won in the simplest way and then processed alone to change its character for production of desired products. It is interesting to have confirmation of our observations on the reaction of air with the products of carbonization. The major reaction is with the char, fol-

Jan 1, 1957

By Claudio Barsotti, Leonard C. Kitchener

INTRODUCTION The major mining operations of the Ontario Division of Inco Metals Company are located in the Sudbury Basin. Around the rim of this geo- logical formation and within thirty miles of the City of Sudbury are located eleven under- ground mines of the Company, two of which are on standby. In addition, there is one mine in Northwestern Ontario at Shebandowan, 1127 Km (700 miles) northwest of Sudbury. In 1980 ore production totalled 10.6 x 10 mt (11.7 million tons) from underground and open pit operations. Underground mining methods include blasthole, vertical retreat, sublevel caving, cut-and-fill and undercut-and-fill. Inco reduction operations in the Sudbury area include two concentrators, one smelter, one iron ore recovery plant, a copper refinery a nickel refinery and a high purity plate rolling mill. As well, an electrolytic nickel refinery is located on Lake Erie at Port Colborne, near Niagara Falls. In the Sudbury District, Inco employees total 14,278 of whom 6,490 are directly employed in the mining and milling operations. I T H DRILLING Background - The use of long blastholes in underground operations at Inco mines in the Sudbury district started more than 30 years ago at the Levack Mine. At that time, diamond drills were used to mine ore by open stoping and for pillar recovery. By the 1950's the concept had been extended to all mines. The heavy percussion drill was also developed by this time and led to the acceptance of the 11.43 cm (4% in.) piston diameter drifter for bar and arm and fan drill applications. The use however, of the nominal 5.08 cm (2 in.) diameter blastholes drilled radially from the level or sublevel causes overdrilling at the periphery. As well, the smaller holes are subject to hole deviation, are difficult to drill beyond 38.1 m (125 ft.) and require the need for several drilling horizons or sublevels. The need to improve blasthole stoping techniques and our experience with large diameter blastholes in open pit mining led to the trial of an I T H drill in 1962. The test was unsuccessful however, since button bits were not available at the time and the tungsten carbide cross bit experienced short life, gauge loss, and caused hole deviation and poor penetration rates. The successful application of the raise borer beginning in 1964 and the ability to drill 20.32 cm (8 in.) to 27.94 cm (11 in.) diameter pilot holes led to the development of smaller, more portable, rotary drills for blasthole mining. As a result, a mining method based on the use of 20 cm (7 718 in.) diameter, 60.1 m (200 ft.) long rotary blastholes was developed and tested successfully at our C.C.North Mine. Between 1972, when the method was first tested, and 1973 over 4572 m (15000 ft.) of large holes were drilled with rotary drills in the recovery of 175,960 mt (194000 tons) of primary stoping and pillar remnants. A new mining method was developed that made use of this large hole drilling equipment. Instead of longhole carbide drilling by bar-and-arm or fan drill set-ups at sublevels, the large diameter holes were drilled full stope height from the top sill, which substantially reduced development, drilling time and improved fragmentation. These drills however, were difficult to move and set-up, and had a high maintenance cost and low productivity. The capital outlay and extensive technical development required to improve these drills and reduce the high drilling costs however, was economically unattractive. New development in drills and button bits INTRODUCTION The major mining operations of the Ontario Division of Inco Metals Company are located in the Sudbury Basin. Around the rim of this geo- logical formation and within thirty miles of the City of Sudbury are located eleven under- ground mines of the Company, two of which are on standby. In addition, there is one mine in Northwestern Ontario at Shebandowan, 1127 Km (700 miles) northwest of Sudbury. In 1980 ore production totalled 10.6 x 10 mt (11.7 million tons) from underground and open pit operations. Underground mining methods include blasthole, vertical retreat, sublevel caving, cut-and-fill and undercut-and-fill. Inco reduction operations in the Sudbury area include two concentrators, one smelter, one iron ore recovery plant, a copper refinery a nickel refinery and a high purity plate rolling mill. As well, an electrolytic nickel refinery is located on Lake Erie at Port Colborne, near Niagara Falls. In the Sudbury District, Inco employees total 14,278 of whom 6,490 are directly employed in the mining and milling operations. I T H DRILLING Background - The use of long blastholes in underground operations at Inco mines in the Sudbury district started more than 30 years ago at the Levack Mine. At that time, diamond drills were used to mine ore by open stoping and for pillar recovery. By the 1950's the concept had been extended to all mines. The heavy percussion drill was also developed by this time and led to the acceptance of the 11.43 cm (4% in.) piston diameter drifter for bar and arm and fan drill applications. The use however, of the nominal 5.08 cm (2 in.) diameter blastholes drilled radially from the level or sublevel causes overdrilling at the periphery. As well, the smaller holes are subject to hole deviation, are difficult to drill beyond 38.1 m (125 ft.) and require the need for several drilling horizons or sublevels. The need to improve blasthole stoping techniques and our experience with large diameter blastholes in open pit mining led to the trial of an I T H drill in 1962. The test was unsuccessful however, since button bits were not available at the time and the tungsten carbide cross bit experienced short life, gauge loss, and caused hole deviation and poor penetration rates. The successful application of the raise borer beginning in 1964 and the ability to drill 20.32 cm (8 in.) to 27.94 cm (11 in.) diameter pilot holes led to the development of smaller, more portable, rotary drills for blasthole mining. As a result, a mining method based on the use of 20 cm (7 718 in.) diameter, 60.1 m (200 ft.) long rotary blastholes was developed and tested successfully at our C.C.North Mine. Between 1972, when the method was first tested, and 1973 over 4572 m (15000 ft.) of large holes were drilled with rotary drills in the recovery of 175,960 mt (194000 tons) of primary stoping and pillar remnants. A new mining method was developed that made use of this large hole drilling equipment. Instead of longhole carbide drilling by bar-and-arm or fan drill set-ups at sublevels, the large diameter holes were drilled full stope height from the top sill, which substantially reduced development, drilling time and improved fragmentation. These drills however, were difficult to move and set-up, and had a high maintenance cost and low productivity. The capital outlay and extensive technical development required to improve these drills and reduce the high drilling costs however, was economically unattractive. New development in drills and button bits

