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By A. S. Yue, A. G. Guy

A study was made of the effects of a prolonged flux of zinc atoms through the a solid solution of zinc in copper. The experimental arrangement consisted essentially of a copper disk about 0.01 in. thick, at one of whose surfaces a gaseous atmosphere containing zinc atoms was maintained, and at the other surface a gaseous atmosphere with a minimum of zinc atoms was maintained. During prolonged theothersurfaceexposure at high temperatures the zinc content of the copper disk gradually built up to the steady-state concentration distribution and then remained at this value. The concentration-distribution curves for various conditions were determined by chemical analyses. The results showed that the condition of steady-state diffusion was achieved. The diffusion coefficients calculated from the experimental data, although not of high precision, agreed with the values obtained by other workers using unsteady-state methods. Relatively slight porosity developed in the specimens in the course of diffusion. A LTHOUGH most diffusion studies have been made under unsteady-state conditions, it is known' that the steady-state method is often superior with respect to the directness and accuracy of interpretation of the data. Steady-state diffusion of gases through metal diaphragms is well known. Also, Harris' and Smith" have used the steady-state method in studying the diffusion of carbon in aus-tenite. The accepted mechanism in this system involves the motion of the interstitial carbon atoms in the rigid framework of the lattice of iron atoms. Thus, there is little difficulty in visualizing the steady flow of the small carbon atoms through the austenite. The situation in substitutional diffusion is quite different. Here the atoms are comparable in size, and it is not evident how a steady flow of one of the atoms through the solid solution might be achieved. At the time the present research was started, it was known that a previous exploratory attempt to produce steady-state diffusion in a substitutional alloy, the Au-Ag system,' had been unsuccessful and had indicated that perhaps there were basic difficulties that could not be ovei-come. Therefore, the present research began as a study of the effect of a prolonged flux of metal atoms through a substitutional solid solution. Eventua.lly, it was possible to produce actual steady-state diffusion in the system chosen for study, the a Cu-Zn alloys. Experimental Procedure The aim in the experiments was to maintain a high zinc content, about 30 pet, at one surface of a copper sheet, and to maintain a low zinc content, near 0 pet, at the opposite surface. The zinc would then diffuse into and through the copper, first building up to the steady-state concentration distribution and then maintaining this distribution. The three types of specimens that were used are shown in Fig. 1. In type A specimens the copper disk through which diffusion occurred was welded to the top of a cylindrical molybdenum tube, the bottom of which also was sealed by welding. At the diffusion temperature the brass chips in the molybdenum container were the source of the zinc vapor which maintained the lower surface of the copper disk at 30 pet Zn. The upper surface was maintained at 0 pet Zn by the vacuum in which type A, and also type B, specimens were diffused. Since the molybdenum container was impervious to zinc vapor, it was intended that the only path of escape for the vapor from the brass chips would be through the thin copper diffusion disk. However, it was found that small leaks often developed at the welded joints during the diffusion treatment, and in most specimens some of the zinc was lost in this manner. Although even small losses of this kind were a serious handicap in attempting to determine the flux through the disk, they did not prevent the maintenance of satisfactory boundary conditions for the attainment of the steady-state condition. Type B specimens differed from type A in having a weight of about 300 g supported on the copper disk by 15 to 20 short quartz rods. This change was made when it was observed that the copper disk was being bowed upward by the difference in the pressures acting on its two surfaces. Since the grain-boundary cracking which occurred in the bowed specimens could be attributed largely to the accompanying creep,3 it was desirable to minimize this effect. The counterweight was effective in significantly decreasing both bowing of the disk and cracking at grain boundaries. Type C specimens differed considerably from the others in that the low-zinc atmosphere at one sur-

Jan 1, 1959

By A. R. Hendrickson, C. F. Smith

Hydrofluoric-hydrochloric acid mixtures have been successfully used to stimulate sandstone reservoirs for a number of years. Hydrofluoric acid (HF) has a specific reactivity with silica which makes it more effective than HCl for use in sandstone. Kinetics of the reactions of HF have been studied to determine the related effects of reservoir composition, temperature, acid concentration and pressure on the spending rate of HF. Secondary effects from by-product formation are noted and described. Predictions are made concerning the improvement in productivity resulting from HF treatment of skin damage. The kinetic order of HF reaction in sandstone was experimentally determined to be first order, i.e., the reaction rate is proportional to concentration. HF reacts faster on calcite than on clay, which, in turn, is faster than the reaction rate of HF on sand. Static conditions retard the HF reaction rate. As HF is forced into cores, there is a temporary reduction as a function of flow rate and acid concentration. Extensive deposition of calcium fluoride in acidized cores was not observed. Although some CaF, was defected, it was not considered a major source of damage in cores containing moderate amounts of carbonate. Other fluosilicates could be potentially more dangerous than CaF, in reducing permeabiliry. INTRODUCTION Hydrofluoric acid has been widely used in stimulation treatments since 1935, when mud acid was introduced to the petroleum industry. Originally, this hydrochloric-hydrofluoric acid mixture was intended to remove mud filter cake, but it has since been successfully applied to many other oilfield problems. Mud acid treatments have been unusually successful in sandstone reservoirs where hydrochloric acid is unreactive due to a lack of enough calcite in the formation. The relatively small amount of hydrofluoric acid present (2.1 per cent) reacts with sand grains, clays and traces of calcite which are generally present in sandstone reservoirs. Since hydrofluoric acid (HF) is the key to mud acid success, this research effort has been dedicated to gaining a more thorough understanding of the basic chemical and physical principles involved as HF reacts. Hydrofluoric acid's reactivity with silica makes it unique in application. Other mineral acids such as hydrochloric, sulfuric or nitric are unreactive with most silicious materials which comprise sandstone formations. A typical sandstone reservoir may contain 50 to 85 per cent silicon dioxide, more commonly called sand or quartz. Hydrofluoric acid reacts as follows: 4HF + SiO2 + SiFO + 2H2O The silicon tetrafluoride (SiF,) is a soluble gas, in some ways similar to CO2, and is capable of undergoing further reaction when held in solution by pressure. These reactions will be considered in detail later. Kinetics of the reactions of HF have been studied to determine the effect of reservoir composition, temperature and pressure on the spending of the acid. Secondary effects from by-product formation have been noted and described. The individual reactions of HF on quartz, glass and clay are reported. Mathematical correlations have been drawn, then applied to studies of HF spending in cores obtained from actual producing sandstone formations. The research reported herein is only the beginning of a continuing approach to better understanding and use of HF in petroleum reservoirs. THEORY AND DEFINITIONS Through the years, a concentrated effort has been made to understand the effects of many variables on hydrochloric acid (HCI) spending in limestone. Hendrickson el al., have given mathematical relationships for HC1 reactions which made possible the engineered approach to acidizing. The same variables—temperature, acid concentration, formation composition, pressure and permeability-porosity relationships—which affect HC1 behavior in limestone also govern HF behavior in sandstone. Insoluble by-products of HF reaction have been isolated and identified. Their effect on fluid flow has been measured under varying conditions in an attempt to evaluate the extent of possible damage and means of eliminating it. In general, HF follows the same reaction paths as HCI. It will react with limestone and dolomite with speed and ease. Thin sections of acidized cores show the reaction of HF with limestone or calcite faster than its reaction with either clay or sand. When HF reacts with calcite (CaCO,), theoretically, calcium fluoride (CaF2) is precipitated, and has been blamed as a major cause of reduced permeability. On the other hand, pH and pressure such as that encountered in an underground formation under acid treatment definitely retard CaF2 formation,' so the whole question of CaF, deposition in wells is a subject for study.

