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By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine (— 325-mesh) sand assaying 95.5 per cent SiO2, and a very he (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotation Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine fractioh was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1947

By Ronald C. Koo

THE effect of grain size on the mechanical properties of the bcc metals has been a subject of intensive theoretical and experimental study.'-l5 Quantitative relationships have been established experimentally between yield stress and grain size and between the ductile-brittle transition temperature and grain size in a number of metals.6"15 Much significance has therefore been attached theoretically to the grain size dependence. In all these experiments, different grain sizes were always achieved by annealing specimens at various temperatures. The implicit assumption was that any change in the dislocation substructure or in the distribution of impurities which might occur simultaneously with the production of various grain sizes had only a negligible effect on the mechanical properties. The validity of this assumption, however, is questionable. transformation in iron-nickel alloys is actually an extraneous phenomenon due to inadvertent compositional changes in the martensite if the heating rate is not sufficiently rapid. This complication can be avoided by up-quenching for the reversal treatment,5 and then the stabilization does not appear. Clearly, the lattice imperfections and strengthening produced by the reverse transformation are not responsible for the marked stabilization which has been observed by other investigators in these alloys. Data will be presented in this note to show that, at least in recrystallized tungsten of commercial purity, the difference in the ductile-brittle transition temperature of specimens annealed at various temperatures is more a result of a variation in the distribution of impurities rather than of the difference in grain size produced by the anneal. Ductile-brittle transition temperatures in tension were determined on powder-metallurgy tungsten specimens recrystallized at various temperatures. Tensile specimens having a gage length of 1.50 in. and gage diam of 0.18 in. were recrystallized at 1450°, 2000°, 2350°, 2550°, 2750°, or 2800" for 30 min in a vacuum furnace at a pressure of 1 x 10"5 mm of Hg and then tested at a constant extension rate of 8 x 10 per sec in an argon atmosphere from 100" to 800". Typical quantitative analyses of impurities are given in the Table. These results show that, within the precision of the analyses, see Table, annealing did not result in any detectable change in the impurity contents of the specimens, nor was there any detectable difference in purity between specimens having large differences in grain size annealed at the same temperatures . The results of the tensile tests yielded three distinct ductile-brittle transition curves approximately 225' apart. As shown in Fig. 1, data of specimens annealed at 1450°C and those of specimens annealed at 2000°C (O) fell on Curve A. Data of specimens annealed at 2350" and 2550°C fell on Curve B, and those of specimens annealed at 2750" and 2800°C fell on Curve C. The decrease in ductility with increase in annealing temperature became so pronounced that one third of the specimens annealed at 2750" and two thirds of the specimens

