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By F. E. Jaumot, R. L. Smith

Self-diffusion in zinc at temperatures below 200°C has been studied using both single crystal and polycrystal samples. Anomalous results were obtained for single crystal samples, the data indicating that in some cases grain boundary diffusion predominated. These anomalous results are presumed to be due to low angle lineage boundaries in the single crystals. When volume diffusion occurred in either single or polycrystal samples, the values for the diffusion coefficient were as much as several orders of magnitude larger than would be expected from high temperature data. ONSIDERABLE work has been done on self-^-*diffusion at temperatures in the neighborhood of two thirds of the melting temperature (in OK) and higher, but very little has been done at lower temperatures. This is particularly true of self-diffusion in single crystals. This paper reports work on self-diffusion in zinc at temperatures below 200 °C where both polycrystalline and single crystal samples have been used. The measurements were made using both the sectioning and absorption techniques. The experiments on diffusion at low temperatures were initiated primarily for three reasons: to obtain data from single crystal diffusion covering a wide range of temperatures, to obtain values of the activation energy for grain boundary diffusion, and to obtain, if possible, a lower limit to the temperatures at which the absorption technique may be used. It is possible to determine whether volume or grain boundary diffusion predominates at low temperatures by analyzing the manner in which the concentration of the diffusing atoms varies with the depth of penetration. The analysis is possible only for the sectioning technique. For volume diffusion and for the boundary conditions of the present experiment, the curve of the logarithm of the concentration, C, vs the square of the penetration depth, x, is a straight line with the slope proportional to — 1/D. If grain boundary diffusion predominates, Fisher' has shown that a curve of In C vs the first power of the penetration depth should be a straight line. This linear dependence of concentration on depth has been observed experimentally by several investigators. (See, for example, refs. 3 and 4.) Following Fisher's analysis, the grain boundary diffusion coefficient can be written as where 8 is the grain boundary width, D, is the volume diffusion coefficient at the temperature involved, t is the time of diffusion, C is the concentration of diffusing material, and x is the depth of penetration. A more general analysis employing the same model as Fisher's but with fewer assumptions has been given by Whipple.' In contrast to Fisher's analysis the more general analysis of Whipple does not always yield a straight line relation between In C and x. Recently Turnbull and Hoffman have discussed both analyses and have applied the Fisher-Whipple model to a more refined dislocation model of the grain boundary. They have also discussed the possibility of a large effect of grain boundary direction on diffusion. In the case of the absorption technique, for which results are also given, one simply gets a value for the diffusion coefficient with no indication of the predominating mechanism. Experimental Techniques Single crystals of 99.99+ pct Zn were grown using a modified Bridgman method. Polycrystal samples were prepared in three grain sizes (small, about 4 mm2; medium, about 9 mm'; and large, about 25 mmz) by quenching, air cooling, and furnace cooling. The grains of the polycrystalline samples tended to be columnar, with some preferred texture such that the c-axis was inclined at about 20" to 25" from the normal to the diffusion face, particularly in the medium and large grain size samples. The samples were cut from the rod, polished, and heavily etched, and faces cut accurately parallel using a jeweler's lathe. They were again etched to remove the lathe smear and annealed for 3 hr at 250" to 300°C. After annealing, they were etched, examined, and the orientation determined by Laue back reflection photographs. They were then electroplated with Zn. The plated surfaces were examined for uniformity; nonuniform coatings were removed by etching and the samples replated without additional preparation. For the diffusion anneals, the samples were placed in pairs, with active faces together, in evacuated Pyrex tubes. Constant temperature baths were used, and the variation in temperature did not exceed ±l°C, Diffusion runs were made at l00°,

Jan 1, 1957

The following resolution was passed by the Military Engineering Committee of New York on April 12, 1917. Copies are being sent to each member of Congress and to each of the five members in every State forming the committee representing, the five National engineering societies which carried on the industrial census under the direction of Howard Coffin. The Committee is urging every man to wire his Congressman and his Senator, asking him to do everything in his power to obtain favorable action by Congress on this resolution: Whereas in any large army to be created for the war, engineer troops will be needed in large numbers, and Whereas they should be officered by skilled engineers only, and Whereas the composition and training of such troops differ so much from the composition and training of non-technical troops that they should be organized under one central authority rather than under many scattered authorities. Now, therefore, be it resolved: That the members of the Senate and House of Representatives be requested to insist that all new units of engineer troops be organized and maintained by the War Department and not by the individual States.

