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By T. L. MacKay

Oxidation rates of single-crystal and poly crystalline zirconium in oxygen at temperatures from 307° to 815°C obey the parabolic rate law for short ex-posure time, 4 to 6 hr. The activation energy for the oxidation of single-crystal zirconium between 420° and 790°C is 42.6 ± 0.7 kcal per mole, and in the temperature range 307" to 600°C the activation energy for oxidation of poly crystalline zirconium is approximately the same. The high-activation energy is indicative that diffusion through the bulk oxide film is the primary mode of mass transport for both types of metal. The higher oxidation rates for poly -crystalline zirconium in this temperature range were attributed to differences in the orientation of the grains in the metal with respect to the oxidizing surfaces. Above 600°C, vain growth was observed in polycrystalline zirconium, and the oxidation rates approached those of single-crystal zirconium. ThE kinetic data of previous oxidation studies1-' of zirconium in oxygen have been interpreted by both parabolic and cubic rate laws. There is some evidence that there is a transition from the parabolic to the cubic rate law at prolonged exposures, but the question is still controversial. For the parabolic rate law activation energies are reported in the range 18.6 to 35 kcal per mole, and for the cubic rate law in the range 38 to 47 kcal per mole. So far as the mechanism of zirconium oxidation is concerned, inert marker studies10,11 have indicated that the oxidation proceeds by oxygen (anion) diffusion through the oxide film toward the metal-metal oxide interface. Pemslerl2 observed that the orientation of the grains in the zirconium metal substrate affected the rate of formation of the oxide film on the surfaces of the grains and that the orientation dependence of the corrosion rate persisted beyond the initial stages of reaction. The rate of oxidation was a minimum when the c axis of the grain was parallel to the surface of the sample, and rose to a maximum when the c axis was inclined at about 20 deg to the plane of sample surface, and decreased again at higher inclinations. cox13 observed that in 300°C steam a thin oxide film was formed initially on zirconium and that this oxide film, which exhibited interference colors, became dark first along the grain boundaries and then over the whole surface in an inhomogeneous manner as the film thickened. Cox proposed a mechanism in which oxygen diffused along preferred paths created by grain boundaries in the metal and formed a much thicker film at or near the grain boundary than on the central zone of the grain. In the present study, the oxidation rates of single crystals of zirconium were measured in oxygen and compared with the oxidation rates of polycrystalline zirconium of the same bar stock. It was felt that such a comparison would elucidate the role of grain boundaries in the metal substrate. SAMPLE PREPARATION Single crystals of zirconium were prepared by following the procedure of I3apperport,14 starting with 1/4-in. rod purchased as crystal-bar zirconium. Zirconium rods 2 in. long were wrapped in tungsten foil and sealed in quartz tubes at pressures of less than 10-6 mm of mercury. Large single crystals were grown by thermal cycling above and below the a-/3 transformation temperature, 862°C. Several specimens were simultaneously subjected to the same cycling procedure, heating to 1200°C, holding for 4 hr, then cooling in the furnace and holding at a temperature of 840°C for 5 to 10 days. This cycle was repeated five or six times for each set of specimens. The grain size of the crystal-bar zirconium before thermal cycling was between 10 and 30 p. Fig. 1 shows the microstructure of an end section of as-received crystal-bar zirconium. A longitudinal section of each zirconium rod after thermal cycling was polished and examined under polarized light, see Fig. 2, and the largest single crystals were selected for this study. Zirconium rods 1/8 in. in diameter and 1/2 in. long with spherical ends were machined from the single crystals and from the as-received bar stock. An X-ray examination showed that the c axis of the single crystals made either a 34-deg or an 89-deg angle with the rod axis. The specimens were chemically etched for 2 min in solution consisting of 15 parts hydrofluoric acid (48 pct), 80 parts nitric acid, and 80 parts water. The chemical polish removed 1 to 2 mils from the surface. EXPERIMENTAL The Sartorius vacuum microbalance used in this study has a sensitivity of 0.5 pg and a capacity of