Jan 1, 1963

By M. J. Stewart, F. Weinberg

PREVIOUS investigations into convective flow in molten metals have examined systems in which the length-to-height ratio of the enclosure is large, usually using long graphite boats.''2 In normal castings this ratio is generally small and it is not possible to extrapolate the results of previous work to casting configurations. The present investigation was undertaken to examine liquid flow in systems of low length to height ratio. The apparatus used for the experiments is shown in Fig. 1. The molten zone of tin is contained in an aluminum mold of inside dimensions 6.4 by 6.4 by 0.31 cm. A heating block containing a resistance coil is attached to one end of the mold and a cooling block is attached to the other end. These are used to produce a wide range of temperature differences across the mold. The mold is contained in a stainless steel tank which is heated from the outside by resistance heaters to give the required operating temperature during the experiment. Temperature measurements in the molten tin are made with an iron-constantan thermocouple PT equal to 5 atm. The phase diagram derived by us was the same as that found by Krivsky and Schuhmann, except for a similar discrepancy in one boundary line representing the gas composition in equilibrium with SO a. The vapor pressures of the pure components can be neglected at 1700°K, 1 atm and 2500°K, 5 atm. There-fore, in these cases PT is essentially the total pres-sure in the system. This is valid for all the diagrams presented by Krivsky and Schuhmann except for the one at 2500°K and 0.01 atm, where the vapor pressure of silicon is comparable to PT.6 This work was supported in part by the American Iron and Steel Institute. 'C. E. Wicks and F. E. Block: Thermodynamic Properties of 65 Elements, U S. Bur Mines, Bull. No. 605, 1963. R. P. Elliott: Constitution of Binary Alloys, 1st supplementary, McGraw-Hill Book Co., New York, 1965. 3W. A. Krivsky and R. Schuhmann, Jr.: Trans. TMS-AIME, 1961, vol. 221, pp. 898-904. 4M. F. Ancey-Moret, M. Olette, and F. D. Richardson: Mem. Sci. Rev. Met., 1964, vol. 61, pp. 169-76. 5J . F. Elliott and M. Gleiser: Thermochemistry for Steelmaking, vol. 1. Addison-Wesley, Reading, Mass. 1960. 6 J.Drowart, G. De Maria, and M. G. Ingraham: J. Chem. Phys., 1958, vol. 29, p. 1015. probe of 0.4 mm diam inserted into the open top of the mold. Radioactive sn113, in the form of a small sphere, was gently lowered into the molten tin at point A in Fig. 1 THERMOCOUPLE> WATER ARGON END HEATER QUENCH ARGON Fig. 1—Apparatus for detecting liquid flow. Point A indicates position the tracer was introduced.

Jan 1, 1970

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine (— 325-mesh) sand assaying 95.5 per cent SiO2, and a very he (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotation Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine fractioh was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1947

By G. T. Higgins

PREVIOUS workers1,2 have found evidence of exaggerated grain growth or secondary recrystallization on annealing sponge zirconium at temperatures high in the a, phase field, but no details of the orientation relationship between the secondary grains and "as-recrystallized" matrix were reported. In other hexagonal metals, namely dilute Mg-A13 and Cd-zn4 alloys, secondary recrystallization has been observed in which the secondary grains are related to the primary recrystallized structure by rotations about the c axis. These rotations are thus comparable with the rotations about the (111) axis observed in the secondary recrystallization of fcc metals. In the current work secondary recrystallization has been observed on annealing iodide zirconium at 800°C and the associated changes in crystallographic texture have been examined. The material employed was arc-melted iodide zirconium of the following composition: Impurity O H Fe Hf Pb I Ni C1 A1 ppm by wt 130 5 230 98 23 28 200 39 30 This was received as 0.25-in. plate, and, prior to the annealing studies, was cold-rolled to 0.040 in. Specimens 1 in. sq were chemically polished and annealed for various times at 800°C in a vacuum better than 5x 10-6 Torr. For metallographic examination specimens were first chemically polished and then anodized8 to enhance contrast between the grains when examined under polarized light. Changes in crystallographic orientation associated with the development of secondary grains were followed by (1011) and (0002) pole-figure determinations using a conventional Schulz goniometer in reflection. Filtered Cr Ka radiation was employed and great care was taken to avoid spurious re- sults due to the close proximity of the Bragg angles for the (1011) and (0002) reflections. Figs. 1 and 2 illustrate the change in grain structure on annealing at 800°C. After 24 hr the structure has ceased to be equiaxed due to the development of certain grains in preference to others. It is notable that the secondary grains do not grow to the extent observed in sponge zirconium.1,2 This appears to be due in part to the fact that normal grain growth is inhibited in the less pure sponge zirconium, with the result that the driving force for secondary recrystallization remains high, while at the same time the number of grains able to develop in the presence of the impurities is also smaller. As a consequence, in sponge zirconium those grains that do develop preferentially are able to grow into the fine -grained matrix without impingement, while in iodide zirconium the preferential growth of many grains leads to early impingement. The pole figures determined for specimens annealed for 5 min and 24 hr at 800°C are illustrated respectively in Figs. 3 and 4. These indicate that the dominant feature of the initial recrystallized texture consists of basal planes at an angle of 321/2 deg to the sheet surface, with a (1120) axis lying parallel to the