Jan 6, 1917

By Thomas T., Read

THE education of adolescents to perform the duties and assume the responsibilities of maturity has been a characteristic of human society since the dawn of history. In the beginning the members of the immediate family performed this function, and in modern life they still have an important part in it. Possibly religion was the first field in which education began to be functional; young people were sent for instruction to a teacher who had a broader and deeper knowledge of the subject than was possessed by the family. It does not seem necessary for our purpose to attempt to determine how, when, or where instruction in the practical arts first' began to become functional, and the brief outline which follows must suffice. The discovery and utilization of mineral substances to improve and maintain the conditions of human living is a practical art, which must have had an almost accidental origin and have been developed by empirical experiments. We do not know, nor would it be useful to try to fancy, how men first learned that they could make use .of mineral substances to their benefit, but how- ever that knowledge was initially gained it was certainly trans mitted through instruction in the family. At first such activities must have been merely a .minor part of the making of a-living, but in time those who excelled found it better to devote them-

Jan 1, 1941

By D. L. Wood, J. H. Westbrook

The tensile behaviors of the CsCl structure compound AgMg are extensively documented in terms of strain, strain rate, temperature, composition, and metallurgical processing treatment. The observations lend themselves to presentation in terns of three regimes of deformation behavior; 1) low temperatures where deformation is primarily by slip; 2) intermediate temperatures where the deformation mode is also slip but with the detailed behavior dominated by dislocation interactions with solute atoms; 3) high temperatures where defomation is primarily by diffusion controlled processes. Of all the material groups of potential interest as high-temperature structural materials, the inter-metallics have been the least studied, particularly with respect to their mechanical behavior. Moreover, the application and processing of intermetallics for uses which exploit their often unique physical properties have been impeded by a lack of understanding of their mechanical properties. Previous work in this area* has been largely *For a recent review, see Westbrook.' exploratory, aimed on the one hand at the direct empirical development of materials of engineering utility and ,on the other at identification of the important parameters affecting the mechanical behavior of inter metallics. As a consequence, there has not been available, heretofore—for any inter-metallic—data, sufficient in extent or precision to provide an adequate phenomenological description of the effects of metallurgical variables on deformation behavior. Such documentation is prerequisite to intelligent application or processing design and is also necessary for testing present and future theoretical analyses of mechanical behavior. It was therefore an objective of the present investigation to document the deformation behavior of a simple ordered intermetallic over as wide a range as possible of all the usual metallurgical variables. The compound AgMg was chosen as the subject of this investigation because it met all of a group of desired criteria, namely: 1) congruent but moderate melting point; 2) simple crystal structure; 3) ordered structure persisting to the melting point; 4) broad solubilities for the component elements. The first and last criteria were expected to aid in the preparation of homogeneous single-phase specimens: the second and third to help simplify the

