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By William B. Senseman

FoR reasons well known to mining engineers, wet grinding is quite universal in plants having to do with the extraction of metallic values from crude ores. In the processing of the nonmetallic and industrial minerals, dry grinding is the more common method. The crude materials usually contain less moisture than is required for wet grinding and the products usually are marketed in dry form; most of them as powders. To grind wet, therefore, would entail the addition of water and an expense for drying the product, which is not justified. Furthermore, the material would be a dried cake that would still have to be pulverized or disintegrated before use. For producing fine products, air separators have largely replaced the earlier practice of sizing with screens and bolting reels. Mills in which the air-separating feature is an integral part of the design are now commonplace. Mill designs are many and air systems have developed along various lines, but for the purpose of this discussion, only the fundamental idea need be emphasized— the idea of using air for sizing and removing pulverized material from a grinding mill. About 20 years ago, when the use of mills equipped with air separation had become common practice, heated air or gas was introduced to such a system for the removal of moisture. The purpose of this discussion is to outline the developments and trends that have followed this experiment. It is an important development, for mills equipped with air separation are now universally used for pulverizing not only nonmetallic and industrial minerals, but a great variety of other materials. All such mills are essentially the same. Dried material is pulverized, removed by an air stream, trapped in a cyclone collector, and relatively clean air from the cyclone is returned through a fan to the mill. There is no theoretical need for a vent from the system. The practical need is to vent the air that leaks into the system; and, since the cyclone is not 100 per cent efficient as a dust collector, this vented air carries some dust with it. The initial attempt at drying was made on a system like that described, by the addition of a furnace. The minus pressure within the mill draws hot gas from the furnace. Infiltration air, along with the drying gases and evaporated moisture, is vented as before. The first application was made to a mill used for pulverizing coal. The coal contained very little moisture, so very little drying effect was needed for the success of this experiment. Actually, some calculated efficiencies of over 100 per cent were obtained before due allowance was made for the conversion of mill power into useful heat. When moisture is low, the heat obtained from the conversion of milt power is an appreciable part of that required. That drying can be effected in the short time interval available in a grinding mill of this type is better understood by visual-

Jan 1, 1948

By William B. Senseman

FOR reasons well known to mining engineers, wet grinding is quite universal in plants having to do with the extraction of metallic values from crude ores. In the processing of the nonmetallic and industrial minerals, dry grinding is the more common method. The crude materials usually contain less moisture than is required for wet grinding and the products usually are marketed in dry form; most of them as powders. To grind wet, therefore, would entail the addition of water and an expense for drying the product, which is not justified. Furthermore, the material would be a dried cake that would still have to be pulverized or disintegrated before use. For producing fine products, air separators have largely replaced the earlier practice of sizing with screens and bolting reels. Mills in which the air-separating feature is an integral part of the design are now commonplace. Mill designs are many and air systems have developed along various lines, but for the purpose of this discussion, only the fundamental idea need be emphasized the idea of using air for sizing and removing pulverized material from a grinding mill. About 20 years ago, when the use of mills equipped with air separation had become common practice, heated air or gas was introduced to such a system for the removal of moisture. The purpose of this discussion is to outline the developments and trends that have followed this experiment. It is an important development, for mills equipped with air separation are now universally used for pulverizing not only nonmetallic and industrial minerals, but a great variety of other materials. All such mills are essentially the same. Dried material is pulverized, removed by an air stream, trapped in a cyclone collector, and relatively clean air from the cyclone is returned through a fan to the mill. There is no theoretical need for a vent from the system. The practical need is to vent the air that leaks into the system, and, since the cyclone is not 100 per cent efficient as a dust collector, this vented air carries some dust with it. The initial attempt. at drying was made on a system like that described, by the addition of a furnace. The minus pressure within the mill draws hot gas from the furnace. Infiltration air, along with the drying gases and evaporated moisture, is vented as before. The first application was made to a mill used for pulverizing coal. The coal contained very little moisture, so very little drying effect was needed for the success of this experiment. Actually, some calculated efficiencies of over 100 per cent were obtained before due allowance was made for the conversion of mill power into useful heat. When moisture is low,, the heat obtained from the conversion of mill power is an appreciable part of that required. That drying can be effected in the short time interval available in a grinding mill of this type is better understood by visual-

Jan 1, 1945

By Walter Miller

During the second year of America's active ia in the war the inain objectives of the petroleum-refining industry were again to provide the four most important product needs for war: 100-octane aviation gasoline, toluene for T.N.T. production, high-quality lubricating oils for the needs of aviation and the armed forces, and petroleum chemicals for synthetic rubber manufacture. All other materials supplied by the petroleum industry took an inferior priority ranking, depending on the degree of essentiality. To accomplish the above objectives the industry initiated and carried on a building program during 1942 and 1943 which will put those two years down in petroleum-refining history as the greatest construction years of all time, a record which will hold for decades to come. Led by an estimated total of $ 900,000,000 going into 100-octane and contributory plant investment, it is easy to picture a total of two billion dollars and more going into additional refining-industry plant investment during 1942 and 1943, most of it privately paid for, but a substantial part covered by R.F.C. Government money financing. Some of the new plants will not be completed until 1944, but a large proportion of the program was finished and put into operation, adding substantially to the output of the four principal products during 1943- lne most important and spectacuiar activity of the refining industry is of course the 100-octane gasoline program necessitated by the fact that nearly 90 per cent of the requirements of the United Nations is being furnished by the United States. Recent P.A.W. figures mention $goo,-ooo,ooo as the cost of the construction looking to increasing the output of this all-important munition. Thirty-four major plants have been completed, 11 of them during the last quarter of the year. Thirty-eight more will be completed and put into operation during the first four or five months of 1944. Twenty-two additional plants authorized during 1943 are already well under way and scheduled for production late in 1944. Early in 1942 the aim was to treble the capacity for making 100-octane gasoline then existing; later, plans were to make it five times as great, to match the increased warplane building program; and toward the end of the year the sights had been set at a still higher but unannounced target, representing six to seven times the early 1942 figure. Comparative figures issued at the end of 1943 enable one to guess a program by the middle of 1944 of eight to nine times the former production, with an ultimate production in 1944 of eleven or more times the early 1942 output. It became obvious in 1943 that building of new units would be materially slowed because of delay in getting construction materials and that they would reach operation at considerably later dates than