Jan 1, 1967

By W. S. Pellini, F. N. Rhines

IN many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummer1 have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium 0f experimentation. New values obtained in this way are believed to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by R. S. Dean2 and by E. E. Schumacher and F. C. Nix.3 Their points are represented in Fig. I. In their work the solidus was not located at antimony concentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228°C.; J. E. Stead,7 247°C.; Campbell,8 228°C.; W. Gontermann,9 245° to 252°C.; R. Loebe,10 245°C.; E. Heyn and 0. Bauer,11 245°C.; H. Endo,12 250°C.; R. S. Dean,2 249° to 258°C.; E. Abel, 0. Redlich, and J. Adler,13 245°C.; W. Broniewski and L. Sliwowski,14 250° to 252°C.; H. Seltz and B. De Witt,4 250°C. A temperature of 249°C- appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 249°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1942

By John Riegle

To date. utility company underground storage of gas has generally been restricted to depleted dry gas fields. The Playa del Rey project is probably the first to successfully store gas in a partially depleted oil reservoir with the recovery of large volumes of pas at high rates as the main objective. Oil recovery has been a secondary consideration. Problems encountered unusual to those of storage in a dry gas zone were: (1) the removal and retardation of formation of emulsion. (2) the upstructure movement of fluid during withdrawal periods which formed fluid blocks, and (3) reservoir shrinkage resulting from encroachment of edgewater. The solution of these problems as outlined in the paper has resulted in increasing the withdrawal rate from the original design capacity of 4,000 Mcf per hour to the current 10.000 Mcf per hour. Additional increase is anticipated as the operations continue. Migration. reservoir performance. operational procedure and a historical record are included to make this a resume of the project from its war-time inception in 1942 to the first of 1952. INTRODUCTION The Playa del Rey underground gas storage project is probably the first project in which gas has been stored in a partially depleted oil reservoir, with the recovery of large volumes of gas at high rates as the main objective and the recovery of oil a secondary consideration. Problems unusual to those of storage in dry gas zones have made this a pioneer endeavor. The total storage capacity of approximately 1,500,000 Mcf of this reservoir is small in comparison with other underground gas storage projects. However. by study and experiment the deliverability into transmission lines. operating at pressures in excess of 150 lbs., has been nearly tripled in the past three years. to the current 10.000 Mcf per hour late, without the use of compression. It is anticipated this rate will gradually increase as additional fluid is removed from the formation. LOCATION AND HISTORY Playa del Key is located on Santa Monica Bay about two miles south of the beach commuity of Venice and 15 miles southwest of the renter of the City city Los Angeles. Fig. 1. The discovery well was completed at 6,194 ft in 1929. An upper zone at 3,905 ft was found on June 18. 1930. Townlot development was very rapid and by the end of 1930 there were 141 producing wells in the field. The Union Oil Co. completed a lower zone well south of the Townlot Field in May, 1931, which was believed to be an extension, until additional drilling of about 50 wells during 1934 and 1935 indicated this area to be a separate accumulation as shown on Fig. 2. The lower oil horizon, which is now the storage zone, had no original gas cap and is believed to be a continental detrital deposit of conglomerate that accumulated in valleys and depressions of a weathered schist high. which later subsided and was overlain by an impervious nodular shale. This type of formation has rapid variation of porosity. permeability and thickness due to lack of sorting action common to marine deposition. and the uneven surface of the original schist high. Production was limited on the upstructure sides by the pinching out of the conglomerate, and downstructure by edgewater. Unrestricted production, together with high permeabilities, led to large wastage of gas from this new area as facilities were not available for transport of gas to market. The decline was very rapid and by 1942 the portion of the new area south of Ballona Creek was nearly depleted. ACQUISITION OF PROPERTY The rapid increase in industrialization of Southern California during World war 11 forced upon the local gas com-