Jan 1, 1963

By Brian F. Dyson

The surface tensions at 1550°C of some Fe-S alloys (in the range 0.008 to 0.052 wt pct S), Fe-Sn alloys (0.31 to 48.4 wt pct Sn), Fe-P alloys (0.038 to 2.38 wt pct P), Fe-Cu alloys (2.15 to 22.8 wt pct Cu), and Fe-1 pct C-S alloys (0.005 to 0.076 wt pct S) along with the surface tension of the base iron have been measured by the sessile-drop method. A mean value of 1754 dynes per cm was found for the surface tension of the base iron. Sulfur was found to be highly surface-active, the surface-tension results being in quantitative agreement with existing data. Tin and copper were found to be less surface-active than sulfur while phosphoms was completely nonsurface-active. The surface tensions of Fe-1 pct C-S alloys were found to be lower than those of the Fe-S alloys containing the same sulfur content. This was shown to be a mmzifestation of the increase in the thermodynamic activity of suZfur by carbon. It is only in recent years that attempts have been made to measure the surface tension of liquid iron of known high purity.1-3 Earlier measurements4-7 were made on liquid iron containing variable amounts of what are now known to be surface -active solutes. The exact value of the surface tension of liquid iron is still, however, open to some doubt. Halden and Kingery' reported a value of 1720k 34 dynes per cm at 1570°C, Kozakevitch and Urbain8 gave 1790k 25 dynes per cm at 1550°C, while Van-Tszin-Tan et al. obtained a value of 1865k 37 dynes per cm at 1550°C. The first systematic investigation into the effect of controlled solute additions on the surface tension of iron was made by Halden and Kingery.' They showed that sulfur and oxygen were highly surface-active, whereas nitrogen was only slightly active, and carbon inactive. A subsequent investigation by Kingery indicated that two other group-6B elements, selenium and tellurium, were also surface-active. This highly surface-active nature of sulfur and oxygen has recently been substantiated by Kozakevitch and Urbainla and Van-Tszin-Tan et al. l1 Kozakevitch and Urbainl2 have also conducted an experimental survey of the effects of a number of metals on the surface tension of liquid iron. Their surface-active nature was, in all cases, less than that of the group 6B elements. The present investigation was undertaken to study in more detail the surface tensions of dilute Fe-S alloys and to measure the surface tensions of binary alloys of iron containing phosphorus, copper, and tin. The effect of sulfur additions on the surface tension of Fe-1 pct C alloys was also determined. EXPERIMENTAL PROCEDURE The sessile-drop method was employed in the present investigation. An apparatus was built similar in principle to that described by Humenik and Kingery.lS It consisted of a horizontal silica tube, which could be evacuated to pressures less than 10-5 torr, with its central portion surrounded by a water jacket within which was a high-frequency coil. This generated heat in a tantalum susceptor placed inside the silica tube, which in turn radiated heat to the specimen mounted on a recrystallized alumina plaque. Temperatures were measured by an optical pyrometer and photographs of the molten drop were taken on a fixed-focus plate camera giving a magnification of X2. Surface-tension values were determined from the resultant drop using the method described by Baes and Kellogg.l4 The high vapor pressure of molten iron made it necessary to conduct all the experiments under a 1/4 atm of argon (greater than 99.995 pct purity). The analysis of the base iron used in the investigation is given in Table I. Each sample was approximately 3 g in weight and had a hemispherical base to ensure a uniform advancing contact angle on melting. The iron alloys were prepared individually in the sessile-drop apparatus by drilling a hole in the top of each sample and adding the required amount of solute, the drops being analyzed after the experiment. This method of preparation had the advantage of ensuring a consistent minimal contamination by oxygen due to refractory attack and also allowed surface tension to be measured at the same time. Every precaution was taken to ensure that the specimen was not contaminated by grease when it was introduced into the apparatus, the samples being cleaned in acid, dried in alcohol, and rinsed in petroleum ether. All handling was done with tweezers. Once the specimen had been placed inside the susceptor, the furnace was evacuated and the Sample leveled. The furnace was then degassed at approximately 1000"C before the argon was introduced. In every case the surface tension was determined at 1550" C.

Jan 1, 1963

By G. E. Johnson

LEAD SMELTERS AND REFINERS in 1932 were confronted with the problem of adjusting operations and costs to curtailed production and consumption at reduced prices, a problem which has been partially solved at least by improvements in operating technique and increased efficiency. At the Mount Isa properties in Australia, a third blast furnace and additional Dwight-Lloyd sintering machines were installed during the year, designed to increase the production to 6,000 tons of bullion per month. The large proportion of lead carbonate in the ores to be treated has presented metallurgical problems. Of the total lead contained in the concentrates to be smelted, two-thirds is Dresent as carbonates and one-third as sulfides. In the iiitial operations, the resulting Dwight-Lloyd sinter was soft, contained an excessive amount of fines, and was easily fusible. When charged to the blast furnaces it developed accretions in the upper part of the furnace owing to the easily fusible lead carbonates softening and fusing at the top of the charge column. This was remedied by the addition to the sinter feed of diluents of higher melting point, granulated slag and crushed limestone. The sinter feed consists of concentrates, Cottrell dust and wind-box cleanings, totalling 57 per cent of the charge; return sinter fines 15 per cent; granulated slag 23 per cent; and crushed limestone 5 per cent. The sinter produced contains 34 per cent lead and 0.5 per cent sulfur. Experiments indicated that double sintering under these conditions was of no advantage, so the original plan of single sinter treatment was retained.

