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By Jesse O. Betterton

In the Parkes process of lead refining, after desilverization has been completed by means of zinc additions, there will remain in the lead from 0.5 to 0.6 per cent zinc. At this stage in the refining practically all impurities are reduced to refined lead specifications except zinc and antimony. All excess of copper and nearly all the arsenic goes out with the silver. Silver remaining should not exceed 0.1 oz. per ton. It thus remains only to remove zinc and antimony to produce refined lead. The older practice was to complete refining by means of oxidation processes in reverberatory furnaces. Essentially this consisted of heating the lead to 1200' to 1300" I?. and allowing it to come in contact with a considerable excess of air passing through the furnace, or accomplish the same result by blowing the lead with steam by means of pipes introduced for that purpose, at the same time allowing air to enter the furnace. Usually some procedure involving alternate oxidation and reduction with fine coal or coke was employed in order to reduce the weight of dross or skim finally removed from the furnace. This practice had many elements of weakness in that the main flour of lead, after the preceding expensive operations had been performed, and the whole refining process nearly completed, was subjected to an operation at a comparatively high temperature, which involved much lead loss if the furnaces were not on bags, and the production of 3 to 5 per cent of the weight of the lead as dross or skim, which had to be resmelted and the lead either refined or produced as antimonial lead. In addition, the operating expense of the process was a considerable item. The process of dezincing with chlorine was developed as a substitute for the foregoing described oxidation process, and finally resulted in such advantages as nearly equal operating costs, a practical elimination of the lead loss, and the direct production of a very valuable byproduct, zinc chloride, that may be sold as such or retreated for its zinc and chlorine contents, both of which can be reused in the refining processes. Essentially this process consists of circulating the lead by means of a pump in a kettle through a closed reaction cylinder, gaseous chlorine entering the reaction cylinder with the stream of lead from the pump. Molten zinc chloride is thus produced and is discharged together with

Jan 1, 1937

By O. D. Sherby, J. E. Dorn, C. D. Wiseman

MCLEAN' has shown that the total strain obtained during creep of aluminum polycrystals arises exclusively from the mechanisms of 1) microscopically observable slip, 2) subgrain tilting, and 3) grain boundary shearing. Extensive analyses, however, suggest that the high temperature creep of metal polycrystals is controlled by a single thermal activation process."" These somewhat contradictory observations might be reconciled if it could be shown that the activation energies are identical for each of the mechanisms isolated by McLean. Such identity of the activation energies, of course, would demand that the same unit process controls the functioning of each individual mechanism. Under these conditions the activation energies for creep of single metal crystals and polycrystalline aggregates and for grain boundary shearing should be identical. This paper is primarily concerned with the possible identity between the activation energies for high temperature creep of single crystal and polycrystalline metals. In addition, comparisons will also be made between the activation energies for creep of single crystals and polycrystals with previously reported activation energies for grain boundary shearing.0"8 Materials and Techniques The same high purity aluminum, lead, and tin were used in the creep tests for single crystals and polycrystalline aggregates. Single crystals of aluminum and tin were prepared by the strain-anneal technique, whereas lead single crystals were prepared by growth from the melt. The tensile creep stress was maintained constant by Chalmers-Andrade parabolic-type lever arms. Strains were measured to &0.0002 in. per in. with rack and pinion type extensometers, and temperatures were maintained to within & 0.2"C of the reported values by mercury-thermoregulated resistance-heated silicone oil baths. The previously reported unambiguous technique for determination of the activation energy for creep was employed throughout this investigation.' ." It involves periodic abrupt small changes in temperature during the course of creep, accomplished by rapidly replacing one creep bath at temperature TI by a second bath at T,. The abrupt change in creep rate from i, to & attending the abrupt change in temperature is due exclusively to the change in temperature, since both the stress and the substructure are identical the instant before and the instant after a change of temperature. Therefore, all other factors being identical where AH is the activation energy for creep and R is the gas constant. Results Typical examples of the creep rate vs creep strain data during temperature cycled creep tests of single

Jan 1, 1958

By Harold R. Bradford

EXPANSION initiated during and after the war has placed industrial plants in new areas and increased reduction and manufacturing facilities in communities already established. With added expansion interest has grown in possible area contamination from waste products. Evolved flue waste contains many chemical contaminants that may or may not cause concern; however, atmospheric pollution has always been a problem to industrial communities. For some time effects attributed to small quantities of compounds of fluorine in various waste gases have been studied by industrial, medical, agricultural, and associated interests.1'2 Aside from an article by Churchill, Rowley, and Martin in 1948," little has been published on the subject of fluorine in coal except by foreign investigators. The first indication of fluorine compounds in coal was noted in England in 1934 by R. Lessing,4,5 who found that the presence of fluorine in Midland and West County coals was definitely established by etching of glass and by severe corrosion of porcelain fillings in a gas works scrubber. Etching of glass in a direct contact annealing kiln initiated research, and in 1944 four papers were published by H. E. Crossley,6-9 giving results of investigations of fluorine in coal of England by the Fuel Research Board, Department of Scientific and Industrial Research. These investigations studied methods of determining fluorine, the quantities present in various coal deposits, the geographical distribution of fluorine in British coals, occurrence of fluorine in minerals associated with coal, amounts of fluorine compared to other constituents of coal, the nature of fluorine compounds, and industrial significance of fluorine in coal. It was shown that British coals contain from 5 to 200 ppm of fluorine, which is probably present as fluorapatite [Ca10F2(PO4)6], often written as [3Ca3P2O8.CaF2]. The fluorapatite is intimately associated with shale in some coals and can often be separated from these coals along with the shales. H. E. Crossley8 also reported no correlation between the amounts of chlorine, sulfur, or ash and the amount of fluorine in different coals. He found, however, a relationship between the content of fluorine and phosporus in many British coals. Thus it should be possible to anticipate likely fluorine-rich coals from existing data giving phosphorus content. Behavior of the fluorine compounds of coal was compared with that of 12 fluoride-phosphate minerals in sink-float separations and solvent ex-

