Search Documents

By J. S. Fulton

Those who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer's patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangemerit, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartmerit septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries); portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. Phases Of the many Papers published On various phases of the Bessemer process, nearly '7' according to one bibliography, Over go per 'ent were concerned with the metallurgical phase and less than '0 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to One of the causes of the Bessemer process. IS it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By J. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies. THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.'-" This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications. Geology The geology of the Picher mining field is similar to that of the entire Tri-State district because the sedimentary horizons that are found here are found throughout the district, and the ore bodies in the respective horizons have similar characteristics. The beds that contain the ore bodies in the Picher field are illustrated and described in fig. 2. The five unconformities found in the mines of the Picher field are indicated on the geologic section, fig. 2. The unconformity shown at the base of Meramec (B bed) is relatively unimportant since B bed was mostly eroded from the area of the Picher field before the Chester beds were deposited. B bed has been observed in the cuttings from only a few churn drill holes. The Pennsylvanian (Cherokee shale) formation is the top horizon found in the Picher mining field. It has been eroded from the southeastern part of the field, but because of the regional dip of the sedimentary beds to the west, it attains thicknesses of 100 ft to 200 ft along the west edge of the field. It is 200 ft to 300 ft thick in the Miami trough. It was deposited on the Boone limestone surface, which contained relatively few shallow erosion channels and very few depressions. Subsequent to the deposition of the shale, solution of limestone from underlying limestone horizons by circulating solutions caused the overlying beds, including the Cherokee shale, to slump into the larger openings formed by the solution and removal of the limestone. Chert The origin of the chert in the Tri-State district has been a controversial subject among geologists. Tarr7 advocated a syngenetic origin for the chert, postulating that it formed from colloidal silica deposited in the Mississippian seas. Leith, Dake and Leighton' argued in favor of silicification of erosion

Jan 1, 1951

By J. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies. THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.'-" This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications. Geology The geology of the Picher mining field is similar to that of the entire Tri-State district because the sedimentary horizons that are found here are found throughout the district, and the ore bodies in the respective horizons have similar characteristics. The beds that contain the ore bodies in the Picher field are illustrated and described in fig. 2. The five unconformities found in the mines of the Picher field are indicated on the geologic section, fig. 2. The unconformity shown at the base of Meramec (B bed) is relatively unimportant since B bed was mostly eroded from the area of the Picher field before the Chester beds were deposited. B bed has been observed in the cuttings from only a few churn drill holes. The Pennsylvanian (Cherokee shale) formation is the top horizon found in the Picher mining field. It has been eroded from the southeastern part of the field, but because of the regional dip of the sedimentary beds to the west, it attains thicknesses of 100 ft to 200 ft along the west edge of the field. It is 200 ft to 300 ft thick in the Miami trough. It was deposited on the Boone limestone surface, which contained relatively few shallow erosion channels and very few depressions. Subsequent to the deposition of the shale, solution of limestone from underlying limestone horizons by circulating solutions caused the overlying beds, including the Cherokee shale, to slump into the larger openings formed by the solution and removal of the limestone. Chert The origin of the chert in the Tri-State district has been a controversial subject among geologists. Tarr7 advocated a syngenetic origin for the chert, postulating that it formed from colloidal silica deposited in the Mississippian seas. Leith, Dake and Leighton' argued in favor of silicification of erosion

Jan 1, 1951

By J. S. Fulton

Those who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer's patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangemerit, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartmerit septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries); portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. Phases Of the many Papers published On various phases of the Bessemer process, nearly '7' according to one bibliography, Over go per 'ent were concerned with the metallurgical phase and less than '0 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to One of the causes of the Bessemer process. IS it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By N. K. Chen, C. H. Mathewson

Recrystallization of aluminum single crystals after plastic extension is carefully studied in relation to the structure of the deformed matrix. The shapes of the new grains are analyzed with regard to slip planes and to the presence or absence of deformation bands. A mechanism by which the orientations of the grains are related to the parent lattice is described. EXPERIMENTS previously reported&apos; have been extended to develop some of the characteristics of the new crystals which are formed on annealing axially strained crystals whose deformational characteristics had been documented with special care. Thus, the presence of deformation bands affects the growth contours of the crystals, some of the strained crystals produced single crystals anew, and some, polycrystals, on annealing, while others merely "recovered" or "polygonalized" after the 600°C annealing treatment generally adopted in these tests. In the matter of orientational relationships between new crystals and the strained matrix, the present experiments have added little to previous experience, which had demonstrated great variety in the range of orientations encountered and no simple theory or correlation. For example, there has been ample evidence for the predominance in various face-centered cubic metals of a favored orientational relationship; viz., a rotation of 30° to 40° around a <1ll> axis, between grains growing in a matrix with a strong single orientation texture and the matrix itself.&apos;-&apos; This reorientation has been interpreted by various investigators in support of both the "oriented nucleation" and the "oriented growth" hypothesis. In the case of axially extended single crystals of aluminum, no general relationship, such as the one stated above, can be used to correlate the orientations of the recrystallized grains with that of the original crystal. Thus, Carpenter and Elama and Burgers and Basart7 were content to assume that the orientational relationships so developed were random in nature. Mathewson, however, in the Campbell Lecture of 1943 "rgued on the basis of <112> slip that a complex strain, chiefly characterized by rotation around a variable axis in the slip plane combined with a principal rotation around the pole of the slip plane, could be responsible for such devious relationships. Nevertheless, owing to the limited data now available dealing with orientational relationships between new grains and the single crystals strained in tension from which they have recrystallized, no adequate examination of the above generalization could be made. Here, there is the disturbing preliminary condition that any desired orientational relationship may be expressed by means of two rotations about mutually perpendicular axes, so the process lacks a certain critical flavor and any successful choice of axes meeting certain theoretical requirements could be replaced by another differently selected pair. With this reservation clearly in mind the process of double rotations, as previously indicated, was used to relate the orientations of the single crystals which grew out of the strained single crystalline matrix and was construed as certain evidence in favor of the theory of incongruent shearing action proposed by Mathewsons as a necessary element in the (111) slip process with close-packed metals. There is here