Jan 1, 1933

By Thomas R. Smith

This paper covers oil shale resources in those countries that border the Pacific Rim. The major known resources around the Pacific Rim occur in the Western United States, Australia, the People's Republic of China, (PRC) and the Thailand/Burma region. The location of these deposits is shown in Figure 1. In 1965, the U.S. Geological Survey estimated world oil shale deposits of over 4 quadrillion tons having a potential oil yield of over 2 quadrillion barrels. If all this were extracted, it could meet the world's entire energy needs far into the future. However, the Survey also estimated the spent shale waste could cover all of the surface of the world to a depth of about 10 feet. Thus, for this and many other technical and economic reasons, it does not appear to be feasible to develop a large portion of the world's oil shale resources in this century; nor will shale in itself solve our energy problems. Nevertheless, shale oil and other ' synthetic fuels are expected to play an important role in new energy supplies in the longer term. WHAT IS OIL SHALE OR SHALE OIL? The term "oil shale" is sometimes a misnomer, in that the rock is often more of a limestone or siltstone than a shale. The common link between resources termed “oil shale" is that they all contain an insoluble substance cal led kerogen (which is from the Greek words for waxmaking). Kerogen is a form of organic carbon derived from a variety of plants ranging from algae to higher plants. When heated sufficiently, the kerogen generates hydrocarbons called shale oil, a form of synthetic crude oil that in most cases is lower in hydrogen content than conventional crude oil. The amount of oil in oil shale is relatively small --roughly 10 percent (by weight) in the richer shales. To upgrade this synthetic oil to usable products, additional processing is necessary. This brief sketch gives an idea of what this different, but significant, form of hydrocarbon is like. ENVIRONMENTS OF DEPOSITION Most oil shale deposits fall into three environments of sediment deposition: 1ake (called lacustrine), sea (marine) and river (fluvial-deltaic). In each case, the deposition of oil shales took place in quiet water environments where plant life, particularly algal plants, could flourish and, after dying, be deposited in unoxygenated water where the kerogen precursors would be safe from destruction by oxidation. The oil shales that were deposited in large lake basins (lacustrine) have attracted the most attention for development over the years. They often have multiple seams, deposited in a cyclic nature with extensive areal distribution and rapid vertical changes in kerogen content. Grades are moderate to high, ranging from 80 to 200 liters per tonne. Rundle in Australia and the Piceance Creek Basin in Colorado are examples of this type. Both deposits represent large volumes of oil shale in small areas which could provide the large volume of feedstock needed for future commercial operations. The stratigraphic sections of these two deposits feature thick oil shale seams with average grades of 80 - 125 liters/tonne conducive to both open pit, and underground operations. However, the rock strength of the Rundle shale is not sufficient to - support underground mining. On the other hand, the Colorado deposits, being more carbonate in nature, are sufficiently strong to support either type of mining depending on the overburden to ore ratio. These latter types of deposits will likely provide the first target for development of a commercial industry. The marine type is characterized by extensive areal distribution with relatively thin seams. The grades are generally low to moderate, ranging from 50 to 120 liters per tonne. The marine oil shales are common worldwide, and their attractiveness for mining is dependent on the overburden to ore ratio. Because of their widespread areal distribution, their in situ resources can be quite large. The Toolebuc Formation in Central , Queensland, Australia is a good example of this type of deposit being 7-10 meters thick over an extensive area. The Julia Creek deposit with its favorable overburden-to-ore ratio is being studied for possible development. In a fluvial-deltaic environment, there are many small lakes or bogs associated with rivers in which a very pure type of oil shale called torbanite could form. Torbanites are very high grade containing up to 75 percent hydrocarbons. The known occurrences are generally small lenticular deposits associated with coal seams. Even with the high grades, it is not likely that any of the known deposits would warrant commercial development because of their small size. The torbanite deposits in New South Wales, Australia were processed prior to World War I1 near the town of Glen Davis. However, today's known resources of this type are not large enough to warrant a commercial plant.

Jan 1, 1982

By R. M. Waterstrat, E. C. van Reuth

BINARY- alloy phases having the A15-type crystal structure have been described as occurring at a simple and more or less invariant stoichiometric composition (A3B) which corresponds to the relative number of atoms occupying each of the two crystallographi lattice sites in this structure.1,2 It is frequently assumed, therefore, that each crystallographic site is occupied exclusively by one kind of atom. In most cases, however, there have been insufficient experimental data to establish whether atomic ordering is, in fact, complete. Recent studies have shown that binary A15-type phases are sometimes stable over an appreciable composition range3''* and, occasionally, the composition range of stability does not even include the "ideal" A3B stoichiometric composition.5-7 We have observed the existence of nonstoichiometric A15-type phases in the binary systems Cr-Pt and Cr-Os. This has not been reported in previous work on these alloy systems.1,8-11 A series of alloys, each weighing approximately 30 g, was prepared by are-melting in an Ar-He atmosphere using 99.999 pct Cr, 99.999 pct Os, and 99.99 pct Pt as starting materials. Each alloy was melted four times with a total weight loss of less than 1 pct. The stoichiometric (A3B) alloys were sealed in evacuated quartz tubes and annealed at 1200°C for periods of time ranging from 3 days to 2 months. Examination of the alloy microstructures revealed that little change had occurred over this time interval and it was therefore assumed that the microstructures were fairly representative of equilibrium conditions. No evidence of contamination was observed although there was apparently some loss of chromium which was confined to a thin layer at the surface of the specimens. The quartz tubes were quenched from the annealing temperature into cold water. X-ray diffraction and metallographic examination of the stoichiometric alloys revealed an estimated 10 to 30 pct of second phases which were tentatively identified as phases previously reported in these binary-alloy systems.8-11 A second series of alloys was prepared by mixing -325 mesh metal powders having a nominal purity of 99.9 pct and compressing these mixed powders in a cylindrical die at a pressure of 43,000 psi. These alloys, each weighing 15 g, and some of the arc-melted alloys were annealed in a high-temperature vacuum furnace heated by tantalum strips at a pressure of 10-8 Torr and were rapidly cooled by turning off the furnace power. X-ray and metallographic examination of both series of alloys served to establish the composition ranges of the A15-type phases. Although some chromium losses occurred during the vacuum annealing, they were largely confined to a thin layer on the outer surfaces of the samples. It was established that the A15 phases occur in the Cr-Pt system at 21 ± 1 at. pct Pt after 1 week at 1200°C and in the Cr-Os system at 28 ± 1 at. pctOs after 1 day at 1400°C (see Table I). We also observed that an arc-melted stoichiometric (A3B) alloy in the Cr-Ir system was single-phase (A15-type) in the "as-cast" condition in agreement with previous work.8,13 In addition we obtained a sample of the Cr-Os A15-type phase from Argonne National Laboratory. This alloy contained less than 1 pct second phase12 and was submitted to a density measurement. The density measurement yielded a value of 11.14 g per cu cm in comparison to a theoretical value of 11.25 g per cu cm calculated using the observed lattice constant (4.6806Å) of this alloy. The uncertainty in measurement was 0.1 pct but the sample may have contained some cracks or minor imperfections which could account for the low experimental value. We have also studied the atomic ordering in these phases by means of integrated line intensity measurements using thick, flat, rotating powder samples and CuK a radiation in an X-ray diffractometer. We have obtained order parameters of 0.90 for the Cr-Pt phase, 0.89 for the Cr-Ir phase, and 0.64 for the Cr-Os phase using the formula: where s is the usual Bragg and Williams order parameter, ra is the fraction of chromium atoms in A sites, and FA is the fraction of chromium atoms in the alloy. The values obtained are estimated to be accurate within ±4 pct. If the unusually small value for the order parameter of the Cr-Os A15 phase were due to the existence of lattice vacancies on the "B-atom" sites, then a density of 10.04 g per cu cm would be expected in contrast to the observed value of 11.14 g per cu cm. We, therefore. conclude that the fraction of lattice vacan-