Jan 1, 1953

By J. B. Clemmer, F. D. DeVaney, H. A. Doerner

PRODUCTION of magnesium metal in the United States during the past decade has increased from less than 6oo,ooo lb. in 1928 to more than 4,800,000 lb. in 1938.1 The growing industry has stimulated interest in methods of production and in sources of raw material. All of the present domestic production is from brines. However, the availability of large tonnages of magnesite in the state of Washington, together with the possibility of cheap power, have created interest in the utilization of magnesite for the production of magnesium metal as well as for other purposes. Magnesite, the carbonate of magnesium (MgCO3), usually is associated with limestone (CaCO3) and dolomite (MgCO3CaCO3). It occurs in crystalline and microcrystalline (sometimes termed amorphous) forms.2 The more common crystalline mineral is found in various shades of white, gray, yellow and brown, the colors being due to impurities, chiefly iron. Magnesite has a hardness of 3.5 to 4.5 and a specific gravity of 3.0 to 3.1. It forms rhombohedral crystals in the hexagonal system, having a vitreous, pearly luster. The quarries and mines of the Northwest Magnesite Co. near Chewelah, Wash., are large producers of magnesite for refractories. The deposits are extensive, some veins being hundreds of feet wide. The boundaries of the veins are indefinite, and the magnesite is interfingered with dolomite. Calcite, talc, serpentine, quartz and shale are disseminated through the deposits. The quality of the ore cannot be determined by appearance or by simple tests; chemical analysis is required. These features make it difficult to determine the boundaries or total quantity of workable ore.3 Only the higher-grade ores are mined, and a considerable proportion of the magnesite content is discarded by hand-sorting and log-washing methods. After calcining, the sorted product meets the specifications for usual refractory material, as it contains approximately 81 per cent MgO, 7 per cent Si02, 6 per cent CaO and 6 per cent Fe203 + A1203. A sample of the reject material had the following analysis after calcining: 65.4 per cent MgO, 6.3 CaO, 21.1 Si02 and 6.5 R203. The percentage reported as R203 includes compounds whose chlorides are acid-soluble but give precipitates in ammoniacal solution that are ignited and weighed. The more common constituents are Fe203, A1203 and Ti02. The sorted magnesite product is not the best grade, even for refractory purposes, and leaves much to be desired for a reduction process. The rejected material contains a large proportion of magnesite. It is apparent that an effective concentration method would yield a higher recovery and a better product. In general, the refractory grade is not suitably pure for other uses. Recent developments in the production of

Jan 1, 1940

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine ( — 325-mesh) sand assaying 95.5 per cent SiO2, and a very fine (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotalion Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine frac- . tion was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1948

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine ( — 325-mesh) sand assaying 95.5 per cent SiO2, and a very fine (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotalion Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine frac- . tion was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1948