Jan 1, 1962

By P. Lindstrom

Retreat mining, using yielding steel friction props, over a 7-year period has been successful at a uranium mine operated by Hecla Mining Co. in southeast Utah. The support system allows good roof control, maximum profit, complete extraction, and good ventilation. Unusual subsidence observations were made in that some of the surface was raised rather than lowered. Longwall mining, commonly practiced in European coal mines, has a potential of broader application because of mechanization possibilities and better roof control and ventilation at greater depths. The Radon mine was one of the first American metal mines to use yielding steel props for supporting the relaxed core of the pressure arch which is induced by retreating longwall mining. Full caving was induced. After more than 7 years of stoping experience, the method has proved very satisfactory for the conditions encountered. The mine and method have been described in references listed in the bibliography. U.S. Bureau of Mines Information Circular 8004 by Wilbert Dare and Philip Lindstrom gives the most information. Stoping experience at this mine indicates that there are many advantages to be gained by using yielding supports; such as in safety, timber cost, roof control, ventilation, ore dilution, and low cost per pound of metal produced. Subsidence measurements show that the surface will rise rather than slump in some areas over the mine. This appears to be an unusual observation and is presented as a new development in subsidence studies. The Radon mine is located 35 miles southeast of Moab, Utah in the north end of the Big Indian mining district in San Juan County. Hecla Mining Co. operated the mine from early 1955 to early 1964 through an operating agreement with Federal Resources, Inc. Development consisted of a 3-compartment, 690-ft shaft, 4 main levels driven on the ore horizon and a haulage level below the ore. Evaluation of physical and economic factors showed that this flat-dipping ore occurrence could be mined by a low-cost coal mining method. The value of the deposit was high and unusual premiums were possible by clean mining. Complete extraction without loss of ore pillars, minimum ore dilution and high production per man were obtained by longwall mining. The principle of working under the relaxed core of

Jan 1, 1964

By Y. C. Liu, G. A. Alers

measurements of the anisotropy in Young's modulus produced in copper by rolling 95 pct reduction in thickness below room temperature have been carried out in order to study the dependence of the texture on rolling temperature. The results clearly show the transition from a copper-type texture to a brass-type texture as the temperature of rolling is lowered. The intermediate textures observed can be described very well as a simple mixture of the two terminal textures. These results cormbined with other texture measurements make possible afresh review of the experimental facts velating to rolling textures in fee metals and, as a consequence, a critical examination of the current theories is presented. PREVIOUS experiments have shown that the transition from the copper- to the brass-type rolling texture is clearly displayed and can be quantitatively analyzed by measurements of the anisotropy of Young's modulus.' Application of this method to the Cu-Zn alloy system showed that the description of the texture transition as a gradual rotation of the grains from the orientation characteristic of the copper texture to the {110}(112) texture of brass2 was inconsistent with the data. Instead, the data suggested that the texture within the transition region could be described as a simple mixture of the two terminal textures.5 Unfortunately, it was difficult to establish this point conclusively because of the inadequacy of corrections for the composition dependence of the single-crystal elastic constants. Since a rigorous establishment of the nature of this texture transition is essential to our understanding of the formation of rolling textures in fee metals, it is clearly important to undertake an investigation in which the composition dependence of the elastic constants would not enter. A suitable composition-independent texture transition is provided by the well-established variation in the rolling texture of copper with rolling temperature. This temperature-dependent texture transformation has been studied by smallman' in several fee alloys and by Müller5 and others"' in copper. They observed that the texture characteristic of copper rolled at room temperature changed to a brass-type texture when the rolling temperature was lowered to 77°K. Although it is not possible to decide unequivocally from the published pole figures whether or not the 77°K rolling texture of copper is entirely of the brass type,' this complication does not affect the main purpose of the present investigation. In addition to establishing the nature of the texture within the transition region, the modulus data should also provide a determination of the temperature at which the transition occurs as well as the temperature range over which the transition extends. This information when combined with the modulus data on Cu-Zn alloys would then provide a considerable body of new information on textures in fee metals. Since these modulus results and the data obtained from pole-figure studies must be internally consistent, it is appropriate to compile a brief summary of the experimental observations based on all available methods rather than on the pole-figure data alone as has been done in the past. The primary purpose of such a summary would be to yield a more precise definition of the experimental facts on the rolling textures of fee metals, and thus greatly facilitate our evaluation of various proposed theories in this field. The final section of this paper is devoted to this compilation of consistent, experimental facts and their application to the various theories. EXPERIMENTAL PROCEDURE Two 18-lb ingots of cathode copper of 99.99 pct purity were induction-melted under a nitrogen atmosphere in a graphite crucible and chill-cast into a steel mold. The ingots were repeatedly cold-rolled and annealed (I hr at 500°C) into slabs about 1 1/8 in. thick. Blocks 3 1/4 in. wide, 2 1/4 in. long, and 1.000 in. thick were machined from each slab. The rolling schedule used was the same as in the previous investigation1 and the final thickness of the sheet was 0.050 in. with a rolling reduction of thickness of 95 pct instead of 97.5 pct as in the previous work.' The compositions and temperatures of the cold baths used for the low-temperature rolling were as shown in Table I. After each pass the rolled strip was immediately immersed in the cold bath for about 1 min or until the bubbling of the bath had subsided. The modulus data were taken within 2 hr after the rolled strip was warmed to room temperature for the first time, so that effects due to recrystallization were minimized. The modulus specimens were in the shape of flat bars, 3 in. long, 4 in. wide, and 0.050 in. thick, cut with their long dimensions oriented at 15-deg intervals between the rolling direction and the transverse direction. The values of Young's modulus were deduced from measurements of the frequency at which these long narrow bars were set into longitudinal, resonant vibration as previously described.9 To excite the mechanical vibrations in the specimen, an electromagnetic drive similar to that employed by Thompson and lass" was used. The maximum in the amplitude of