Jan 1, 1966

By C. A. Stickels

The preferred crystallographic orientations developed during recrystallization of polycrystalline electrolytic iron sheet, cold-rolled 90 pct, were ivestigated. Recrystallization at 500° or 565° C for relatively short limes produces a texture which is similar to the rolling texture. A duplex partial fiber texture, significantly different from the rolling texture, is found when the annealing time is increased. Recrystallization at 700°C also produces a sequence of textures with increasing annealing time. In order of their appearance, these textures are: 1) the duplex partial fiber texture found at lower temperatures, 2) a four-component texture "near {322}(296)", 3) a {112)(110) +(111)(110) texture, and 4) a two-component "near {554)(225)" texture. Secondary recrystallization, or discontinuous grain growth, accompanies the development of the latter texture. However, the "near {554} (225)" texture was nol observed when secondary recrystallization occurred under other conditions. All of the ideal orientations found in recrystallization textures can be accounted for by the growth of minor components of the deformation texture. IN recent years there has been increased interest in improving the drawability of metals by controlling the preferred crystallographic orientation of the sheet.1-l3 Since more low-carbon steel is drawn than any other material, considerable attention has been focused on the properties of sheet steel. Efforts to improve drawability through texture control have been hampered by the lack of any published systematic study of the recrystallization textures developed in iron annealed below Acl. The purpose of the present work was to supply some of this missing information, specifically, the recrystallization textures obtained by isothermal anneals of polycrystalline iron, cold-rolled 90 pct. LITERATURE REVIEW—DEFORMATION TEXTURES Barrett14 reviewed and summarized the investigations of rolling textures in iron and low-carbon steel prior to 1952. The texture of heavily deformed iron (rolled 90 pct or more) is described as consisting of two partial fiber textures. The dominant fiber texture (designated here as fiber texture A) has a (110) fiber axis in the rolling direction and includes the orientations (001)[110], {112}( 110), and {111}(110). The secondary texture (designated here as fiber texture B) is described as having a (111) fiber axis in the sheet normal direction, and includes the orientations {111)( 110) and (111)(112). Since the publication of Barrett's book, there have been two detailed studies of the deformation texture in polycrystalline iron. In both instances, the more sensitive diffractometer methods of pole-figure determination were used. Bennewitz15 studied the cold-rolling textures developed in polycrystalline low-carbon steel and a 3 pct Si steel. He determined (110), (2OO), and (222) pole figures for specimens reduced 30, 50, 60, and 90 pct and analyzed his results in terms of partial fiber textures. He distinguished three stages in the development of the final deformation texture. 1) Grains rotate to form two incomplete fiber textures, with (110) fiber axes inclined 30 deg to the sheet normal toward the rolling direction (fiber texture B). After 50 pct reduction, the highest density of poles is near an ideal orientation {554}(225), the two components of which are members of this duplex fiber texture. 2) With increasing amounts of reduction, grains rotate about the former fiber axes toward ideal orientations of the type {112)( 110) (common to fiber textures A and B). 3) Finally, grains rotate about their ( 110) axis in the rolling direction, clockwise and counterclockwise from the orientations {112}(110). This produces the range of orientations from (111)(110) to (001)(110) commonly found in the rolling texture of heavily deformed iron (fiber texture A). No significant difference was found between the deformation textures of low-carbon and silicon steels. A few years earlier, Haessner and weik16 had determined (110) pole figures for carbonyl iron rolled to 30, 60, 80, and 90 pct reduction in thickness. heir data agree quite well with the more complete data of Bennewitz, but a somewhat different description of the evolution of the deformation texture was given. The appearance of (110) poles in the transverse direction is ascribed to a (100)[011] component rather than "near {554}( 225) " components, and the (110) fiber axes of fiber texture B are described as located 35 deg rather than 30 deg from the sheet normal. Both of these studies agree that the secondary texture present in heavily rolled iron, the duplex fiber texture B, has (110) fiber axes and not a single ( 111) fiber axis normal to the sheet, as

Jan 1, 1965

By Charles L. Mantell, James E. Hoffmann

Mechanical inclusion, electrophoretic deposition, and adsorption were studied as mechanisms for code-position of aluminas present in copper-plating electrolytes as an insoluble disperse phase. Mechanical inclusion was not a significant factor. That codeposi-tzon of aluminas by an electrophoretic mechanism was unlikely was substantiated by measurements of the potential of the aluminas. The alumina content of the deposits was studied as a function of the pH of the bath. These tests in conjunction with sedimentation studies demonstrated the absence of an isoelectric point for the alutninas over the pH range examined. Thiourea in the electrolyte (a substance known to be adsorbed on a copper cathode during electrodeposition) affected the amount of alumina in the electrodeposit. However, no adsorption of thiourea on aluminas in aqueous dispersions was detected. If it were possible to produce a dispersion-hardened alloy of copper and alumina by electrodeposition, an alloy possessing both strength and high conductivity at elevated temperatures might be anticipated. Investigation of the mechanism of codeposition of aluminas with copper was undertaken with the hope that knowledge of the mechanism would aid in the development of such an alloy. The word "codeposit" here does not necessarily imply an electrolytic phenomenon but rather that the materials codepositing, the various aluminas, are transported to and embedded in the electrodeposited copper by some means. Mechanical inclusion in electrodeposition implies a mechanism of codeposition which is wholly mechanical in nature; the only forces acting on a particle are gravity and contact forces. Such a particle is presumed to be electrically inert and incapable of any electrical interaction with electrodes in an electrolytic plating bath. Processes for matrices containing a codeposited phase by electrodeposition from a bath containing a disperse insoluble phase frequently state that code-position is caused by mechanical inclusion.10,2,12 If settling, i.e., gravity, be the controlling mechanism for codeposition of aluminas, then assumptions may be made that 1) the content of alumina in the electrodeposit should be enhanced by increasing the particle size, 2) the geometry of the system, that is, the disposition of the cathode surfaces relative to the di- rection of the falling particles, should affect the alumina content of the electrodeposit, 3) in geometrically identical systems the chemical composition of the electrolyte employed should exercise no effect on the alumina content of the deposit, that is, the alumina content should be the same in all cathode deposits irrespective of bath composition. A bent cathode19 evaluates the clarity of filter effluent in electroplating baths by comparing the roughness of the deposit on the vertical surface with that on the horizontal surface. Two difficulties are inherent in this technique: 1) the current density on the horizontal portion of the cathode would be substantially greater than that on the vertical surface; 2) should the deposit obtained be rough, projections on the vertical face could act as horizontal planes and vitiate the relationship between the vertical and horizontal surfaces. Bath composition should have no substantial effect on the alumina content of the deposit. Two different electrolytic baths were employed. They possessed variant specific conductances and substantially different pH ranges. The experimental tanks were rectangular Pyrex battery jars 6 in. wide by 3 1/4 in. long by 9 3/4 in. deep. The cathodes were stainless steel 316 sheet of 0.030 in. thickness, cut to 7.5 by 1.75 in. and bent at right angles to form an L-shaped cathode whose horizontal surfaces measured 1.75 by 3.0 in. All edges and vertical surfaces were masked with Scotch Elec-troplaters Tape No. 470. The anodes were electrolytic cathode copper 9 in. high by 2.25 in. wide by 0.5 in. thick. To eliminate inordinately high current densities on the projecting edge of the cathode, the anode was masked 1 in. above and below the projected line of intersection of the cathode with the anode. The exposed area of the anode was equal to that of the cathode, providing both with equal average current densities. The agitator in the cell was of Pyrex glass and positioned so its center line was equidistant from cathode and anode, and a plane passed horizontally through the center of the blade would be located equidistant from the bottom of the cathode and the bottom of the deposition tank. The assembled apparatus is depicted in Fig. 1. Hatched areas on anode and cathode represent the area of the electrodes wrapped with electroplaters tape. MATERIALS The chemicals were copper sulfate—CuSO4 • 5H2O— technical powder (Fisher Scientific Co.). Spectro-graphic analysis showed substantial freedom from antimony, arsenic, and iron. Traces of nickel were present.