Jan 1, 1981

By M. R. Tek, F. F. Craig, J. O. Wilkes, C. S. Goddin

The waterflood performance of a water-wet, stratified system with crossflow is computed by a finite difference procedure. The effects of five dimensionless parameters on tile oil displacement efficiency, water saturation con-tour.7 and crossflow rates are evaluated in the absence of gravity forces. Crossflow due to viscous and capillary forces is shown to exert a significant effect on oil recovery in a field-scale model of a two-layered. water-wet sandstone reservoir. The crossflow is at a maximum in the vicinity of the front advancing in the more permeable layer. Under favorable mobility ratio conditions, the comparted oil recovery with crossflow always is interrnerliate between that predicted for a uniform reservoir and that for a layered reservoir with no crossflow. INTRODUCTION The important erects of reservoir heterogeneity on waterflood performance are commanding increased attention in the technical literature. Much of this attention is centered on two categories of layered reservoirs: those in which layers are non-communicating and those in which crossflow of fluids occurs between the layers. In the first category, the reservoir is assumed to consist of discrete layers, each uniform within itself and differing from the others only in such properties as thickness, porosity and absolute permeability. The performance within each layer is calculated by one-dimensional flow theory, and the performance of the total reservoir is obtained by summing individual layer performances. Capillary and gravity effects usually are not considered. Representative publications dealing with thi5 type of reservoir are those of Stiles,' Dykstra and Parsons,' Hiatt,3 Warren and Cosgrove' and Higgins and Leighton." Prediction of performance for reservoirs in the second category is considerably more difficult since viscous, capillary and gravitational forces all play important roles in causing crossflow between layers. A number of authors have investigated the simpler problem of two-dimensional displacement flow in a stratified system with a mobility ratio of unity and negligible capillary and gravity effects.'; Others have considered two-dimensional, non-steady-state flow of a single, slightly compressible fluid in a stratified reservoir. A limited number of laboratory oil displacement tests in layered models with crossflow have been reported. Miscible floods (with resultant zero capillary forces) in layered five-spot models were conducted by Dyes and Braun," who studied the effect of mobility ratio with zero gravity forces, and by Craig et al. 12 who studied the effect of gravity forces at constant mobility ratio. Waterfloods in layered five-spot models (with cross-tlow due to capillary, viscous and gravity forces) were conducted by Gaucher and Lindley,"' who showed the effect of gravity forces in causing underrunning of the injected water and by Carpenter, Bail and Bobek, 14 who demonstrated the reliability of Rapoport's" dimension-less parameters for scaling layered systems. Waterfloods in rectangular layered models were conducted by Richardson and Perkins."' who investigated the effect of velocity at constant mobility ratio and with zero gravity forces, and by Hutchinson," who studied the effects of varying mobility, layer permeability and layer thickness ratios. The differential equations which rigorously describe waterflooding in a heterogenous porous medium are non-linear and do not facilitate analytical solution. By using finite difference approximations it is possible to obtain a solution to any desired degree of accuracy. Such a solution, using an alternating direction implicit procedure (ADJP), is described by Douglas, Peaceman and Rachford.18 In the present study, a computer program using ADJP explores systematically the effects of important parameters on waterflood performance of a two-dimensional, two-layered, field-scale model of a water-wet sandstone system. Particular attention is given to evaluation of the water saturation contours and crossflow rates at the interface between layers to gain improved understanding of the crossflow mechanism. PROCEDURE BASIC: FLOW EQUATIONS The basic flow equations for two-dimensional, two-phase, immiscible, incon~pressible flow in a porous medium are:

Jan 1, 1967

By R. G. Garlick, H. B. Probst

Tungsten single-crystal specimens of various orientations were deformed in tension at room temperature. Slip traces indicated both (112)(111) and (110) (111) slip; however, about 10 pct plastic dejormation was required bejore these traces could he seen. Resolzled shear-stress considerations indicated that at least some of the particular systems observed were not those on which slip initiated hut were secondary systems. This is highly probable, considering the high plastic strains involved. Analysis of the stress data with respect to possible slip systems indicated that slip must have been initiated at stresses below the proportional-limit stresses measured. ALTHOUGH there is general agreement that slip deformation in fcc and hep metals takes place on the plane of close packing and in the direction of close packing, there is no such agreement for slip in bcc metals. It is generally agreed that the close-packed direction (111) is the slip direction, but investigations have led to conflicting descriptions of the slip plane. As Hoke and Maddin1 point out, there are essentially four points of view. 1) Deformation in bcc metals is composite shear on (112) and (110) planes or on nonparallel (110) planes, and any apparent slip on other planes can be accounted for completely by slip on these planes. Chen and Maddin have reported this to be the possible case for molybdenum." 2) Slip occurs in the (111) direction and is limited to {110), {112), and (123) planes (the three closest packed planes of the lattice). 3) Slip occurs in a (111) direction, but not necessarily on planes of close packing (banal slip). 4) Slip occurs in those directions and on those planes for which ß, the ratio of Burgers vector to interplanar spacing, is a minimum. The slip systems of the bcc metal tungsten have never been fully determined, although several investigators have reported pertinent results.3"7 The present work was initiated to determine the active slip systems in tungsten at room temperature, the critical resolved shear stresses associ- ated with these systems, and the orientation dependency of operative systems. These features of tungsten deformation at room temperature have never been reported in the literature. The authors find this somewhat surprising, particularly in view of the availability of tungsten single crystals since the advent of electron-beam zone-melting techniques and the widespread interest in refractory metals. It would seem apparent that such work has been attempted but the results have not been reported, possibly due to the conflict with deformation theory. The results of the present work conflict with any straightforward description of deformation based on the proposed explanations of slip in bcc metals. Although these conflicts have not been resolved, a presentation of the problem seems in order and should be of value to others working in this field. MATERIALS AND PROCEDURE Single-crystal tungsten rods of 1/8-in. diameter were grown from undoped commercial rod by one-pass electron-beam zone melting in apparatus previously described by witzke.8 Representative analyses of the rod before and after melting are given in Table I. There was no detectable zoning of impurities during melting. Buttonhead tensile specimens, as shown in Fig. 1, were machined from single crystals. Two flats 90 deg apart were ground in the gage length of each specimen. These flat surfaces facilitated the analysis of slip traces. No attempt was made to position these flats with respect to the crystal orientation. The worked surface layer of the machined specimens was removed by electrolytic polishing in a NaOH solution. Tensile-axis orientations were determined by standard Laue back-reflection techniques. The sharpness of the Laue spots indicated that the crystals were free of strain.

