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By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757' and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick 'needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,' are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed' by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke's law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

By John R. Low

A number of cases of low-temperature, intergranu2ar brittle fracture of metals containing small amounts of certain impurities, have now been identified. Some degree of understanding of this phenomenon exists for the simpler binary systems of a metal and a single impurity, but the profound effects of other impurities and alloying elements in modifying this type of behavior remain unexplained. Current research in this area is reviewed and some of the newer techniques of investigation which should make possible a more quantitative study of the structure and composition of grain boundaries in impure metals are described. To indicate the subject matter of this lecture, we may begin by reviewing the experimental observations concerning low-temperature intergranular brittleness in impure metals, particularly those examples in which the embrittlement appears to result from what has been called "equilibrium grain boundary segregation."' These are the systems in which it has been impossible, at least up to now, to detect the presence of any second phase film at the brittle interfaces. When second phase films are present they are usually readily detectable by fractographic methods, often appearing as epitaxial films in geometric or dendritic patterns. An example is shown in Fig. 1 for the case grain boundary carbides in a sensitized stainless steel which failed by intergranular brittle fracture at 78?k2 In contrast to this type of embrittlement there are numerous examples of low-temperature intergranular embrittlement in which the fractographs are essentially featureless, for example, that of an oxygen-embrittled iron shown in Fig. 2. The only second phase particles visible are the small, widely separated, round oxide particles typical of the bulk material. The fracture surface is extremely smooth and the fracture path appears to follow the intergranular interface without deviation. This type of fractograph also implies that crack propagation has occurred without plastic deformation at the crack tip, since localized slip or twinning ahead of the crack would be expected to distort the interface and be readily visible in the fractograph. Such indications are occasionally seen in these fractographs, but are not characteristic. A second example of this type of fractograph is shown in Fig. 3, which is from a temper-embrittled, carbon-free, Fe-Cr-Ni alloy containing Sb, broken at 1OO?C.3 The similarity to the oxygen embrittled iron case will be apparent. In the case of the temper embrittled Cr-Ni ferrite containing antimony, it is possible to remove the embrittlement by suitable thermal treatment. The grain boundaries may then be examined by thin film transmission in the electron microscope for the material in both the nonembrittled condition and in the embrittled condition. Two boundaries are shown in dark-field transmission in Fig. 4, one in the nonembrittled

Jan 1, 1970

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

Granduc lies near the Alaskan border in British Columbia, about 600 miles (960 km) north of Vancouver. Prospecting in the area must take place in the short summer months of fog and rain because the winter is bitter cold, with snowfall up to 960 inches (24.4 m) accompanied by avalanches. Despite these difficulties, the mineral ized area was discovered in the 1920's. By 1956, Newmont Mining Corporation had developed mineable ore reserves estimated at 32,500,000 tons of 1.93% copper. Newmont and ASARCO, in a joint venture, then began development of the ore body, which was partially covered by glaciers. It was apparent a concentrator could not be built at the mine site where overland access was impossible due to the weather conditions and the terrain. Years of engineering studies of all possible access routes finally dictated the driving of an 11 mi long (17.6 km) tunnel passing under three glaciers and three mountain ranges to the nearest feasible concentrator site at Tide Lake. Even then, a mountain road subject to an average snowfall of 800 in. (20. 3 m) had to be built 32 mi (51 krn) from the concentrator through Alaska to Stewart, British Columbia, the nearest port. At Stewart, which is located at the head of a fjord 120 mi (192 krn) from the Pacific Odean, a fully equipped marine terminal was built. The tunnel, the lifeline between mine and mill, was to be driven from both ends; however, in 1965, an avalanche occurred at the Leduc portal, killing 26 crew members and wrecking much of the camp. The tunnel was then driven from one heading adjacent to the concentrator site at Tide Lake, a distance of 53,744 ft (16,381 m) to a point under the ore body. The remote location, type of terrain, and bad weather made supply of crews, equipment, and construction materials difficult; but in spite of these extremely adverse conditions, the tunnel crews set many world records. Mineralization throughout the ore zone is generally uniform in grade and composition and is primarily chalcopyrite and pyrrhotite associated with pyrite. Mining is mainly by sublevel caving. After blasting, rubber-tired load-and-haul equipment moves from level to level by means of an internal connecting ramp system on a 15% slope. At the gathering haulage level, 15-ton bottom-dump cars deliver the ore to a 600-ton pocket equipped with a Hudson "Rock-Flo" dump. The bottom of the ore pocket forms the feed chute to the primary