Jan 1, 1953

By N. S. Stoloff, M. Gensamer

Pyramidal (1122) slip was observed in cadmium single crystals deformed in compression and bending at room temperature and —196°C. Crystals tested in tension twinned with no evidence of pyramidal slip. A critical resolved shear stress law for the propagation of twin nuclei appears probable. Twinning and low-stress kinking are believed to inhibit the appearance of pyramidal slip under ordinary experimental conditions. SEVERAL reports of nonbasal slip in cadmium have appeared in the literature recently, two of the reports having appeared after work on this project was in progress. Brown1 reported cross slip on electron micrographs, but did not identify the cross-slip plane. Wernick and Thomas2 observed nonbasal slip traces parallel to [1123] on a crystal bent with a pair of tweezers, but this too was an isolated observation, with no confirmation of the glide plane. The critical stress for pyramidal glide, and the temperature and strain rate dependence of glide on this system were not discussed. price3 has reported some observations of nonbasal slip in thin films of cadmium with the aid of transmission electron microscopy, but a full publication of these observations was not available at this writing. Pyramidal (1122) <1123> slip also has been observed on zinc single crystals4, 5 and (1122) <1010> slip on magnesium single crystals,6 all oriented with the basal plane nearly parallel to the specimen axis. Since the choice of slip system in the hexa- gonal metals is generally believed to depend on the axial ratio, with basal slip predominating for high-axial ratios, the occurrence of pyramidal slip in zinc and cadmium is unexpected. The objectives of the present investigation were to confirm the existence of nonbasal slip in cadmium, to identify the slip system, and to obtain an estimate of the critical resolved shear stress, assuming that the resolved shear stress law is applicable. EXPERIMENTAL PROCEDURE Two purities of cadmium, 99.95 pet and 99.99+ pet, were employed. As received bars were cold swaged to 3/16 in. rounds. Bicrystals and tricrystals were prepared by passing the polycrystalline rods through a gradient without seeds. It was desired to obtain a large yield of single crystals oriented xo* < 5 deg, in order to be able to suppress basal slip during deformation by keeping the resolved shear stress on the basal plane to a minimum. Cylindrical single crystals of cadmium were prepared by a seeding technique developed by Weiner,7 to obtain a predetermined orientation. The single-crystal rods were sectioned to specimen size by an acid-cutting technique originally developed for zinc crystals.&apos; An aqueous solution of nitric acid was the cutting agent. The acid was picked up by a plexiglass disc spinning at an optimum cutting speed through the acid, which was contained in a sump-like arrangement. The section to be cut, the acid bath, and the spinning disc were enclosed in a plexiglass case. The rod to be sectioned was coated with a thick layer of collodion. At the points at which sectioning was to be effected, the collodion was removed over a length of about 1/8 in. by dissolving it in acetone. To prepare a surface suitable for microscopic exam-

Jan 1, 1962

By Ervin E. Underwood

IT has been recognized for many years that dis-persed particles have great value in raising the creep resistance of metallic alloys. In fact, some of the most successful high-temperature alloys owe their superiority to this factor above all others. A recent observation by Glen1," indicates that even better high-temperature resistance to deformation results in alloys capable of two successive precipitation reactions. The ramifications of this finding are of great interest. Unfortunately, our understanding of the reasons for such notable improvements has not kept pace with technical developments. In an effort to uncover some of the basic facts governing strengthening by particles, a program was initiated at the Battelle Memorial Institute with the primary goal of comparing creep strengths in single-phase and two-phase (precipitating) alloys. The effects of precipitation from solid solution on the creep properties of alloys are generally such that the resistance to creep is increased. However, if alloys are heat treated to different degrees of hardness before creep testing, it is often found that those possessing the maximum hardness initially do not necessarily have the maximum creep resistance. Depending on the stresses and temperatures involved other structures may prove more desirable. Considerations of the above nature indicate the importance of defining the initial state of the alloy. Here, it was decided to start with quenched single- phase alloys in which precipitation and creep deformation proceed concurrently. Equipment and Experimental Procedures Preparation of the Specimens—Four 25 lb ingots were prepared from 99.999 pct Cu and 99.996 pct Al to compositions of 1, 2, 3, and 4 wt pct Cu. Spec-trographic and chemical analyses are listed in Table I. After heat treatments and intermediate reductions, the alloys were cold rolled to 1/8 in. thick sheet. The final cold reductions amounted to 50, 40, 20, and 10 pct for the 1, 2, 3, and 4 pct Cu alloys, respectively. The specimens for creep testing were machined into tensile flats 7 in. long, 3/4 in. wide (at the shoulders), and 1/8 in. thick. The reduced sections were 1/4 in. wide and 21/2 in. long. After heat treatments at 540°C to an ASTM grain size of 1 1, the specimens were quenched into water at room temperature, then electropolished in a glacial acetic acid and perchloric acid solution. The gage marks were Knoop impressions placed 2 in. apart on the reduced sections. Blanks of 1 x 1 in, were cut from the same sheets for the age hardening runs and were given the same grain size heat treatments. The specimens and blanks were stored in a refrigerator at —40°C until needed for testing. Creep Measurements—Creep tests were conducted in a constant temperature room which was maintained at 26° ±1°C. A split-type, hinged, vertical-tube furnace was mounted on a horizontal track so that the specimen could be enclosed suddenly. Thus, it took about 15 min for the specimen to come within 5°C of the test temperature. The temperature variation along the specimen was controlled to about