Jan 1, 1964

By I. Javandel, P. A. Witherspoon

The finite element method was originally developed in the aircraft industry to handle problems of stress distribution in complex airframe configurations. This paper describes how the method can be extended to problems of transient flow in porous media. In this approach, the continuum is replaced by a system of finite elements. By employing the variational principle, one can obtain time dependent solutions for the potential at every point in the system by minimizing a potential energy functional. The theory of the method is reviewed. To demonstrate its validity, nonsteady-state results obtained by the finite clement method are compared with those of typical boundary value problems for which rigorous analytical solutions are available. To demonstrate the power of this approach, solutions for the more complex problem of transient flow in layered systems with crossflow are also presented. The generality of this approach with respect to arbitrary boundary conditions and changes in rock properties provides a new method of handling problems of fluid flow in complex systems. INTRODUCTION Problems of transient flow in porous media often can be handled by the methods of analytical mathematics as long as the geometry or properties of the flow system do not become too complex. When the analytical approach becomes intractable, it is customary to resort to numerical methods, and a great variety of problems have been handled in this manner. One such method relies on the finite difference approach wherein the system is divided into a network of elements, and a finite difference equation for the flow into and out of each element is developed. The solution of the resulting set of equations usually requires a high speed computer. When heterogeneous systems of arbitrary geometry must be considered, however, this approach is sometimes difficult to apply and may require large amounts of computer time. The finite element method is a new approach that avoids these difficulties. It was developed originally in the aircraft industry to provide a refined solution for stress distributions in extremely complex airframe configurations. 27 Clough has recently reviewed the application of the finite element method in the field of structural mechanics.6 The technique has been applied successfully in the stress analysis of many complex structures.l, 27, 28 Recognition that this procedure can be interpreted in terms of variational procedures involving minimizing a potential energy functional7 leads naturally to its extension to other boundary value problems. In the field of heat flow, there recently have been introduced several approximate methods of solution that are based on variational principles.2-4, 17 By employing the variational principle in conjunction with the finite element idealization, a powerful solution technique is now available for determining the potential distribution within complex bodies of arbitrary geometry. In the finite element approximation of solids, the continuum is replaced by a system of elements. An approximate solution for the potential field within each element is assumed, and flux equilibrium equations are developed at a discrete number of points within the network of finite elements. For the case of steady-state heat flow, the technique is completely described by Zienkiewicz and Cheung.33 Since the flow of fluids in porous media is analogous to the flow of heat, Zienkiewicz et al. have employed the finite element method in obtaining steady-state solutions to heterogeneous and anisotropic seepage problems. 34 Taylor and Brown have used this method to investigate steady-state flow problems involving a free surface.25 The work of Gurtin has been instrumental in laying the groundwork for the application of finite element methods to linear initial-value problems.12 As a result, Wilson and Nickell have recently

Jan 1, 1969

By Milton R. Pickus, Earl R. Parker

THE modern theories of creep¹-4 in general have been based upon the concept of generation and migration of dislocations, with the generation process normally assumed to be rate controlling. The theories are generally deficient in that they fail to take into account many factors that are known to influence creep. The influence of the state of the surface of the test specimen has been almost completely overlooked; yet the present report shows that the nature of the surface may, in certain cases, govern the creep characteristics of a specimen. In the period since Taylor" applied the concept of dislocations to a study of metals, a school of thought has developed that closely relates the plastic deformation of metals to the generation and migration of dislocations through the crystal lattice. It might be expected that the thermal energy required for the generation of a dislocation would be different from that for migration of the dislocation through the lattice. Furthermore, the activation energy for generation would be expected to vary for different parts of the solid metal. It has been predicted that dislocations would be generated most easily at external surfaces, but could also be activated at certain internal surfaces such as grain or phase boundaries. Within the body of the metal a range of values for the activation energy might be expected because of different degrees of disorder at such regions as grain boundaries, impurities, and second-phase particles. The particular value of the activation energy that was rate determining could then depend on the specific conditions of a test. If, for example, the surface atoms were by some means constrained, the generation of dislocations in the body of the metal might become the important factor. On the other hand, other conditions may favor generation at the surface. It is possible then that the creep behavior may not be completely determined by the inherent properties of the metal. Even the environment in which a test is carried out could have a significant effect. In fact it is conceivable that in order to obtain the maximum creep resistance from a given alloy, the surface atoms must be so constrained that the activation energy for generating dislocations on the surface is at least equal to that required for generation in the body of the metal. On the basis of such considerations, and in view of the limited number of publications discussing this subject, it seemed that an investigation of the influence of the state of the surface on creep might yield information of both theoretical and engineering interest. Experiments on single crystals, demonstrating a variation in the mechanical properties due to alterations in the surface layer, have been reported by several investigators.6-13 he results of these experiments have been briefly summarized;14 consequently, the earlier work will not be reviewed here. As an example of these findings the observations of Cottrell and Gibbons may be cited. They reported the critical shear stress of a lightly oxidized cadmium single crystal is greater by a factor of 2½ than a specimen with a clean surface. Materials and Methods Single crystals M in. in diam and 8 in. long were prepared from Horse Head Special zinc, melted under an atmosphere of helium in a large pyrex test tube, and drawn up into a long ½ in. diam pyrex tube by means of a vacuum pump. The cast zinc rods thus produced were cut into convenient lengths and sealed in evacuated pyrex tubes. Single crystals were grown by gradual solidification of the remelted rods. Cleaving the ends of the single crystal specimens chilled by liquid nitrogen proved a simple method for determining orientations from the exposed basal plane from the markings left on the cleaved surface that gave the slip directions with sufficient accuracy for the experimental work. The specimens chosen for the experiments were those having the angle between the basal plane and the specimen axis within the range of 15" to 65". Since zinc single crystals are quite delicate, it was necessary to devise an appropriate method of gripping the specimens in order to suspend them in the furnace and apply the load. Stainless steel collars were prepared having an inside taper, the smaller end of the taper being of such a size that the specimen could just pass through freely. The tapered hole did not extend the full length of the collar; a sufficient thickness of metal remained so that a hook could be attached to provide a means of applying the load and suspending the specimen. One of the collars was slipped over the upper end of a specimen which was supported vertically in a steel jig. The collar was then heated electrically until the end of the crystal melted and filled the collar with molten zinc. At this point the application of heat was discontinued, whereupon the molten zinc quickly solidified, due to the chilling effect of the jig. The specimen was then inverted and the second collar applied in a similar manner. The jig served several purposes: limiting the length of specimen that was melted, providing excellent alignment of the collars with respect to the specimen axis, and protecting the specimen from mechanical damage. Once the specimen was suspended in the furnace and loaded, it was desired to accomplish the surface treatment with a minimum of disturbance of the specimen. Around the specimen was a long pyrex tube, the upper portion of which was approximately 1 in. in diam, and in it was a copper coil of such a diameter to fit snugly against the tube. A specimen, approximately ½ in. in diam and 4 in. long, was suspended by means of a stainless steel rod so that it hung within the copper coil. The lower portion of the glass tube was approximately ¼ in. in diarn, and passing through it was a 5/32 in. diam stainless steel rod which hung from the lower specimen collar. This portion of the glass tube and the stainless steel rod extended through the bottom of the furnace. A T-connector, with suitable packing, was attached to the lower end of the stainless rod to provide a water-