Jan 1, 1978

By L. B. Herring, Harold Decker

The South Texas area, discussed herein, represents districts 2 and 4 of the Texas Railroad Cominission and extends from Jackson, Lavaca, and Gonzales Counties on the northeast to the Rio Grande River, comprising a total of 26 counties.$ The present boundaries of this district do not coincide with those of earlier reports published in the annual volumes of Petroleum Development and Technology. The war, in its various ramifications, determined and controlled all the phases of the oil and gas industry. Priorities for material and governmental subsidies determined all new operations. New Pools In our opinion, the combine' quantity of crude and distillate reserves added in '943 approached Or possibly exceeded the amount produced. Thirty-five new pools were added to the area' Of these, five have significant reserves and ten offer possibilities of containing consequential reserves. The largest proven reserve discovered during the year was the Slick pool, on the DeWitt-Goliad County line. This is also the most important Wilcox discovery to date in the area. The most significant extension was at Willimar, Willacy County. Other important extensions were developed at Agua Dulce, Seeligson, and Odem. Except for the Porter field, in Karnes County, the Laredo trend, which produces lrom the Jackson and Yegua, proved very disappointing, and this pool is o:C secondary importance. The Scott and Hopper pool, Brooks County, has only orie well, but offers excellent possibilities of becoming an important discovery. It represents at this time the major Frio discovery of the year. The Hobson pool, Karnes County, is not a major reserve, but can be classed as important in that it produces at a shallow depth from the Wilcox. This proves that the potential area of production for this zone occupies a broad trend. Gas and Condensate During the year construction was begun on only one recycling plant, this being in the Sejita field, Duval County. Several others were colltemplated, but no actual operations were begun. The most important development in recycling was the rebuilding of old plants to allow for the fractiona-tion of isopentane, n-butane, isobutane, and propane. Heretofore all pentanes plus have been marketed as cLdistillate,n only a minor portion of the butanes being isolated and sold for fuel purposes. All these new the except propane, are considered vital to the war effort and propane is being marketed as fuel gas. In other instances propane is being isolated and then pumped back into the gas reservoirs for storage. It is anticipated that the demands for this product will increase in the future. Drilling in the Wilcox trend during the year showed the existence of valuable gas

Jan 1, 1944

By L. B. Herring, Harold Decker

The South Texas area, discussed herein, represents districts 2 and 4 of the Texas Railroad Cominission and extends from Jackson, Lavaca, and Gonzales Counties on the northeast to the Rio Grande River, comprising a total of 26 counties.$ The present boundaries of this district do not coincide with those of earlier reports published in the annual volumes of Petroleum Development and Technology. The war, in its various ramifications, determined and controlled all the phases of the oil and gas industry. Priorities for material and governmental subsidies determined all new operations. New Pools In our opinion, the combine' quantity of crude and distillate reserves added in '943 approached Or possibly exceeded the amount produced. Thirty-five new pools were added to the area' Of these, five have significant reserves and ten offer possibilities of containing consequential reserves. The largest proven reserve discovered during the year was the Slick pool, on the DeWitt-Goliad County line. This is also the most important Wilcox discovery to date in the area. The most significant extension was at Willimar, Willacy County. Other important extensions were developed at Agua Dulce, Seeligson, and Odem. Except for the Porter field, in Karnes County, the Laredo trend, which produces lrom the Jackson and Yegua, proved very disappointing, and this pool is o:C secondary importance. The Scott and Hopper pool, Brooks County, has only orie well, but offers excellent possibilities of becoming an important discovery. It represents at this time the major Frio discovery of the year. The Hobson pool, Karnes County, is not a major reserve, but can be classed as important in that it produces at a shallow depth from the Wilcox. This proves that the potential area of production for this zone occupies a broad trend. Gas and Condensate During the year construction was begun on only one recycling plant, this being in the Sejita field, Duval County. Several others were colltemplated, but no actual operations were begun. The most important development in recycling was the rebuilding of old plants to allow for the fractiona-tion of isopentane, n-butane, isobutane, and propane. Heretofore all pentanes plus have been marketed as cLdistillate,n only a minor portion of the butanes being isolated and sold for fuel purposes. All these new the except propane, are considered vital to the war effort and propane is being marketed as fuel gas. In other instances propane is being isolated and then pumped back into the gas reservoirs for storage. It is anticipated that the demands for this product will increase in the future. Drilling in the Wilcox trend during the year showed the existence of valuable gas