Jan 1, 1967

R,. P. JaRvis,* El Oro, Estado de México, México.—The practical problem raised by Mr. Wisser—that is, the determination of the lower limit of ore deposition, below which it is useless to look for ore shoots—is one of the most important in economic geology. He asks: "Can we learn to determine the position of such a line?" For individual districts, yes; but its determination has always been by empirical methods; that is by actually exploring the veins to such depths that the values drop below the economic limits. Usually the signs are plain enough that values have been bottomed without confirmation by the chemist or assayer. Most veins, when approaching their limit, begin to split into branches or stringers; the vein matter itself undergoes a change from "lively looking" rock to one that is dull and unpromising, the quartz, instead of having segregated into clean vein matter, has simply spread itself into the country rock, rendering this more siliceous but no richer—these, together with inclusions of the country rock in the vein, are all positive indications of the limit. Mr. Wisser seems disposed not to accept the law of cause and effect, which he calls "empiricism." He says: "Empiricism embodies an assumption perhaps not evident at first glance. It is this: that like effects spring from like causes and therefore necessarily have a common meaning." There can be no doubt as to the validity of this law, since it is the foundation stone upon which are built all inductive sciences, including economic geology. When demonstrable, proved facts become confused with inferences, as they seem to be generally in the paper under examination, no sound conclusions can be reached. Mr. Wisser has failed to give sufficient data covering the two vein systems which he cites as examples. Presumably they are situated in the Pachuca District of Mexico, but not everybody is familiar with the vein systems there in spite of the fact that it is world famous as a silver producer. Are these two systems separated some distance horizontally from one another and how far? He has given no estimate of the amount and kind of rock that has been eroded from over the present veins. His description of the two systems appears on page 100, beginning: "1. East-west veins," and ends on page 101, "they would lack spaces there in which to deposit." On page 101, with the paragraph beginning "On the other hand," he gives a picture of what he believes takes place in class 2 veins. The sum of this seems to be, according to Mr. Wisser's observations, that, in the east-west veins, class 1, there has been an invasion of an "altering solution," which I judge has been responsible for the formation of extensive "alteration haloes"; that these alteration solutions have followed along pre-existing fractures or fissures; and that after these alteration solutions finished their work the mineralizing solutions deposited the vein matter and metallic values. Mr. Wisser does not specify clearly what the "alteration haloes" consist of; in other words, what change the original rock has suffered, whether oxidizing, carbonating, or sulphidizing. If they came from depth they could not be oxidizing or carbonating, and in this case it is a bit

Jan 1, 1941

By R. C. Gifkins

R. C. Gifkins (CSIRO)—In this paper evidence is put forward to support the idea of grain boundary shearing in aluminum at 4.2°K and the phenomenon is explained in terms of a low-temperature "equicohesive temperature". It is stated that these findings show that grain boundary shear cannot be ruled out in any situation by temperature arguments alone. We believe, from our own recent study of "apparent grain boundary sliding'' at temperatures below 0.45 Tm, that it can be ruled out on temperature arguments alone.45 Our experiments were made principally with magnesium and a Ms-A1 alloy ("Magnox A12"). Careful examination of offsets of marker lines or steps at grain boundaries produced by deformation at room temperature (-0.3 Tm) showed many of these to result from curvature over narrow zones along the grain boundaries. A significant residuum did, however, appear as a sharp offset or step. It was found that the mean value of this step rose to a small value during the first 0.5 to 1 pct strain and then remained at this level with further strain. Moreover, exactly the same values were obtained (at the same stress) at 75°C instead of 21°C. That is, in this range of temperature the "apparent sliding" was not temperature-sensitive. At 125°C and above there was sliding which increased with strain and which was temperature-dependent. When this temperature-dependent sliding was used to calculate the sliding to be expected at room temperature, this underestimated the "apparent sliding" by a factor of 104. The conclusion drawn is that the "apparent sliding" consists of shear localized in a zone of a width measured perhaps in microns, whereas it seems that true sliding occurs on the boundary surface.46 A model for such localized shear has been developed in general terms, following a similar model of Urie and Wain.47 Other strong evidence for low-temper- ature sliding has been based on the offsets of marker lines consisting of a substructure seen using the electron microscope to resolve these.48 We have repeated this work and found that the effects can be accounted for in terms of cracks in an oxide film which is produced when the substructure is etched up; these cracks form over zones of shear rather than at actual interfaces. However, in aluminum at room temperature (-0.3 Tm) there is no "apparent sliding" which is optically detectable. We suggest that, when the temperature is much lower (and possibly the rate of strain higher, too), as in the experiments of Chin et al., then aluminum behaves like magnesium at room temperature, and a narrow zone of shear develops to accommodate differences in strain across the grain boundary. Such a zone could well give rise to triple-point cracks. It is hoped to investigate these suggestions further. B. Y. Chin, W. F. Hosford, Jr., and W. A. Backofen (authors' reply)—It is interesting to have Dr. Gif-kin's comments, although it is somewhat difficult to reply in detail without the reference containing the work that he describes. Apparently though, he does find a low-temperature temperature-independent sliding that would seem to be related to the observations reported here. Perhaps some of the difficulty has semantic origins, growing out of the distinction between ('true sliding" and "apparent sliding".

Jan 1, 1965

R,. P. JaRvis,* El Oro, Estado de México, México.—The practical problem raised by Mr. Wisser—that is, the determination of the lower limit of ore deposition, below which it is useless to look for ore shoots—is one of the most important in economic geology. He asks: "Can we learn to determine the position of such a line?" For individual districts, yes; but its determination has always been by empirical methods; that is by actually exploring the veins to such depths that the values drop below the economic limits. Usually the signs are plain enough that values have been bottomed without confirmation by the chemist or assayer. Most veins, when approaching their limit, begin to split into branches or stringers; the vein matter itself undergoes a change from "lively looking" rock to one that is dull and unpromising, the quartz, instead of having segregated into clean vein matter, has simply spread itself into the country rock, rendering this more siliceous but no richer—these, together with inclusions of the country rock in the vein, are all positive indications of the limit. Mr. Wisser seems disposed not to accept the law of cause and effect, which he calls "empiricism." He says: "Empiricism embodies an assumption perhaps not evident at first glance. It is this: that like effects spring from like causes and therefore necessarily have a common meaning." There can be no doubt as to the validity of this law, since it is the foundation stone upon which are built all inductive sciences, including economic geology. When demonstrable, proved facts become confused with inferences, as they seem to be generally in the paper under examination, no sound conclusions can be reached. Mr. Wisser has failed to give sufficient data covering the two vein systems which he cites as examples. Presumably they are situated in the Pachuca District of Mexico, but not everybody is familiar with the vein systems there in spite of the fact that it is world famous as a silver producer. Are these two systems separated some distance horizontally from one another and how far? He has given no estimate of the amount and kind of rock that has been eroded from over the present veins. His description of the two systems appears on page 100, beginning: "1. East-west veins," and ends on page 101, "they would lack spaces there in which to deposit." On page 101, with the paragraph beginning "On the other hand," he gives a picture of what he believes takes place in class 2 veins. The sum of this seems to be, according to Mr. Wisser's observations, that, in the east-west veins, class 1, there has been an invasion of an "altering solution," which I judge has been responsible for the formation of extensive "alteration haloes"; that these alteration solutions have followed along pre-existing fractures or fissures; and that after these alteration solutions finished their work the mineralizing solutions deposited the vein matter and metallic values. Mr. Wisser does not specify clearly what the "alteration haloes" consist of; in other words, what change the original rock has suffered, whether oxidizing, carbonating, or sulphidizing. If they came from depth they could not be oxidizing or carbonating, and in this case it is a bit