Jan 1, 1967

By M. O. Abo-el Fotoh, J. B. Mitchell, J. E. Dorn

The effect of strain rate and temperature on the tensile flow stress of a polycrystalline bcc alloy of magnesium containing 14 wt pct Li and 1.5 wt pct Al was investigated for strain rates of 3.13 x lom5 to 3.13 x 10-3 per sec over the range from 20° to 300°K. From about 180° to 300°K the alloy exhibited an ather-ma1 deformation behavior where the flow stress was independent of strain rate and increased only slightly with decreasing temperature. At lower temperatures the flow stress was strongly strain-rate- and temperature-dependent, characteristic of deformations controlled by thermally activated mechmzisms. The activation volume for thermally activated plastic defornzation was between 5 and 30 cu Burgers vectors, independent of plastic strain. This low-temperature thermally activated deformation behavior was found lo be in satisfactory agreement with the theoretical dictates of the Dorn-Rajnak1 formulation of the Peierls mechanism where deformation is controlled by the rate of nucleation of pairs of dislocation kinks over the Peierls energy barriers. SEVERAL studies of the low-temperature thermally activated deformation of bcc metals and alloys (molybdenum,1 tantalum,1 Fe-2 pct Mn,2 Fe-11 pct MO,3 and AgMg4) have revealed that the strain rate is controlled by the activation of dislocations over the Peierls-Nabarro energy hills. Although there is some uncertainty as to the nature and effect of solute atom-dislocation interactions during low-temperature deformation of bcc metals, it has been concluded by Dorn and Rajnak,1 Conrad,1 and Christian and Masters6 among others that overcoming the Peierls-Nabarro stress which arises from the variations in bond energies of atoms in the dislocation core as it is displaced is the probable mechanism controlling low-temperature deformation. The purpose of this research was to investigate the low-temperature plastic deformation of the bcc alloy Mg-14 wt pct Li-1.5 wt pct A1 to determine if the behavior of this alkali metal alloy might be analogous to that for other bcc metals. This alloy was selected because of its availability and its current industrial importance as a lightweight material for aircraft and aerospace applications. I) EXPERIMENTAL PROCEDURE Polycrystalline tensile specimens having cylindrical gage sections 2 in. long by 0.2 in. in diam were machined from as-received alloy sheet stock of Mg-14 wt pct Li-1.5 wt pct Al. Specimens were annealed in an argon atmosphere at 423°K for 4 hr and maintained in a kerosene bath together with the sheet stock to prevent corrosion. The resulting specimen microstructure consisted of a coarse uniform dispersion of incoherent precipitate MgLi2Al particles7 in a bcc 0 phase matrix having an average grain size of 150 p. Prior to testing the specimens were chemically polished in dilute hydrochloric acid. Comparison of tensile properties and microstructures of specimens cut from center and edge sections of the sheet stock revealed no effects of inhomogeneities in the sheet material. Tensile tests were performed on an Instron machine at crosshead speeds corresponding to tensile strain rates of 1.56 x 10-5 and 1.56 x 10"3 per sec. Stresses were determined to ±2 x 106 dynes per sq cm and strains to within ±0.0001. Average values of shear stress t and shear strain y reported were taken as one half the tensile stress and three halves the tensile strain, respectively. Flow stresses were taken at 0.05 pct strain offset. Test temperatures down to 77°K were obtained by immersing the specimens in constant-temperature baths. Lower-temperature tests were performed in a liquid helium cryostat to within ±2°K of the reported values. Prior to testing at the various temperatures and strain rates all specimens were prestrained at 2 35°K at a shear strain rate of 3.13 x 10-5 per sec to a stress level of 0.606 x 10' dynes per sq cm to obtain a uniform initial state. Additional tests were made to determine the effect of changes in strain rate and strain on the flow stress by rapidly changing the crosshead motion during testing. Shear moduli of elasticity, needed for analyses of the data, were obtained at several temperatures by a common technique of determining the resonant frequencies of vibrations of rectangular test specimens. 11) EXPERIMENTAL RESULTS Fig. 1 shows the experimentally determined flow stress vs temperature for two strain rates. Two distinct regions of behavior are evident. Below about 180°K the strong increase in flow stress with increased strain rate and decreasing temperature indicates that deformation is controlled by a thermally activated dislocation mechanism. At higher temperatures an athermal region is evident where the flow stress is independent of strain rate and only slightly dependent on temperature. The applied stress t to cause plastic flow was separated into two components:

Jan 1, 1969

By H. B. Pulsifer

ABOUT 15 varieties, or modifications, of the best magnesium available were prepared and subjected to etching tests, then examined for microstructure. Of the 30-odd etching reagents that were tried, nearly half, mostly ammonium salts, etched the metal satisfactorily. The surfacing and etching of magnesium is shown to be a very simple and quick operation. The density and hardness of magnesium were determined. The most interesting new observations relate to the finding of the hexagonal etch figures, the crystal laminations, and the fact that the metal is plastic, cold, when restrained or quickly deformed. Under slowly applied pressure cold metal deforms slightly, then shears to fracture without plastic flow. The chief structural features of magnesium are presented in two reduced photographs and 30 photomicrographs. MATERIALS TESTED There are only two sources in the United States from which new metal can be procured: the American Magnesium Corpn. and the Dow Chemical Co. No pronounced structural or property differences in the metals from these two companies were disclosed by the work of this investigation. The following materials were obtained from the manufacturers: 1. Massive crystals of distilled metal (American Magnesium Corpn.). 2. Rods of hot-extruded metal, ½ -in. squares and 5/8-in. rounds (American Magnesium Corpn.). 3. Sheet magnesium, 0.005-in. thick (American Magnesium Corpn.). 4. Cast stick metal, 1 3/8-in. dia. (Dow Chemical Co.). 5. Magnesium-aluminum alloy, hot-rolled plate, ½ in. thick (American Magnesium Corpn.). From these materials, were prepared: 6. Sections from a furnace-cooled ingot made from distilled crystal. 7. Cold-strained pieces from (6), (4) and (2). 8. Pieces cold-squeezed to fracture from (6), (4) and (2). 9. Hammer-struck pieces from (6), (4) and (2). 10. Steam-hammer struck pieces from (6), (4) and (2). 11. Sections from furnace-cooled ingot of the magnesium-aluminum alloy.

Jan 1, 1928

By Frederick O?Neil

SCOPE OF THIS REPORT THE object of this paper is to describe the present status and possibilities of liquid oxygen as an explosive based upon the investigations, research and practical work of the Ingersoll-Rand Co., and of the Air Reduction Co., from early in 1922 to date. The following work was done. 1. A study of the history and physical theory of L. 0. X. as an explosive. (No attempt will be made in this paper to give the history or theory, as this has already been covered by the literature on the subject.) 2. An investigation of the use and the practice with L. 0. X. in the iron mines of Lorraine where L. 0. X. has its largest application in Europe. Although L. 0. X. is extensively employed in the; iron mines of Lorraine, many of the mines using it exclusively, and blasting with it a total of approximately three million tons of iron ore per year, the fact that the mining practice in Lorraine1 is to drill comparatively shallow holes and blast only a few holes at a time, renders the data obtained there of very little value in estimating the possibility of replacing dynamite with L. 0. X. in American mining methods. In fact, in the iron mines in Lorraine, L. 0. X. replaced black powder, or its equivalent. 3. Laboratory research work on properties of absorbent materials. 4. Work in the Bureau of Mines explosive laboratory at Pittsburgh, Pa., on the properties of L. 0. X. cartridges. 5. Practical work underground with L. 0. X. cartridges in the Witherbee-Sherman iron mines at Mineville, N. Y. 6. Practical work in the quarries of the Calcite Quarry Co., Myers-town, Pa. 7. Practical blasting in several quarries and open-pit mines.

Jan 2, 1926

By H. B. Pulsifer

.ABOut 1.5 varieties, or tnodifications, of the best rnagnesiurn available were prepared and subjected to etching tests, then examined for micro-structure. Of the 30-udd etching reagents that were tried, nearly half, mostly ammonium salts, etched the metal satisfactorily. The surfacing and etching of magnesium is shown to be a very simple and quick operation. The density and hardness of magnesium were determined. The most interesting new observations relate to the finding of the hexagonal etch figures, the crystal laminations, and the fact that the metal is plastic, cold, when restrained or quickly deformed. Under slowly applied pressule cold metal deforms slightly, then shears to fracture without plastic flow. The chief structural features of magnesium arc presented in two reduced photographs and 30 photomicrographs. Materials Tested There are only two sources in the United States from which new metal can be procured: the American Magnesium Corpn. and the Dow Chemical Co. No pronounced structural or property differences in the metals from these two companies were disclosed by the work of this investigation. The following materials were obtained from the manufacturers: 1. Massive crystals of distilled metal (American Magnesium Corpn.). 2. Rods of hot-extruded metal, ½-in. squares and 5/8-in. rounds (American Magnesium Corpn.). 3. Sheet magnesium, 0.005-in. thick (American Magnesium Corpn.). 4. Cast stick metal, 13/8-in. dia. (Dow Chemical Co.). 5. Magnesium-aluminum alloy, hot-rolled plate, ½-in. thick (American Magnesium Corpn.). From these materials, were prepared: 6. Sections from a furnace-cooled ingot made from clistilled crystal. 7. Cold-strained pieces from (6), (4) and (2). 8. Pieces cold-squeezed to fracture from (6), (4) and (2). 9. Hammer-struck pieces from (6), (4) and (2). 10. Steam-hammer struck pieces from (6), (4) and (2). 11. Sections from furnace-cooled ingot of the magnesium-aluminum alloy.

By Howard Eavenson

EARLY in 1917, the United States Coal & Coke Co. secured options on several tracts in Harlan County, Ky., aggregating about 1.9,000 acres in area, and after careful prospecting by outcrop openings and diamond drilling, completed the purchase late in July of that year. This property is situated in the eastern end of Harlan County, south of the Poor Fork f Cumberland River, and extending across Big Black Mountain to the Clover Fork of Cumberland River, a distance of about 7 mi. (11.3 kg.). It extends from the Kentucky-Virginia line westward for about 6 mi. Looney Creek, which empties into Poor Fork, crosses the property for about 4 mi. (6.4 kg.), and as several of the seams within the property outcrop along this stream, it afforded an easy, and the logical, place for development. The property is on the northern side of the geological trough formed by the uplifting of Stone Mountain, on the southern, and Pine Mountain, on the northern side; the northern boundary along Poor Fork is practically at the base of Pine Mountain. This, area has been described in various geological reports.1 The main seam on this property is the one known variously as the "C," Benham, Keokee, Taggart, and Roda; it is, also called, by the Kentucky Geological Survey, the Kellioka seam of the western portion of Harlan County. This seam averages, in this property, about 5 ft. (1.5 m.) in thickness, although local rolls reduce this thickness considerably over small areas; and at the extreme western end of the property the seam splits. It is usually clean, although occasionally a small parting occurs within a few inches f the bottom f the seam; it is one f the best