Jan 1, 1944

By J. R. Craig, T. N. Solberg, M. A. Linden

The central and southern Appalachian Mountains were the major sources of domestically produced gold throughout the first half of the 19th century and continue to yield gold today. Small amounts of gold were probably extracted by the Indians and the Spaniards but the first documented report of gold in the region was made by Thomas Jefferson who found, in the Rappahannock River of Virginia in 1782, a 1.8 kg (4 lb) lump of gold ore that yielded 26 g (0.85 oz). Gold was subsequently discovered in North Carolina between 1793 and 1799, in Virginia in 1806, in South Carolina in 1827, in Georgia in 1829, and in Alabama about 1830 (Becker, 1894-5; Pardee and Park, 1948). Production climbed to more than 933 kg/a (30,000 oz per year) between 1830 and 1852, but dropped sharply after the California gold rush in 1849 as experienced miners moved west in search of bigger and easier stakes. The Civil War briefly halted gold mining in the Appalachians, but production rose to an average of about 249 kg/a (8,000 oz per year) from 1865 until 1878 and to about 404 kg/a (13,000 oz per year) from 1881 until 1915 when it again fell to near nil (Pardee and Park, 1948). Minor resurgences occurred in the 1930s and 1940s. Although there has been no reported production in recent years, it is likely that "weekend panners" still remove hundreds of ounces from streams annually. The total reported production for the area through 1959 is more than 77 t (2.5 million oz). This paper reports some initial findings of a long-term project designed to investigate the mineralogy, chemistry, mode of occurrence, and petrology of gold occurrences in the Appalachians. The goal of the initial phase was to determine the compositional range of gold in the Appalachians as a step toward deciding if sufficient variations were present to allow the definition of "compositional signatures." The very few published data on gold fineness in the Appalachians are based on assays that commonly include gold and silver from several mineral species. Analyses in the present study were performed on individual grains of electrum using a spot size of 10 µm x 10 µm to 100 µm X 100 µm (394 X 394 micro in. to 3,940 X 3,940 micro in.), and thus reveal the true composition of the principal precious metal-bearing phase.

Jan 1, 1984

By J. M. Sands

Production of oil in Oklahoma during 1927 amounted to 273,256,900 bbl. (Table l), an increase of nearly 100,000,000 bbl. over the previous year. All of the major fields declined with the exception of those of the Seminole district which produced 136,105,000 bbl., almost one-half of the total production of the state. Because of this large new production, most of the development in the state during the year took place in that district. The Seminole City pool located in T.-9-N., R.-6-E., was the first of these pools to be developed. The Indian Territory Illuminating Oil Co. brought in the first well in this field in March, 1926, for 1100 bbl. This well is located in Sec. 24-T.-9-N., R-6-E., and produced from the Hunton lime reached at depth of 3900 ft. The first Wilcox production was developed by the Independent Oil & Gas Co. and R. S. Garland in Sec. 26, T.-9-N, R-6-E. This well was being drilled for production in the Hunton lime but was dry in this horizon and was deepened to the Wilcox sand in July, 1926, and at the total depth of 4069 ft. developed a maximum production of 8000 bbl. daily. It held up in wonderful manner and was the cause of not only the development of this pool but the prospecting of the whole district for the Wilcox sand. This led to the discovery of the other major pools in that district. Seminole City pool reached a peak production of 264,500 bbl. on February 22, 1927, and slowly declined so that by December it had a daily average of 56,200 bbl. from 321 wells. The second pool in this district to be discovered was the Searight pool which was discovered by F. J. Searight et al. in Sec. 33, T-10, R-6, in April, 1926. The first well was drilled to the Hunton lime encountered at 4115 ft., and came in for 1300 bbl. daily. During August, 1926, the second well was drilled on the same farm through the Hunton lime to the Wilcox sand which was encountered at 4360 ft. It came in for an initial production of 4000 bbl. daily. This started active drilling in this field for the Wilcox sand. The field had a peak production of 40,621 bbl. on June 15, 1927, and declined to a daily average of 22,300 bbl. from 73 wells during December.