Jan 1, 1941

By Philip R. Strand, O. F. Stewart

Vermiculite is the name generally applied to the group of hydrated ferromagnesian aluminum silicates that are characterized by the ability to expand when heated. This process, called exfoliation, results in a lightweight product of commercial value. Most uses of vermiculite are for the expanded material. The chief markets are in construction, agriculture, and horticulture, with lesser uses in general industry. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit, a perfect basal cleavage which causes splitting into thin laminae that are soft, pliable, and inelastic. The structure of vermiculite is basically that of a talc. The prominent monoclinic crystal faces are often marked by lines at 60° and 120°. Hardness varies from 1.5 to 2 or more; specific gravities are between 2.1 and 2.8; color varies from almost clear to amber, bronze, brown, green, or black. Vermiculite feels like talc, especially when wet. Although much research has been performed on the chemical and structural composition, there is not yet complete agreement on the exact formula. This is to be expected when different workers have examined the many different varieties. Vermiculite is not considered to be a single mineral species but a family of related minerals. The structural formula for a trioctahedral vermiculite may be written: (H20)-(Mg,Ca,K)-(A12,Fe,Mg)-(Si,A1,Fe)4O10 (OH) 2 Hydrobiotite also occurs with vermiculite and is usually considered a vermiculite for commercial uses. When heated quickly to elevated temperatures, vermiculite expands by exfoliating at right angles to the cleavage into wormlike particles. The name vermiculite is derived from the Latin vermiculare, to breed worms. This characteristic of expansion is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The decrease in bulk density of commercial grades is usually approximately 10 times, from 50 to 5 lb/ft3, but varies depending on the quality, size, and furnace efficiency. Individual flakes may expand up to 30 times. Vermiculite may also be expanded by soaking in chemicals such as hydrogen peroxide, weak acids, and other electrolytes. Color change during expansion is dependent upon the type of vermiculite and furnace conditions. Heating in an oxidizing atmosphere produces a dull gray or tan color, whereas a reducing atmosphere can produce a bronze or gold color. The expansion of the vermiculite crystal results in large pores being formed between the platelets. Thus, exfoliation makes available a large increase in void volume which is important in the application of vermiculite as a chemical carrier. Mathieson and Walker (1954) state vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation exchange capacity, organic complexing ability, and variable interlamellar distance are very similar to those of montmorillonite. The cation exchange capacity of vermiculite is one of the highest of all the clay minerals. The interplatelet space is accessible to penetration by some electrostatically neutral molecules. Water and glycerine are two common substances whose molecules may be so imbibed. In the natural state and under normal atmospheric conditions, water occupies the spaces between the silicate layers. The crystal d-spacing is near 14.2A. By differential thermal analysis, it has been determined that the water

Jan 1, 1983

By J. A. B. Forster

W. G. WOOLF*—The paper has a wealth of data that take careful, detailed study. As has been indicated the highlights can be only touched in the paper. The design and the arrangement of the rabble teeth as well as some of the other details of operation show a very careful study and a scientific approach to the problem which in most plants using hearth roasters are matters of trial and error with empirical conclusions and, perhaps too often, just arbitrary supervisory preferences which may be erroneous. Here the problem has been approached from a scientific angle which think well merits careful study. The ability to treat the tonnages they get through these furnaces think is made easier by reason of the high sulphide sulphur in the resulting calcines which the balance of the plant—the leaching and so on—can cope with. As indicated by Mr. Weldon in his dis- cussion earlier this morning, in most zinc plants an attempt is made to have as low a sulphide sulphur content in the roaster calcine as possible. But in the operation of the Risdon plants, they are able to cope with sulphide sulphur content up to 5 pct which is far beyond the amount of sulphide sulphur that can be handled elsewhere. I think the autogenous roasting is made easier because driving out the last percentages of sulphide sulphur brings on the necessity for extraneous heat, and that is further exemplified because even at Risdon the author shows the desirability of using some oil to better the operation, particularly for uniformity of roasting results and to obtain more regularity of furnace operation. A. A. CENTER*—Regarding the hard crusts in the beds of the furnace and autogenous roasting, the paper speaks of the former being due, at least to a considerable extent, to lead sulphide in the crusts. I wonder if the author has considered the hard crusts as being due in large part to zinc sulphate. While I was developing large zinc operations we ran into hard crusts which had to be dug up. I took several lumps which were so hard they showed the marks of the rabble teeth very plainly and kept them in my office for some weeks. A visitor came along one day, and as he was having similar troubles, I told him what we were doing about ours. I started to pick up one of these lumps and to my amazement the thing crumbled in my hands whereas originally it had been so hard it wore the rabbles down very rapidly in the furnace. I sent the sample to the laboratory and found that it analyzed very high in water-soluble zinc and sulphate-sulphur. The crumbling of the lumps was evidently due to the anhydrous zinc sulphate gradually taking on moisture from the air and forming crystalline zinc sulphate seven parts water. The increase in volume would, of course, result in disintegration of the lumps. As to getting a high tonnage in the autogenous roast, that is partly because of finishing at about 5 pct sulphide sulphur. It is a real job to get down to, say, ½ pct sulphide sulphur, which is what is usually desired, and still put through a good tonnage.