Jan 1, 1958

By William S. Hannan, H. Rush Spedden

Flotation may be defined as a process whereby mineral particles are concentrated by selective adhesion to air-liquid interfaces. The process involves attachment of desired mineral particles to air bubbles, and removal of the mineralized air bubbles from the surface of the pulp as a mineral concentrate. Problem Although great strides have been made in understanding the principles of flotation, one part of the process which has not been adequately explained is the mechanism by which selected mineral particles become attached to air bubbles. A glance at the froth of an operating flotation cell demonstrates adequately that use of proper reagents and conditions mill result in such attachments; but how such attachment takes place is not definitely known. A better knowledge of this factor might lead to improved flotation practice either through altered machine design or the application of scientific innovations. Direct observation of the behavior of mineral particles and bubbles in an operating cell does not appear promising because of the complexity of the system. For this reason, conclusions concerning the problem must be deduced from theoretical considerations or from observation of simplified systems designed to reproduce conditions thought to exist in an operating cell. Present Theories Two mechanisms have been recognized as fundamental in particle-bubble attachment: gas precipitation and direct encounter. It is a simple matter to demonstrate in the laboratory that attachment can be brought about by either mechanism. As to the relative importance of the two in a particular flotation system, however, there is a divergence of views. Taggart1 states, Under exceptional circumstances sufficient force and time to effect attachment may conjoin in an ore pulp undergoing agitation, and a preformed bubble adhere to a collector-coated mineral particle, but the occurrence is rare. . . . Pulp-body froth flotation effects selection in the body of a conditioned pulp by causing gas bubbles to precipitate from solution in the liquid phase preferentially at the surfaces of collector-coated particles, and to cling to these particles, Gaudin2 states that, within the pulp body of an agitation machine, attachment of mineral particles to air bubbles occurs as a consequence of contact between the two. This theory has been supported by theoretical reasoning and much circumstantial evidence. Perhaps the most interesting bit of evidence in favor Of this theory js the difficulty in the flotation of fines. If attach-

Jan 1, 1949

By V. R. Garfias, R. V. Whetzel, J. W. Ristori

Since the entry of the United States into global war, virtually all data and information necessary for compiling figures on world petroleum consumption have become unavailable. This situation undoubtedly will continue until the world petroleum industry can return to a peacetime basis. During the past 10 years, the authors, by publishing annual estimates of .world consumption, have attempted to emphasize the importance of a yearly world-wide survey of petroleum supply and demand. It is beconling more and more evident that statistics for the United States alone can no longer give a comprehensive idea of the state of the petroleum industry, even within the United States itself. Therefore, when conditions in the industry again become normal, it is the hope of the authors that those bureaus equipped to do so will carry forward the study of petroleum supply and demand on a world-wide basis. Enough data and information are available, however, to attempt a rough estimate of world output of crude petroleum and petroleum substitutes for 1942, which to some extent may reflect the trend of world consumption. This estimate by countries, as compared with the output in 1941, is shown in Table I. The world production of crude petroleum and petroleum substitutes for 1942 is estimated at 2,208,000,000 bbl., or a decrease of 171,000,000 bbl. under 1941. Crude production is believed to have decreased by about 200,000,000 bbl., (about 9 per cent); while petroleum substitutes increased by 28,500,000 bbl., (nearly 20 per cent). The decline of crude output in the United States is estimated at 19,000,000 bb1.—less than 2 per cent; while that in foreign countries is estimated at 180,000,000 bbl., or more than 20 per cent. The marked decline abroad is due largely to losses in Venezuela and Colombia, where the lack of ocean transportation became the controlling factor, and in the East Indies and Burma, where military invasion brought about the destruction of the fields. The production of petroleum substitutes in 1942 apparently reached a new high figure of 7.5 per cent of the total world petroleum output. The important features of petroleum production outside of the United States are the changes that have taken place during the year in the supply of the Axis countries. In Japan the output for 1941 was estimated at 8,800,000 bbl., 5,500,000 of which were petroleum substitutes. It is believed that the output of synthetic oils during 1942 substantially increased, raising the total interior production of Japan to nearly 10,-ooo,ooo bbl. Also, during 1942 Japanese armed forces gained possession of oil fields having a normal peacetime output of about 78,000,000 bbl. per year. The production of these areas for 1942 is estimated at some 23,000,000 bbl., which indicates that Japan is now getting at least 33,000,000 bbl. a year, which exceeds by 8,000,000 bbl. Its

Jan 1, 1943

By J. W. Ristori, V. R. Garfias, R. V. Whetzel

Since the entry of the United States into global war, virtually all data and information necessary for compiling figures on world petroleum consumption have become unavailable. This situation undoubtedly will continue until the world petroleum industry can return to a peacetime basis. During the past 10 years, the authors, by publishing annual estimates of .world consumption, have attempted to emphasize the importance of a yearly world-wide survey of petroleum supply and demand. It is beconling more and more evident that statistics for the United States alone can no longer give a comprehensive idea of the state of the petroleum industry, even within the United States itself. Therefore, when conditions in the industry again become normal, it is the hope of the authors that those bureaus equipped to do so will carry forward the study of petroleum supply and demand on a world-wide basis. Enough data and information are available, however, to attempt a rough estimate of world output of crude petroleum and petroleum substitutes for 1942, which to some extent may reflect the trend of world consumption. This estimate by countries, as compared with the output in 1941, is shown in Table I. The world production of crude petroleum and petroleum substitutes for 1942 is estimated at 2,208,000,000 bbl., or a decrease of 171,000,000 bbl. under 1941. Crude production is believed to have decreased by about 200,000,000 bbl., (about 9 per cent); while petroleum substitutes increased by 28,500,000 bbl., (nearly 20 per cent). The decline of crude output in the United States is estimated at 19,000,000 bb1.—less than 2 per cent; while that in foreign countries is estimated at 180,000,000 bbl., or more than 20 per cent. The marked decline abroad is due largely to losses in Venezuela and Colombia, where the lack of ocean transportation became the controlling factor, and in the East Indies and Burma, where military invasion brought about the destruction of the fields. The production of petroleum substitutes in 1942 apparently reached a new high figure of 7.5 per cent of the total world petroleum output. The important features of petroleum production outside of the United States are the changes that have taken place during the year in the supply of the Axis countries. In Japan the output for 1941 was estimated at 8,800,000 bbl., 5,500,000 of which were petroleum substitutes. It is believed that the output of synthetic oils during 1942 substantially increased, raising the total interior production of Japan to nearly 10,-ooo,ooo bbl. Also, during 1942 Japanese armed forces gained possession of oil fields having a normal peacetime output of about 78,000,000 bbl. per year. The production of these areas for 1942 is estimated at some 23,000,000 bbl., which indicates that Japan is now getting at least 33,000,000 bbl. a year, which exceeds by 8,000,000 bbl. Its