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By Cuppam Dasarathy

THE object of this note is to report briefly certain results of investigations on the Fe-In phase diagram. BISRA-high purity H-iron and 99.9 pct pure indium were used to prepare the alloys. The experimental techniques consisted of thermal analysis, optical metallography, and X-ray diffraction. A phase diagram based on the present results as well as those reported earlier by the author' is shown in Fig. 1. It is seen that the liquidus points fall on a smooth line which meets the monotectic isotherm at 1470°C. The liquidus extends up to 3.4 at. pct In. The phase boundary separating the two liquidus L1 and L2 is shown dotted. The experimental solidus meets the monotectic isotherm at -0.9 at. pct In. The 6/6 + L2 boundary drops steeply to the 6 + La/y + L2 boundary at -1350°C. In this region, it is impossible to detect satisfactory thermal arrests because of the steep phase boundary. The present diagram shows that indium lowers the temperature of the d/y transforma-tion and raises the temperature of the y/a transfor-mation. The y +d region is found to be very narrow. Indium gives rise to a restricted y field when alloyed with iron. The width of this field is between 0.4 and 0.5 at. pct In. Details of the alloys containing 40 and 50 at. pct In have already been reported by the author' and the transformation temperatures of these alloys are included in Fig. 1. It appeared from optical metallography and X-ray diffraction that the room temperature solubility of indium in a iron is less than 0.28 at. pct since alloys of 0.28 at. pct In and above, slow cooled to room temperature, contained dark etching second phase particles situated both in the matrix and grain boundaries of the a-grains, see Figs. 2 and 3. These particles were identified to be unalloyed indium by X-ray diffraction. The lattice parameter of the a phase reached a maximum of 2.8672A at the indium level of -0.28 at. pct. The present diagram, Fig. 1, is in substantial agreement with that of Stadelmaier and Fiedler' except for certain differences in detail. For example, they found the monotectic composition and temperature to be 7.0 at. pct In and 1443oC, respectively, while the present work indicates them to be 3.4 at. pct In and 1470°C. The 6 + L2/y + L2 transformation is indicated in the present work to occur at -1350°C, whereas Stadelmaier and Fiedler find this to occur at -1320°C. They also claim that the width of the y field is 0.2 at. pct In while the present work shows the width to be between 0.4 and 0.5 at. pct In. 1) Indium, when alloyed with iron, gives rise to a restricted y field, the width being >0.5 at. pct In.

Jan 1, 1970

By C. E. Webber

The economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro- carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,~ who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40' to zoo°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33' to r8oUF. and from 100 to 5000 lb. per sq. inch. Materials The absorber oil was a typical naturally occurring, Straw-colored distillate that had previously been steam-distilled to an initial boiling point of 300 F. The physical and chemical properties, including the results of an Engler distillation, are presented in Table I. A large volume of this oil was obtained and it was used throughout the complete set of experiments. Table i.—Properties of the Absorption Oil Gravity .......................... . . 32.5' A.P.1. Molecular weight by benzene freezing- point depression.................. 183 Viscosity, poises; at 100°F........... 0.0a80 At 200°F...................... 0.0102 Composition, PeR Cent Aromatics........ 24.0 Naphthenes..... 36.7 unsaturates,Aromatics...... .I24.00.3 1 Parafins Naphthenes.....36.7 39.o EngLeR Distillation Per Cent /ncg. F. Per Cent Dez. P. Initial boilins rmint.. 300 I 60....... 523 5.................. 402 I 70....... 538 10.................. 421 180....... 557 20.................. 462 90....... 570 30.................. 480 1 95....... 623 40.................. 49 .................1 511 Residue, z .o per cent; loss, 0.3 per cent. See refrence I. The n-hexane was obtained from the Ohio Chemical and Manufacturing Co., Cleveland, Ohio. This liquid had a boiling range of from 149" to 152.6'F., with a density of 0.667 at 60°F. and a molecular weight of 85 by benzene freezing-point depression. The propane, isobutane, wbu-tane, isopentane and n-pentane were ob-ta,ined from the Philgas Department of the Phillips Petroleum Co. Certified analyses of these compounds showed their purity to be in excess of 99.5 per cent and they were riot further purified.