Jan 1, 1944

By William B. Senseman

For reasons well known to mining engineers, wet grinding is quite universal in plants having to do with the extraction of metallic values from crude ores. In the processing of the nonmetallic and industrial minerals, dry grinding is the more common method. The crude materials usually contain less moisture than is required for wet grinding and the products usually are marketed in dry form; most of them as powders. To grind wet, therefore, would entail the addition of water and an expense for drying the product, which is not justified. Furthermore, the material would be a dried cake that would still have to be pulverized or disintegrated before use. For producing fine products, air separators have largely replaced the earlier practice of sizing with screens and bolting reels. Mills in which the air-separating feature is an integral part of the design are now commonplace. Mill designs are many and air systems have developed along various lines, but for the purpose of this discussion, only the fundamental idea need be emphasized— the idea of using air for sizing and removing pulverized material from a grinding mill. About 20 years ago, when the use of mills equipped with air separation had become common practice, heated air or gas was introduced to such a system for the removal of moisture. The purpose of this discussion is to outline the developments and trends that have followed this experiment. It is an important development, for mills equipped with air separation are now universally used for pulverizing not only nonmetallic and industrial minerals, but a great variety of other materials. All such mills are essentially the same. Dried material is pulverized, removed by an air stream, trapped in a cyclone collector, and relatively clean air from the cyclone is returned through a fan to the mill. There is no theoretical need for a vent from the system. The practical need is to vent the air that leaks into the system, and, since the cyclone is not 100 per cent efficient as a dust collector, this vented air carries some dust with it. The initial attempt at drying was made on a system like that described, by the addition of a furnace. The minus pressure within the mill draws hot gas from the furnace. Infiltration air, along with the drying gases and evaporated moisture, is vented as before. The first application was made to a mill used for pulverizing coal. The coal contained very little moisture, so very little drying effect was needed for the success of this experiment. Actually, some calculated efficiencies of over 100 per cent were obtained before due allowance was made for the conversion of mill power into useful heat. When moisture is low, the heat obtained from the conversion of mill power is an appreciable part of that required. That drying can be effected in the short time interval available in a grinding mill of this type is better understood by visual-

Jan 1, 1947

By William B. Senseman

For reasons well known to mining engineers, wet grinding is quite universal in plants having to do with the extraction of metallic values from crude ores. In the processing of the nonmetallic and industrial minerals, dry grinding is the more common method. The crude materials usually contain less moisture than is required for wet grinding and the products usually are marketed in dry form; most of them as powders. To grind wet, therefore, would entail the addition of water and an expense for drying the product, which is not justified. Furthermore, the material would be a dried cake that would still have to be pulverized or disintegrated before use. For producing fine products, air separators have largely replaced the earlier practice of sizing with screens and bolting reels. Mills in which the air-separating feature is an integral part of the design are now commonplace. Mill designs are many and air systems have developed along various lines, but for the purpose of this discussion, only the fundamental idea need be emphasized— the idea of using air for sizing and removing pulverized material from a grinding mill. About 20 years ago, when the use of mills equipped with air separation had become common practice, heated air or gas was introduced to such a system for the removal of moisture. The purpose of this discussion is to outline the developments and trends that have followed this experiment. It is an important development, for mills equipped with air separation are now universally used for pulverizing not only nonmetallic and industrial minerals, but a great variety of other materials. All such mills are essentially the same. Dried material is pulverized, removed by an air stream, trapped in a cyclone collector, and relatively clean air from the cyclone is returned through a fan to the mill. There is no theoretical need for a vent from the system. The practical need is to vent the air that leaks into the system, and, since the cyclone is not 100 per cent efficient as a dust collector, this vented air carries some dust with it. The initial attempt at drying was made on a system like that described, by the addition of a furnace. The minus pressure within the mill draws hot gas from the furnace. Infiltration air, along with the drying gases and evaporated moisture, is vented as before. The first application was made to a mill used for pulverizing coal. The coal contained very little moisture, so very little drying effect was needed for the success of this experiment. Actually, some calculated efficiencies of over 100 per cent were obtained before due allowance was made for the conversion of mill power into useful heat. When moisture is low, the heat obtained from the conversion of mill power is an appreciable part of that required. That drying can be effected in the short time interval available in a grinding mill of this type is better understood by visual-