Jan 1, 1943

By J. J. Lillie

Sublevel stoping was first developed in the Michigan iron mines many years ago. Since that time this method, and modifications with long hole drilling, have been used in a number of non-ferrous mines and have been described in various papers and articles. With a few exceptions, the operations where sublevel methods have been applied are producers of large daily tonnages from ore bodies of considerable size. In selecting mining methods for small properties or relatively small detached ore bodies, sublevel methods often have been overlooked. The method has been used successfully in relatively small operations at Copper Canyon, Nevada, and, more recently, in mining small ore bodies at Darwin, Calif. As a result of this experience, we believe that a review of the general procedure, the advantages noted, and the results obtained will be of interest to many operators of relatively small mines. General Description Briefly, sublevel stoping consists of, first, driving sublevel drifts at predetermined vertical intervals through the length of the stope block; second, breaking an initial mining slot across the stope; third, driving crosscut benches from each sublevel by slabbing into the slot; and, fourth, breaking the ground between benches. Applicability Since this is an open stope method, it requires wall rock that will stand over reasonable stope lengths without caving or excessive slabbing. Ore must be moderately firm but need not be hard. The method is best adapted to steep dipping, tabular or lenticular ore bodies but may be applied to ore bodies of almost any shape if their vertical extent is appreciable. It can be used with dips that are too flat for successful shrinkage stopes and can be modified for use with slushers on dips below about 40". Initial mining at the Copper Canyon operation consisted of sublevel stopes for the wider ore sections and shrinkage stopes for the narrow sections where ore widths averaged about 15 ft. After some experience and a study of comparative results on completed stope blocks, sublevels were substituted for shrinkage stopes even in the narrow ore widths. Practical stope lengths depend upon the character of the walls and the continuity of values within the ore body. Where blocks of low grade or waste are included in the stoping limits, these areas can readily be left as pillars for intermediate wall support and longer stope lengths may be planned. Raises can be spotted in narrow or low grade areas and stope lengths adjusted accordingly. Stoping Details To illustrate stoping details, assume that we have an ore shoot 15 to 30 ft wide and about 200 ft long, with walls that would stand over a stope length of 80 to 90 ft (Fig1). PRELIMINARY DEVELOPMENT Preliminary development for sublevel stoping would be simple. A service raise is driven at about the center of the block and stope limits planned to leave a pillar around this raise. Sublevel drifts driven each way from this central raise will outline the

Jan 1, 1950

By W. T. Isbell

IN the Parkes process of lead refining, after desilverization has been completed by means of the addition of zinc, there remains in the lead from 0.5 to 0.6 pct zinc. At this stage in the refining operations virtually all impurities are reduced to refined lead specifications except zinc and antimony. All excess copper, nickel and cobalt have been removed by the zinc additions. The silver remaining should not exceed 0.1 oz per ton. It then remains only to remove the zinc and antimony in order to produce refined lead. At the Herculaneum plant of the St. Joseph Lead Co., practice formerly was to complete the refining by means of oxidation in a reverberatory furnace. This process consisted of heating the lead to 14000 to 1500°F and allowing it to come in contact with excess air passing over the surface of the lead and periodically agitating the bath of lead with air. This procedure not only resulted in the loss of zinc but of a considerable quantity of lead converted to the oxide in the form of dross and fume. The fume, collected in the baghouse, together with the dross was returned to the blast furnace, thus adding appreciably to the circulating load on the blast furnace and refinery. In addition, operation and maintenance of the reverberatory furnace was expensive and required the performance of disagreeably hot and somewhat hazardous work. The process of dezincing with high vacuum was developed at this plant as a substitute for the oxidation process and finally led to lower operating costs, the practical elimination of dross and fume and the direct production of metallic zinc, which is very suitable for re-use in the desilverization process. Essentially this process consists of subjecting the lead to high vacuum, in a kettle provided with means for heating, a bell-shaped member open at the lower end so constructed that it can be immersed in the molten lead, and means for evacuating the interior of the bell and for sealing an agitator. Metallic zinc is thus produced and collects on the upper cooled part of the bell member. This metallic zinc is periodically removed and re-used in the desilverization process. The process is quite simple. It is conducted at a low temperature, thus permitting the use of iron equipment, and shows a material saving in refining costs over the old method. EQUIPMENT AND ITS USES Dezincing Machine.-The equipment employed in this process consists of a dezincing machine, a steel kettle of 120 tons capacity, a vacuum system and equipment for handling the dezincing machine (Fig I). The dezincing machine consists of a compact assembly, suitable for handling with an overhead crane, consisting of a treating chamber and the agitating mechanism. Treating Chamber.-The treating cham¬ber is a bell-shaped shell (4), similar in shape to a hemispherical kettle with a lid

Jan 1, 1947

By C. W. Donnelly, Louise B. Freeman, Coleman D. Hunter

It is with pride that the authors of this paper report. that during 1944 the production of petroleum in Kentucky passed its all-time peak, 9,496,985 bbl. being contributed. The delivery of natural gas, especially from eastern Kentucky, was maintained and possibly exceeded the highest deliveries of the past. To raise the production of oil and gas was not easy with inferior and worn-out equipment and the shortage of skilled labor. Reminiscent of the early days of the industry in the state, particularly in the hills of Elliott County, where mud roads often have gradients of 45º, was the replacement of worn-out trucks and tractors by oxen. Of the total 9,496,985 bbl., 17 per cent was contributed by the part of Kentucky that is east of the Cincinnati arch, as compared with the total of 7,010,776 bbl. contributed in 1943, of which 25 per cent was contributed by eastern Kentucky. This discrepancy is due to the discovery of more new fields in western Kentucky rather than to a decrease in production in the eastern fields, where the average has been maintained by reconditioning and secondary recovery of old fields and further development of new pools reported for the first time in 1943. In all, 1103 wells were known to have been drilled in the state during 1944, of which 659 were drilled in western Kentucky and 444 in eastern Kentucky. The exact number of wells drilled for any year is never known, as drilling permits are not required except 'when it is planned to drill through a workable coal seam. Of the total number of wells drilled, 459 were oil wells, 229 gas wells and 415 dry holes. The monthly production was as follows: January........................... 659,496 February.......................... 658,606 March...................... ...... 711,619 April............................. 649,926 May............................... 754,892 June.............................. 730,369 July.............................. 761,762 August............................ 878,053 September...................... 863,150 October........................... 968,732 November........................ 961,999 December........................ . 898,636 Western Kentucky In western Kentucky 352 wells were completed as oil wells with a total initial production of 47,922 bbl. of oil, the average being 136 bbl. per well. Two wells produced gas, the total initial production being 1,594,000 cu, ft. One hundred and eighteon wildcat wells were drilled, of which 107 were dry holes and 11 were oil wells. Three of the latter proved to be the discovery wells of commercial pools. Twelve new pools were discovered during 1944, none of major importance, as indicated in Table 2. The Utley pool, due to a stratigraphic trap on the flank of a closed structure, found oil in the Mcclosky at 2565 ft. in the discovery well, with initial productioil of 1000 bbl. The average daily production is now 227 bbl. from seven wells. The East Poole field, with the discovery well in the Tar Springs sandstone at 1811