Jan 1, 1968

By H. L. Overton, J. B. Lipson

The concept of sodium single-ion equivalent activity as developed by Gondouin, Tixier and Simard,' was used to determine the filtrate resistivity-activity relationships for 150 laboratory and 49 field drilling muds. With the exception of the native and phosphate high-resistivity muds and the calcium-treated muds, the filtrate resistivity-activity relationships were found to be within 20 per cent of that for pure sodium-chloride solutions. Gondouin, et al,* previously suggested a method of treating the high-resistivity muds in quantitative electrical log analysis. A new treatment is presented which uses the P-alkalinity of the filtrate as a correlating parameter in handling the calcium-treated muds in quantitative electrical log analysis. INTRODUCTION Gondouin, Tixier, and Simard in 1957 introduced new interpretive procedures for analyzing the self-potential curve of electric logging. They re-emphasized the previous work of the Schlumberger brothers, Wyllie and others, and re-defined the activity concept in terms of a number which they termed the effective resistivity. Their procedures are particuarly effective when the connate-water resistivities are less than 0.08 ohm-m or greater than 0.3 ohm-m. For gyp muds where the calcium content is known, a procedure was presented which allows calculation of the connate-water resistivity with improved accuracy. These procedures assume that one of the fluids in the system is a pure sodium-chloride solution, but they are not limited by the assumptions. For the fresh and saline connate waters, for instance, it is assumed that the drilling mud filtrate is a pure sodium-chloride solution. For the gyp mud interpretive procedure, it is assumed that the connate water is a pure sodium-chloride solution. Brown,' on the other hand, has suggested that it would be extremely fortuitous if drilling mud filtrates could all be treated electrochemically as sodium-chloride solutions, and he cites some examples where discrepancies exist. A study has been made of the deviations of sodium single-ion equivalent activities, an of drilling mud filtrates from that of pure sodium-chloride solutions. Drilling fluids in common use on the Texas and Louisiana Gulf Coast and laboratory-controlled muds were investigated. Using a cell patterned after Gondouin, et al, (Fig. I), the equivalent activities were measured. It should be remembered here that the activity measured is merely an index which uses numbers that represent the sodium single-ion equivalent activity a,., of the mud filtrate. The membrane potential developed across the cell was determined with a null-type potentiometer. The resistivities of the solutions were measured by the four-electrode method. The resistivity system was calibrated by using saturated KC1 solution as a standard. Chemical properties of the drilling fluids studied were measured with standard API-approved equipment for the particular property in question. For the activity measurements, two shale discs were chosen to serve as cationic membranes. These two discs were both 1 1/4 in. in diameter and, respectively, 1/4 and 1/8 in. in thickness. The membrane potential, Em, was determined using the shale discs as cationic selective membranes separating two standard sodium-chloride solutions of known mean activity. Then by comparing the constant Km in the following equation, with the theoretical value of — 59 mv at 75OF, the perfection of the membrane was determined. The variation of Km for the two membranes used in this experimental work, as well as one of the many unsuitable membranes, is shown in Fig. 2. The measurement of the activity of mud filtrate involves the balancing of its combined individual activities against a standard solution of known mean activity. At the point where there exists zero potential across the membrane cell, the activity effects may be assumed equal for all practical purposes. The mechanics of making a null reading of this sort requires having a large number of different mean activity solutions. A more practical method involves