Jan 1, 1958

By R. Maddin, A. Lawley

Single crystal Mo-Re alloys (99.99+ purity), grown by electron bombardment floating zone heating, were deformed in tension at temperatures from -196° to +200°C. At -196oC, Mo-6 pet Re and Mo-20 pct Re alloys deform by slip on systems of the type (101) [1ll]. Above-78oC, the operative slip system is of the type (112) [111], (101) [1ll], or (211) [1ll], depending upon orientation. Mo-39 pct Re alloys deform by twinning and slip at all test temperatures with a (112) [111] type twinning system. Critical resolved shear stress for slip and twinning is calculated as a function of composition and temperature, and the mechanical properties compared with those of less Pure polycrystalline alloys. HEXAGONAL close-packed rhenium, c/a = 1.615, is highly soluble in molybdenum. The bee molybdenum-rich solid solution extends to approximately 42 at. pet Re* at 2500°C,&apos; Fig. 1. Recent work on polycrystalline alloys has shown conclusively that the addition of rhenium to molybdenum improves both the fabricability and the low-temperature ductility.2"5 Similar behavior is observed for W-Re and Cr-Re alloys.5 Initially, Geach and Hughes2 found that the Mo-30 pct Re alloy could be cold rolled to approximately 90 pct reduction before the onset of cracking. The remarkable effect of the rhenium was later confirmed by Jaffee et al. 3-5 with an optimum condition of maximum strength combined with maximum ductility at the Mo-35 pet composition. At higher rhenium contents, the ductility was severely impaired due apparently to the presence of brittle tetragonal s phase, Fig. 1. In the Mo-35 pet Re alloy, at least 110 ppm (parts per million) oxygen could be tolerated before cold workability was reduced. By comparison, the corresponding tolerance figure in unalloyed molybdenum is ~ 10 ppm. The effect of rhenium was considered in terms of: 1) a reduction in oxygen solubility in the lattice; 2) a redistribution of intergranular oxide from grain boundary films to isolated spheres; and 3) the promotion of twinning as a further mode of plastic deformation. Paradoxically, twinning is often associated with brittle fracture in iron and the silicon irons.6&apos;7 Work to date has been restricted to are-melted and powder metallurgy polycrystalline material of ~ 99.9 pet purity. The present investigation was initiated for the purpose of determining the mode and crystallography of plastic deformation of a series of bee Mo-Re alloy single crystals over a wide temperature range from -196o to +200°C. Using high-purity zone-melted material (~ 99.99 + pet purity), the specific role of rhenium in the molybdenum lattice may be understood more fully since effects due to grain boundaries and oxide redistribution will be absent. At the same time, the study provides a comparison of single and polycrystalline deformation behavior. EXPERIMENTAL TECHNIQUES A) Preparation and Purity of Single Crystals. Alloys in the form of either are-cast and swaged or sintered and ground bar, 0.120 in. diam, were obtained from the Chase Brass and Copper Co. Alloy single crystals ~ 8-in. long were grown from the

Jan 1, 1962

By E. F. Bradley, R. I. Jaffee, H. R. Ogden, E. S. Bartlett, D. N. Williams

The mechanical properties of solid-solution-strengthened columbium alloys have been assessed as a function of alloying additions. Studies included the effects of tungsten, tantalum, molybdenum, and vanadium. Elevated temperature fabrication was required at alloying levels above about 15 pct W or 10 pct Mo. Tungsten, molybdenum, and vanadium additions increase tensile strength at room temperature and 2200°F, but tantalum additions exert little strengthening. Similarly, tungsten, molybdenum, and probably vanadium additions increase the ductile-to-brittle transition temperature, and tantalum additions decrease this parameter. The 2200°F stress-rupture strength is increased by tungsten and molybdenum additions; with 20 to 25 at. pct additions, 100-hr rupture strengths of 30,000 psi are obtainable. Small vanadium additions exhibit mild stress-rupture strengthening, and tantalum additions are innocuous. At 2500°F, tungsten additions retain stress-rutpure strengthening capability, but molybdenum additions are much less effective. Tantalum additions augment the stress-rupture strengthening of tungsten plus molybdenum additions at 2500°F. Of the refractory metals, columbium possesses specific potential for structural use in the temperature range from 2000" to about 2500°F. Desirable features of columbium are its good low-temperature ductility, ease of fabrication, oxidation mechanics (lack of a volatile oxide at moderate temperatures), good availability and reserves, and relatively low density. However, alloying is required to provide attractive strength at elevated temperatures. Published information concerning alloying be- havior of columbium relative to mechanical properties is sketchy, particularly in consideration for long-time applications at temperatures in excess of 2000°F. Only a few stress-rupture data at temperatures from 2000" to 2500°F have been reported;&apos;-&apos; these are too meager to allow rationalization of the effects of various alloying additions on creep or stress-rupture properties. Additional published data do, however, give some insight toward understanding of systematic alloying behavior for columbium relative to low-temperature strength4-&apos; and ductility,&apos; and elevated temperature tensile behavior.4,6 This paper is intended to augment previous knowledge, and to promote understanding of the alloying behavior of columbium for long-time structural service at elevated temperature. BASIC CONSIDERATIONS Solid-solution strengthening is recognized to be of prime importance in improving strength in columbium-base alloys. Other strengthening mechanisms may be (and are, in current alloys) used to augment solid-solution strengthening. As strengthening results primarily from lattice distortion, the strengthening effectiveness per atom depends upon atomic size mismatch between solvent and solute. Another factor in this regard is conformance to ideal solution behavior in the solid solution. Thus, for example, despite appreciable differences in the degree of mismatch between tungsten (5 pct), molybdenum (5 1/2 pct), and vanadium (7 1/2 pct) in solution in columbium, all are about equally effective in straining the columbium lattice at room temperature.&apos;-&apos; Similarly, tantalum additions do not strain the columbium lattice, and little strengthening is expected. Size effects being equal, maximum solution strengthening at high temperatures is anticipated to result from the addition of elements that increase the melting temperature of columbium. This expectation is based on an increase in the electronic bonding forces exhibited in the transition metal series as electronic structures approach those of the Group Vl metals. Of the metals that exhibit ex-