Jan 1, 1947

By B. F. Oliver

A levitation zone melter is described which has the necessary characteristics for processing metals of controlled purity. No crucible is required; control of the solidification variables is stable; the environment of the charge is chenzically controlled. Rotation of the solidifying interface and mixing in the liquid by the magnetohydrodynamic stirring produce an eight-fold increase in freezing velocity over former melting units with better resulting solute redistributions. The smooth appearance of processed specimens, resistivity ratios as a hnction of position, as well as a segregation curve, are presented as evidence of smooth continuous solute fransport over distances in excess of ten zone lengths. THE difficulties of the floating zone-purification of higher density metals in large quantities under conditions of lowered surface tension are well known and have hindered fundamental research programs for some time. The inordinate amount of time required to obtain a small reproducible yield of high-quality metal has excluded the use of such material for many important material research programs. However, with the use of controllable induction levitation forces' to accomplish stable liquid zones with nearly flat solidifying interfaces, and with good physical and chemical control of the processes involved, these difficulties can be overcome. A zone melter that is to be used for both high-purity and controlled composition work in metal systems must have the following three characteristics: 1) The process must avoid the use of containers. 2) Physical control of the solid-liquid interface and of the mixing within the liquid phase must be stable. 3) The chemical environment of the melt chamber must be controllable. A description of an apparatus that accomplishes these objectives follows.* APPARATUS One of the basic features that is necessary for good process control of large sections is that the charge, the coil, and the motion mechanisms be within the same chamber. This arrangement permits a close coupling between the work coil and the load, which then provides a good flexibility for adjustments of coil dimensions, for controlling the amount of levitation needed for stable operation at a given power level. An overall view of the melter is shown, with the melt-chamber door open, in Fig. 1. The radiation shields surrounding the single-turn induction coil are of water-cooled copper. The chamber is stainless steel, as are most of the components within the chamber. The control panel for the scanner is located at the immediate lower right of the melt chamber. This panel controls the operation of the scanner. The operations controlled are the interface rotation rate, the stretch-squeeze or diameter control, the up and down scanning speeds, and the induction power. All of the drive motors are constant-torque variable-speed motors. The scanning speeds are set with precision helipots and continuously observed with the voltmeter on the control panel and checked with a mechanical indicator within the melt chamber. The rotation rate is also set with a precision helipot. The up-scanning speeds are 2 to 300 in. per hr.

Jan 1, 1963

By Arthur B. Yates

Diamond drilling has advanced and expanded during the past few yean. Along with this increase there has been a marked trend to rely more and more upon drilling for the outlining of ore for reserve purposes. This is especially true underground, where men have not been available for opening up ore by crosscuts, drifts and raises. During the recent heavy call upon known ore reserves, more drilling has been done for exploration and it has become expedient to drill longer lateral holes from underground and deeper holes both from surface and from exploration headings in the mines. Furthermore, these deeper holes have to be drilled closely enough to warrant calculation of "probable" if not "proven" ore, from the results obtained therefrom. Interpretation of diamond-drill results has become more precise and reliable with the growing knowledge and understanding of the geologic structures that control the geometry of ore distribution, and this has broadened the field of usefulness of the drill. All of this has created a necessity and a demand for more accurate control of the hole as to direction, a more precise and reliable method of surveying for position, and a need for better and more complete core recovery, as well as larger cores, to provide an adequate sample. At depth the control becomes more difficult and, at the same time, more important. Control A close study of drilling in various parts of the world for a period of more than 20 years has brought to light one definite rule, practically invariable; namely, that diamond-drill holes tend to deviate into a position normal to any structure existing in the rocks, such as bedding, schistosity, gneissosity, or even parting or jointing— even if the hole is started at almost any angle other than parallel with the structure. It also appears that the better developed the structure is, the more quickly will the hole get into a position perpendicular to it. It has often been said that there is a tendency for holes to "drift" in the direction of rotation. This is obviously untrue, for in a vertical hole the measure of deviation would depend upon the azimuth chosen as zero, and there is an infinite number of choices. It has been proved. however, that in homogeneous rocks there is a tendency for the hole to corkscrew, and that the direction of the spiral is the same as the direction of rotation. This may account for the belief that holes drift in that direction. Some tests have been made using right-hand and left-hand rods, and these show that no matter what the direction of rotation the hole will swing into a position perpendicular to the structure. Methods of Control The foregoing empirical rule may be used as an indirect method of control. If the prevailing structure is known, it may be advantageous to start the hole as nearly normal to it as possible, for the

Jan 1, 1946

By T. E. Tietz, J. E. Dorn

Activation energies for creep of copper at intermediate temperatures, where crystal recovery was negligible, were determined by the simple technique of rapidly alternating the test temperature between and T2 (T2 = TI + about 10°K) throughout a constant stress creep test. The activation energy for creep H was found to be 37,000± 3,000 cal per mol, independent of stress and strain. The same creep laws as have been previously established for high temperature creep were found to be valid for creep at intermediate temperatures. But the AH was found to be lower than that for self-diffusion in the intermediate temperature range whereas it is known to be equal to that for self-diffusion at high temperatures. IT is now well established that creep at high temperatures can be correlated by the functional relationship'-" e = f(?) s = constant [I] where E is the total plastic strain, f is the function that depends on the stress, ? = f e -- dt, t is the duration of test, e is the base of natural logarithms, AH is the activation energy for creep, R is the gas constant,T is the absolute temperature, and s is the stress. Thus, identical values of are achieved during creep under a given stress at two alternate temperatures at the same total strain. At the same strain therefore where subscripts refer to the two alternate temperature conditions of test. Consequently, the activation energy for high temperature creep is readily obtained with the aid of Eq. 2. Activation energies so obtained have been observed to be insensitive to the creep strain at which they are evaluated, the applied stress, grain size, minor alloying additions,'-' cold worked state, and the presence of thermally stable dispersions of intermetallic compounds in an a solid solution matrix Furthermore, the activation energy for high temperature creep is very nearly equal to that for self-diffusion in all cases where adequate data are available for comparison." " The apparent identity of the activation energies for high temperature creep and self-diffusion strongly suggest that high temperature creep arises from a dislocation climb process. This hypothesis is further strengthened by the fact that the energy of activation for high temperature creep is insensitive to the applied stress," and by the observations that the correlation suggested by Eq. 1 cannot be ex- tended to temperatures below those for rapid crystal recovery. When using the activation energy for self-diffusion, Eq. 1 fails to give the required correlations between creep curves at various intermediate temperatures.' This suggests that the dislocation climb mechanism for creep might be superseded by some alternate mechanism in the intermediate range of temperatures. This investigation was initiated in a preliminary attempt to ascertain the type of creep law that might be valid in the intermediate range of temperatures. Special consideration, however, was given to the determination of the activation energy for creep in this range because the Becker-Orowan', " and the Mott-Nabarro10 theories for transient creep suggest that the activation energy should increase