Jan 1, 1952

By C. Feng

HE sensitivity of twinning in molybdenum alloys containing 20 or more at. pct Re was reported by Dickenson and Richardson&apos; and Sims et a1.&apos; The latter3 also studied the effect of twinning on plastic deformation of these alloys. Recently, in this laboratory, the twinning planes in a series of Mo-Re alloys were successfully identified by tracing their boundaries on two known surfaces of the crystals, with the aid of stereographic projection. The nominal alloy composition and the results of the determination are listed in Table I. Metallic powders of molybdenum and rhenium with 99.9 pct purity were mixed, pressed and arc-melted into buttons under purified argon in a water-cooled copper hearth; the buttons were annealed at 2400 °C in vacuum (10-&apos;mm Hg) for 1 hr, remelted under argon and finally reannealed in vacuum at 2400°C for another hour. This treatment yielded a homogeneous alloy. Large-grain specimens devoid of subgrains were obtained with grain diameter varying from 1/8 to 1/2 in. A typical specimen weighed about 15 g. Orientations were determined by taking X-ray back reflection photographs for each grain on a polished surface of the specimens. Two surfaces were cut and polished; the angle between the two surfaces was measured with an accuracy of *2o. The twins were produced by compression in a hydraulic press at room temperature. Usually, several sets of twins could be obtained within each grain. Except in cases where no twins were formed, (Crystals 7, 8, and 9) the twinning planes were identified consistently as the (112) family over a wide range of alloying compositions and surface orientations of the crystals, as indicated in the stereo-graphic triangle in Fig. 1. The twins, however, were not broad enough to accommodate a conventional X-ray beam and no identification could be made of the twinning direction. Nevertheless, the direction must be one that lies in a plane of symmetry perpendicular to the twinning plane. There are only two such possible planes in a bcc lattice, namely the (110) and the (100) planes. Of these, only the (110) planes are perpendicular to (112), and the <111> direction is the intersection of the two perpendicular planes. It can thus be concluded that <1l1> is the twinning direction. The twinning elements of molybdenum have been reported as the (112) planes and the <111> directions,4 which are also the operative elements in other body-centered-cubic metals, such as W, a-Fe, and ß -brass.5 Thus, the present finding of the twinning elements in Mo- Re alloys supports the concept that twinning formation is mainly governed by the lattice structure. It is of interest to note that for specimens containing 12 at. Pct Re or less, no twins were found after being plastically deformed to as much as 30 pct reduction in height by compression, while for the 35 at. pct Re alloy, twins were formed with less than 1 pct deformation. This, of course, does not exclude the possibilities that for Re-Mo alloys containing 12 pct Re or less, twins could be formed under different conditions, such as at liquid air temperature or under impact loading. The present results, however, suggest that under the same conditions twinning is increasingly sensitive with increasing rhenium content. Consequently, the plastic strain at which twinning starts was found inversely proportional to the amount of rhenium in solid solution with molybdenum. This plastic strain necessary to cause twinning may be used as a criterion in the study of twinning characteristics.

Jan 1, 1961

By W. D. Forgeng, R. E. Grace

The rate of copper corrosion in liquid lead was studied as a function of flow rate and temperature in a closed isothermal loop system between 350" and 500°C. Kinetic data were interpreted with the Nernst-Brunner equation and the Chilton-Colbum mass transfer analogy to heat transfer. Over the range of temperatures and flow rates employed the solution rate constant varied from 2 x 10-3 to 20 x 10-3 cm per sec. The rate constant was found to vary with the 0.76 power of the Reynolds number in the range 7500 < Re < 40,000. The results of this investigation indicate that the Cu-Pb corrosion process is controlled largely by diffusion across a boundary layer. particularly at the higher temperatures. The effective boundary layer for diffusion is found to be approximately three to four times smaller than the momentum boundary layer. CORROSION by liquid metals has long been a problem during melting, static containment, and casting. Recently, considerable emphasis has been placed on the understanding of liquid metal corrosion mechanisms in an effort to prevent mass transfer and eventual failure in liquid metal heat exchangers and in liquid-metal-fueled nuclear reactors. The present investigation was conducted to determine the relationships which exist between corrosion kinetics and hydrodynamic conditions in an isothermal loop containing a simple liquid metal-solid metal corrosion system. The Cu-Pb system was chosen for its simplicity and ease in handling. Previous isothermal Cu-Pb corrosion studies1-3 have been conducted in both static and dynamic systems but not under conditions which allow easy "scale-up" to engineering systems, such as liquid metal heat exchangers. On the other hand, most liquid metal loops which have been used to evaluate mass transfer rates4 have been driven with temperature gradients under conditions of natural convection and unknown flow rates. The primary contributions of this research are twofold: 1) to evaluate the design of a simple isothermal loop corrosion system and 2) to investigate liquid metal corrosion behavior under well-defined hydrodynamic conditions. MATERIALS AND EXPERIMENTAL WORK The apparatus used to measure the Cu-Pb corrosion rates is shown schematically in Fig. 1. The loop system consisted of 1) a reservoir made of Type 316 stainless steel containing a centrifugal pump and 2) stainless-steel tubing containing a removable copper test section. The copper test section was OFHC hard-drawn tubing, 11.0 0.05 cm in length and 0.775 ±0.005 cm ID. A Type 316 stainless-steel venturi meter* was inserted in place of the copper test sec- tion in order to determine the lead velocity as a function of pump speed at each temperature. The Cu-Pb system was chosen for this study because the solubility of copper in liquid lead is large enough to measure accurately but small enough that the diameter of the copper tubing was not changed significantly by corrosion. There are no intermediate phases formed in the system, and the solid solubility of lead in copper is vanishingly small so that back-diffusion cannot occur. Molten lead (corroding grade; 99.94+ pct Pb, 0.0015 max pct Cu) was charged from an auxiliary melting furnace into the system under an argon cover to minimize oxidation. The lead was then maintained at constant temperature by a stirred molten salt bath in which the loop was immersed to a depth just above the lead level in the reservoir, Fig. 1. The total volume of lead in the system was 320 2 cu cm.