Jan 1, 1941

By C. E. Webber

The economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro- carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,~ who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40' to zoo°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33' to r8oUF. and from 100 to 5000 lb. per sq. inch. Materials The absorber oil was a typical naturally occurring, Straw-colored distillate that had previously been steam-distilled to an initial boiling point of 300 F. The physical and chemical properties, including the results of an Engler distillation, are presented in Table I. A large volume of this oil was obtained and it was used throughout the complete set of experiments. Table i.—Properties of the Absorption Oil Gravity .......................... . . 32.5' A.P.1. Molecular weight by benzene freezing- point depression.................. 183 Viscosity, poises; at 100°F........... 0.0a80 At 200°F...................... 0.0102 Composition, PeR Cent Aromatics........ 24.0 Naphthenes..... 36.7 unsaturates,Aromatics...... .I24.00.3 1 Parafins Naphthenes.....36.7 39.o EngLeR Distillation Per Cent /ncg. F. Per Cent Dez. P. Initial boilins rmint.. 300 I 60....... 523 5.................. 402 I 70....... 538 10.................. 421 180....... 557 20.................. 462 90....... 570 30.................. 480 1 95....... 623 40.................. 49 .................1 511 Residue, z .o per cent; loss, 0.3 per cent. See refrence I. The n-hexane was obtained from the Ohio Chemical and Manufacturing Co., Cleveland, Ohio. This liquid had a boiling range of from 149" to 152.6'F., with a density of 0.667 at 60°F. and a molecular weight of 85 by benzene freezing-point depression. The propane, isobutane, wbu-tane, isopentane and n-pentane were ob-ta,ined from the Philgas Department of the Phillips Petroleum Co. Certified analyses of these compounds showed their purity to be in excess of 99.5 per cent and they were riot further purified.

Jan 1, 1941

By E. D. Hummer

During the planning of the fine coal cleaning addition at the Gary, W. Va., Coal Preparation Plant of United States Steel Corp. careful consideration was directed toward the problem of minus 48 mesh refuse disposal. The plant flow sheet included wet screening the raw coal at ¼ in., pumping the minus ¼ in. raw coal to bowl desiltors for desliming, and then cleaning the deslimed raw coal on tables. The material to be removed from the circuit as minus 48 mesh refuse consisted of the minus 100 mesh desiltor overflow thickened in two 120 ft diam thickeners and minus 1 mm screened from the table refuse. Later a flotation plant was added to recover coal from the desiltor overflow, and a classifier replaced the screens to make a sharper size separation of the table refuse at 48 mesh. Today the minus 48 mesh refuse at Gary consists of thickened flotation tailing and thickened spiral classifier overflow. The transportation of large quantities of fine, wet refuse filter cake mixed with jig and table refuse over existing conveying equipment would have been neither dependable nor economical. Filtration was therefore impractical, and disposal of the fine materials was a problem. The decision was to pump the material to storage ponds.

Jan 3, 1965

By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By M. K. Yen

The distortion of crystal structures referred to as "biege gleitung",1 "local curvature"2-4 and "deformation bands"5,6 is believed to be an unavoidable characteristic of deformed single crystals. The presence of asterism on Laue photograms of Al single crystals either deformed by pure shear7 or extended in a condition relatively free from the grip effect2 indicates strong evidence substantiating this point of view. The type of localized bending described in connection with the bending test of Al single crystals by Yen and Hibbard8 could conceivably exist either microscopically or submicroscopically in all types of deformation. The purpose of this note is to extend this idea to the postulate of a hypothetical "microbending site," as applied to the mechanism of slip in a general sense. The mosiac structure, as postulated by Darwin,9 is that crystals were actually composed of small blocks which have a linear dimension 10—4to 10-6 cm on the edge and deviate from each other by an angle of about one-tenth of a degree. The following discussion is based on the assumption that when slip is propagated from one mosaic block to the adjacent one, bending of the lattice at the region of their boundary is produced in order to maintain the continuity of the gliding process along a certain slip plane. Consider a two-dimensional diagram of two ideal mosiac blocks on the cross-section perpendicular to the slip plane and containing the active direction of slip. When an external force is applied, the localized bending or "microbending site," would be generated at the region as illustrated in Fig 1A at point B. A schematic diagram of a "microbending site," generated at a mosaic boundary, is illustrated in Fig IB. It may be seen that once the curvature of the bending site reaches sufficient magnitude, the interaction force encountered by pairs of atoms symmetrical with respect to the center of the bending is equal but opposite in sign. Consequently, the overall energy required to displace the atoms near the center is approximately zero.10"12 Based upon the finding that the misalignment between two mosaics is 0.1 degree,9 the assumption is made that "microbending sites" may possibly exist in the region where one plane will have one more row of atoms than an adjacent plane. It is probable that the origin of the bending site will be where the distance between two mosaic boundaries is "2d" as shown in Fig 1A at point B, where " d" is the interatomic distance. Thus, the distance between two "microbending sites" is in the range of about 600 interplanar spacings. In the case of aluminum, the spacing between two octahedral planes is about 2.33 A. The distance between two bending sites will be approximately 2.5 X 10"5 cm. It is interesting to note that according to Woods13 these values approach closely the size of the domains of a cold-worked metal whose minimum