Jan 1, 1928

ALBERT Ladd Colby, who died suddenly of influenza at Torquay, England, on Apr. 30,1924, was born in New York City, on June 26,1860. He was educated in the public schools of New York, at the College of the City of New York, and received the degree of Ph. B. from the Columbia School of Mines in 1881. He continued his studies at Columbia, acting occasionally as assistant to Prof. C. F. Chandler, until 1883. For the next three years he was Assistant Professor of Chemistry in Lehigh University; then head chemist and metallurgical engineer of the Bethlehem Steel Co., at Bethlehem, Pa., occupying the latter position until 1903. As head chemist his active and inventive mind devised several improvements in apparatus for increasing the rapidity and accuracy of the analytical work; as metallurgical engineer, he was, from time to time, in charge of the blast-furnace, open-hearth, bessemer, and puddling departments; he had entire charge of the inspection, assignment, and economic use of all metallurgical materials, and he early gave his attention to the formulation of specifications for metallurgical materials—an activity in which he long held a distinguished part in this country, and as a representative of his own country in England and Europe. He also sewed as expert for his company in patent suits, again laying the foundation for valuable service later as a consulting engineer. In this latter capacity he was excelled by few, if any, contemporaries in the iron and steel industry. His mind was ingenious, thorough, clear, and keen, both in the preparation of evidence and its presentation to the Court. He very quickly appraised the value of evidence, or of an answer to a question, and knew how to secure the infermation, either from the available literature of any language, or by special researches or plant studies. In the executive control of literary research for patent purposes, his long training, infinite capacity for digging through long series of articles in English, German or French, and clear formulation of the vital subject matter for the guidance of assistants, made him invaluable. He was also an adept in collecting information on special branches of his profession. For example, when the science of metallography began to assume importance, he made the first really comprehensive bibliography covering the literature of all siderurgical countries; for the newly formed International Nickel Co. he gathered all the information extant on the subject of nickel steel, both in the literature and in the minds of experts in America and Europe. Two books testify to the thoroughness of his work in this capacity, vie.: "American Standard Specifications for Steel,"

Jan 1, 1924

By David P. Hale

THE Cartersville barite district is near Cartersville, Ga., in the southeastern part of Bartow County, about 43 miles northeast of Atlanta. The area over which active mining is being done extends about six miles in a northeasterly direction and is about three miles wide. Barite production in Georgia began about 1907,1but the existence of the mineral was known much earlier. At present four companies are operating washing plants and three other plants are operating on leases from those companies. The chief impurities in the ores are silica and iron oxide. The silica is easily washed and jigged out and gives little trouble. Any gravity separation between the iron and the barite is generally poor, owing to the slight difference in specific gravity. Two operators have turned to magnetic separation as the solution to the problem and have made remarkable improvements in the finished product. By very close sizing prior to jigging, the separation between iron and barite has been greatly improved. In some localities manganese occasionally appears as an impurity, but is fairly easy to eliminate by gravity methods. A considerable percentage of iron and silica is eliminated by being broken free in crushing. Until methods for the recovery of fine ore were introduced a minimum of crushing was done, but modern methods allow more than formerly. The depression years brought about the need for increased recovery of ore handled on the part of the producers and a demand for a higher grade of product on the part of the buyers. Improvements in milling and mining practice have had a far greater effect, however, than merely the production of a better grade of ore with greater recovery. They have opened for mining large areas that a few years ago were considered noncommercial deposits because of their inaccessibility and their high iron content. It is no exaggeration to say that the new methods have more than doubled present known reserves of barite ore of economic value.