Jan 1, 1963

By Donald L. Katz

THE Oklahoma City Wilcox sand, discovered on March 26, 1930, has produced 394 million barrels of crude oil and 819 billion cubic feet of natural gas as of July 1, 1941. The 100,000-bbl. wells, pressures of 2600 lb. per sq. in., and flows of "Wilcox" sand caused exciting moments in the early life of the field. Today the reservoir is substantially at atmospheric pressure and produces 75,000 bbl. of crude oil daily through 466 pumping wells. Early estimates of the initial crude-oil content of the "Wilcox" sand&apos; indicated that about 600 million barrels of crude oil would remain after the pumping wells ceased to produce economically. The Oklahoma City Wilcox Secondary Recovery Association was organized in March 1939, to study the possibilities of recovering a portion of this oil. Only a very brief summary of the information available can be presented in a paper of this nature. Some simplification and generalizations are necessary to give the over-all picture in so short a space and statements made may not apply to a specific well or small area. Since the area under consideration by the Association is that north of the south line of section 22-11-3, some information will be presented for areas A, B, C, r, 2, 3 and part of 4 of Fig. 2, and some will be for the entire Wilcox zone west of the fault. This paper is essentially an abstract of an engineering report made by A. D. Small, B. T. Murphree, M. C. Sons and the author for the Oklahoma City. Wilcox Secondary Recovery Association on Sept. 5;.1940. Some information is taken from a report to the Association by C. V. Sidwell on March 1, 1940, and some data are from a recent report by A. D. Small. It gives a brief history of the Wilcox zone, estimates of the initial oil contents of the reservoir, present conditions in the reservoir, and probable results from several programs of "secondary recovery." HISTORY OF WILCOX ZONE The Wilcox sand lies on the flank of the general structure, as shown by cross section of Fig. 12.1 .4 and areal map of Fig. 2. The sand is of Ordivician age and is composed of well assorted, rounded&apos; sand grains with no apparent cementing material. The loose texture of the sand is shown by the enormous quantities of sand production from the wells and from the soft cores. The productive sand varies from zero thickness on the east to 220 ft. maximum and to zero thickness on the west because of water. The development of the pool4 was dependent upon drilling restrictions within the city limits, which accounts for the spacing of drilling operations listed in Table I by years. In 1931, areas I through 7 of Fig. 2 were open for drilling with the exception of some west-edge properties, and all wells drilled before Feb. I, 1935, were in this portion of the field. Nearly all wells drilled from 1933 to 1937 were in areas A, B and C. Since 1939, the newly drilled wells have gradually enlarged the producing area toward the west in the northern portion.

Jan 1, 1941

By R. L. Stephenson

The effect of fabrication variables on the creep-rupture properties of TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C), Cb-TZM [columbium-modified TZM (7140-1.5 pct Nb-0.5 pct Ti-0.8 pct Zr-0.05 pct C)], and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C) has been studied at 982º. 1093º, 1204º, and 1315°C for rupture times up to 1000 hr. The creep tests were performed in vacuum creep furnaces, employing cold-trapped oil-diffusion pumps, operating at pressures 2 X 10-7 tory. After-test chemical analyses showed no significant changes in interstitial content. The creep-rupture properties of TZM, fabricated according to current mill practice, were determined in the stress-relieved and in the re crystallized conditions to provide control data. Specimens of TZM, Cb-TZM, and TZC fabricated according to each of two experimental fabrication schedules were then tested. The schedules differed in terms of in-process annealing temperatures and warm -working temperatures. The data make several conclusions evident. Fabrication variables do indeed have a profound effect on the long-time creep-rupture properties of molybdenum alloys. Strengths of these alloys compare very favorably with those of other refractory metal alloys in the temperature range studied. FOR several years we have been engaged in the evaluation of the creep-rupture properties of promising refractory metal alloys. We consider the determination of these properties to 1000 hr at several temperatures necessary for a valid comparison. Such an evaluation indicated that the creep strengths of Mo-0.5 pct Ti and TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C) compare favorably with those of other refractory metal alloys. Tensile and recrystallization data of other investigators1,2 show an effect of fabrication variables. More specifically, those fabrication schedules which produce high strength through work hardening exhibit the least thermal stability. A similar conclusion was reported by perkins3 for Cb-TZM. This would lead one to expect that, in terms of creep, those materials showing higher strength at short times and low temperatures would exhibit lower strength at long times and high temperatures. If these expectations were fact, a substantial improvement could be made in these alloys by optimizing their fabrication schedule in terms of their anticipated service temperature. We therefore undertook a study of the effect of fabrication variables on the long-time creep properties of TZM, Cb-TZM (Mo-1.5 pct Cb-0.5 pct Ti-0.08 pct Zr-0.05pct C) and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C). MATERIALS All materials used were supplied by the Climax Molybdenum Co. of Mich. Our original intention was to test the same heat of each alloy in different conditions. Fabrication difficulties prevented this; however, heats with nearly identical analysis were selected. The compositions of the materials used are listed in Table I. All materials were supplied in the