Jan 1, 1945

By K. T. Koone, R. J. Blackwell

One of the more important problems to be solved in designing a miscible flood is related to the size of the solvent bank used. Size of the bank may be critical to economic success. Too large a bank loses money; too small a bank may deteriorate and fail to maintain the miscibility needed for high recovery. An important factor in deterioration of a small bank is permeability channeling. In a highly stratified reservoir, solvent speeds ahead in the more permeable zones and mixes laterally with fluids bypassed in adjacent, low-permeability strata. Numerical solutions have been obtained .for the differential equations that describe the movement of a slug through a two-layer system in which mixing occurs both in the direction of flow and transversely. The solvent slug is assumed to have the same density and viscosity as the resident fluid and the pushing fluid. These solutions have been verified by comparing them with similar concentration profiles obtained in the laboratory in a 36-ft stratified model packed with glass beads. The theoretical study revealed that when the dominant mechanism causing a bank to fail is lateral mixing the bank size needed for a given recovery may increase with length rather than decreasing as the square root of reservoir length, as suggested by one-dimensional mixing theory. From a comprehensive examination of the variables, a generalized correlation is developed that relates strata thicknesses, bank size, fluid velocity, mixing coefficients, system length and simple solvent-resident fluid phase behavior to the area miscibly swept. INTRODUCTION Miscible displacement, or solvent flooding, continues to receive widespread attention as a method for increasing oil recovery over that possible in conventional gas-drive or waterdrive projects. A basic economic requirement in the application of such processes is the use of as little solvent as possible. A basic physical requirement is that enough solvent be used to maintain miscibility. Economics places an upper limit on the size of a solvent slug, and physical considerations establish a lower limit. Consequently, the practicality of any given miscible process requires that the economic limit be greater than the lower limit imposed by physical requirements. Procedures exist for determining the economic limit; however, procedures for determining realistic minimum bank sizes exist for only special reservoir situations. In the past, bank size has usually been selected on the assumption of a piston-like displacement for which only longitudinal mixing is important. This assumption leads to the favorable conclusion that bank size, expressed as per cent of pore volume, is inversely proportional to the square root of length. Collins considered the problem of transverse mixing of solvent with fluids in bypassed zones with the assumptions that no forward mixing occurs and that the concentration is uniform in the permeable stratum of interest. 1 Lauwerier considered a mathematically similar problem in thermal recovery operations.2 Their work suggests the much less favorable conclusion that bank size could be directly proportional to the length or even higher powers of the length. This paper considers the physical behavior of a small solvent bank as it moves through a real reservoir, without imposing many of the restrictive assumptions of past treatments. To facilitate mathematical description, an idealized, two-layer model that permits mixing both laterally and in the direction of flow will be considered. A calculation procedure for solving the descriptive equations will be developed for a displacement involving fluids of equal density and viscosity. In addition, laboratory experiments designed to check the computational results will be described, and the coincidence of calculated and observed results will be discussed. The use of many solutions for a variety of bank sizes, strata thicknesses and characteristic system lengths to develop a usable correlation between

Jan 1, 1966

By D. H. Polonis, Gary A. Dreyer

This investigation involved a study of the reactions occurring during aging of supersaturated a phase in a CIL-Si alloy. The aging processes at temperatures below 552°C were studied by means of metallography, microhardness, and electrical resistivity measurements. During the initial stage of aging in the temperature range 275o to 525oC an anisotropic phase, which is visible in the form of striations in the micro-structure formed prior to the appearance of the -phase. This transition phase has been designated k' due to its structural similarity to the k phase. The rate of K' formation during aging increased with aging temperature. At 450o and 525°C the reaction appeared to reach completion before significant amounts of precipitation were observed. The overall precipitation reaction in this system involved four stages: formation of formation of at a grain boundaries, growth of particles in 7-egions, and coagulation of into large particles. The relative role of each of these processes is dependent on the temperature of aging. The formation of phase from supersaturated a during aging increases the electrical resistivity and slightly increases the hardness of a 4.9 pct silicon alloy. The formation of during aging decreases the electrical resistivity and increases the hardness until coalescence of particles begins during the final stages of aging. The coalescence of results in a decrease of both electvical resistivity and hardness. THE available literature does not record a detailed analysis of the aging processes in Cu-Si alloys. Such an analysis has been difficult due to both the limited data available and misleading microstructural observations which have been reported. Previous work suggests that a rather complicated series of processes may be involved in the aging of supersaturated a. The present investigation is concerned with an analysis of the sequence of these aging processes in a 4.9 pct Si alloy. The currently accepted version of the Cu-Si equilibrium diagram, Fig. 1, was published by C. S. Smith in 1940.' This diagram shows a eutectoid at 5.2 pct Si with the high temperature phase, having its composition range entirely to the right of this value. By quenching alloys in the composition range 4.6 to 5.2 pct Si from the region, Smith was able to retain the phase. However, this phase exhibited a striated microstructure which was anisotropic to polarized light. These striations were suggested by Smith to be duplex twins. Using an oscillating crystal X-ray method Barrett2 studied alloys containing 4.0 to 5.4 pct Si quenched from the and regions. The striations observed in quenched specimens were attributed by Barrett to quenching stresses. He found that striations could also be formed by deformation after quenching and identified them as stacking faults in alloys containing 4.0 to 5.0 pct Si. Barrett related the striations in alloys containing 5.0 to 5.4 pct Si both to stacking faults and to a metastable phase which he called The striated structure reported by smith' was also obtained by Hoffmann, et al. 3 By deeply etching their specimens the anisotropic phase on the surface was removed, leaving a structure which was microscopically similar to pure copper. By means of X-ray analysis before and after deformation at room temperature it was concluded that the anisotropic phase was metastable This conclusion has been questioned by Barrett who attributes the discrepancy to superposition of k and lines on the powder patterns of Hoffmann, et alm3 The decomposition of supersaturated according to smith' and Anderson,4 is very sluggish. However, Nony and Dreyer,5 and Hoffmann, et al.' found that deformation increases the rate of decomposition. X-ray studies by Hoffmann, et al on