Jan 1, 1957

By Haydn H. Murray

The term clay is somewhat ambiguous unless specifically defined because it is used both as a rock term and as a particle size term. Actually most persons using the term clay realize that it has a double meaning and in most instances define it. As a rock term, clay is difficult to define because of the wide variety of materials that compose it so that the definition has to be general. Clay is a natural, earthy, fine-grained material composed largely of a limited group of crystalline minerals known as the clay minerals. Many definitions state that a clay has the property of plasticity when wet, but some clays are not plastic, i.e., halloysite and flint clay; however, most clay materials are plastic when wet. As a particle size term, clay is used for the category that includes the smallest particles. The maximum size particles in the clay size grade are defined differently on some grade scales. Soil investigators and mineralogists generally use 2 microns as the maximum size. The Wentworth scale' defines clay as material finer than approximately 4 microns. Grim' has found it convenient to use the term clay material for any fine-grained, natural, earthy, argillaceous material and in this way can include clays, shales, or argillites, and some soils if they are argillaceous. Even though no standard definition of the term clay is accepted by geologists, agronomists, engineers, and others, still the term is generally understood by all who use it. Clay is an abundant natural raw material and has an amazing variety of uses and properties which will be discussed in this chapter. In order to understand better the relationships between the clays and their uses, a brief discussion of the structure, chemical composition, and identification of the clay minerals is given. Mineralogical Composition of Clays Clays are composed of certain groups of hydrous aluminum, magnesium, and iron silicates that may contain calcium, potassium, and other ions, which are called the clay minerals, and other minerals of variable composition, which are nonclay minerals. Both clay minerals and nonclay minerals influence the properties of a clay material. In order to understand the relationship between clay minerals and the properties of a clay material, a short summary of the structure and composition of clay minerals is necessary. Any scheme of classification tends to impose a certain rigidity and as new and additional data become available it is necessary to revise classifications. Brindley3 has discussed the classification and structural mineralogy of clays in very lucid fashion and chose a classification based on structural features and chemical composition. Grim2 proposed a tentative classification which is based on the structural attributes of the various clay minerals. This classification is relatively simple and workable, and is shown as follows: I. Amorphous Allophane group II. Crystalline A. Two-layer types (sheet structures composed of units of one layer of silica tetrahedrons and one layer of alumina octahedrons). 1. Equidimensional Kaolin group kaolinite, dickite, nacrite 2. Elongate Halloysite group

Jan 1, 1960

By A. D. McMaster, M. L. Gimpl, N. Fuschillo

Low-power, high-speed, radiation-resistant, monolithic thin-film integrated circuits require thin-film resistors of high sheet resistance which are compatible with the processing requirements for monolithic silicon devices. For this purpose the structure and electrical resistance as a function of temperature were investigated for Nichrome-silicon monoxide cermet films on passivated single-crystal silicon substrates. A suitable material was found to be a mixture of 50 vol pct Nichrome-50 vol pct silicon monoxide. This mixture, when evaporated onto 300°C substrates. showed a low temperature coefficient up to 400°C, at both 270 and 1100 ohms per square. Resistors deposited on room-temperature, 300°, and 500°C substrates were heat-treated at 600°C in air for short periods of H- seed, low-power, radiation-re sis tant, monolithic thin-film integrated circuits'-3 require thin-film resistors of high sheet resistance and low temperature coefficients of resistance which are compatible with the processing requirements for monolithic silicon active devices. The present investigation is directed towards the replacement of the Nichrome in the sandwich-type SO2-Nichrome-SiO resistors, currently used for DTL monolithic thin-film integrated circuits, with codeposited Nichrome-SiO cermet resistors. These Nichrome-SiO resistors are provided with an overcoat of SiO and are deposited onto thermally oxidized silicon wafers used in monolithic mi-crocircuit technology. The cermet resistors are shown to provide a lower temperature coefficient of time totaling up to 45 min. Electron nzicrogvaphs and diffraction patterns were taken of the as - deposited and heat-treated films. These results were then compared with electrical-resistance measurements for each condition. The room-temperature and 300°C substrate films showed a large decrease in resistance. The 500°C substrate film remained stable throughout the entire cycle. Electron-microscopy results show that the increased stability after heating to 600°C is largely due to crystallization of the films which begins in the vicinity of 400°C. The slight oxidation of the films when heated in air had a negligible effect on the resistance. The resistance of the film was a function of the substructure. resistance and a more versatile compatibility with silicon monolithic processing. Previous work3, on chromium-SiO coevaporated cermet resistors on glass and ceramic substrates without overcoats of SiO has been reported. For the present application, the thin films should possess the following ideal requirements: a) a temperature coefficient of resistance as near zero as possible up to 300°C; b) have a sheet resistance higher than 200 ohms per sq to conserve space on the chip; c) be easy to evaporate; d) be oxidiation- and radiation-resistant; e) show long-time stability at 100°C; } be stable in N2 atmospheres up to 600°C for short periods of time (5 to 45 min). Requirements a to e are well-known. The last requirement was optional and was due to a mask elimi-