By Luis Toron, Salvador Cortes-Obregon

John D. Price (Colorado Fuel and Iron Corp., Pueblo, Colo)—The paper on the coal fields of the Oaxaca district as prepared by engineers Toron and Cortes-Obregon of the staff of the Bank of Mexico bears witness to the thorough and careful way in which the men associated with this organization perform their work. There is little to be added to their paper in way of discussion other than to confirm and amplify some of their statements. Since the only extensive and well-developed field of coking coal lies in the northeastern section of the country adjacent to Sabinas in the state of Coahuila, it follows that blast furnace plants would be located in that same region. Two such plants are now operating at Monterrey and Monclova, using coke produced at the Sabinas district mines. But the nearer of these two plants is 600 miles from Mexico City and even farther from the center of population. Transportation of products from these mills to the market area is therefore expensive, both because of the distance and the difficulty of the terrain over which it must be carried. The development of an integrated steel industry closer to the center of population has therefore long been a goal toward which the Mexican technicians have been striving. While the presence of coal of some grade has been reported in many of the states, and many ideas have been advanced regarding its possible uses in iron and steel production, deposits of anthracite in Sonora and the various coals of the Oaxaca district as reported on in this paper are the only ones that have been explored in a serious manner. The coking coal from the Mix-tepec zone appears to offer promise of producing a coke which could be used in a standard blast furnace. Several problems are indicated, however: 1—The ash in the coal is high as mined, but indications are that it can be washed to an ash content of 15 pct with a recovery of 70 pct of washed coal. 2—Such washing would increase the volatile content from 17.4 pct to about 20 pct, and in a byproduct oven this should give a coke yield of close to 80 pct with an ash content of coke under 20 pct. 3—A free swelling index of 5 appears low for a good coking coal, and below that of the coals from the Sabinas district, which show between 6 and 9. But washing of the coal should result in an improvement in this regard; in the United States coals from Utah with an index even lower than 5 have made a usable coke. 4—A coal with volatile as low as 17.4 in raw coal and 20 in washed coal would come close to being classed as a low-volatile rather than medium-volatile coal, and low-volatile coals are notorious for their high expansion properties. Several plants in the United States are making coke from straight medium-volatile coal of 26 to 28 volatile content, and one at Rosita,, Mexico, from coal of 25 volatile. But no plants to my knowledge are using coal as low as 20 volatile. Since the Rosita coal appears to be a borderline coal from the angle of its expansion properties the coking of one of the straight lower volatile must be approached with caution. 5—There are few coals possessing any degree of coking properties which cannot be used in coke production by careful attention to its preparation and blending. The fact that coals of other types are available in this same region make improvement through blending very possible. 6—There are other workable methods of reducing iron ore other than the conventional coke-blast-furnace method. These will not be discussed here but it is known that their use has been considered. The technicians of not only Mexico but also of the other Latin American countries are keenly aware of their natural resources and their national needs. This paper emphasizes the fact that the Mexican technicians are working on their problem and attempting to speed the day of self-sufficiency for their country. Salvatore Cortes-Obregon (author's reply)—I wish to thank Mr. Price for his kind remarks. The Mixtepec coal as shown in Table II has 30 pct ash and a free swelling index of 5, but when the same coal is washed to 15 pct ash it has a free swelling index of 8 to 9 and the volatiles increased from 17.4 to 20.7 pct. A satisfactory coke has been produced from blends made in the Mexican laboratory using at least 40 pct of the Mixtepec coking coals with the other Oaxaca non-coking coals. Koppers in Germany report good coke obtained from the Oaxaca coal with a blend of 80 pct Mixtepec coal. Consideration is being given the possibility of using methods other than the conventional blast furnace for the reduction of iron ore near the Oaxaca area; electric furnaces appear promising. The non-coking coals could be used to produce cheap electric energy and the coking coals to make metallurgical coke.