Jan 1, 1962

By Strathmore R. B. Cooke, Thomas E. Ban

MUCH experimental work has been performed on the mechanism of agglomeration and pelletizing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiöld and Ilmoni1 much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the microstructures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was. added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.2 Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl methacrylate monomer.3 The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45°C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer's method.4 Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wüstite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1952

By D. W. Levinson, L. F. Mondolfo, N. A. Gjostein

MANY investigations are reported in the literature on the age hardening of Al-Mg-Zn alloys but most of them are concerned mainly with mechanical property changes. The present investigation was started to determine the structural changes in an AlMgZn alloy. The alloy composition was chosen in the existing phase diagram" so as to lie on the quasi-binary section Al-(AlZn)Mg Actually, it was found that the diagram as published was inexact at the lower temperatures and that the phase in equilibrium with aluminum at the lower temperatures is not the ternary compound. Technique The alloy used for the investigation was prepared from high purity materials and the resulting composition as determined by chemical and spectro-graphic analysis was: Zn, 6.17 pct; Mg, 2.13 pct; CU, 0.03 pct; Si, 0.009 pct; Fe, 0.005 pct; and the remainder, aluminum. An ingot -in. thick was cast, homogenized, hot and cold-rolled to strip 0.064-in. thick for dilato-metric and powder work, and to foil 0.005-in. thick for single crystal work. Solution treatment temperature for all specimens was 475°±5°C for periods of at least 1 hr, either in air furnaces or lead baths. Aging was done in oil or Pb-Bi baths controlled to within ±3°C. The aging was investigated at the following temperatures: room (30°), 130°, ZOO0, 260°, and 300°C. For the dilatometric study, the length changes were measured continuously, at temperature, using strips of alloy 10 in. long, shaped as channels to eliminate undesirable deflection due to bending. To compensate for thermal expansion and contraction due to the variations in the temperature of the aging baths, the dilatometers were built of the same alloy as the one being tested, with the same shape and size, but with material fully annealed. Gages on which 0.0005 in. could be read and 0.0001 in. estimated were used to measure the dilation. Length changes were also measured at room temperature. Strips approximately 10 in. long were solution-treated, quenched, and measured in a supermicrome-ter in which 0.0001 in. could be read and 0.00001 in. estimated. The specimens were immediately aged for a given time, remeasured, and then the cycle was repeated, including the solution treatment. The error of measurement with this technique was somewhat larger, but the results confirmed those obtained by continuous measurements. The sheet used for the dilatometric work was checked to determine grain orientation. Both X-rays and etching methods revealed a rather coarse grain size but only a negligible amount of preferred orientation. Thus, volume changes calculated from length changes are not invalidated by preferential orientation effects. Pieces of the sheet used for the dilatometric work were also used for the metal -lographic work. Filings for the powder X-ray study were produced from a homogenized piece of sheet. These filings were magnetically purged of iron, screened to 200 mesh, sealed in a Pyrex tube containing an argon atmosphere, and solution-treated. When quenching, the glass tube was broken, so that the powder dropped directly into cold water. After drying with alcohol, the powder was sealed into capillary tubes containing an argon atmosphere and then aged for the required times. In spite of all these precautions the three strongest lines of a( Al2o) appeared in all patterns, and were used as internal standards. By the use of these standards, accurate corrections for film shrinkage were obtained. For the back reflection patterns, annealed nickel powder was mixed with the specimen to act as internal standard. A preliminary investigation was made in small (57.3 mm diam) powder cameras. From these patterns the changes which took place in the solid-

Jan 1, 1957

By L. W. Reynolds, R. F. Campbell, K. G. Carroll, S. H. Ballard

Based on metallographic and X-ray data probable equilibrium conditions from 1340" to 2400°F are presented for the composition range investigated. These are correlated with investigations of Takei and Kuo. Provision is made for existence of Mo, C and (Fe, Mo)2,C, carbides heretofore omitted in diagrams in this composition range. These carbides and (Fe, Mo),C, in equilibrium with ferrite and austenite, restrict the austenite and austenite + ferrite fields to lower carbon contents and higher temperatures than in the Fe-C system. OK groups of steel of different molybdenum content, but with approximately the same carbon variation in each group, Table I, were studied. The alloys were melted in an acid-lined 30-lb high-frequency induction furnace, and the ingots forged to l-in. rounds, which were then ground to 0.75-in. diam. To minimize chemical segregations a short length of each bar was given a high-temperature heat treatment as listed in Table I. Specimens 0.062 to 0.125-in. thick were thereafter cut from the homogenized bars for heat treatment to determine phase changes in the alloy. Heat treatments were performed in either a lead bath or muffle-type electric furnace, depending upon the temperature required. Maximum temperature variation was * 2" F in the lead bath and * 5"F up to 1900°F and +8"F above 1900°F in the electric furnace. Adequate protection of the specimen from the oxidizing atmosphere in the electric furnace was obtained by sealing the specimen in either a pyrex or a silica capsule which was evacuated or not as circumstances required. For austenitizing followed by quenching to an isothermal temperature, the specimen was placed in a closed-end refractory tube the mouth of which, extending beyond the furnace, was connected to a vacuum pump. The specimen could be withdrawn from this tube and quenched as desired. IDENTIFICATION OF PHASES The principal method of identification of phases was metallographic examination conducted on surfaces well removed from exposure to lead or atmosphere effects during heat treatment. Hardness measurements (Dph/lOkg) were also made on these surfaces. The etching reagents used and their effects are listed in Table II. Martensite and ferrite were readily recognized by their customary appearance after etching with saturated picral or 1 pct nital. The presence of liquid at high temperature was indicated by curved interfaces characteristic of boundaries between solid and melt, by intergranular pools of dendritic areas in a carbide matrix, and by a black network coincident with austenite grain boundaries. Examples of these structures are shown in Figs. l(a) and (0). The types of carbide which were attacked by the electrolytic chromic acid etch and the alkaline KMnO, etch, Table 11, were identified by X-ray analyses of extracted carbides of five alloys. Carbide residue was obtained from a metallographic specimen by etching the specimen for 24 hr in hydrochloric-picric acid in alcohol (grain-size reagent), after which the carbides, standing in relief, were scraped from the surface of the specimen and mounted on a glass slide. Diffraction patterns were obtained with a Philips spectrometer using iron-filtered cobalt radiation. Figs. 2, 3, 4, and 5 illustrate typical etching behaviors with chromic acid and alkaline KMnO,. Chromic acid attacked Mo,C as shown in Figs. 2(a) and (b)-but not (Fe, Mo),C, Fig. 3(b). Alkaline KMnO, attacked (Fe, Mo),C, Fig. 3(c), and also attacked M0,C. In accordance with these behaviors, a typical differentiation of coexisting Mo,C and (Fe, Mo),~ is shown in Figs. 4(a) and (b). The carbide (Fe, Mo),,C, could not be obtained free of other coexisting carbides for etching experiments. The behavior. however. of coexisting carbides identified by x-ray diffraction as Mo,C ind (Fe, Mo),,C, indicate that (Fe, Mo)23C6 is not etched by chromic