Jan 1, 1950

By R. A. Stauffer

THE chief ore of lithium is spodumene, a lithium-aluminum silicate containing up to 3 pct lithium. The preparation of lithium salts from spodumene is costly because of the low concentration of the metal and the difficulty of separating it from the other alkali metals present. Dr. Kroll's and Dr. Schlecten's recent paper' has reviewed various methods proposed for preparation of lithium. It will be seen from this paper that the methods proposed to date have required one or another of the lithium salts as a raw material. The high cost of these salts has been the chief item of expense in the lithium metal produced. This situation has made it interesting to investigate the possibility of producing the metal directly from spodumene. When spodumene is calcined at 1000°C in the presence of lime, lithium oxide is replaced in the ore as is evidenced by the fact that it may be leached from the reaction mixture with water.2 Free energy calculations suggested that lithium oxide might be reduced with aluminum or silicon and the lithium produced distilled from the reaction mixture by heating to about 1000°C in a vacuum. These facts taken together suggested that it might be possible to prepare lithium metal directly from spodumene by heating a mixture of the ore, lime, and a suitable reducing agent in vacuum and distilling off the lithium metal as formed. THE REPLACEMENT OF Li20 IN SPODUMENE A series of experiments were undertaken to determine the ratio of lime to spodumene necessary to free substantially all the lithium oxide present in the ore. The spodumene used in these experiments was supplied by Foote Mineral Co. in the form of powder of about 200 mesh. Analysis of the spodumene was as follows: [ ] Lime (cp -200 mesh) was added in various ratios to spodumene and thoroughly mixed in a ball mill. Two hundred gram samples of spodumene-lime mixtures were charged loosely in fireclay crucibles and held at 1000°C in a gas-fired furnace for 5 hrs. The product in each case was ground to pass 140 mesh and then placed in a thimble in a soxhlet extractor. Extraction with water was carried on for 6 hrs. After this period the extract was reduced in volume by evaporation in order to precipitate dissolved lime and was then filtered and titrated with 1/4 normal hydrochloric acid. After correcting for residual calcium oxide in solution, the alkali present was calculated as lithium oxide. The results of these experiments are shown in Table I and Fig I. At lime-spodumene ratios less than 1.5, the products were invariably fused. At the ratio of 1.5 and above, the product was loosely sintered with little evidence of fusion. When the ratio of lime to spodumene was three, replacement of alkali oxides in the