Jan 1, 1955

By J. L. Huiatt, D. G. Foot

The Bureau of Mines, U.S. Department of the Interior, investigated methods of recovering potash values from process and waste brines. Laboratory pan evaporation of four chloride brines produced crude salts containing predominantly sylvite, halite and carnallite. Six sulfate- chloride brines produced crude salts containing primarily schoenite, kainite, leonite, sylvite, carnallite, and halite. Potash grades ranged from 7.2% to 22.2% K20, and recoveries by crystallization ranged from 85% to 99%. Sylvite flotation from chloride evaporites with amine collector, recovered 90% to 97% of the potash in a concentrate containing 54.3% to 60.3% K20. Fatty acid flotation of the high sulfate evaporite recovered 78% of the sulfate minerals in a 28%-K20 concentrate. Flotation of the remaining chloride minerals with amine collector recovered 80% of the potash in a 59.7%-K20 concentrate. Solar evaporation of 37 854 L (10,000 gal.) of brine recovered 99% of the potash in a crude evaporite containing 24.5% schoenite and 20% sylvite. Flotation in a 45-kglh (100-lblh) continuous flotation unit recovered over 95% of the potash in schoenite and sylvite concentrates, containing 28% and 62.3% K20, respectively. An economic evaluation is included.

Jan 1, 1985

By P. W. Bridgman

Flow and fracture are admittedly complicated phenomena of which we are yet only partially masters. There is not even nni-.persal agreement as to the details of the language best adapted merely to describe the phenomena, to say nothing of any theory. Certain points of view, however, are widely held, and there are certain general expectations as to what sort of procedures will prove permissible. A complete description of any situation involving fracture would demand a complete history of all the variables in the control of the experimenter. The experimenter endeavors so to choose his independent variables that they are adequate to determine completely the situation in the sense that when an experiment is repeated on the same initial material and with the independent variables running through the same sequence, all the other measurable properties of the system will also run through the same course. It is, I think, the universal conviction that when we are dealing with phenomena of flow and fracture, the most important of the necessary variables are the external forces acting on the various parts of the body; when the force history repeats, with certain obvious restrictions such as that temperature must be constant and non-mechanical forces, such as magnetic field, must be small enough to be ineffective, then the history of all measurable properties will repeat; in particular the alteration of geometrical shape due to flow will run through the same course, and when fracture comes, the character of the fracture will be reproduced. Complete mastery of merely the descriptive aspects of flow and fracture would demand the ability to predict the entire course of flow and complete characterization of the final fracture for every possible combination of forces, varying in time in all possible ways, when applied to bodies of all possible shapes. This full situation is obviously of prohibitive complexity. The first stage in reduction to manageable simplicity is to resolve the total situation into the sum of contributions made by small elements. Our thesis is that if each of the elements is adequately characterized, the behavior of the whole system is fixed. The element is usually taken of a simple geometrical shape, suggested by the mathematics best adapted to the particular situation. The forces acting across the faces of the elements are ultimately determined by the forces acting across the free faces of the whole system. The detailed process of finding the precise forces on the faces of all the elements in terms of the external forces involves the use of a special mathematical invention, the stress, a constructional quantity consisting of six components. The stress at any point in the body is determined by both the external force system and by the physical properties of the body at all points; quite different stresses prevail at the interior of bodies of the same shape under the same external forces in the elastic and plastic ranges. The forces on the faces of any element are, however, uniquely determined by the stress system at the element. Our fundamental thesis

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