Jan 1, 1969

By J. W. Bolton, S. A. Weigand

This paper discusses some fundamental metallurgical principles involved in production of sound cast bronze. In a previous paper the writers advanced the theory that "oxidation" in bronze castings is due to incipient shrinkage, and showed the effect of reducing melting atmospheres.&apos; In the present paper the effects of certain impurities and of actual oxidizing conditions are shown. The appendix deals with the appearance of various inclusions. For many years the prevailing opinion has been that unsoundness, dark colored fractures and other phenomena accompanying porosity and weakness in bronzes are due to oxidation. The actual troubles are caused by fissures of intercrystalline type, which are often mistaken for intercrystalline films. These weaken the metal and make it porous. Grave doubt regarding the accuracy of the oxidation theory appears when several research papers presented within the last 10 years are reviewed critically. In 1919, Comstock2 conducted metallographic researches, attempting to identify "oxides" in synthetically prepared metals. He found that oxides of tin, aluminum, zinc, etc. are different from the intercrystalline films (or cavities) to which porosity is due. Apparently he believed that these "oxide films" may be caused by volatile oxides of zinc or of phosphorus or by dissolved gases thrown out of solution during solidification of the metal. In 1923, Woyski and Boeck3 definitely questioned the accuracy of the oxidation theory and indicated the danger from reducing atmospheres. They say that "oxidation, gassing and shrinkage may produce effects very similar." In 1926, investigations by Iwasé4 showed marked change in absorp-tion coefficients for various gases in copper above and below the liquidus.

Jan 1, 1930

By Axel Hultgren

IN ingots of silicon-killed carbon steel made without addition of - aluminum, transparent spherical or nearly spherical inclusions, up to about 0.15-mm diameter, are generally present. They may be glassy or crystallized, wholly or partially. In steels of high carbon contents they consist of silica,4,12 in steels of lower carbon contents arid, in consequence, higher oxygen contents, of iron-manganese-silicate with higher iron and manganese contents the lower the carbon content. Small silicate inclusions, about 0.01 mm or smaller, may occur, just as sulphide inclusions do, in portions that have been the last or nearly the last to freeze,10,12,17 this location being verified by primary etching.10 Hence, it may be concluded that they have separated from liquid steel that has become enriched in oxygen through segregation during freezing. Silicate inclusions with a diameter larger than about 0.02 mm appear, at least in ingots of moderate size, to be distributed at random in relation to the primary structure and therefore may be assumed to have existed as droplets in the liquid steel before freezing started at the point in question. The average size of such large inclusions has been found to increase toward the axis17 and their amount to increase from the top downward in the axial region .2,10 It has been assumed that this accumulation is a result of the droplets being brought down by the slowly settling metal crystals.2 It has been suggested that large silicate inclusions generally form,6 or may form," by coagulation of smaller ones, or by small drops being caught by larger ones during the rising of the latter.9 The occasional occurrence of a large inclusion surrounded by a swarm of small ones has been taken as a proof of this mechanism but, as suggested later, may be explained in another way. It has been pointed out that an inclusion droplet in the liquid steel may grow at the expense of an adjacent one, which implies diffusion of soluble inclusion-forming elements in the liquid steel.15 Further, it has been pointed out that, on cooling in ladle or mold, the metal-silicate equilibrium is displaced in the direction of separation of silicate. Thus inclusions may grow in size and amount.2,3,8,12,13,17,19,20 The exposure of the liquid steel to the oxygen of the air during tapping and pouring, and the consequent reaction, has been mentioned as a source of the formation of inclusions19,20 but this possibility has not received particular attention. Further, the admixture of furnace slag during tapping&apos; or of refractory material from various sources1,20 has been considered. The inclusions due to the latter may be recognized, however, through their resistance to hydrofluoric acid, imparted by the alumina content. Silicate inclusions, are often referred to as. the natural and inevitable product of reaction on adding silicon or silicon

Jan 1, 1948

By R. B. Gilmore, Lewis W. MacNauhgton

The North Texas district, as&apos; herein defined, includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita, and Wilbarger. This area covers generally the crest and south flank of a system of buried mountains known as the Red River uplift. The oil and gas accumulations along this feature are in traps, which, although localized by structures incident to the regional uplift, usually are modified by stratigraphic changes in the sediments. Excepting those in southeastern Baylor, southern Archer, and southwestern Clay counties, all the fields within the district are on this Red River uplift. These exceptions, which have the same type of oil and gas accumulation as the other fields, are on the extreme north end of the Bend arch, which is a broad anticline plunging northward from the Llano uplift in central Texas to Archer County. The larger part of past oil and gas production has come from Pennsyl-vanian strata, with less important amounts from the Permian, and minor but increasingly important quantities from the Ordovician. Developments during 1942 Approximately 500 wells were drilled in the district during 1942, in contrast with some 1600 wells drilled during 1941, and only some goo oil wells were completed, a decrease from 1941 of more than 10 per cent in the number of successful drilling operations of the total wells drilled. Production increased slightly over the previous year in spite of a decrease in the number of producing wells. The average depth of discovery wells was some 600 ft. deeper than in 1941. Although more discoveries produced from horizons above the base of the Strawn series than those below the Strawn, the deeper horizons, including the Bend series of the Pennsylvanian, the Mississippian limestone, and the Simpson and Ellenburger of the Ordovician, furnished most of the addition to oil reserves. The largest single addition to the reserves was again in the Ellenburger formation in the K. M. A. field. During the year 47 wells were completed, bringing the total developed acreage in this horizon to some 5450 acres. The most active area was Montague County, in which eight fields, or potential fields, were discovered although only 39 oil wells were completed. K. M. A: Pressure Maintenance Satisfactory progress was made by the K. M. A. Pressure Maintenance Association in 1942, At the end of the year, 100 wells were being used for input and total monthly volume of gas returned to the reservoir reached a high of 430,971 M cu. ft. in December, with an input ratio of 587 cu. ft. of gas returned for each barrel of oil produced during the month. This represents a utilization of 50 per cent of the gas available for return during that month. Comparison of the present average bottom-hole pressure by means of a decline