Jan 1, 1967

By C. E. Sims, H. M. Banta, S. L. Hoyt

Over the past few years, metallic arc welding has been extended to steels of the hardenable type. As compared with other methods of fabrication, production has been facilitated, service performance frequently has been improved, and the overall results have been so favorable that engineers and production men have placed great emphasis on this application of welding. The metallurgist and welding engineer, however, have been confronted with new problems, since, for one reason, the harder steels are more apt to crack and special precautions must be taken if sound joints are to be procured. Some of the factors that are pertinent to this problem are metallurgical, and it is an object of this contribution to discuss steel manufacture and processing methods and to show how their control assists in reducing the hazard of cracking. By this time, the problem of cracking— specifically underbead cracking, or "hard cracks," or parent-metal cracks-—is well known, and a large amount of work has been published, both here and abroad, dealing with this subject.' The tests described are made under restraint to facilitate cracking and arc so designed that a semiquantitative, or at least a relative, value of the cracking tendency is obtained. As one would expect, it has been reported that the incidence of cracking increases with the carbon and alloy content of the steel. More specifically, the cracking tendency is said to increase with the hardenability of the steel, though it is now recognized that the situation is not so simple. The phenomenon itself, on the other hand, has been but loosely described, and it is in only broad generalizations that this cracking has been related to steel metallurgy. Thus, while it has been abundantly demonstrated that the hardenable aircraft steel, S.A.E. 4130, must tend to crack when are-welded, the problem still remains of why two lots of the same composition and the same hardenability can vary so greatly in cracking tendency, or what it is about the prior metallurgical history that so strongly affects the results. Further, while the efficacy of preheating and postheating in preventing cracking is recognized and utilized in production, the mechanism by which they function seems not to have been described. These points are thought to be significant in the production of steel for fabrication by metallic arc welding and, hence, of interest to mill and process metallurgists and welding engineers. Consequently, it is another object of this paper to discuss the mechanism of parent-metal cracking, including the influence of the condition of the steel and the control of cracking by manipulation of the time-temperature conditions during and after welding. A new method of rating the cracking tendency is also discussed, and the results of the test are related to steel composition and structure or prior history. The work to be described was the outgrowth of work in 1940-41 at Battelle Memorial Institutc on two projects, one

Jan 1, 1945

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

By Stanley L. Lopata, Eric B. Kula

SEVERAL methods are available for determining pole figures by X-ray means.' The earlier film methods have been replaced by techniques in which the intensities are measured by Geiger counters on an X-ray diffractometerZm7. These methods utilize either flat transmission or reflection samples,214°8 cylindrical specimens,3 or spherical specimens.7 A single transmission or reflection sample will not yield information over the complete pole figure. The cylindrical specimens suggested by Nortod and the spherical specimen of Jetter and Borie7 have the advantage of allowing the whole pole figure to be obtained without any corrections to the intensity for absorption, There is a lower limit to the size of sheet which can be conveniently studied, however, and sample preparation can be rather tedious. Probably the most common method today for determining the complete pole figure is that developed by Schulz. A flat reflection sample is used for determining the pole figure from the center out to about 70". Because of the geometry of the system used, little or no correction for absorption or irradiated volume is necessary.4'6 A separate transmission sample is used for the region near the edge of the pole figure. This procedure requires two separate samples, one of which must be a thin carefully-prepared transmission sample. Furthermore, since the reflection and transmission data are in different arbitrary intensity units, a region of overlap must be obtained, and the intensity data from one set of measurements converted to units of the other. These are serious disadvantages of this method, and they point out the need for a simplified procedure. Since the reflection technique can be used for planes whose normals lie up to about 70° from the sample surface normal, it is apparent that a complete pole figure can be obtained by reflection alone if sample surfaces are cut at oblique angles to the rolling plane Specifically, if a rolled sample is cut so that the normal to the surface formed lies equidistant (54" 44') from the rolling plane normal, rolling direction, and transverse direction, then complete information for one quadrant of the pole figure can be obtained by reflection from the surface. Fig. 1 shows this oblique surface, as well as the position of the pole of this surface in the pole figure. When a surface has been cut oblique to the rolling plane, the standard polar stereographic net is inconvenient to use, and it would be more desirable to have the center of the net coincide with the pole of the oblique plane. Fig. 2 shows such a net, where the center has been offset 54' 44' to correspond to a specimen cut as in Fig. 1. This net was in effect obtained by rotating a standard polar stereographic net 54" 44' with the help of a Wulff net. With the experimental setup used. a sample can be cut from plate of 1/2-in. thickness or br Gen- erally thinner sheet is under investigation, and a composite specimen must be used. A convenient procedure has been to bond together, using epoxy resin, sufficient sheets to form a cube. These are clamped in a vise, and when dry, the whole vise is rotated and a flat surface ground at the required angle. The sample is then mounted inside a larger steel ring using Koldmount, the backside ground flat and parallel to the approximate desired thickness. The sample is then polished and etched to remove any effects of cold working during grinding. With this method only one quadrant of the pole figure is obtained. Often pole figures show symmetry around the rolling and transverse directions, and any slight asymmetry is due to scatter. Should the pole figure not be symmetrical, four oblique surfaces, corresponding to the four quadrants of the pole figure, would have to be examined. In most cases there is symmetry at least around the rolling direction, which reduces to two the number of quadrants to be investigated. For many purposes all that is required is an average polefigure for the four quadrants. This canreadilybe obtained with composite specimens of sheet material, where sheets Corresponding to each of the four quadrants can be intermixed. The four quadrants can be obtained by considering sheet in the normal position, and by rotatiolls of 180" around the sheet normal, the rolling direction, and the transverse direction. If desired, the whole thickness of the sheet can be used, yielding an average of the surface and interior textures; or the surface material can be removed from each sheet, resulting in a pole figure for the center alone. Eugene S. Meieran of the Massachusetts Institute of Technology has independently developed the same method. His results, adapted to a pole figure goniometer with a specimen spiraler, will be described in another publication.