Jan 1, 1970

By K. A. Johnson, F. H. Ellinger, C. C. Land

The Pu-In phase diagram has been determined by thevmal, filtvation, micrographic, and X-ray diffraction methods. This alloy system is characterized by 1) limited solubility of indium (-2 at. pet) in 6 and e plutonium, 2) one eutectic, and 3) fizte intermediate phases. Of the latter, PuIn and PuIn3 melt con-gruently, and Pu31n, Pu31n5, and the high-temperatuve 7 solid solution are formed peritectically. The n phase decomposes eutectoidally into Pu3In and PuIn at 865°C. Although the 6 phase can readily be retained to room temperature, it is not thermo-dynamically stable below 300°C. The Pu-In system has been investigated at Los Alamos as part of a study of the alloys of plutonium with the group 111-B elements. Constitutional studies of the Pu-A1 and Pu-Ga systems have been reported earlier.&apos;9&apos; To date, published information on the constitution of Pu-In alloys covers only the identification of the intermediate phases Pu3In and PuIn3.3,4 EXPERIMENTAL The alloys were prepared from five different lots of plutonium and three different lots of indium. The principal impurities in the plutonium differed from lot to lot within the following limits (in ppm): iron, 30 to 80; nickel, 30 to 60; aluminum, 15 to 30; silicon, 20 to 145: thorium, 50 to 300; carbon, 75 to 335; and oxygen, 20 to 135. Spectroanalysis of the indium showed that two of the lots were 99.9 wt pct pure, and the third was 99.98 wt pct pure. The alloys, in the form of about 5-g buttons, were prepared by arc melting in conventional equipment. The components for each alloy were weighed to the nearest 0.1 mg. In most instances the weight losses during melting were negligible; therefore confirmatory chemical analyses were usually not made. A few results are given in Table I. Density measurements of the arc-cast buttons were made by the liquid displacement of bromoben-zene. Heat treating was done in muffle furnaces controlled to +2°C. The alloy buttons were wrapped in tantalum foil before being enclosed in evacuated clear silica capsules. As a precaution against breakage, each capsule was in turn placed in a silica tube closed with a refractory wool plug prior to being charged into the furnace. For a moderately fast quench of the alloys, the outer protection tubes containing the capsules were plunged into cold water. Differential thermal analyses (DTA) in racuo were performed at heating and cooling rates of about 1.5°C per min. Tantalum crucibles having inverted thermocouple wells were used for most of the analyses. It was found micrographically, however, that the liquid alloys containing more than about 35 at. pct In reacted with the tantalum, resulting in contamination of the surface of the alloy. A search for a more satisfactory crucible material was not successful: tungsten and yttria behaved comparably to tantalum; thoria, vitrified magnesia, and vitrified alumina severely contaminated the alloys. So as to minimize the contamination by the crucible mater-

Jan 1, 1965

By H. H. Johnson, Eric W. Johnson

A newly developed ac technique was used to measure the electrical-resistivity changes associated with both cyclic stressing and subsequent annealing of high-purity and OFHC copper. The early stage of push-pull fatigue was explored at 293° and 4.2°K, with stresses chosen for an expected fatigue life of 2 to 8 X 105 cycles. For high-purity copper, fatigue at 293°K was accompanied by an initial increase in resistivity. After about 5000 stress cycles, no further increase was observed. Annealing studies showed that the resisticity increment could be accounted for solely in terms of an increased dislocation density, to about 2 x 1010 disl pev sq cm. Fov 42°K fatigue, however, the resistivity increased continually, with no evidence of saturation, as approximately (No. of stress cycles)1/4. This is intevpreted to result from both dislocation multiplication and vacancy production; estimated vacancy concentrations are 10-4 to 10-9. The continuous resistivity increase was inhibited by interspersed annealing treatments at 293°K, which also raised the level of the stress-strain curve. These effects are attributed to annealing of vacancies into dislocation loops. In contrast, OFHC copper fatigued at 4.2°K showed saturation of electrical vesistivity after only a few hundred cycles, and it appeared that vacancies annealed out completely between 77° and 293°K. MaNY observations suggest that both dislocation multiplication and point-defect production are important aspects of fatigue deformation. An increase in dislocation density with number of stress cycles has been demonstrated or implied by several experimental techniques, including optical metallography with lithium fluoride,&apos; electron microscopy with copper,2 thermal conductivity of Cu-Zn alloys,3 and peak-stress measurements during cycling at constant plastic strain amplitude.4,5 At low amplitudes and/or stresses saturation of fatigue hardening and dislocation density occurs early in the expected fatigue life,4-6 frequently by a few hundred cycles. The evidence for point-defect production is somewhat less extensive, but it is nonetheless persuasive. Rosenberg7 reported briefly that, for equal stresses, copper fatigued at liquid-hydrogen temperature displays an increase in electrical resistance some ten times that which accompanies unidirectional stressing. Further, the extra resistance saturates after a few hundred stress cycles, and does not anneal significantly until a temperature of about 170°K is attained.&apos; Point-defect production during fatigue is also suggested by 1) the softening during cyclic stressing of initially strain-hardened polycrystal-line copper9, 2) the strong temperature dependence of the yield strength of fatigue-hardened mono- and polycrystalline copper,579"0 and 3) the influence of intermediate annealing upon slip-band formation in copper fatigued at 90°K.8 It is evident that characterization of the fatigued state requires a knowledge of both point-defect and dislocation densities. For this purpose electrical-resistivity measurements are useful, but they are difficult to perform because of geometric limitations. Push-pull fatigue is necessary to obtain a macroscopic ally uniform deformation over the specimen cross section; however, the specimen must then have a low slenderness ratio to avoid plastic buckling, while the standard dc resistivity technique requires a very slender specimen for