Jan 1, 1961

By H. L. Shergold, O. Mellgren

Concentration of fine quartz particles at the iso-octane/water interface has been investigated under different conditions of pH and dodecylamine concentration. The results obtained from the related studies on the effect of amine concentration and pH on the interfacial tension, adsorption density, electrokinetic potential, contact angle, and concentration of the various amine species in the system are presented. A good correlation was obtained between these different variables. It is well-known that very fine mineral particles are difficult to float in conventional flotation machines. Flotation rate studies have revealed that the rate of flotation of fine mineral particles is much smaller than that of coarser size fractions. The theories accounting for this behavior have been discussed by Arbiter and Harris1 and also Meloy.2 Theoretically, a hydrophobic fine particle might never make contact with a bubble because of the presence of an energy barrier in the vicinity of the air/water interface.' This energy barrier will have electrostatic, hydrodynamic, and Van der Waals force components. It was thought that by using an oil phase instead of air the energy barrier would be decreased so that fine particles could be concentrated at the oil/water interface more readily than at the air/water interface. The technique used involves dispersing the fine particles in water, containing the appropriate chemical reagents, and injecting a fine dispersion of iso-octane oil droplets into the pulp. After vigorous conditioning, the pulp is passed into a separating column where the oil droplets coated with a layer of mineral particles rise to the surface to form a separate layer. Air is introduced into the base of the separating column to ensure that heavy agglomerates of oil and particles report with the organic layer. This technique has been described previously4 and adopted by Lai and Fuerstenau5 who studied the alumina-dodecyl sulfonate system. The interfacial phenomena in the system composed of hematite, water, and iso-octane in the presence of sodium dodecyl sulfate have been studied and the results reported" earlier. This paper describes the results obtained from investigations into the interfacial phenomena in the quartz/water/iso-octane system in the presence of dodecylamine. The technique used in measuring the interfacial tension, electrokinetic potential, contact angle, and adsorption density were similar to those described previously? Materials Selected pieces of a high purity natural quartz, from the Isle of Man, were crushed in a laboratory jaw crusher and pulverizer. The — 52+72 mesh size fraction was retained and leached with successive washes of hot concentrated hydrochloric acid to remove iron impurities. When no iron was detected in the solution by ammonium thiocyanate, the quartz was washed thoroughly with distilled water until the conductivity of the wash water assumed that of the distilled water. Samples of 25 g of the —52+72 mesh quartz were ground for 5.25 min in an agate vibratory mill. The ground product was 100% —44 m and 57% —10 am, as determined by the Andreasen pipette. The specific surface area of the sample used for the adsorption and flotation tests was 0.94 sq m g-l. This corresponds to a mean particle diameter of 2.4 am. The —44 am quartz sample was stored under vacuum in the presence of silica gel crystals. For the contact angle determination between the three phases, quartz, iso-octane, and water, a piece of the natural quartz was ground into a block about 15 mm long, 15 mm wide, and 5 mm thick. One surface of the block was then polished by successively finer grades of silicon carbide "paper." The final polishing was conducted with alumina on a "hyprocel" paper. The polished quartz specimen was cleaned using nitric acid and ethyl alcohol followed by a wash with distilled water and then stored under distilled water. This pro-

Jan 1, 1971

By Goldye Leeds, Marian Balicki

A SURVEY of literature reveals the scarcity of experimental evidence relating to work hardening and reannealing of silver.'-'" With the exception of the well-known X-ray investigation of silver and other metals by W. A. Wood? the effect of progressive cold working has not been studied. The determination of thermal stability of silver in the work-hardened state by means of isochronal or isothermal annealing has been confined apparently to very high reductions only. In the survey made, no study was encountered which endeavored to produce a complete picture of the changes in various properties due to cold working and subsequent reannealing. To fill these gaps and to assemble data that could be used for the determination of activation energies and of frequency coefficients of primary recrystallization, a systematic experimental approach, which was developed by one of the authors, has been applied to pure silver. Material and Processing The silver used was Handy and Harman fine silver, with a spectroscopic analysis at the testing stage of Cu, 0.0001 to 0.001 pct; Te, 0.0001; Pb, Si, Ca, Mg, and Mn, traces. The material was supplied in the form of a rod 0.406 in. diam and was converted into test samples according to the procedure condensed in Table I. It should be mentioned that air annealing was adopted to simulate industrial practice, though it was realized that annealing in a neutral gas or in a vacuum would be preferred. The usual precautions have been taken to eliminate any structural changes and property changes resulting from the storage of the samples prior to annealing or testing. Thus the wires were kept at the fully annealed stage, and the final wire drawing, which produced the desired degree of work hardening, was done just prior to the final annealing or testing. During the short waiting period, the samples were kept in a thermosflask filled with ice. Even with these precautions some strain-age-hardening or self-annealing could occur. To test such a possibility, wires of different reductions were prepared in the manner adopted and portions of them were immediately tested. The remaining portions were similiarly tested after different periods of storage, both at room and melting-ice temperature. Within experimental error, all samples obtained from a wire of a given percentage of reduction yielded identical values. This result qualified the material for further tests and interpretations, because it showed that either strain-age-hardening and self-annealing were absent, or that these effects fully balanced each other. The final annealing was carried out in an electric resistance furnace automatically controlled to within a 10°F. It was realized that the temperature fluctuations were greater than desired for this type of work. TO diminish the errors due to fluctuations of temperature, the hot junction of the thermocouple was placed as close to the samples as possible; the time of soaking was reduced to 15 min; and the number of samples annealed at different temperatures was increased. It will be seen from Table I that some tests were performed on the same material at rising temperature. These will be discussed elsewhere. Room temperature testing was limited to the determination of some of the mechanical properties that are known to be additive in a degree sufficient to be used for indirect study of the kinetics of the reannealing process, Tensile tests, carried out on a manually operated J. Camillon machine, accurate to within permitted the determination of the ultimate stress (U.S.1 and of the 2 in. elongation, (A,). The proof stress (d,e) has been determined from a series of bend tests carried out on a Tinius Olsen Stiffness Tester by using the offset method. This involved accurate determination for each sample of load-angular deflection curves, finding a