Jan 1, 1962

By W. H. Porter, M. E. Wadsworth, J. R. Lewis, K. L. Leiter

The oxidation of Cu2S in oxygen and the sulfating of Cu2O in oxygen-sulfur dioxide atmospheres was carried out under a variety of conditions. The oxidation of Cu2S was found to be retarded by entrapment of SO, and O2, which stabilized internal sulfates for long periods of time. The course of the reaction was followed by measuring weight changes and also by SO, evolution. Sulfating of Cu2O was a maximum at ratios of SO, to O2 approximating maximum SO, production. At elevated temperatures SO, was found to increase the rate of oxidation of Cu2 O to CuO even though sulfates did not form. All sulfating reactions followed the parabolic rate law indicating diffusion. MANY studies of the roasting of copper sulfides have been reported in recent years. Diev et al.1 investigated the roasting of chalcocite (Cu2S) in air, and oxygen enriched air. Lewis et al.2 also studied the oxidation of natural and synthetic chalcocite in air and oxygen atmospheres and their studies indicated that the maximum formation of water soluble sulfates occurred at approximately 450oC. Ashcroft3 reported that oxide production during the roasting of chalcocite resulted only from secondary decomposition of sulfates which were formed as primary products. peretti4 refuted this claim by showing that a layer of Cu2O appeared directly adjacent to the Cu2S during roasting of cylindrical briquettes of cupric sulfide, CuS. The linear advance of the Cu2S-Cu2O interface was used as a measure of the kinetics of the roasting reaction. The reactions proposed were: 2 CuS—Cu2S + 1/2 S2 [4-1] 1/2 S2 + O24 SO2 [4-2] cuzs +3/2 O2 4 Cu2O + SO2 [4-3] cu2o + 1/2 O2—2 cuo [4-4] At temperatures above 663oC, CuO was the only final solid phase reported. Below 663" C increasing amounts of sulfate were found mixed with the CuO. McCabe and Morgan5 investigated the roasting of discs of synthetic chalcocite and reported the following sequence of products beginning at the sulfide surface: Cu2O, a mixture of Cu2O and CuSO4, Cum,, CuO . CuSO4, and CuO. The principal reactions were reported to be: Cu2S + 3/2 O2-Cu2O + SO2 [5-1] CU2O + 2 SO2 + 3/2 O2—2 CUSO4 [5-21 2 CUSO4— CUO . cum, + SO3 [ 5-31 cuo . cuso4—-2 cuo + SO, [ 5-41 Eq.15-11 supports the claim of Peretti, Eq. [4-31, that CuzO is formed directly from Cu2S rather than as a secondary product from a sulfate as suggested by Ashcroft. On the other hand CuO was found to form as a secondary product from the decomposition of copper sulfate and basic copper sulfate, Eqs. [5-31 and [5-41. The formation of sulfates was explained by McCabe and morgan5 to be a direct reaction of Cu2O with 0, and SO, or SO, at distinct regions in which the partial pressures of each were such as to form the sulfate. Thornhill and pidgeon6 roasted both natural and synthetic chalcocite grains in air at temperatures between 420" and 550° C. They found a dense primary oxidation layer in contact with the sulfide. A secondary layer of porous oxidation products was found to expand with roasting time. The oxide products were leached away and the remaining core was studied by X-ray diffraction. The X-ray patterns showed an increased conversion of chalcocite to digenite with time. Digenite,7 a defect structure of cuprous sulfide, occurs naturally as Cu,-,S where x = 0.12 to 0.45, with an average analysis of Cu, ,S. The mechanism of digenite formation was proposed as: Cu2S + oxygen—Cu1-8S + 0.1 Cu2O [6-1] Cuj.eS + oxygen—0.9 Cu2S + SO2 [6-2] It is apparent from the above studies that the oxidation of Cu2S, ultimately ending in CuO, may be divided into ihree general stages (all of which may occur simultaneously): 1) primary oxidation to Cu2O; 2) secondary sulfate formation; and 3) sulfate decomposition. Consequently reactions of O2 and SO, with Cu20 constitute important aspects of the roasting of chalcocite. Virtually no studies have been made regarding sulfating reactions involving Cu,O. Mills and Evans8 noted the effect of sulfur dioxide on the oxidation of copper at low temperatures and low SO, partial pressures. They reported a measurable increase in the oxidation rate of copper when SO2, was present. Interest in the Cu2O-CuO-0, system has been limited predominantly to misciblllty studies and determinations of heats of formation by