Jan 1, 1950

By R. E. Cole, A. M. Gaudin

OLEIC acid, a standard flotation reagent, has generally been preferred to other fatty acids. Because oleic acid differs from saturated fatty acids by the presence of one carbon-to-carbon double bond and because the flotation operation is one in which extremely intimate exposure of the reagent to oxygen is obtained, it appeared possible that the value of oleic acid as a flotation collector was related to the oxidizability of its double bond. To test this hypothesis, the floated mineral, fluor-ite, was leached with a solvent capable of extracting the adsorbed reagent and the extract was analyzed.' Results show that oleic acid is not oxidized during flotation, although some oxidation can be obtained if the flotation operation is repeated many times and if oxygen in place of air is employed as the gas during flotation. Incidentally, it was found that lino-leic acid which has two nonconjugated double bonds is not affected appreciably more than oleic acid. Linolenic acid which has three nonconjugated double bonds is measurably altered even during one flotation step, using air. The fatty acids used, from the Hormel Foundation, were of the highest purity. The quantity of fatty acids employed in each test was sufficient to float the mineral, but less than the theoretical amount required to form a monolayer at the mineral surface. The purpose of this limitation was to eliminate droplets of oil smeared on the adsorbate-covered mineral surface. The mineral was dried in vacuum at about 60 °C. Effective leaching was obtained by use of a solution of 1 pct hydrochloric acid in absolute alcohol. The extract was separated from the solvent by distillation, with final recovery of the extract in carbon tetrachloride. The identity of the extract was tested by a combination of analytical procedures including infrared spectroscopy, saponification number, iodine number, and index of refraction. At the outset, great hopes for accurate quantification of oleic acid oxidation had been entertained in regard to the method of infra-red spectroscopy. Unfortunately, because the double bond in the oleic acid is so sym- metrically located at the center of the molecule that it provides very weak absorption bands, accurate quantitative analyses were not obtained. Nevertheless, infra-red spectrograms suggested the absence of double-bond oxidation during flotation. Iodine number, semi-micro method, provided a critical test of the extent to which fatty acids oxidized during flotation, see Table I. The index of refraction was used in a qualitative rather than quantitative fashion, and its findings corroborated those obtained by the iodine-number method. It is concluded, in the case of fluorite and C-18 fatty acids having one or two nonconjugated double bonds, that there is practically no change of the fatty acid molecule or ion during the flotation operation. It would appear, therefore, that the extraordinary utility of these reagents is related to some property of the compounds other than the oxidizability of their double bonds. Acknowledgment The research reported herewith was sponsored by the Research Division, U. S. Atomic Energy Commission, and for this help the authors express their appreciation. Reference 'R. E. Cole: "Double-Bond Reactivity of Oleic Acid During Flotation." Thesis submitted in partial fulfillment of the requirements for the degree of M.S. at the Massachusetts Institute of Technology.

Jan 1, 1954

By D. H. Thompson, A. W. Tracy

E. A. ANDERSON*—At the outset, I note that you are using a humid atmosphere containing ammonia but that you make no reference to the variable of carbon dioxide content. Edmunds in his work in this laboratory found very marked effects on the rate of failure due to variations in carbon dioxide in the environment. This point is, of course, strongly related to the overall corrosion rate problem since the role of the carbon dioxide seems to be to permit the formation of hygrogroscopic salts which give a controlled moisture film on the specimen surface, which in turn seems to support the intergranular penetration more consistently than would otherwise occur. (2) Your results with various copper binary systems are very striking. It is curious, however, that the time-to-failure minima all occur at percentages of the alloying element which are considerably below the solubility limits as given in the conventional equilibrium diagrams. If your theory regarding the presence of these impurities in some concentration in the grain boundaries is correct, then either the existing diagrams are not accurate in the room temperature region, or there is a difference in solubility in the grain boundaries as compared -with the grains. A study along these lines might be very revealing. (3) The undesirable effect of silicon in copper calls to mind our own observations on the influence of silicon on the stress corrosion cracking resistance of alpha brass. In this case, silicon was found to have a very marked beneficial effect, particularly when a heat treatment capable of producing a grain boundary constituent was used. I should appreciate it if in the discussion of your paper this point should arise, you would attempt to clarify the difference between the copper-silicon binaries and the copper-zinc-sili-con ternary alloys. D. H. THOMPSON and A. W. TRACY (authors' reply)—(1) We have no data on the constancy of the carbon dioxide content of the air used for the test atmosphere but have believed that the normal carbon dioxide content of the air was as constant as could be obtained by using Edmunds' method of removing carbon dioxide from the air and then adding a measured quantity. In any event, the test atmosphere was the same for all specimens in a test run. We agree with Mr. Anderson that the carbon dioxide content is important in the formation of a hygroscopic film on specimens. (2) We can imagine that there could be a concentration of solute atoms at the grain boundaries which would be so small that present methods would not detect it even if it exceeded the solubility limit of the alloy. There could be somewhat greater solubility at the grain boundaries for an interstitial solute. There is a possibility that phosphorus dissolves in this way but we believe that none of the other solutes studied does. In our present studies we hope to find out something about conditions at the grain boundaries of some of the systems mentioned in the paper. (3) Mr. Anderson points out that silicon brass, which has had a high temperature heat treatment followed by a quench. is highly resistant to stress-corrosion cracking. Although the test conditions used by Anderson* et al were different from our test conditions, it is noted that the silicon brasses which had not had the special heat treatment were less resistant to stress-corrosion cracking than copper containing approximately equal amounts of silicon. G. R. GOHN†—Nonferrous metallurgists and particularly, materials engineers, have been accustomed to thinking

Jan 1, 1950

By R. T. DeHoff

Saltykov's meihod for the determination of the size distribution of spherical particles from measurements made on random plane sections is extended to particle shapes which are not equiaxed. The analysis permits the deterrrzination of the size distribution of aggregates of ellipsoidol particles provided all particles have tlze same shape. V ARIOUS solutions to the problem of the determination of the size distribution of spherical particles from measurements made on random plane sections have appeared in the literature since the original solution was first published by Scheill in 1934. Solutions have been offered utilizing measurements of the diameter1y2 or area3'4 of circular sections that result when a test plane is passed through an aggregate of spherical particles, and the length of intercept5y6 that results when a test line is passed through the aggregate. To the best of the knowledge of the author, no method has been proposed which permits the determination of the size distribution of particles that are not equiaxed. The purpose of this paper is to develop a method which permits the determination of the size distribution for a specific class of particle shapes which cover awide range of axial ratios; namely, ellipsoids of revolution. In the interests of simplicity, it is necessary to limit consideration to aggregates of particles which are all similar in shape; that is, the ellipses which, by rotation about one of their axes, generate the particles, all have the same axial ratio. The size distribution, which is to be determined by the analysis, is arbitrary. It is also assumed that the section, or sections, upon which the measurements are made represent the average of all possible sections through the structure. This ideal condition can be approached as nearly as may be desired by observing a sufficient area of sections taken at random positions in a randomly oriented aggregate, and in random positions and orientations in an aggregate that has one or more axes of orientation. SIZE DISTRIBUTION FOR PROLATE ELLIPSOIDS Consider an aggregate of cigar shaped, geometrically similar particles (prolate ellipsoids), dispersed in an opaque matrix. Let the size of each particle be specified by the length of its minor axis, By Fig. 1, and the shape, q, be defined by the ratio of its minor to its major axis, B/A. Let the index, j, refer to dimensions of ellipsoids in a particular size class, and the index, i, to dimensions of an ellipse resulting from the intersection of a test plane and a particle. The size of such a section is specified by the length of its minor axis, b. Let the particles be arbitrarily divided into k size classes, and let the increment of size between each class be A, where A = &,$, B,,,being the minor axis of the ellipsoids in the largest size class. Since all sections are represented on the test plane, the minor axis of the largest of the sections observed, results from the intersection of the test plane with an ellipsoid in the largest size class at its center, and is therefore equal to Bmax Thus the increment, A = The final result will consist of the k numbers which represent the number of particles in each size class per unit volume of aggregate:

Jan 1, 1962

By Stephen Royce

[PAGE Ground Movement Adjacent to a Caving Block in the Climax Molybdenum Mine (TP 2000 by JOHN W. VANDERWILT, Min. Tech., May 1946. Discussion by STEPHEN ROYCE and the Studies of the Design of Shaped Explosive Charges and Their Effect in Breaking Concrete Blocks (TP 2157 by GEORGE B. CLARK, Min. Tech. May 1947. Discussion by PHILIP B. BUCKY, V. H. CLARK, E. D. GARDNER, M. H. HAWKINS, H. L. WALKER, and the author) 2 See TP 2377, Min. Tech., May 1948 for discussion of San Manuel ProsPect (TP 2255 by H. J. STEELE and G. R. RUBLY, Min. Tech., Sept. 1947. Discussion by L. KENNETH WILSON, ELDRED D. WILSON and the authors)] Ground Movement Adjacent to a Caving Block in the Climax Molybdenum Mine STEPHEN ROYCE•-It is interesting to note from B, Fig 2, how closely the subsidence limits approximate to the 60° angle of draw, which is so commonly found to rule in large scale rock subsidence. The tension cracks shown at B are commonly found in the initial stages of subsidence movement and spread like a halo about subsidence limits as movement extends. These tension cracks usually grow into escarpments later on. Apparently from the illustrations and description given, a system of vertical fractures is the predominating weakness in the wall rock at Climax, and therefore both tension cracks and escarpments are prevailingly vertical in attitude. The illustrations in Mr. Vanderwilt's article seem to conform to the general rule that yield by subsidence is heralded by tension cracks which foreshadow the appearance of the subsidence scarps which are both described in the paper and shown in Fig 2. The difference between the B side and the A side of Fig 2 is apparently caused mainly by the vertical fracturing which controls subsidence at Climax as compared to the relatively homogeneous rock formation at A upon which the original figure in Peele's Handbook was based. The draw at B is exactly 60°, while the draw at A is a little flatter. The influence of the vertical fractures explains the difference. The surprising feature is the relatively small deviation from the general 60° draw line, which is about the average of rock subsidence experience. The influence of local fracture systems, faults and bedding in controlling subsidence all the way from extremely low angles of draw to vertical is rather fully discussed in the Peele's Handbook article referred to. The more illustrations of subsidence there are published the better will be our knowledge. The general principles are pretty well established. The wide local differences reflect the effect of local conditions. This paper is a very valuable contribution to the subject, and for the benefit of the mining industry, it is to be hoped that there will be many more such clear and concise presentations. Particularly block caving is apt to be of greatly increasing importance in the future of a mining industry that must meet high labor costs. More examples of block caving from small scale to large scale operations like those at Climax will serve a vital need. JOHN W. VANDERWILT (author's reply)-I would like to thank Mr. Royce for his discussion; however, in his comments the meaning of subsidence, draw and tension cracks is not entirely clear. As used in my discussion of subsidence at Climax, subsidence refers to movements involving appreciable downward displacement. Tension cracks indicate only

Jan 1, 1947

By W. L. Worrell

R. C. Gifkins (CSIRO)—In this paper evidence is put forward to support the idea of grain boundary shearing in aluminum at 4.2°K and the phenomenon is explained in terms of a low-temperature "equicohesive temperature". It is stated that these findings show that grain boundary shear cannot be ruled out in any situation by temperature arguments alone. We believe, from our own recent study of "apparent grain boundary sliding'' at temperatures below 0.45 Tm, that it can be ruled out on temperature arguments alone.45 Our experiments were made principally with magnesium and a Ms-A1 alloy ("Magnox A12"). Careful examination of offsets of marker lines or steps at grain boundaries produced by deformation at room temperature (-0.3 Tm) showed many of these to result from curvature over narrow zones along the grain boundaries. A significant residuum did, however, appear as a sharp offset or step. It was found that the mean value of this step rose to a small value during the first 0.5 to 1 pct strain and then remained at this level with further strain. Moreover, exactly the same values were obtained (at the same stress) at 75°C instead of 21°C. That is, in this range of temperature the "apparent sliding" was not temperature-sensitive. At 125°C and above there was sliding which increased with strain and which was temperature-dependent. When this temperature-dependent sliding was used to calculate the sliding to be expected at room temperature, this underestimated the "apparent sliding" by a factor of 104. The conclusion drawn is that the "apparent sliding" consists of shear localized in a zone of a width measured perhaps in microns, whereas it seems that true sliding occurs on the boundary surface.46 A model for such localized shear has been developed in general terms, following a similar model of Urie and Wain.47 Other strong evidence for low-temper- ature sliding has been based on the offsets of marker lines consisting of a substructure seen using the electron microscope to resolve these.48 We have repeated this work and found that the effects can be accounted for in terms of cracks in an oxide film which is produced when the substructure is etched up; these cracks form over zones of shear rather than at actual interfaces. However, in aluminum at room temperature (-0.3 Tm) there is no "apparent sliding" which is optically detectable. We suggest that, when the temperature is much lower (and possibly the rate of strain higher, too), as in the experiments of Chin et al., then aluminum behaves like magnesium at room temperature, and a narrow zone of shear develops to accommodate differences in strain across the grain boundary. Such a zone could well give rise to triple-point cracks. It is hoped to investigate these suggestions further. B. Y. Chin, W. F. Hosford, Jr., and W. A. Backofen (authors' reply)—It is interesting to have Dr. Gif-kin's comments, although it is somewhat difficult to reply in detail without the reference containing the work that he describes. Apparently though, he does find a low-temperature temperature-independent sliding that would seem to be related to the observations reported here. Perhaps some of the difficulty has semantic origins, growing out of the distinction between ('true sliding" and "apparent sliding".

Jan 1, 1965

By J. W. Peirce

Advances in instrumentation now make it possible to measure accurately flaw of such difficult-to-mea-sure liquids as mining slurries. A mass flowmeter, which introduces no restrictions in the line, will measure the mass flow of slurry equal to the volume flow times the mms/unit volume. In the mass flowmeter system a volume flow measurement is electrically multiplied by a density measurement in order to give mass flow. Fig. 1 shows a typical mass flow measuring system. The volume flow is measured by a magnetic flowmeter and the density is measured by a gamma gauge cell, neither of which have any restrictions in the line. Consequently, there is no clogging and no more loss of head than there would be in a similm length of standard pipe. None of the parts extend into the flowing stream and there are no moving parts in the measuring elements. PRINCIPLE OF OPERATION OF THE VOLUME FLOW TRANSMITTER The magnetic flowmeter, which is used for the volume measurement, operates on the principle of a generator (Fig. 2). This principle states that when a moving conductor cuts lines of force in a magnetic field, a voltage is induced in it. Moreover, if the dimensions of the conductor remain constant, then the induced voltage is directly proportional to the velocity of the conductor. Since the voltage is strictly a function of flow velocity, the transmitter output can in no way be influenced by such factors as temperature, viscosity, turbulence, or conductivity. The linear output is detected by flush mounted electrodes (as shown) and transmitted to a potentiometer flow receiver. Magnetic Meter Construction: The metering tube is constructed of nonmagnetic stainless steel. (See Fig. 3.) To prevent shortcircuiting of the generated voltage, the tubes are lined with a suitable liner, depending upon the corrosive, erosive or other properties of the liquid or slurry to be measured. A uniform magnetic field is produced by two saddle-shaped coils of insulated copper wire. A laminated iron core focuses the magnetic field at a 90' angle to the flowing liquid. The voltage generated by a flow of liquid through the magnetic field is detected by two point electrodes mounted flush with the inner wall of the metering tube, 180' apart. Electrodes are made of Type-316 stainless steel or other material suitable to the application . Volume Flowmeter Operation: The millivolt output of the metering transmitter is transmitted to a potentiometer-type receiver (Fig. 4). The self-balancing, self-standardizing receiver has a drive unit for circuit rebalancing. The measurement change imposes an unbalanced input on the twin windings of the drive unit. The resulting unequal pull on a segmental rotor provides the motion which drives a pen, while simultaneously and steplessly repositioning a rebalancing element. Changes in conductivity have no effect on the accuracy of the measurement or the calibration of the instrument. The minimum conductivity values are determined by the length of the transmission cable and the size of the transmitter. They can be as low as five micro mhos, since there is such a small load on the electrodes. Because the meter electrically averages all of the incremental velocities in an irregular flow profile, it is ideally suited for turbulent flow and suspended solids. Straight runs of pipe are therefore not required. The transmitter can be installed close to