Jan 1, 1965

By C. C. Herrick

The vapor pressure of indium has been measured by the torque-effusion technique, as a function of temperature between 1102o and 1422oK. For liquid indium, the vapor pressure (in atmospheres) can be represented by the equation -R In P = 5.782 x104/T - 25.29from 1000o to 1422oK. Extrapolation yields a calculated normal boiling point of 2329°K and a heat of vaporization at 298 oK of 58.09 kcal per mole by the third-law method and of 58.39 kcal per mole by the second-law method. Calculations indicate that the free-energy functions of Hultgren are to be preferred to those of Guruich. BECAUSE of the potential uses of liquid metals, it is important that convenient experimental methods be developed which will lead to a sufficient body of thermodynamic data so that reasonable estimates of properties of liquid metals can be made. Indium is particularly well-suited to investigation, since it remains liquid over a long temperature interval, it alloys readily, suitable containers for it are easily procured, and relatively few investigations of its thermodynamic properties in the region above 1000°K have been made. PREVIOUS RESEARCH The first determination of the vapor pressure of indium was made by Anderson,&apos; using the Knudsen method and silica-lines stainless-steel cells. Kohlmeyer and spandau2 determined the normal boiling point, and a mass-spectroscopic investigation has been made by Lyubimov and Lyubitov.3 (Unfortunately, only an equation representing the data of the latter investigators has been available to us.) Hultgren et al.4 and Gurvich5 have published discordant tables of the free-energy functions for indium. EXPERIMENTAL METHOD The torsion-effusion principle has been described amply in the literature.8,7 With this method, one observes the angular deflection induced by effusion of vapor from a multihole effusion cell which is suspended from a filament producing a small rotational restoring force. The pressure within the effusion cell can be computed from the relation ziaifiai where k is the torsion constant of the filament, 6 is the observed angular deflection, and ai, fi, and qi are the area, force factor, and moment arm of the ith effusion orifice. The force factor f is analogous to the Clausing factor,&apos; and corrects for the reduction in effusive force attributable to the finite geometry of the effusion orifice. Schultz and Searcy&apos; have tabulated the force factors for various tube geometries. EXPERIMENTAL APPARATUS The physical arrangement employed in this study is shown in Fig. 1. The furnace elements are six Globar heat rods with 15-in. hot zones. Temperature is maintained to * 1°K by a Beck mechanism driving two 26-amp Powerstats in parallel. A Pt (Pt, Rh 10 pct) thermocouple serves as the sensing element. Four inner tubes act as vibration isolators; the air pressure required for maximum isolation was determined empirically, and is maintained by a solenoid valve. The tungsten fiber, 9 by 0.002 in., is joined to an 0.008-in. tungsten wire or graphite rod via a machined lightweight chuck.

Jan 1, 1964

By Strathmore R. B. Cooke, Marcus Digre

That calcium will activate quartz for flotation with anionic collectors such as soaps has been known for a number of years,12&apos;3 and the method has been applied to the concentration of various iron ores4 5 6 as well as to other materials. Clemmer gives the permissible pH range for the activation of quartz by calcium as between 9.5 and 12.5 with an optimum value of 11.0, and Hertzog7 has determined the calcium abstraction of iron ores and of Ottawa sand, but otherwise little quantitative data are available. The purpose of the present investigation was to determine those conditions under which dilute solutions of calcium chloride will activate quartz for anionic flotation and to determine the amount of calcium ion adsorbed by quartz. Those variables, the influence of which was primary, such as calcium, sodium, and hydrogen ion concentrations, were studied. Other factors which influenced the results are discussed in the description of the experiments. Three different experimental methods were used to determine the activation of the quartz. The first method was to treat a sample of ground, deslimed quartz with solutions of calcium chloride and sodium hydroxide, and to determine the calcium adsorbed by chemical analysis of the solution. Advantages are that a direct value for the amount of calcium adsorbed is obtained, and introduction of a collector which may affect the adsorption is avoided. The difficulty is to determine the extremely small differences in the calcium concentrations before and after the abstraction. The second method was to determine the activation of the quartz by observing the contact angle obtained on pressing an air bubble against the polished surface of a piece of quartz immersed in a solution of calcium chloride, sodium hydroxide, and sodium oleate. This is the well-known "contact angle" method. The third method was to determine those conditions under which an air bubble will pick up quartz particles immersed in a solution of the desired reagents. Disadvantages common to the sec- ond and third methods are that introduction of a collector is necessary to obtain bubble contact with the mineral; very small quantities of contaminant can give erroneous results; and no information is obtainable concerning the amount of calcium adsorbed. Advantages are that tedious analyses, which at best give approximate results, are avoided, and the conditions, especially for the third method, closely simulate those of actual flotation. Although the most consistent results were obtained with the third method, this paper describes the techniques used and the results obtained from each of the three methods. Distilled water and analytical grade reagents were used throughout except where otherwise stated. Between tests all glass articles were cleaned with a chromic-sulphuric acid mixture and sodium hydroxide. Abstraction Method The raw material for the tests was Ottawa sand sized between 14 and 28 mesh. Batches of 500 g of this sand were dry ground for 1 hr in an Abbe porcelain mill with 2700 g of quartz pebbles. The batches were split down to samples weighing approximately 30 g, and the weight of each sample was adjusted to exactly this value.