Jan 9, 1921

By H. B. Smith, B. Egererg

In a previous paper1 the authors dealt with the physical properties of cold-rolled and heat-treated Britannia metal of the approximate composition Sn, 91 per cent., Sb, 7 per cent. and Cu, 2 per cent. It was found that cold rolling to more than 50 per cent. reduction produced a continuous softening of the metal when measured by the Brinell machine, whereas the Shore instrument indicated increased hardness; that the strength of the material followed the Brinell hardness and that the metal therefore became weaker the more it was cold-rolled; and further, it was found that hardness and strength could be largely restored to the cold-rolled metal by "baking" for about one hour at any temperature between 200" and 450" F., the melting point. The higher the baking temperature, the more effective was the heat treatment as far as increased hardness was concerned. It seemed to be of little importance whether the metal was soaked or not at the baking temperature for a great length of time and the rate of cooling seemed to be immaterial. The present paper deals with the same alloy and more particularly with the resistance towards various forms of stress — tensile, bend and deep drawing. The metallography of Britannia metal has in part also been covered and an explanation attempted for the abnormal behavior of this alloy. Tensile and Bend Tests Two ingots 73/4 in. wide, 11 in. long and ¾ in. thick were cast from the same pot. One ingot was cold-rolled in one direction to a strip 0.241 in. thick, which furnished the tensile test specimens; the other ingot was rolled in the same way to 0.253 in. and furnished the specimens for the bend tests. The ingots were cast as described in the previous paper and cold-rolled in six passes.

Jan 1, 1930

By R. W. Winson

Asbestos is the generic name given to a group of fibrous mineral silicates found in nature. They are all incombustible and can be separated by mechanical means into fibers of various lengths and cross sections, but each differs in chemical composition from the others. The commercial grades of asbestos consist of a spectrum of lengths and sizes and are not definitive as are most organic fibers. It is generally recognized that there are two main groups of asbestos. The first only contains the fibrous serpentine called chrysotile and comprises about 94% of the world production of asbestos. The second group contains five minerals in the amphibole series+rocidolite, amosite, anthophyllite, tremolite, and actinolite. The latter two have no commercial importance. Properties Physical The structures of asbestos fibers have been studied intensively over a number of years. X-ray diffraction patterns have been used as a means of identification and classification. Low angle X-ray scattering techniques have shown that chrysotile fibers are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 18014 to 300A units, while the amphibole fibers are many times larger in cross section. Electron micrographs of the more common types of as- bestos are shown in [Figs. 1-4]. [Fig. 1] illustrates the softness and flexibility of chrysotile which make it suitable for textile-type products. For a number of years there was considerable controversy over the exact nature of chrysotile fiber, but the photographic evidence in [Figs. 5-7] clearly show that it is tubular in structure. The curvature is the result of the mismatch in the dimensions of the silica [Si,O,l and brucite [Mg(OH),] layers which are on the inside and outside, respectively, of a double sheet. This curvature had been predicted by Pauling (1930) years ago based on the molecular dimensions of the two component structures.

Jan 1, 1975

By George M. Enos, Robert J. Anderson

This paper gives a summary of tests made on the accelerated electrolytic corrosion of the tin brass, 70:29:1 copper-zinc-tin (admiralty metal), of different grain sixes in various electrolytes. There has been great difference of opinion as to the effect of grain size on the corrosion rate of brass, particularly in condenser-tube practice, but so far as is known no information has been published on the subject. It has been assumed, on the basis of the amorphous-cement theory, that fine-grained brass would corrode more rapidly than coarse-grained because the amorphous phase is more soluble than the crystalline and there is more cement per unit area exposed in the fine-grained material. In previous work on the corrosion of metals and alloys in acid mine waters from coal mines,1,2 it was found that the grain size, within a restricted range, had practically no effect on the corrosion of the brass 70:29:1 copper-zinc-tin: In the tests made, samples of three grain sizes were included; viz., 0.025, 0.035, and 0.075 mm. diameter (1600, 817, and 177 gr. per sq. mm., respectively), and the average losses on exposure to the most acid of three waters were 7.07, 6.80, and 6.72 mg. per sq. cm. per day (24 hr.), respectively. No distinguishing features were observed on microscopic examination of the corroded samples. In two other mine waters, the corrosion losses were substantially the same for the respective samples. These tests were -incidental to other tests and were not sufficiently comprehensive to warrant drawing definite conclusions. In further work with the accelerated electrolytic corrosion test, as developed recently in the Bureau of Mines, tests were made

Jan 1, 1924

By G. S. Brooks

WITH the gradual depletion of the natural-gas pools of the Kansas district, together with the uncertainty of further cheap fuel developments, some. of the western zinc companies turned to the coal fields, attracted by their permanency and the 'success of the Matthiessen & Hegeler Co. and the Illinois Zinc Co. Being then confronted with the problem of using a relatively high-priced fuel, although the ultimate' supply was very great, the fuel economies of the kilns and furnaces became of far more importance, and the more modern equipments, as a result, embodied distinct gads in this phase of the business. In addition, there have been some pronounced advances in the actual making of gas from these coals. Increased efficiency in gas making has contributed its share to lowering costs and those plants located in the higher priced fuel districts have probably been obliged to study these economies somewhat more closely. Naturally, many beneficial changes have resulted in both practice and apparatus in these sections. On, certain western coals, for instance, the actual saving in fuel consumption has been 50 per cent. By this is meant that, where about 1.75 tons were burned to smelt 1 ton of oxidized ore, 0.7 to 0.9 ton is now required. While comparisons by W. R. Ingalls1 of fuel economies in smelting in this country and Germany before the war may, in general, be correct, they do not appear to-do justice to the more progressive. American practice. It is doubtful whether German plants were substantially bettering these fuel ratios. Data furnished by Bender and Frams do not afford records averaging less than 0.9 ton coal per ton ore on materials from 40 per cent. to 50 per cent. zinc.