Jan 1, 1961

By E. A. Ernst, N. F. Carpenter

The benefits derived from an acidizing treatment are a function of the penetration achieved by the acid before complete spending. Additional penetration may be achieved by (1) controlling acid leak-08 into formation pores in the channel faces, and (2) retarding the reaction rate of the acid. A recently developed chemical additive consists of a synthetic polymeric material which absorbs hydrochloric-acid solutions, when suspended therein, swelling up to 40 times its original volume. These swollen particles have the ability to deform and seal-08 formation pores, providing fluid-loss control. In addition, they provide a diffusion barrier between the fracture face and the acid solution, prolonging the spending time of the acid. Field applications of this new technique have shown promising results. A method of conducting acid fluid-loss tests, using carbonate cores, is believed to provide fluid-loss data that are more representative of formation conditions than the conventional filter-paper determinations. INTRODUCTION The concept of oilwell acidizing has changed since its first commercial application, 30 years ago. Originally, it was visualized that the acid penetrated thousands of tiny pores and flow channels in the matrix rock, enlarging them by dissolving the carbonate walls. The resultant permeability increase was assumed to be the responsible factor in increasing production from the well. Recent laboratory studies,' however, have shown that this does not provide the complete picture. Although this type of individual pore penetration by the acid does take place during acid "soaks", designed to overcome "skin effect" due to mud invasion in the immediate vicinity of the wellbore, many years of experience have shown that considerable pressure is required to attain any appreciable injection rate into the fine capillary pores of the rock. During most acidizing treatments, the bottom-hole pressure build-up due to the restriction of flow into the formation exceeds the "breakdown" pressure of the rock so that a fracture is induced. In most cases, such fractures open up along natural, incipient fissures and zones of weakness in the rock and, therefore, tend to follow the natural stress pattern of the rock—whether it be horizontal, vertical or inclined. Because of the comparatively greater permeability of the channel in relation to that of the matrix, the bulk of the acid volume is diverted into the newly opened fracture. Here it quickly penetrates the formation, opening and ex- tending the fracture in much the same manner as a conventional fracturing fluid. Unlike the fracturing fluid, however, most acidizing solutions contain no propping agent; thus, the open fracture will again close when the injection pressure is relieved. Laboratory studies2 have shown that in many cases the etching of the fracture faces, resulting from the reaction between the acidizing solution and the carbonate rock, is nonuniform due to the heterogeneity of the rock structure. As a result, the two fracture faces no longer match when pressure is released, and support pillars and intermediate voids remain, forming a high-conductivity channel for well fluids. Unfortunately, this is not true over the entire area of the fracture, but only over that portion of the fracture where the rock has been partially dissolved by the acid. The acid solution spends as its travels away from the wellbore; once it has completely spent, even though it may provide additional mechanical fracture extension, no additional benefit due to etching of fracture faces can be expected. Studies of acid reaction rates under formation conditions,3 observing the effect of different variables upon spending time, have shown that the reaction was often so rapid that very little penetration of the formation occurred before the acid was spent. Study was undertaken to devise methods of increasing the penetration of the acid before spending, so as to provide greater benefit from the acidizing treatment by etching a greater portion of the fracture faces. Several techniques were devised to accomplish this purpose. First, chemical additives were developed which were designed to retard the reaction rate of the acid, causing it to penetrate a greater distance from the wellbore before finally becoming spent. Another method was to increase the injection rate of the acid. However, it was found that the resultant increased shear tended to accelerate the reaction rate of the acid, partially offsetting the benefits of the higher injection rate insofar as achieving increased penetration before spending was concerned.' Another approach to the problem of achieving increased penetration was the development of fluid-loss additives for acid solutions, which would minimize the volume of acid lost into formation pores in the fracture faces and provide maximum fracture extension for the volume of acid injected during the treatment. The use of fluid-loss additives is now considered the most effective method of providing maximum fracturing-fluid efficiency.~ Unfortunately, this latter technique does not solve the problem of rapid reaction rate, with consequent limitation of the fracture area benefited by reaction with unspent acid. A newly developed acid additive overcomes many of these limitations by providing the dual benefits of fluid-loss control and mechanical retardation of acid reaction

By C. R. Watts

The feasibility of producing composites containing nickel or molybdenum fibers in a beryllium matrix was inrestigated. The composties studied were jabricaled by powder mallurgical techniques. The 1-mil-diarr nickel fibers reacled completely below 900°C, converling the fibers .from nickel to Ni5Be2,. As the /LO/-pressing temperalure as raised above 1110oC, tlie nickel diffused outward from the beryllide fibers. The solid solubility of nickel in beryllium was clboul 20 wt pet at the 1100°C pressing temperature a1 the zone-fiber interface. The 1.5-mil-diam molybdenum fibers slzolred no evidence of reaction and little evidence of diffitsion after pressing at 900°C. Between 1000° and 1050°C pressing conditions, the fibers began lo react , producing 1ayers of MoBe2 and MoBe12, respectively surrounding the molybdenurn core. The struture remained the same at 1100°C with no evidenre of solid solubility of the molybdenum in the berylium or vice versa. In recent years a considerable amount of attention has been devoted to the determination of methods for improving the mechanical properties of materials through the use of fiber or whisker reinforcement. Previous work with metal matrix composites indicates that the study of the chemical compatibility of the fiber and matrix is an area requiring greater understanding. The metal-metal or ceramic-metal interface is frequently subject to chemical reactions that may result in the formation of hard brittle intermetal-lic compounds and/or low melting point eutectic compositions. The reaction products may reduce both the low-temperature and elevated-temperature strength of the composite by weakening the fiber-matrix bond, producing premature failure at the interface. It is well-known that most metal-metal systems and many metal-ceramic systems of interest for structural composites are thermodynamically unstable,'-" particularly at elevated temperatures. If, however, the rate of reaction under the conditions of fabrication is sufficiently low. composites can be fabricated that can be used efficiently for indefinite periods at low temperatures and for short periods at elevated temperatures. This paper presents the results of a series of tests to determine the compatibility of nickel and molybdenum fibers with beryllium at various hot-pressing temperatures. Nickel was selected as a candidate fiber material primarily because the relatively ductile fibers might be useful as crack arresters in applications such as ballistic impact where crack growth can result in catastrophic failure. The high density and the reactivity of nickel were primary factors detracting from its selection as a possible reinforcement. Molybdenum with a modulus of elasticity of 52 Xlo6 psi is one of the few metallic materials having a modulus higher than beryllium (42 X lo6). Its high modulus, coupled with its refractory characteristics, made molybdenum an attractive candidate for a relatively stable fiber reinforcement for beryllium. Its density, being higher than that of nickel and over five times that of beryllium: detracted from its other characteristics. EXPERIMENTAL PROCEDURE The specimens were prepared from beryllium powder with a dispersed phase of fibers by powder metallurgical techniques. P-20 grade powder, Table I, from Berylco was used as the matrix material. Short lengths of 0.001-in.-nominal-diam nickel fibers supplied by the Sigmund Cohn Corp. and 0.0015-in.-nominal-diam molvbdenum fibers obtained from the General Electric Co. were used as the dispersed phase. The composite constituents were combined under an argon atmosphere by mechanically mixing the powders and fibers. The compositions used were nominally 1 vol pct fibers. After mixing. the composites were hot-pressed into a-in.-diam pellets under an argon atmosphere at 900°, 1000". 1050". and 1100°C at a pressure of 6000 psi with no hold time at these temperatures so that a comparison could be made between the resultant microstructure and hot-pressing temperature. The billet was heated at a rate on the order of 30°C per min to the desired temperature and then cooled at a somewhat slower rate. The microstructure obtained should be considered as characteristic of the integrated time-temperature history of the sample, as well as the maximum temperature attained. Upon removal from the hot-pressing dies. the specimens were cut. mounted. and polished by standard procedures. No etchant was used in specimen preparation. Photomicrographs, electron microprobe scans, and electron back-scatter pictures were made. X-ray dif-fractometer patterns were made of several of the specimens. but only the lines for beryllium could be resolved. Specimens for optical and electron microprobe examination were selected partially for the roundness of the cross section. A round cross section was taken to indicate that the body of the fiber was approximately normal to the surface and that therefore effects due to fiber material immediately below the surface could be neglected. RESULTS AND DISCUSSION The microprobe scans indicated that nickel reacted as low as 900°C, converting the entire fiber cross section to NisBe21. Fig. l(a). There was no evidence of further reaction from the optical or the back-scatter pictures, Figs. 2(n) and 3(a).