Jan 1, 1950

By H. E. Montgomery

Engineering trends for some years have been toward higher temperatures, both in process work and in steam generation. Progress in design has been dependent upon the development and evaluation of suitable alloys. Elementary knowledge of the limitations of copper-base alloys indicate their unsuitability for the higher ranges of operating temperatures; say, for steam to 950°F. Emphasis upon the more severe conditions perhaps is a reason why more complete evaluations have not been made for copper-base alloys over their range of suitability. However, the few studies made show clearly the need for more accurate evaluations. Some copper-base alloys long looked upon favorably because of superior room-temperature properties are not as desirable as some others perhaps not so "strong" and "hard," as measured by usual acceptance tests. Load-carrying capacity and structural stability arc two important factors. Structural stability as influenced by temperature, by presence of corrosive media, or by the effects of stress itself, frequently is a limiting factor. An early reference to creep properties of the cast copper-base alloys is that of Brown1 (Admiralty gun metal, Cu 87.5, Sn 10.1, Zn 2.3 and Pb 0.08). His tests were similar to present-day stress-rupture tests without measurement of creep elongrttion. Loading was in steps with usually 24 hr. between steps, and continued until failure. He advocated a "useful strength value" of 61/2 tons (I4,560 Ib.) per sq. in. at 572°F. (300°C.). A specimen broken in 1/2 hr. at 572°F. had a strength of 21 tons (26,880 Ib.) per sq. in. The strength values as determined by 1/2-hr. tests and those by the longer stress-rupturc start to differentiate at 392°F. (200°C). This is the temperature at which time at load began to play an important part. Bolton, Price and Hebemann2 give creep curves on 88-10-2 (A.S.T.M. B-60, CU 88, Sn 10, Zn 2) and steam or valve bronze (A.S.T.M. B-6I, Cu 87.50, Sn 6.00, Zn 3.75, Pb 1.70) at 500°F. Direct comparison of the two alloys under 7500 lb. per sq. in. stress showed the steam bronze (A.S.T.M. B-61) superior in creep strength to the 88-10-2 (A.S.T.M. B-60). The steam bronze shows no creep after 700 hr. (1540-hr. test). The 88-10-2 shows a rate of about 7.0 per cent in 100,000 hr. over the last 700 hr. of the test. Creep curves on the steam bronze are also given at the same temperature (500°F.) with loads of 6500 lb. per sq. in. and 8000 lb. per sq. in. These indicate "creep strengths" (creep rate within I per cent in 100,000 hr.) in excess of 8000 lb. per sq, in. for this alloy. It was found that higher percentages of tin are detrimental to creep resistance. This is caused by the presence of or formation during test of considerable alpha-delta eutectoid in the higher tin alloys. Bolton also states that the high

Jan 1, 1945

By L. Guttman

THE equilibrium diagram of the indium-thallium system was of interest to us in connection with a study of the superconducting properties of metallic solid solutions in progress at this Institute. For this purpose, a series of alloys was prepared covering the range from pure indium to 75 atomic pet TI, and X-ray diffraction patterns were obtained. Roughly speaking, the results indicated a region of continuous decrease in the axial ratio of the face-centered tetragonal structure from the value ca. 1.08 in pure indium to unity at about 23 atomic pct TI. From this concentration to the solubility limit, the structure was face-centered cubic, a form not reported by Hansen.1 At this point we became aware of the work of Valentiner,2 who had found the same structures at room temperature but had not investigated further the relationship between them. To study the transformation f.c.c.??f.c.t., and to clarify the phase diagram, we undertook the work reported in this paper and that which follows." Preparation of Alloys Pure indium and thallium* (both about 99.9 pct, as estimated from spectroscopic analyses) were weighed out in quantities sufficient to prepare 10 to 25 g of alloy of the desired concentration. (Occasionally indium was mixed with a previously pre- pared solution.) The metals were melted over a flame, in an open graphite crucible, stirred with a graphite rod, and poured into a graphite trough. The rough slug was hammered and swaged into a rod of 2 to 3 mm diam, and annealed in a drying oven at about 125°C for 1 to 2 days. Samples were taken from the rod for analysis, as well as for diffraction and other measurements. The thallium was determined by electrometric titration, using a modification of the method of Beale and co-workers.&apos; The precision of analysis was generally about 2 0.2 pct of the thallium content. The rods were sometimes found to vary in thallium content as much as 1.5 pct from end to end, but since analyses were also made close to the segments used in the various studies, the composition was usually known as accurately as the analyses could be made. Where one less significant figure is given, the error is estimated to be ±0.4 pct of the thallium content. X-Ray Diffraction Measurements Three different cameras were used: (1) A 7 cm Debye camera, with oscillating specimen (manufactured by the Picker X-ray Corp., Cleveland, Ohio); (2) a 9 cm diam Debye camera of the type designed by Bradley;" (3) a 10 cm diam symmetrical focusing back-reflection camera (manufactured by Geo. C. Wyland, Ramsay, N. J.). Samples were prepared from the homogenized rods, either by filing under liquid nitrogen, or more often, in the form of wires or foils made by working at room temperature or liquid nitrogen temperature. Sharp patterns were obtained from specimens annealed at room temperature, although higher annealing temperatures were also used (cf. below). Generally, copper radiation was used; a few patterns were obtained with

Jan 1, 1951

By J. D. Cooner

SINCE my working life of 32 yr has been spent in and about the anthracite mines of the Hudson Coal Co., and the previous 4 yr in a college school of mines, I can write best about the safety program of a coal mining company. However, most of the suggestions, statements and practices mentioned herein are applicable to the members of a safety organization and program of almost any industry. It is realized that industrial officials actually interested in real safety work are fully acquainted with the requirements of a practical safety program. Therefore, for such persons there may be nothing new in this paper. The Hudson Coal Co. of Scranton, Pa., employs 7,000 men and produces 5,000,000 tons of anthracite annually at nine collieries scattered for a distance of 40 miles throughout the Lackawanna and Wyoming valleys of northeastern Pennsylvania. For the past 17 yr of the above mentioned 32, I have been engaged in safety work as a safety inspector, assistant mine superintendent, and at present the safety engineer. I have also had the privilege of visiting coal and metal mines in other parts of the United States and Canada. We Americans are the most careless people in the world. If any one doubts this statement why are 100,000 of our people killed accidentally annually? Or why during the almost four years we were engaged in World War II were more of our people killed accidentally at home than were killed in our army, navy, marine corps, coast guard, and other services during the same period? We are careless everywhere in our homes, on the highway, at work and at play. The purpose of this paper is to outline the requisites of a safety department and its program to stop the accidents occurring to employees at work in mines or industrial plants. The first requisite for a safety program is that the management must be convinced of the need and value of a real safety program. By "management" is meant each department head from the president down. Otherwise a good safety department with a good safety program will not succeed because it will not have the proper personnel and equipment to work with, its rules and regulations will not be enforced, and the members of the safety department will be belittled in the eyes of most of the workmen and supervisors. Next, a safety engineer and his inspectors should have worked in the production end of the mines as workmen and also in an official capacity. They are then in a position to have practical and first hand knowledge of the accident hazards of the industry, how to prevent them, and in general the problems of both the workmen and officials. Some men are appointed as safety inspectors when they are physically unable to carry on as mine officials. Such men may know the safety end of the industry and even be safety-conscious, but if they are physically unable to be mine officials they are also physically unable to be safety inspectors, as a safety inspector in our mines must walk from 2 to 4 miles on each daily inspection-and visit each working