Jan 1, 1962

By S. S. Shen, M. J. Pool, P. J. Spencer, J. R. Guadagno

VERY few thermodynamic data are available for rare-earth alloys, partly because of the difficulties of obtaining the metals in sufficiently pure form and also because of their comparative scarcity up to the present time. The rare earths form a very interesting series in the periodic table in view of the progressive filling of their 4f subvalence electron shell and would be expected to provide useful information with regard to alloying characteristics of transition elements. It has been found in recent calorimetric investigations that the heats of solution of a number of the rare-earth metals in liquid tin are highly exothermic.1-4 Exceptionally strong bonding between rare-earth and tin atoms is clearly indicated in the liquid solutions. Continued thermodynamic studies of the behavior of rare earths in solution could thus contribute a great deal to present theoretical knowledge of alloying behavior and would yield an insight into bonding of a strength hitherto unencountered in liquid alloys. The determination of the heats of solution of the pure components in liquid tin is an essential preliminary to calorimetric work of this nature. Heats of solution of praseodymium, neodymium, and samarium in liquid tin at 750" ' and the heats of mixing of Pr-Nd solid solutions' have already been determined in this laboratory. The present investigations with lanthanum continue the study of rare-earth elements. Details of the construction and operation of the liquid metal solution calorimeter used in this work have been published previously by Pool and Peluso and no further description will be given here. The lanthanum used in heat of solution determinations was supplied by Lunex who quoted the purity as 99.9 pct. Their detailed analysis of the material is given in Table I. Samples of 0.0003 to 0.0005 g-atom were used for each run and great care was taken to remove all surface oxide prior to weighing. The samples were stored at all other times in a beaker of oil to prevent their otherwise rapid oxidation. The compounds LaSn (Cudu, L1P type structure) and La&, (structure not classified) were prepared from the appropriate quantities of the two pure components by arc melting under a purified argon atmosphere and once again great precautions were taken to avoid any subsequent oxidation of the specimens. Although no structural examination of the compounds was made, the consistency of thermodynarnic measurements carried out on twenty or so individual samples of each indicates that the compounds were in fact homogeneous, single phase alloys. Samples of the compounds consisting of 0.0003 to 0.002 moles were used in the calorimetric measurements. A solvent bath consisting of approximately 80 g of 99.9 pct pure Sn was used for each series of runs and its heat capacity was determined at regular intervals throughout the experiments using pure tin or tungsten calibration samples. Measurements were made of the heat of solution of lanthanum in liquid tin at 725", 750C, and 775°K and at compositions up to 2.21, 4.76, and 5.25 at. pct La at the three temperatures respectively. In every case, the heat of solution of lanthanum remained constant at its limiting value, within experimental limits, up to the highest lanthanum concentration investigated. Since no change in was observed, it was concluded that the liquid/liquid + LaSn, phase boundary had not been

Jan 1, 1969

By David L. Holt

It is well-established that hydrostatic pressure distribution is hardly achieved during uniaxial compaction of powders. All the previous investigations1-4 give consistent results and this variation is attributed to the die-wall friction. The conclusions are based on measurements of the density of very small portions of the compact. Although the analysis of the density or the strain distribution in the compact is very helpful in obtaining information about the stress distribution within a powder compact, it does not describe the problem from a more fundamental point of view. The densification in metal powder compacts takes place chiefly by plastic deformation (ignoring particle rearrangement) at the points of contact of the powder particles. The onset of yielding and subsequent growth of the contact areas (for spherical powders) take place fixed by a constant stress equal to three times the yield stress in tension or compression,5-7 assuming little or no work hardening. Therefore, by deforming spherical powders in the die and measuring the contact areas on each particle, the load at each contact point can be determined. In the present investigation, this was done by hot-pressing uniform spheres of lead, K-Monel, and sapphire. The details of the experiment have been described elsewhere.' The spheres were studied for the size and the number of contact points on each particle using a specially designed goniometer. It was found that the deformed faces that were approximately normal to the direction of pressing were about 2.2 times larger than those parallel to the direction of pressing. Fig. 1 shows the typical deformed sphere. A detailed study showed that the mean value of the contact areas on each sphere was within 5 pct for all the spheres in the die (ignoring those touching the die walls and the top and bottom of the die).' The spheres touching the die walls and the top and bottom of the die were found to have larger contact areas (8 to 10 pct) which indicates higher pressures in these regions of the compact and thus higher compact densities in these regions. These results show that density distribution calculated from such an experiment will give results consistent with the previous investigators. It is concluded, therefore, that the pressure distribution in the die is better understood by studying contact areas on each particle. 'R. Kamm, M. A. Steinberg, and J. Wulff: Trans. TMS-AIME, 1947, vol. 171, p. 439. 'Pol Duwez and Leo Zwell: I. Metals, 1949, vol. 1, p. 137. 'G. C. Kucynski and I. Zaplatynskyj: Trans. TMS-AIIME, 1956, vol. 206, p. 215. 'R. P. Seelig and J. Wulff: Trans. TMS-AIME, 1946, vol. 166, p. 492. 'H. Hencky: Z. Angew. Math. Mech., 1923, vol. 3, p. 241. "J. Ishlinsky: I. Appl. Math. Mech. USSR, 1944, vol. 8, p. 233. 'D. Tabor: Proc. Roy. Soc. (London), Ser. A, 1948, vol. 192, p. 247. 'Ashok K. Kakar and A. C. D. Chaklader: 1. Appl. Phys., 1967, vol. 38, p. 3223. Superplasticity in 60Zn-40Al David L. Holt THE occurrence of superplasticity in Al-Zn alloys is of interest because of its possible industrial exploitation.' The eutectoid composition (78Zn-22A1) has been the most extensively studied;'-= neck resistant flow and high strain rate sensitivity of flow stress (characteristic of superplasticity) are associated with a micron-size grain conferred on the alloy by an homo-genization and quench.5'6 Compositions away from the eutectoid have received comparatively little attention, especially from the viewpoint of relating the structural