Jan 1, 1943

By R. B. Gilmore, Lewis W. MacNauhgton

The North Texas district, as&apos; herein defined, includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita, and Wilbarger. This area covers generally the crest and south flank of a system of buried mountains known as the Red River uplift. The oil and gas accumulations along this feature are in traps, which, although localized by structures incident to the regional uplift, usually are modified by stratigraphic changes in the sediments. Excepting those in southeastern Baylor, southern Archer, and southwestern Clay counties, all the fields within the district are on this Red River uplift. These exceptions, which have the same type of oil and gas accumulation as the other fields, are on the extreme north end of the Bend arch, which is a broad anticline plunging northward from the Llano uplift in central Texas to Archer County. The larger part of past oil and gas production has come from Pennsyl-vanian strata, with less important amounts from the Permian, and minor but increasingly important quantities from the Ordovician. Developments during 1942 Approximately 500 wells were drilled in the district during 1942, in contrast with some 1600 wells drilled during 1941, and only some goo oil wells were completed, a decrease from 1941 of more than 10 per cent in the number of successful drilling operations of the total wells drilled. Production increased slightly over the previous year in spite of a decrease in the number of producing wells. The average depth of discovery wells was some 600 ft. deeper than in 1941. Although more discoveries produced from horizons above the base of the Strawn series than those below the Strawn, the deeper horizons, including the Bend series of the Pennsylvanian, the Mississippian limestone, and the Simpson and Ellenburger of the Ordovician, furnished most of the addition to oil reserves. The largest single addition to the reserves was again in the Ellenburger formation in the K. M. A. field. During the year 47 wells were completed, bringing the total developed acreage in this horizon to some 5450 acres. The most active area was Montague County, in which eight fields, or potential fields, were discovered although only 39 oil wells were completed. K. M. A: Pressure Maintenance Satisfactory progress was made by the K. M. A. Pressure Maintenance Association in 1942, At the end of the year, 100 wells were being used for input and total monthly volume of gas returned to the reservoir reached a high of 430,971 M cu. ft. in December, with an input ratio of 587 cu. ft. of gas returned for each barrel of oil produced during the month. This represents a utilization of 50 per cent of the gas available for return during that month. Comparison of the present average bottom-hole pressure by means of a decline

Jan 1, 1943

By R. W. Guard

ALTHOUGH etching techniques have been developed for revealing dislocation sites in several metals and ionic crystals,h t is valuable to extend the technique to new metals. An etch pit method for nickel has been developed on the basis some suggestions of Dr. John R. Cuthill of the National Bureau of Standards who had observed etch pits in creep specimens of nickel. The etchant used was proposed first by wensch2 for revealing grain size in nickel. The present paper describes the evidence that the technique can be used to reveal dislocations and gives the conditions under which etching can be carried out. The specimens examined were vacuum melted high-purity Ni (99.985 pct Ni) and commercial "A" nickel (99.8 pct Ni). Both materials contained greater than 0.008 pet C and had been annealed in nitrogen or dry hydrogen at 1100o to 1200°C. This gave a grain size of 1.5 mm in the high-purity nickel and 0.050 mm in "A" nickel. Tensile specimens (0.254 in. diam) were deformed from 0.25 to 10 pct at room temperature and then heated for 1/2 hr at different temperatures from 400" to 900°C. The specimens were sectioned longitudinally then polished electrolytically in 60 pct H2SO4 and etched in 35 pct H3PO4 solution at 0.2 to 0.4 v for 30 sec to 3 min. The best method for setting the proper voltage for etching is to increase the voltage until gas bubbles are evolved vigorously from the specimen and then cut it back by 10 pct. It is necessary to heat the specimen above 500°C after deformation in order that etch pits will be formed. This "decoration" treatment permits carbon to segregate to the dislocation rendering them sensitive to etching. It was demonstrated that carbon was the decorating impurity by decarburizing some specimens in wet H2 at 1200°C. The susceptibility to etch pitting was lost following this treatment but could be restored by carburizing in contact with graphite. Some rearrangement of the dislocations in the as-deformed structure occurs on heating at 500oC and above so that the technique can not be used to study the nature of dislocation patterns in deformed specimens. Extended etching does not change the number of pits although the background becomes rough and the pits quite large. The polycrystalline specimens with various strains were examined after annealing at different temperatures. Typical patterns are shown in Figs. 1 and 2. In the unstrained specimen, Fig. 1, the density of pits is 2.5 X 10&apos; per sq cm. All grains show pits regardless of their orientation although there is a

Jan 1, 1961

By B. N. Bose, M. F. Hawk

SINCE Davenport and Bain&apos; introduced the isothermal transformation technique for the study of austenite decomposition in steels, a new field of investigation has opened up. Extensive research has been carried out on many different steels, but relatively little work has been done on eutectoid transformations in analogous alloy systems. The researches of Smith and Lindlief,² Mack,³ and Klier and Grymko²0 on the beta-phase transformation in copper-aluminum alloys, of Hibbard, Eichelrnan, and Saunders4 and Smith5 on the kappa-phase transformation in copper-silicon alloys, of Chaudron and Forester6 on the decomposition of "FeO," and of Wasserman7 on similarities between the iron-carbon, copper-aluminum, copper-tin, and copper-beryllium systems essentially comprise the field. The iron-nitrogen system, in view of its remarkable similarity to the iron-carbon system, is particularly attractive for the study of eutectoid decomposition. The present investigation is concerned with the study of isothermal transformation, proceeding by the familiar nucleation and growth processes, and of martensitic transformation characteristics of pure iron-nitrogen alloys. The kinetics of transformation and the morphology of the transformation products have been investigated, for these must be the factors determining the properties and behavior of the final product. The Iron-Nitrogen System he binary iron-nitrogen phase diagram has been a matter of considerable disagreement among vari01.1s investigators. However, the phase diagram according to Eisenhut and Kaupp8 and Lehrer10 is now considered essentially correct as reproduced in fig. 1. The important values, 2.35 pct nitrogen and 591°C, for the co-ordinates of the eutectoid point (obtained from this diagram and used in the re- search to be described) were confirmed in a concurrent study of Paranjpe, Cohen, Bever and Floe." The eutectoid decomposition involves the transformation of the ? face-centered cubic interstitial solid solution of nitrogen in iron to the a body-centered cubic interstitial solid solution of nitrogen in iron and the ?&apos; nitride of iron. This nitride is essentially the compound Fe,N; it also possesses a face-centered cubic lattice but a considerably larger one than the ?; the nitrogen atoms in ?&apos; are arranged in an ordered way in the centers of the unit cubes.8,10,11 A martensitic structure has also been reported8,12 in iron-nitrogen alloys and was studied in the research to be described here. Materials and Methods The specimens used in this investigation were prepared by nitriding "pure" iron. This iron was supplied by the Westinghouse Research Laboratories and is the product bearing their trade name "Puron"; it contains about 0.04 wt pct total impurities, the major portion of which is oxygen. Specimens were ribbons several inches long, a tenth of an inch wide, and 0.125 mm thick; this was the