Jan 9, 1919

By B. L. Landrum, J. Simmons, J. M. Pinson, P. B. Crawford

Patentiometric model data have been obtained to estimate the effect of vertical fractures on the areas swept after breakthrough in water flooding and miscible displacement programs such as gas cycling where the mobility is near one, The data are presented for the case of the fire-spot pattern in which the cemer well is fractured various lengths and orientations, the data indicate that for 10-acre spacing, fractures extetidirrg over 1300 ft in either directior1 from the fractured well may re.srrlt in reductions in sweep efficiencics from 72 to approximately 34 per cent. However. the area swept after break through may be quite largr and only 10 or 12 per cent 1ess than would be obtained if the reservoir were trot fractured. For the specific case when the volume of fluid injected is equivalent to 100 per cent of the pattern vol-unie, the swent area may vary from 80 to 88 per cent, depending on the lenght of the fracture. The former value is that which occurs when the break through or sweep efficiency was orrly 34 per cent and the latter figrrre of 88 per cent is that which is obtained if the reservoir were unfrac-ttm'd. It is pointed out that although the sweep efficiency may he very low in vertically fractured five-spot patterrz.s, the area swept at low water-oil ratios may be only 5 to 10 per cent less than those achieved if the reservoir were unfractured. INTRODUCTION Since the initiation of commercial reservoir fracturing techniques it has been desirable to determine the effect of fractures on the areas swept after breakthrough. Most water flooding or gas cycling projects are continued for substantial periods after the brcakthrough of the injected fluid. Although the sweep efficiency serves as one criterion for rating various flooding patterns. the area swept after breakthrough for various water-oil ratios or percentage wet gas, if cycling. is of perhaps more importance than the sweep efficiency alone. Sweep efficiency data on the vertically fractured five-spot have been presented3. Previous work on the line-drive pattern has shown the effect of vertical fractures on the area swept after breakthrough for the case in which the distance between injection and producing wells divided by the distance between adjacent input wells was equivalent to 1.5 (see lief. 2). The data indicated that for the line-drive pattern it may be desirable to flood or cycle substantially perpendicular to the fractures in order to achieve the greatest recovery for the smallest volume of fluid injected. For this study the center well of a five-spot is assumed as the fractured well. All fractures were assumed to originate at this well and extend into the reservoir for various distances and orientations. All the fractures are straight and are of large permeability compared to the matrix proper. These data are presented to aid the engineer in estimating fractured five-spot pattern performance. ANALOGY The potentiometric model was used in making this study. The model used was 20 20 in. by approximately 1-in. deep. For certain portions of the study one corner of this model was considered to be an injection well and the opposite corner a production well. To simulate vertical fractures a copper sheet was soldered to the wire well and made to conform to the desired length and orientation. In other studies the same model was used except that the four corners of the model might be considered as the corner wells of a five-spot pattern and a fifth well was placed in the center of the model. The well placed in the center of the model was fractured. The total fracture length is L and the well spacing. d. The complimentary fracture angles will be obvious from Figs. 3 and 4. The data obtained on the potentio-metric model assumes the pay to be uniform and homogeneous, the mobility ratio is one, steady-state conditions exist and gravity effects arc neglected. The permeability of the fractures is very great compared to that of the matrix proper. The po-tentiometric model has been used widely both in water flooding and gas cycling projects, and may be used for miscible displacement; how-ever. it is believed that the poten-tiometric model data are more properly applicable to gas cycling than water flooding because the model as-

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

The Pu-La alloy systenz has been studied by thertnal, tnzcrographic, and X-ray diffraction methods. It is churacterized by a liquid miscibility gap, a maximum solubility of about 20 ut. pct PM in y lanthunum and 19 at. pct PI* in 0 lanthanum, very little soluibility of lanthanum in the plulonium allotropes, and the absence of intermediate phases. THE existence of immiscible liquids in the Pu-La system has been reported by Schonfeld.1 A tentative phase diagram based on the results of thermal-analysis experiments has been constructed by Poole et a1 2 This diagram shows a liquid immiscibility loop with a monotectic at 77 at. pct La and 846°C. 7 lanthanum is shown to dissolve 20 at. pct Pu and to decompose by an inverse peritectic reaction (y La = L , + p La) at about 82 at, pct La and 833°C. The ß lanthanum solvus was not determined, but the thermal work indicated a maximum solubility of 16 at. pct Pu in ß lanthanum. The present investigation has defined the solubility limits of plutonium in y lanthanum and 0 lanthanum, and, with the exception of minor discrepancies, has verified the results of Poole et al. 1) EXPERIMENTAL The electrolytic plutonium melting stocks were better than 99.9 wt pct pure, the main impurities being 90 ppm Fe and 50 ppm W. The lanthanum melting stocks, supplied by Research Chemicals and the Cerium Metals Corp., were about 99 wt pct pure, the main impurity detected by our spectrochemical analysis being 2000 ppm Fe. The components for each alloy button (-5 g) were weighed on an analytical balance and were melted together in a conventional arc furnace. If no significant weight loss occurred during melting, the as-weighed