Jan 1, 1952

By C. L. Pillar

INTRODUCTION The location, size, character of the ore de- posit and its adjacent formations will deter- mine the mining system best used for its ex- traction. The mining system chosen will have to be engineered to suit the ore deposit and the people that will extract it. What can be done in the Philippines cannot always be accomplished in the upper Northwest Territory of Canada. Mining operations developed under a free enterprise system are planned to achieve a satisfactory return on the capital required to place them into production. Hence, the choices made in planning and developing the mining system must be dictated by sound economics. The mining system planned must favor: 1. Maximum ore extraction of the deposit with minimal grade dilution. 2. The amount of capital expenditure used to develop and equip the mine must be in harmony with the financial policy of the group yet be sufficient to provide a reliable mining system. Excessive frills and extras that are not required for efficient, safe production should not be provided. 3. Mine production costs are determined by the amount of men, material, equipment and energy used in the production process. These must be kept to minimal limits in order to insure dependable, low cost production. Extras that later are needed in the production operation can be added as required by the operator. Basically block caving is a mining system that is normally used to extract deep seated, massive, low grade deposits of copper, molybdenum and iron where stripping ratios for open cast mining are economically prohibited. The caving system is limited in its selectivity. It is a mass production type of underground ore extraction that under favorable conditions is one of the most efficient, low cost mining systems in the world today. Usually block cave mining systems are large. They are capable of producing ore at a rate of 10,000 to 100,000 tons/day from large deposits at costs that are comparable with many open cast mining systems burdened by high waste to ore ratios. Block cave mining systems differ basically in the plan of the area layout, the method of undercutting and the method of draw. The balance of the mining system is the mechanical transportation of the drawn ore to the surface, the mine supply, drainage and ventilation systems. This paper deals mainly with the methods of draw. The method of draw to be used in a block caving system dictates the development plan of the mining area, is highly influential in the method of undercutting to be employed and the supply and ventilation system to be used. There are three basic methods of draw commonly used in today's operations. They are: Gravity draw Slusher draw LHD draw The type of draw planned will have a major affect on: Capital expenditure and time required to bring a deposit into production. Productivity, efficiency and cost of the production operation. Percent recovery of the ore deposit in both tonnage and grade. Degree of production reliability Fundamentally the type-of draw used must be compatible with the physical characteristics of the deposit to be extracted and the financial position of the mining operation. The type of draw chosen must work to advantage with the size, configuration, depth, strength and fracture pattern of the deposit and its adjacent formations. It must favor the financial protection of the planned mining operation. A Gravity Method of Draw requires a finely fragmented, easy flowing product from the caving action of the deposit. To obtain the desired economic advantage the ore deposit must also have sufficient area and height of column to permit minimal development cost on a per ton basis. The gravity system re- quires the maximum amount of development openings and uses the minimum amount of mechanized equipment of all the caving systems. It is unskilled, labor-intensive and is highly sensitive to size of ore fragmen-

Jan 1, 1981

By H. W. Mead, C. E. Birchenall

The rates of growth of graphite nodules in cast irons are calculated for a model of a growing graphite sphere surrounded by a shell of austenite through which carbon and iron are diffusing. The carbon is supplied by a cementite-austenite mixture at the outer edge of the shell. The calculated rates from carbon diffusion agree fairly well with the measured values, but the rates based on iron self-diffusion are much too low. Because the iron must be removed for the process to continue, o plastic deformation mechanism is suggested. THERE has been an unfortunate tendency in the literature of growth and dissolution reactions to identify the slope of a plot of the logarithm of the growth or dissolution rate vs reciprocal of temperature with the activation energies determined by diffusion measurements in chemically similar systems. If the solubility limits at the growing or dissolving phase interfaces change appreciably with temperature, such procedures may lead to serious errors in specifying the mechanisms controlling the rates of these processes. A reaction involving the simultaneous growth of graphite from and dissolution of cementite in austenite will be discussed here to show that substantial oversimplifications have been made in earlier studies of this process. From a dilatometric study of the overall y-range graphitization process, Bunin and Danil'chenko' found an apparent activation energy of 90 kcal per g-atom. They concluded that, since this value was much nearer the approximately 68 kcal per g-atom observed for self-diffusion in pure iron than it was to 32 kcal per g-atom for diffusion of carbon in iron, the rate-controlling process must be the diffusion of iron away from the growth interface to provide space for graphite to grow. Bunin and Salli' bolstered this agreement with the observation that graphite forms preferentially at surfaces, cracks, and pores where free volume is present initially. Ziegler, Meinhart, and DeaconQ ad found an apparent activation energy for graphitization of 98 kcal per g-atom. This value, like that of Bunin and Danil'chenko, applies to nucleation and growth occurring simultaneously. It is not generally assumed that nucleation is entirely diffusion-controlled. Treatments such as prior cold-working and prequenching, which strongly affect the rate of graphitization, would be expected to have little effect on diffusion processes occurring at the graphitization temperature. In any case 90 kcal per g-atom is not particularly close to the 54 kcal or lower to be expected for diffusion of iron which is carbon-saturated.' The presence of silicon in iron is said to reduce the activation energy for diffusion,' so its presence in cast irons would be expected to have a similar effect. The growth rates of nearly spherical graphite nodules have been studied by Brown and Hawkes." The initial rate of growth before impingement of adjacent carbon-depleted areas was found to be parabolic, and rate constants were measured at several temperatures. Their apparent activation energy for the growth process only was roughly 45 kcal per mol. Burke and Owen' made growth-rate measurements on several alloys, recording appreciable induction periods, initial nucleation rates, and average radial growth rates based on an assumed linear rate of radial growth. They found that increased silicon content increases the ovel-all reaction rate and the initial rate of nucleation, and decreases the induction period. Assuming 1) spherical nodules. 2) constant volume rate of nucleation, 3) austenite in equilibrium with cementite at positions where the cementite is not depleted, and 4) a constant diffusion distance during the growth of a nodule, they calculated an apparent overall activation energy of 68 kcal per mol, which was related to an activation energy for nucleation of 79 kcal per mol and activation energy