Jan 1, 1947

Using 5-p Ni powder and 0.018 ,u A1203, oxide dispersion strengthened nickel alloys were prepared by mechanical mixing of powders, followed by compaction, sintering and extrusion. Processing variables such as cooling of the powder during mixing, electrostatic discharging, mixing time, amount of oxide, and so forth, were studied to determine the effects on room-temperature tensile and high-temperature creep-rupture properties and on the reproducibility of alloys. MECHANICAL mixing of metal and metal oxide powders provides one of the simplest and most inexpensive methods for preparing dispersion strengthened metal-metal oxide alloys;" however, because of large differences in specific gravity, powder particle diameters and other variables, difficulties have been encountered in reproducing alloys and alloy properties. Using 5-p Ni powder and 0.018 p A1203, the following variables were investigated: a) Blending techniques b) Blending time c) Volume fraction of oxide for the selected pow- ders d) Sintering of compacts before extrusion Cooling of Powders During Blending— Cremens and Grant had indicated that dry ball milling of the powder mixture gave superior results over other procedures. When ultra-fine metal and oxide powders became available and comminution was unnecessary or offered little gain, the use of dry mixing in a Waring Blendor gave optimum results.' In the current study, observations of the powder mixtures indicated that considerable heat was generated due to the high speed of the Waring Blendor (15,000 rpm). This heating appeared to produce some degree of clustering and pelletizing. To minimize such agglomeration, a Pyrex cooling coil was installed in the mixing vessel. A double coil, water cooled, proved to be quite satisfactory, providing a fair degree of cooling along with good erosion resistance. Discharge of Electrostatic Charge—Electron-microscopy showed that agglomeration was minimized by the cooling procedure but was not entirely eliminated. It appeared that some of the ag- glomeration had to be explained on the basis of an electrostatic attraction due to the high-speed blending operation. These charges had the effect of promoting the growth of alumina clusters. At the end of the blending procedure such clusters had an effective size which was as much as 50 times that of the individual powder particles and were very tightly bunched. Several methods were utilized to try to discharge the electrostatic forces to minimize the clustering. One successful method, utilized in alloy 17, involved continuous exposure during blending to a radium source of 50 millicuries at a distance of 1.5 ft from the container. A number of other methods were noted to work equally well. Fig. 1 shows the more open oxide structure which results from such a treatment, permitting the matrix metal to penetrate into the cluster more effectively. The combination of powder cooling and discharging led to noticeably improved structures. Fig. 2 shows a cross and a longitudinal section in alloy M-17, one of the best alloys, illustrating the marked decrease

Jan 1, 1961

The amount of coal used in the Colonies before the Revolutionary War was very small, and few records of it can be found, these all being in the Public Records Office in London. The exports and imports for the years 1768 to 1772, inclusive, are shown in Table 3, which apparently do not include the early shipments from the Virginia field. For the three years 1769 to 1771, the imports from Great Britain-their only source-totalled 17,943 tons, or an average of 5,981 tons per year. If the shipments from Richmond for the same period were available, this average would probably not exceed 6,800 tons per year. In Table 4 the shipments of coal from the James River ports for the period 1758 to 1769 are shown. A few of them are re-exports of coal brought from England, but the great majority are undoubtedly of coal produced in Virginia, and the movement was partly to West Indian ports but mainly to Atlantic ports from Baltimore to Portsmouth, N. H. (Piscataway). In Table 5 the data in Tables 3 and 4 are combined, the exports being deducted, and this summarizes all the available data on the amount of coal consumed in the Colonies before the separation from England. As has already been stated there has been a tremendous amount of work done in the Richmond field over a long period of time, many mines were opened and in some cases operated for years, and practically no accurate data remain or have been published to show what was done. There are undoubtedly manuscripts still remaining that will contribute to much of the knowledge of this field, and it is well worth the while of the proper state authorities to collect all the information that can be found anywhere, to enable the future development of these coal deposits to benefit by the record of what was done in the past. Table 22 shows all the methods of shipment from this field, and all of the data available about tonnages moved over each of them. The shipments by the Chesterfield and Clover Hill Railroads are largely duplicated in some of the other columns, but allowance has been made for this in the estimated totals. In addition to the difficulties experienced with similar data for the other states, these Virginia records have one peculiarly their own; it was the custom to allow 5 pecks to the bushel of coal at the pit and only 4 pecks at the docks or at vessel side. In most of the figures it is not stated to which point they apply, and a considerable error may exist due to this cause, although certainly it does not apply to all of them. The notes show the sources of the figures used, and while it is probable that the totals are lower than the actual amounts produced, the data given are the most complete that can now be assembled.

Jan 1, 1942