Jan 1, 1968

By H. N. Eavenson

EaRly in 1917, the United States Coal & Coke Co. secured options on several tracts in Harlan County, Ky., aggregating about 19,000 acres in area, and after careful prospecting by outcrop openings and diamond drilling, completed the purchase late in July of that year. This property is situated in the eastern end of Harlan County, south of the Poor Fork of Cumberland River, and extending across Big Black Mountain to the Clover Fork of Cumberland River, a distance of about 7 mi. (11.3 kg.). It extends from the Kentucky-Virginia line westward for about 6 mi. Looney Creek, which empties into Poor Fork, crosses the property for about 4 mi. (6.4 kg.), and as several of the seams within the property outcrop along this stream, it afforded an easy, and the logical, place for development. The property is on the northern side of the geological trough formed by the uplifting of Stone Mountain, on the southern, and Pine Mountain, on the northern side; the northern boundary along Poor Fork is practically at the base of Pine Mountain. This area has been described in various geological reports. The main seam on this property is the one known variously as the "C," Benham, Keokee, Taggart, and Roda; it is also called, by the Kentucky Geological Survey, the Kellioka seam of the western portion of Harlan County. This seam averages, in this property, about 5 ft. (1.5 m.) in thickness, although local rolls reduce this thickness considerably over small areas, and at the extreme western end of the property the seam splits. It is usually clean, although occasionally a small parting occurs within a few inches of the bottom of the seam; it is one of the best coking and gas coals in the United States. The average analysis of this coal is given in Table 1.

Jan 1, 1922

By F. N. Lathe

In 1882, The Arizona Copper Co., Ltd., acquired producing copper mines at Metcalf and Morenci (locally called Longfellow). Metcalf is situated a distance of 7 miles, and Morenci a distance of 6 miles from the general office of the company at Clifton, Ariz. A reduction works with five blast furnaces was built in the center of the town of Clifton in 1884 and operated until January, 1914. Concentration of oxidized ores was begun in 1890-1891, in a mill built adjoining the smelter, and id October, 1893, a leaching process was started for treating tailings from the oxide mill. A sulphide concentrator with 300 tons capacity was built at Clifton and started treating chalcocite ores in July, 1896. This was the first mill to treat low-grade copper-siilphide ores successfully. Another concentration mill for sulphide ores was erected at Morenci in 1900. The sulphide mills are now being remodeled to treat ores by concentration and flotation, with a capacity of 4,000 tons at Morenci and 500 tons at Clifton. The leaching plant has not been running since September, 1914. The average yearly production from this company's mines and reduction works from 1885 to date has been: Pounds 10 years ended 1894................................... 6,864,902 10 years ended 1904................................... 20,439,614 10 years ended 1914................................... 32,665,905 Part of year 1915, to Sept. 12........................... 30,206,106 4 months of 1916, to June.............................. 15,964,840 June, 1916........................................... 4,900,000 Construction on a new smelting plant was started in February, 1912, and finished in February, 1914. In the Transactions, vol. 49, E. Horton Jones published "Unit Construction Costs from the New Smelter of the Arizona Copper Co., Ltd.," which fully describes the construction of this plant, with details of costs.

Jan 1, 1917

By M. King Hubbert

DuRing the past summer the writer was asked by the Illinois State Geological Survey to make a study of some of its economic geological problems with regard to the applicability of geophysical methods of prospecting to their solution. The following four problems were suggested for investigation: (1) the fluorspar area of Southern Illinois, (2) oil structures in the south central part of the state, (3) the lead and zinc-bearing area of northwestern Illinois, and (4) the water supply and gravel deposits of the glacial drift. The prime requirements were to find a means of obtaining a maximum of useful information with a fairly modest outlay of expenditure for technical staff and equipment. The method of procedure adopted was that of making a preliminary study of each of the problems named by means of available office data and published reports with supplementary field reconnaissance where necessary. Preliminary Studies Fluorspar.—The fluorspar deposits of southern Illinois as shown by Weller,1 Bastin2 and others are of two main types: (1) vein deposits along steeply dipping normal fault planes, and (2) "blanket" deposits occurring practically horizontally along a certain sedimentary horizon. The vein deposits are composed mostly of calcite and fluorspar in sheetlike veins of thicknesses, where mined, ranging from about 2 to 12 ft. The surrounding topography is in a mature state of development with a relief of about 100 ft. or more. Any geophysical prospecting for this ore would have to depend either upon the physical properties of the ore and associated minerals or upon the properties of the geologic structure containing them. Fluorspar has a density of 3.18, which is somewhat greater than 2.7, that of calcite. Its

Jan 1, 1934

By G. W. Housner

The series of earthquakes in the vicinity of Koyna Dam in south- western India, which included a very damaging magnitude 6.5 shock on Dec. 11, 1967 (Dec. 10 GMT), is of much interest. The events are exceptionally well documented, which is a tribute to Indian geologists, seismologists, and engineers. To help in disseminating the information in the United States, this chapter presents a brief summary of the pertinent data and lists references. Koynanagar (Koynatown), which began as the construction camp for the dam, is located about 140 miles southeast of Bombay and 70 miles south of Poona at 17.4ºN and 73.7ºE, about 40 miles inland from the Arabian Sea. Koyna River flows almost due south from its source a distance of about 38 miles and then makes an abrupt turn to the east and travels some 480 miles to empty into the Bay of Bengal. Koyna Dam is located about 3 miles north of this turn. The approximately north-south trending continental divide is a few miles west of Koyna and the terrain drops steeply about 1700 ft to where the hydroelectric generating station is located. The reservoir behind Koyna Dam forms a long, narrow lake (Shiva- jisagar Lake) with mean water level (MWL) at 2160-ft elevation. The 345-sq-mile watershed receives an annual rainfall of about 200 in., most of which falls between mid-June and mid-October. The peak storage is 99 x l09 cu ft. A controlled flow passes under the continental divide in a tunnel and then down to the electric generating station about 5 miles WNW of the dam. The inflow not used for power generation is released to Koyna River. The Koyna project is a major source of electric power for Bombay and produces 540 MW at peak load.

Jan 1, 1970