Jan 1, 1951

By R. A. Flinn, R. D. Pehlke, D. R. Glass, P. O. Hays

Knowledge of the depth of penetralion of an oxygen jet into the bath of the oxygen converter and of the correlation of penetration with driuing pressuve, lance heighl, and nozzle throat area is vital to the understanding of converter operation. If the penetration is too shallow, then severe and hazardous slopping takes place. On the other hand, if the jel penetrates entirely Lhvough lhe bath for an apprcciublc period of time, bottom damage occurs. In addilion to measurement of the penetralion of the jel, knou~ledge of the circulatory movement in the bath is also of interest in order to evaluale various theories oj-concerter operating behavior which have been published. In this investigation, experimental converters were buill of IOU- , 300-, and 4000-lb capacity. Four independent methods were used to determine penelralion: the onset of bottom marking, a nitrogen bubbler probe, observation througlt an optical syslew built into the oxygen lance, and direcl viewing of the jet issuing from the bottom of the vessel. Good correlation zuas obtained, and empirical relalions for pvedicling perletration were found. These relations were conjzrmed by bottom marking tests in 55- and 110-ton vessels. Within the operaling conditions employed in these tests, the depth to which a single oxygen jet penetrated zuas found lo vary according to the relatiorl ThE technical literature is replete with data concerning the successful use of the basic oxygen furnace or converter in steelmaking. Experimental data are lacking, however, on the vital factors of the depth of penetration of the jet into the bath and the induced circulation. Commercial operating conditions usually have been the result of cut and try experiments in lance manipulation until satisfactory results were obtained. There have been, however, two hotly argued opposing theories concerning desirable depth of penetration and these are exemplified by the Schwarz and Miles patents1,2 on one hand and the Suess patent3 on the other. The Schwarz patent teaches that the jet, issuing from the nozzle at supersonic speed, penetrates deeply "so that the reactions between the iron and the oxygen and between the oxygen and the rest of the smelting components take place in the center of the bath". Specific operating suggestions are given by Miles.2 By contrast, the Suess patent calls for surface Circulalion was investigated by lour methods: by direct observation in 200-lb open baths, by the use of graphite rudders in the 300- and 4000-lb converlers, by direct observalion through an oplical system in the lance, and by various models al room temperature. All were in excellent agreement and indicated that the motion of the bath ulas up at the center, radially outluavd at the surface, and down at the sides. Experi-ments in small and in commercial vessels indicate that it is essential to operate with a jet penetration of approximately 50 pct of the bath depth. Surface blowing results in low oxygen eficienty and in hazardous conditions which may render the process inopeuable. RejYactory dartzage al the bottom of the vessel is only encountered when the jet penetrates to the bottom, and this can be avoided by properly applying the penetration formula. The application of this en/pirical formula in commercial peraations is best when limited to combinations of lance size, pressure, and height which are typically encounteved in the use of a single-hole lance. blowing so that "...the oxygen jet does not penetrate deeply into the molten metal bath and is confined to an impingement area at the central portion of the bath surface". These references are given merely to illustrate the basic differences between the two schools of thought and to point out the need for measurement of penetration for the sake of the operator. For example, it is shown later that inefficient and even dangerous conditions can arise if improper blowing conditions are used. Differences are also evident between the two schools of thought as to the mixing, circulation, and agitation which is to be accomplished by the jet. The Schwarz patent states that "surface contact is not sufficient in most cases to bring about quick reaction, the same as the blowing of the gas over the bath surface or the mere blowing of the gas onto the bath surface". The patent goes on to call for active mixing. In contrast the claims of the Suess patent call for "discharging a stream of oxygen ... to an extent to avoid material agitation of the bath by the oxygen stream". In this patent the circulation is said to be downward in the center and up at the sides of the vessel. A number of investigators4-12 have explored penetration and circulation in transparent models. In general, it is agreed in these tests that the circulation is upward at the center (along the sides of the jet cavity),

Jan 1, 1968

By C. R. Taylor, John Chipman

THE study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8: I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. EXPERIMENTAL METHOD Furnace The furnace used in this investigation differed from previous designs and may be considered a fourth modification of the original rotating furnace. Its essential features are shown in Fig. I. The outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base C are alberene stone. The coil supports D are of "Formica," a material formed from phe-

Jan 1, 1942

By W. A. Backofen, D. Lee

The deformation of textured sheet of titanium and several of its all-a (hcp) alloys was investigated with two kinds of experiments: tension testing along different directions in the plane of the sheet, and combined-stress loading along the principal axes of anisotropy (the rolling and transverse directions). Texture and plastic anisotropy were evaluated with pole figures and by measurement, as a function of orientation, of the tensile transverse-strain ratio, or R parameter. The results as a whole can be rationalized qualitatively with the present understanding of deformation mechanisms in titanium. Quantitative agreement between the orientation dependence of tensile yield strength and the Predictions of continuum ANISOTROPY in the properties of engineering materials is more the rule than the exception because anisotropy in structure is so common, and the one generally follows the other. Two broad categories of structural anisotropy are represented by mechanical fibering and crystallographic texture. The former is important in many aspects of fracture.&apos; The latter has more significance for yielding and plastic deformation, theory, using the R measurements, was relatively poor. However, in tension-tension quadrants of the yield-locus diagrams, the difference between theory and experiment was hardly more than 10 pct. The maximum texture-hardening effect was found in a 4Al-1/4O2 alloy to be nearly 50 pct. In the compression-compression quadrant, {1012} deformation twinning prevented the locus from expanding much beyond the Position predicted for isotropic material. With increasing temperature the trend in R was downwards, approaching unity (isotropy) near the a-transus temperature; an accompanying development was large amounts of neck-free extension. which are of special concern in this paper. The tendency has been to view crystallographic texture more as a liability or curio than as an asset. The prominent exception is found in silicon-ferrite sheet for power-transformer cores, which is processed to develop a new optimum texture for high electrical efficiency. Yet it should be possible to find other examples, involving other kinds of properties. More specifically, there is good analytical reason to expect improved combined-stress yielding resistance in suitably textured material,2,3 and it has now been shown by experiment that texture hardening or softening is a potentially useful phenomenon in certain engineering devices and processes.&apos;-I To date, work has included measurements of the transverse (width to thickness) strain ratios in the