Jan 1, 1957

By J. S. Hegwer, P. M. Dunlap

An improved acid for the treatrrzent of sulfate-con-raining limestones and dolomites is described. The acid is designed to reduce he reprecipitation of dissolved calcium sulfate and the possibility of plugging permeable flow channels. In addition, this improved acid has a much lower reaction rate than that of regular acid; the advantages of a "retarded" acid are obtainable. Field testing of the acid has shown it suitable for use in sulfate-containing formations. Substantial improvements in productivity generally resulted. INTRODUCTION Acid treatments of limestones, dolomites and other formations bearing carbonate deposits are frequently unsuccessful when the calcareous formation contains sulfate, either as anhydrite (CaSO,) or gypsum (CaSO4. 2H2O). Preliminary dissolution in acid followed by redeposition of calcium sulfate appears to be a major factor contributing to poor well performance after acidizing. The precipitate is usually the gypsum form of calcium sulfate, but in higher temperature formations it may be anhydrite. The freshly precipitated crystals are nearly always very small and needle-like. They may occupy a gross volume many times that of the original anhydrite crystals and will obviously constitute an impediment to flow through newly enlarged flow channels. It is believed that the redeposition problem is most severe when anhydrite lines the fracture systems and large pores which supply the effective permeability of a formation. Microscopic inclusions of calcium sulfate also present large sulfate surface areas for dissolution in acid. In either case, great amounts of calcium sulfate may dissolve before the acid can be spent on formation carbonates. For regular spent acid (originally 15 per cent hydrochloric acid) the precipitate could be as much as 270 Ib gypsum/1000 gal acid. Two techniques have been applied by the industry for reducing sulfate plugging during acidizing. The method'.' commonly employed in the field is the attempted removal of a quantity of regular treating acid before it has reacted completely with the formation. This is practiced because the solubility of calcium sulfate is greater in a solution that is still acidic than in one which has been largely spent on the formation rock. The chance of precipitative plugging is therefore reduced if the withdrawal is successful. However, it is often impossible to get the acid out of the formation before precipitation occurs. A second possible method, which at first glance appears practical, involves addition to the acid of sequestering agents which form strong soluble complexes with calcium ions. These chemicals do increase the "solubility" of calcium sulfate in fresh acid, but to a lesser extent in spent acid. The sequestering agents have, therefore, proved unsatisfactory because the amount of sulfate eventually deposited from the spent acid may be greater than that from regular acid. Another logical approach to the problem of calcium sulfate reprecipitation is the prevention of the initial dissolution of calcium sulfate by the common ion effect. This may be accomplished by adding a soluble calcium salt to the fresh acid. The use of calcium salts in treating acids is not entirely new. An earlier suggested use of a soluble calcium salt in hydrochloric acid apparently failed to recognize the full extent to which the solubility of calcium sulfate could be suppressed. The present study extends this earlier work and adds certain improvements toward the development of a practical anti-anhydrite acid. LABORATORY DEVELOPMENT Calcium Sulfate Solubility Table 1 shows the results of a laboratory study performed to establish the effect of calcium chloride concentration on gypsum solubility. Because of the strong tendency of calcium sulfate to form supersaturated solutions, accurate solubilities are difficult to determine. These solubility data probably are reliable to within ± 15 per cent. The solubility of calcium sulfate in 15 weight per cent hydrochloric acid increases with increasing temperature. This trend is also followed in hydrochloric acid which cantains calcium chloride. This is contrary to the solubility behavior of calcium sulfate in water, wherein the solubility decreases with increasing temperature.

By D. de Fontaine

A convolution procedure is described for obtaining an analytical expression for the composition profiles of solute concentration:; in binary solid solutions. The free energy of solutions containing such compositional inhomogeneities can then be evaluated and the stability of spherically symmetric clusters (G.P. zones, for short) us a function of their radii and central compositions can be studied accordingly. Two characteristic zone radii are defined: the minimum radius (RM) corresponding to the smallest zone for which growth is energetically favored over dissolution, and the critical radius RK) corresponding to zones associated with the minimum work of formation. The values of RM and RK coincide at the two classical limits of nucleation and growth and spinodal decomposition. As the spinodal is approached, however, RM and RK diverge increasingly and it is proposed that the initial] decomposition morphology is governed more closely by the minimum, rather than by the critical radius since the former possesses no singularity within the m eta stable phase boundary. Reversion is briefly discussed in the light of the foregoing and it is shown that a set of reversion temperatures located between the coherent miscibility gap and the coherent spinodal must correspond to a given distribution of low temperature zones. SINCE the early works of Guinier1 and preston,2 the kinetics and morphology of GP zones have been studied extensively, see Ref. 3, for example, for a recent review. Nevertheless, a completely satisfying theoretical treatment of the decomposition of meta-stable or unstable binary solid solutions is still lacking due to the almost unsurmountable mathematical difficulties that one encounters in attempting to solve the pertinent diffusion equation which, in principle, describes the whole process. This equation, first derived by Cahn for the initial stages of spinodal decomposition,4 is a nonlinear partial differential equation of the fourth order in anisotropic space, a general analytical solution of which is completely out of the question. From this equation, some prediction can be made, however, concerning the later stages of spinodal decomposition5 and a recent numerical solution6 of the equation in the case of one- and two-dimensional composition modulations of a solid solution inside the spinodal has led to the following considerations: the sinusoidal morphology7 is to be expected only for solutions of average composition c, located near the center of the coherent miscibility gap.8 For solutions with co closer to the spinodal decomposition, depleted shell zones9 should constitute the first recognizable decomposition product, later evolving to iso- lated, enriched preprecipitates in a uniformly depleted matrix as this must, in all cases, constitute the final metastable morphology, barring, of course, loss of coherency and change in crystal structure. In agreement with the qualitative description of Bonfiglioli and Guinier,l0 it thus appears that the various models discussed by previous authors are, in fact, idealized successive stages of the general decomposition process. Unfortunately, corresponding calculations for a solid solution outside the spinodal are not yet available because of two additional difficulties: it is essential that the diffusion equation be solved in three-dimensional space, and furthermore, one must include in the equation an appropriate "source term" describing the statistics of the creation of composition fluctuations required to trigger the nucleation events. At present, a general treatment of this problem does not appear to be tractable. Nevertheless, by using a modelistic approach, i.e., by selecting a priori certain composition variation profiles and by evaluating their associated free energies, one can draw certain conclusions relative to the stability of these isolated composition modulations or "zones", both outside and inside the spinodal. This is the object of the present investigation. THEORY We shall now describe a standard four-parameter spherically symmetric GP zone, evaluate its free energy according to the Cahn and Hilliard11 formula (Eq. [5], below), and plot the corresponding energy surfaces as a function of zone amplitude and radius as

Jan 1, 1970