Jan 1, 1970

By J. L. Kenty, J. P. Hirth

The concept of a critical super saturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, is discussed with reference to vapor-solid nucleation. The necessary and sufficient conditions deduced for observations of this type of behavior are: 1) the nucleation rate must exhibit a sharp dependence on super saturation, 2) the growth rate must be sufficiently large that nuclei become observable in the time period of the experiment, and 3) the number of highly preferred nucleation sites must be small. Experiments reveal that the nucleation of silver on sodium chloride is visually detectable at all experimentally accessible super saturations and does not exhibit critical nucleation behavior. Failure to observe a critical super saturation is attributed to the insensitivity of nucleation rate to supersaturation as a consequence of the particular values of the contact angle and the surface free energy for this system. THE concept of a critical supersaturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, arises naturally in homogeneous nucleation theory. Experimentally this type of behavior has been found by Volmer1 and others for water and other low surface tension liquids, as reviewed by several authors.2'3 The same type of behavior has been predicted and observed for heterogeneous nucleation of solids by Yang et al.4 and others,596 as also recently reviewed.2,7,8 In the work reported here on the heterogeneous nucleation of silver on NaC1, however, no critical super-saturation was found. Similar observations have been made recently for other systems.9-11 These results led to a reexamination of nucleation theory which revealed that there are conditions for which critical behavior is not predicted, either for homogeneous or heterogeneous nucleation. Although heterogeneous nucleation is of primary importance in this paper, some insight into critical behavior for such a case can be gained by considering homogeneous nucleation. Accordingly both types of nucleation theory are reviewed briefly. The requisite conditions for critical supersaturation behavior are then considered. The experimental results for the nucleation of silver on NaCl are presented and interpreted in terms of the theoretical presentation. REVIEW OF NUCLEATION THEORY There are essentially two approaches to nucleation theory, the so-called classical theory involving the concepts of bulk thermodynamics, and the statistical mechanical theory in which nuclei are regarded as macromolecules. The classical theory is based on the work of Volmer and Weber12,13 and Becker and. Doring14 and has been extended by Pound et al.15 The crucial assumption in the classical theory is that the small clusters or nuclei can be characterized by the same thermodynamic properties as those of the stable bulk phase. Thus, the nuclei are assumed to have a surface free energy, y, and a volume free energy of formation (relative to the vapor phase), ,, identical to that of the bulk. For deposition under low super-saturation conditions, the nuclei are large and this assumption is satisfactory. However, in many cases of interest, the nuclei contain only a few atoms and this assumption is highly questionable. The statistical mechanical models originated, for the specific case of a dimer as the critical nucleus, with the work of Frenkel16 and were extended later to larger sizes by Walton,17,18 Hirth19 and, more recently, Ht Zinsmeister. These models describe the nucleus in terms of a partition function, the estimation of which is tractable for clusters of 2 to 10 atoms, but extremely difficult for clusters larger than 10 atoms. Although the classical and statistical mechanical models are expected to apply for the limiting cases of large and small nuclei, both are uncertain for intermediate sizes. In this paper we shall treat only the classical model, recognizing that it is exact only for large nucleus sizes and regarding it as a phenom-enological description for small nucleus sizes. When analyses of experimental data using bulk properties show the nucleus size to be small, the resulting parameters should be regarded as largely empirical parameters describing the relative nucleation potency of the system. Considerable justification for the continued use of classical theory is provided by its general success in predicting nucleation behavior as a function of supersaturation and temperature. We emphasize that the qualitative features of the statistical mechanical models, particularly the critical super-saturation behavior that is central to the present work, are the same as those of the classical model. Of course, potential energy terms and surface partition functions replace the volume and surface energy terms of the latter model. The most recent versions of classical nucleation theory have been extensively reviewed.2,3,7 so that only the results are presented here. For homogeneous nucleation of a condensed phase from the vapor phase, the volume free energy change is ?Gv=vrT = =^ln£ [1] where v is the molecular volume of the condensing species. The supersaturation ratio,

Jan 1, 1970

By I. Iwasaki, K. Adam

The oxidation behaviors of simple and complex chloride systems of copper, iron, nickel, cobalt, and manganese in a stream of oxygen were investigated using a thermogravimetric analysis technique. Their reaction mechanisms are discussed from stoichiometry, thermodynamic feasibility, and X-ray diffraction analysis of reaction products. The results are used to determine an optimum operating temperature of the selective oxidation step in a chlorination process for producing nonferrous metal chlorides, elemental sulfur, and ferric oxide from copper-nickel sulfide flotation concentrates.

Jan 1, 1985

By Volker Weiss, George Sachs, AE. P. Klier

PHYSICAL chemistry contributes to the understanding and efficient operation of hydrometal-lurgical processes in many ways, among them by providing quantitative answers to the following questions. 1) Can a given chemical reaction or process be made to operate and. if so, under what conditions? 2) what are the' factors which determine the rate of the reaction and how can this rate be regulated in practice? Thermodynamics attempts to answer the first of these questions and kinetics the second. The answer

Jan 1, 1958

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Jan 1, 1923