Jan 1, 1967

By A. D. Hill, R. S. Schechter, M. P. Walsh, I. H. Silberberg, M. J. Humenick

There are many uranium deposits which are too deep, too poor in quality or too small in extent to be economically strip mined. It now appears that this uranium can be mined using in situ leaching processes. A number of field tests have been, are being or will be conducted to demonstrate the feasibility of In site leaching. Preliminary results are encouraging, but a major question concerns the restoration of the mine site, which is generally contained within an aquifer. It is necessary to ensure that the quality of the water is not adversely affected by the mining operation. One component of the lixiviant is necessarily a cation and, during the course of mining, the ion exchange sites of the minerals in the mine zone become saturated with this cation. Ammonium is the cation now commonly used. Clearly, any restoration procedure or question involving the rate of cation migration with the groundwater all necessarily involve the process of ion exchange coupled with flow in porous media. The equations describing this process are presented in this paper and numerical solutions obtained. Preliminary results showing the effect of isotherm shape, cation exchange capacity, flow and dispersion are presented. These results demonstrate that in many situations cation migration in ground water will be slow.

Jan 1, 1979

By Voyle R. McFarland, Robert A. Burmeister, David A. Stevenson

The distribution of lead between phases in the Ag-Sb-Te system was studied using microautoradio -graphy. Two compositions were investigated, both containing an intermediate phase Known as silver antimony telluride as the major phase, and one containing AgzTe and the other SbzTes as the minor phase. For both compositions, two thermal treatments were used: nonequilibrium solidification from the melt and long equilibration anneals of the as-solidified structure. For each composition, lead was segregated in the minor phase of the as-solidified structure, but was distributed in the matrix after anneal. The electrical resistivity and carrier type were insensitive to the distribution of lead in the two-phase structure. ThERE has been considerable interest in the Ag-Sb-Te system because of its thermoelectric properties. The major interest has been in compositions on the vertical section between AgzTe and SbzTes, particularly the 50 mole pct SbzTes composition AgSbTez (compositions are conveniently expressed as mole percent SbzTes along the AgzTe-SbzTes section). One of the major problems in the proper evaluation and utilization of this material is the inability to control the electrical properties through impurity additions: all alloys prepared to date have been p-type, even with the addition of large amounts of impurities. It has been shown Wit all the compositions previously studied contain an intermediate phase of the NaCl st&apos;ructure as a major phase (denoted by b) and a second phase, either AgzTe or SbzTe3, as a minor phase.&apos;-3 One explanation for the unusual electrical behavior of this material is that the impurity additions have a higher solubility in the second phase than in the matrix; the impurity would segregate to the second phase, leaving the bulk matrix essentially free of impurity.4 In order to investigate this mechanism with a specific impurity element, the distribution of lead between the two phases was determined using autoradiography. Lead 210 was chosen because of the suitability of its 0.029 mev 0 particle for autoradiography and also because of the interest in lead as an impurity in this system.5&apos;6 EXPERIMENTAL PROCEDURE Two compositions were taken from the vertical section between AgzTe and SbzTes, 50 mole pet SbzTes (Viz. AgSbTez) and 75 mole pct SbzTes, in which AgzTe and SbzTes appear, respectively, as the minor phase. Lead containing radioactive lead (pb210) was added to the above compositions to provide a concentration of 0.1 wt pct Pb. The material was placed in a graphite crucible in a quartz tube which was then evacuated and sealed. The samples were melted and solidified by cooling at a rate of 8°C per min and then removed and prepared for microa~toradiography. After autoradiographic examination of these samples, they were again encapsulated and annealed in an isothermal bath at 300°C for a number of days and prepared for examination. An alternate method of preparation employed a zone-melting furnace; the molten zone traversed the sample at a rate of 1.2 cm per hr and the solid was maintained at a temperature of 500°C both before and after solidification. This treatment had the same effect as solidification at a slow rate followed by an anneal for several hours at 500°C. In order to obtain the best resolution, thin sections of the alloy were prepared by hand lapping to a thickness of approximately 20 p. Other samples were prepared for examination by lapping a flat surface on the bulk sample. The resolution, although somewhat better in the former procedure, was adequate in both instances and the majority of the samples were treated in the latter fashion. A piece of autoradiographic film (Kodak Experimental SP 764 Autoradiographic Permeable Base Safety Stripping Film) was stripped from its backing, care being taken to avoid fogging due to static-electrical discharge. A small amount of water was placed on the sample, the film applied emulsion side down on the surface of the sample, and the sample and the film dipped into water in order to assure smooth contact. After drying, the film was exposed for 2 to 5 days, the period of time selected to give the best resolution. The film was developed on the specimen and fixed and washed in place. Two major factors must be considered in establishing the reliability of an autoradiograph: the in-

Jan 1, 1964

By A. R. Denison

The Permian Basin as it appears in the title of this article refers to three rather widely separated areas of production. It includes what are commonly known as the "Panhandle" fields of the northwest part of Texas; the West Texas fields, in the southwest part of Texas; and the New Mexico fields, in the southeast corner of New Mexico. These three areas are all included in a single province and produce the majority of their oil from limestones or dolomites of Permian age. The manner of accumulation of oil in the three areas is somewhat diverse. In the Panhandle, production is found on the flanks of an enormous structural ridge, the core of which is granite. In southwest Texas and New Mexico oil is produced from both gentle and steep folds and from lenticular areas of porosity. Production in Texas During 1927 Texas produced a total of 216,306,000 bbl. of oil of which the Permian Basin contributed 89,797,000 bbl., or 42 per cent. During 1928, Texas produced 255,021,000 bbl. of oil of which the Permian Basin contributed 145,955,000 bbl., or 57 per cent. The increase in total production is entirely due to the West Texas fields. All other districts in Texas declined during the year while the west Texas fields registered an increase of more than 71,000,000 bbl. West Texas daily average production increased from 260,752 bbl, at the beginning of 1928 to a maximum of 406,318 bbl. per day the first week in May. Due to prora-tion agreements, the production was held at a fairly constant level around 340,000 bbl. during the remainder of the year, having 345,660 bbl. the last week in December. Daily average production of the Panhandle fields decreased from 80,178 bbl. at the beginning of the year to 59,025 bbl. at the close of the year. The combined daily average production of the Panhandle and West Texas fields at the beginning of the year was 341,138 bbl. and at the close of the year was 405,408 barrels. Fig. 1 gives a comparison of the production in the Permian Basin in relation to the production of the entire state. It is clearly shown that

Jan 1, 1929