Jan 1, 1969

By Mark J. Klein, Robert A. Haggins

The pesence of a small amount of oxygen was found to cause significant grain growth restraint in 99.99 pct Ag. This behavior does not seem to be due to the presence of an oxide dispersion, but instead, to be related to the existence of minute amounts of oxygen m solid solution. In the amounts necessary to cause the observed effects it was found that oxygen migrates with extreme rapidity, probably along extended structural imperfections, such as dislocations and grain boundaries. A number of years ago, hastton' observed that the presence of small amounts of oxygen caused a retardation of grain growth in silver. He attributed this behavior to the formation of a fine dispersion of oxide particles by the internal oxidation of trace impurities. More recently, wood2 also found that oxygen caused grain growth restraint in copper. Experiments using both copper and a dilute solution of aluminum in copper led to the conclusion that the effects observed in copper were due to oxygen in solid solution, rather than an oxide dispersion. During the course of a study of the influence of several solutes on the recrystallization of Silver, the presence of minute amounts of oxygen was found to exert a very significant influence on grain growth. The experiments reported here were undertaken to determine whether the grain growth restraint observed in silver due to the presence of oxygen is related to oxygen in solution or to an oxide dispersion. Because of the difficulty in measurement and control of the very small oxygen concentrations causing the observed effects no attempt was made to treat the data in a quantitative manner. EXPERIMENTAL PROCEDURE AND RESULTS Silver of 99.99 pct purity was melted and cast into slabs in a vacuum of better than 0.1 p. These slabs were reduced 50 pct by cold rolling to a thickness of approximately 2.5 mm. Samples cut from this material were annealed in vacuum for a series of different times at 803°C. Another group of samples was similarly annealed in air. This temperature is well above the recrystallization range for silver of this purity (150" to 200°C). The mean grain diameter of these samples was measured, both in the center and near the edge, using the line-intel-cept method, and is shown as a function of annealing time in Fig. 1. The grain size in the centers of the samples annealed in air was found to be larger than that of the surface regions, while the grain growth behavior of the edge and center regions annealed in a vacuum was approximately the same. he edge measurements were taken at a distance of 0.2 mm from the surface.) A few samples were annealed in nitrogen. Their behavior was identical to that of the vacuum-annealed samples. Samples annealed in oxygen had approximately the same grain growth behavior as those annealed in air, leading to the conclusion that this behaviouer is due to oxygen. The microstructure of a sample annealed in air at 803" for. 30 minutes is shown in Fig. 2. The smaller grain size near the surface is characteristic of the iir-annealed specimens. Possible causes of this grain growth restraint in the air-annealed specimen are the formation of an im-

Jan 1, 1962

By C. E. Silverblatt, D. A. Dahlstrom

Previous bench-scale studies demonstrated that a substantial moisture reduction can be obtained by the application of steam to coal filter-cakes, particularly to those containing a limited amount of minus 200-mesh material. Consequently, U.S. Steel's Applied Research Laboratory conducted a study to determine the feasibility of steam filtration of 1/4 in. by 0 coal on a continuous pilot-scale installation in which an Eimco extractor is used. The test results showed that the moisture content of this coal could be reduced to 5.5% at a steam loading of about 175 lb of steam per ton of dry cake. In terms of steam consumption, this loading is calculated to be 1-1/2 lb of steam per lb of water removed. In some tests, only 1 lb of steam per lb of water removed was required. These levels of steam consumption are significantly less than the actual heat requirements of conventional thermal dryers. The satisfactory moisture reductions were obtained at filtration rates of 125 to 186 lb of dry solids per sq ft per hour. However, the proper design of commercial filters should improve the potential rates that can be attained. These results indicate that steam filtration has considerable economic potential for drying 1/4 in. by 0 coals and also has additional advantages over the conventional thermal drying of coal. The results of the previous bench-scale studies and those published by Burton' demonstrated that a substantial moisture-content reduction can be effected by the application of slightly superheated steam to coal filter-cakes, particularly to those containing a limited amount of minus 200-mesh material. Consequently, US Steel's Applied Research Laboratory conducted a study to determine the feasibility of steam filtration of 1/4 in. by 0 coal on a continuous basis. In the continuous process, the dewatering operation on the filter is conducted in stages. In the first, the bulk of the water in the feed slurry is removed by conventional mechanical dewatering on a portion of the filter before the steam is applied. In the second stage, steam is applied to the cake. The steam condenses and releases its latent heat, thereby reducing the viscosity of the remaining cake water; this reduced viscosity then facilitates further drainage and produces a cake of lower moisture content. Because of the availability of feed coal on a continuous basis and since steam was readily available from a low-pressure boiler, the Applied Research Laboratory selected for the test site a coal-preparation plant that cleans Pittsburgh Seam coal. A slurry of table and flotation coal in percentages as they occur normally was used as feed stock. Typical analyses of this slurry are shown in Table I. DESCRIPTION OF FILTER AND EXPERIMENTAL PROCEDURES An Eimco Extractor was selected for the evaluation of steam filtration in a continuous process. This unit was chosen because of its availability and its design features that permit relatively simple hood construction, instrumentation, and operation. A photograph of the Extractor is shown in Fig. 1. In the filter a cloth medium is used that travels horizontally and continuously with a grooved, rubber drainage belt. The total effective filter area was 12.5 sq ft. As the feed slurry flows by gravity from the feed box onto the medium,

Jan 1, 1964

By B. Ehgartner, M. Karmis, C. Haycocks

INTRODUCTION Interaction effects between mining operations developed on different levels of contiguously placed bedded deposits are a major problem in many parts of the United States. Efficient design criteria, derived from careful analysis of field studies as well as theoretical and model analysis, have shown that many problems that may result from seam interaction can be avoided, minimized, or on occasion used with beneficial results. Selection of seam mining sequence is rarely based only on ground control considerations, but rather on factors such as seam ownership, characteristics and accessibility. Therefore all possible mining sequences and methods must be considered in the development of multi-seam design criteria. Increased utilization of the longwall method of mining creates special problems in multi-seam mining due to the inevitability of caving and, therefore, subsidence. Considerable valuable experience has been gained in this direction from British mining operations where interaction problems are extremely common and the longwall method is the primary method used. However, limitations persist in the application of much of this information to U.S. conditions due to variation in layouts between advancing and retreating longwall systems and the inherent difference in the geologic environment. Considerable field data is available for U.S. room and pillar operations, and where successful pillaring operations have been carried out close parallels may be drawn with ground control mechanisms in longwall operations. VARIABLES AFFECTING INTERACTION Analysis of ground control multi-seam problems shows that factors contributing to interaction may be classified into variables that are fixed by the geo- logic environment and those that depend on engineering design. These may be described as follows (Haycocks et al, 1982): Fixed: (i) Depth*, (ii) Innerburden thickness*, (iii) Innerburden physical characteristics*, (iv) Stress field, (v) Seam thickness, (vi) Coal characteristics, (vii) Completed mining operations either above or below the seam to ve mined, and (viii) Age of workings. Mining: (i) Height, (ii) Dimensions and geometry*, (iii) Method*, and (iv) Spatial location of entries* *These variables are regarded as being critical effects. Few attempts have been made to quantify the variables controlling interaction. Dunham's (1978) linear regression analysis, combined with the National Coal Board's MRDE Roadway Monogram, is probably the most noteworthy. This study involved eighteen multi- seam longwall mines in the United Kingdom. The following variables were taken into account: seam depth, pillar width, opening shape, floor and roof conditions, rate of face advance, vertical seam interval, and age and geometry of overlying workings. A multi-linear regression analysis of these variables fitted by appropriate field values developed a prediction equation for lower seam stability. Although the study included many variables, it neglected the nature or geology of the innerburden. The prediction equation was found unreliable, but it did show the significance of geometry as a factor controlling lower seam stability. MINING SEQUENCES Irrespective of the type of mining method selected only four possible mining sequences are possible for two seams. Finlay and Winstanley wrote in 1934. .. "Experience has shown that whether the upper or lower seam was worked first, the subsequent working of the other seam in the same area seriously affected the roads in the seam first worked." Those effects depended upon the four basic mining sequences: 1) The upper seam is mined out prior to mining the underlying seam; i.e., the seams are mined sequentially downward and mining of the underlying seam is not commenced until operations above are completed and have ceased.

Jan 1, 1982