Jan 1, 1948

By F. W. C. Boswell, R. L. Cunningham, H. M. Weld

Chemical analysis shows the partition of the magnesium addition between the metal and the graphite is independent of whether the graphite is in the form of nodules or flakes. The bright central spot observed in nodular graphite polished sections is shown to be due to the structure of the nodules. DURING the past few years numerous papers have been published on the production1-7 and heat treatment" of nodular cast irons. However, very little information is available on the structure of the nodules and the reason for their formation. It would appear that an explanation of the phenomenon of nodulation must await a detailed knowledge of the nature of the nodule. Disagreement exists among various workers on such a fundamental point as to whether or not a nodule actually contains a microscopically visible, nongraphitic nucleus.9-11 Work was initiated with a view to obtaining definite information on this and other aspects of the problem. Chemical Separation and Analysis Microscopic appearance had indicated9-11 that a nongraphitic core might exist in nodules (Fig. 1). It appeared that a chemical comparison of separated nodules and flake graphite would be profitable, for if the core is nongraphitic a relatively large amount of certain elements would be found in the nodules as compared to the flake. This comparison could best be made by obtaining nodules and flake from the same melt of cast iron, part of which had been in-noculated with a suitable addition reagent for the formation of nodules. A 300 lb melt was produced. About half of this was innoculated in the ladle with an Fe-Si-Mg alloy to produce nodules and cast into keel blocks; the remaining half of the melt had silicon added in an effort to compensate for the silicon in the innoculant used in the other half of the melt and this was cast into similar keel blocks. The analyses of the resultant irons are given in Table I. Nodules and flake were chemically extracted from 2 kg samples of metal as described in the appendix. While this method dissolved the iron and chromium carbides, it did not dissolve the titanium, vanadium, and molybdenum carbides. These latter carbides could have been removed by nitric acid, but in other experiments it was found that it attacked pools of metallic iron entrapped in the nodules which had, until the nitric acid treatment, been protected from the attack of the sulphuric, hydrochloric, and hydrofluoric acids. It will be shown in the next section that entrapped iron exists in nodules but not in flake. On microscopic examination many tiny irregular particles were observed to accompany both the nodules and the flake. These were identified by tabling a sample of nodules from which a sufficient fraction was obtained for X-ray analysis. A good pattern of titanium carbide was obtained indicating that this was the predominant compound present. Since it was not possible to determine how completely the carbides could be removed mechanically and since their removal from flake is much more difficult, it was decided not to resort to any separation as this would render further comparisons more difficult. The samples were ashed in a combustion

Jan 1, 1953

By J. D. Edwards, C. S. Taylor, A. S. Russell

Solubilities and densities are reported for alumina hydrates in NaOH solutions under the conditions of the Bayer process employed to purify alumina for aluminum production. The equilibrium constants for reactions to form A102- accurately correlate the effects of NaOH concentration on the solubilities; the temperature coefficients of the equilibria lead to heats of solution of 7.34, 4.76, and 5.24 kcal for the a trihydrate, a monohydrate, and ß trihydrate, respectively. Moderate calcination does not change the solubility of the a trihydrate but increases that of the a monohydrate. At solution temperatures above 100°C, the trihydrates transform rapidly to a monohydrate. Hydro-thermally produced a monohydrate is the stable phase above 20°C. CORNERSTONE of the aluminum industry, the Bayer process for alumina production is based on the difference in solubility of hydrated alumina in NaOH solutions between 170" and 40°C. Solubilities and densities in this system were determined thirty years ago by M. Tosterudl under the direction of J. D. Edwards and C. S. Taylor. The solubility data, which still appear more concordant than those in the literature, are employed to sort out the complex equilibria in this system. The nomenclature for the alumina hydrates is that presented in The Aluminum Industry&apos; and more recently summarized in Alumina Properties.3 a trihydrate is the purified phase analogous to gibbsite, a monohydrate is similarly akin to boehmite, and ß trihydrate is sometimes known as bayerite. Literature Goudriaan4 reviewed the early literature on alumina in NaOH solutions and presented data on the solubility at 30°C of several forms. The gel precipitated from aluminum sulphate or chloride with ammonia and dried at 130" to 140°C had the highest solubility but was unstable, its solubility being cut to one-tenth on standing in NaOH. The solubility of the gel was decreased one-third on calcination at 300" to 400°C, while that of the gel transformed in NaOH at room temperature to a crystalline trihydrate was unchanged on calcination. The preparation produced by slow hydrolysis of sodium aluminate solution with CO, in the air gave solubilities in rough agreement with later values for a trihydrate. The solubility of this form was increased slightly by the calcination. Fricke and Jucaitis5 extended the work to 30" and 60°C with a trihydrate. They also gave solubilities for ß trihydrate (bayerite b), although the residue belonging to the left branch of the solubility curve corresponded to a trihydrate. The residues at high NaOH concentrations were mono and trisodium aluminates, the latter being 3Na2O . AL2O3 • 6H2O. Solubilities of a trihydrate at 95°C and of a monohydrate at 150" and 200 °C come from the work of Magarchak.6 a trihydrate transformed to a monohydrate above 95°C. A few measurements on the solubility at 25°C of an alumina trihydrate prepared by slow hydrolysis of NaAIO, solutions were presented by Sprauer and pearce.? Their analyses showed the monosodium aluminate to have the composition Na2O.Al2O3-2.5H2O.

Jan 1, 1956