Jan 1, 1938

By W. A. Backofen, A. T. English

The kinetics of re crystallization were determined metallographically for a 3-1/4 pcl Si-Fe rapidly compressed at temperatures of 710° to 911°C, and held for various times at the working temperature. As in re crystallization following cold wwk, the time for re crystallization was reduced by increased temperature and strain. Nucleation occurred chiefly at grain edges, although other pre-existing interfaces, notably inclusions, also served as nucleation sites. The importance of intragranular nucleation to grain refinement in hot working is pointed out, together with some possible techniques by which nucleation might be induced within the grains. The observed isothermal growth rates are quite accurately described by the equation G = 4 x 10-'/t (cm per sec), independent of temperature and strain at all but the shortest times. Changes in G during recrystalliza-tion can exceed two orders of magnitude. It is argued that release of stored energy associated with lattice defects cannot adequately explain the time dependence. A suggested alternative involves processes of solute segregation and desegregation in the unrecrystallized matrix and at the moving boundary, respectively. EFFORTS to improve hot-working practice are hampered by an incomplete understanding of the fundamental metallurgy involved. Research directed at establishing the required basic foundation falls into two categories, the first concerned with measurement of mechanical properties under the conditions of high temperature and strain rate which characterize such processing, the second focused on structure and its relation to the deformation conditions. Rossard,' Rossard and Blain,2 and Hardwick and Tegart have conducted many high-speed, high-temperature torsion tests on various metals. One of their objectives was interpretation of stress-strain curves in terms of the structures of specimens rapidly quenched following interruption of twisting. They showed that appreciable hardening occurred in the early part of the test, and that this hardening reflected the concurrent development of an increasingly dense substructure within the grains. The detailed nature of this substructure was observed to depend on the ease of polygonization which, at least in fcc metals, varies with the stacking-fault energy.= By holding specimens after interruption but before quenching, the nucleation and growth of new grains could also be studied. Some success has been realized in relating the microstructure of hot-rolled steel to its temperature:strain rate:strain history with such testing.' The same general observations have been made by others investigating rolling4f5 and drop-hammer forging.~-~ Incident to these experiments, some efforts were made to determine the kinetics of re-crystallization as well as the velocity of the migrating boundaries. The results have been largely qualitative, owing to difficulties of interpreting hardness measurements5 and microstructures. The work described here was undertaken to obtain more quantitative information from tests on a material having suitable metallographic properties, and, in this way, to provide further insight into the fundamentals of this practically most important kind of deformation processing. I) MATERIALS AND EXPERIMENTAL TECHNIQUES Materials. Electrolytic etching of a Si-Fe alloy reveals dislocations and substructure in unrecrystallized grains.8'9 This unique characteristic makes possible a precise determination of the extent of recrystallization. For that reason, it was the material selected for all experiments in the present work. The two particular alloys that were used are identified in Table I. A major difference between "A" and "B" is the number of inclusions, as noted in the table. Most of the experiments were made with material "A". It was received as hot-rolled plate 1 in. thick, sawed to 2-in. widths, hot-forged at 1200°C to 5/8-in. rounds, and finally annealed in a mechanical vacuum at 1000°C for 24 hr. The result was substructure-free grains of mean diameter 0.05 cm.*

Jan 1, 1964

By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per 'C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons' interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3' All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.'s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.'s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967

By I. R. Kramer

The delay time for single crystals of iron, zinc, and pre-strained aluminum was measured under conditions of high-speed deformation. The delay time of aluminum was found to be affected by the orientation of the crystal. Under the dynamic conditions employed, tile calculated "activated volume" term appears to be very small for the three metals studied. IN a previous paper,1 it was shown that under dynamic testing conditions at 78° K, there was a delayed yield in single crystals of aluminum and copper which had been cold-worked prior to testing. The experimental results also indicated that the delay-time effect was not due to the interaction of dislocations with impurity atoms or vacancies, but rather to a dislocation-dislocation interaction since aluminum which has not been prestrained shows no delay-time phenomenon. In this paper, some data are reported on the effects of orientation on the delay time of aluminum single crystals; the delay time of zinc single crystals saturated with nitrogen and the delay time of iron single crystals also were measured. EXPERIMENTAL PROCEDURE Aluminum (99.997 pct) and zinc (99.999 pct) crystals, 1/2 in. in diam and 8 in. long were grown by the Bridgman technique. The iron single crystal was supplied by Dr. R. Maddin. The zinc crystals containing nitrogen were prepared by melting high-purity zinc in a graphite crucible and the nitrogen was introduced by additions of ammonium chloride. The liquid zinc was then drawn up into glass tubes of 1/2 in. diam and allowed to solidify. The rods were cooled to room temperature before the transfer to the mold for conversion into single crystals. The orientation of all specimens was determined by the Laue' back-reflection technique, Fig. 2 and Table I. To prepare for the delay-time measurements, the crystals were cut with a fine jewelers saw and the ends carefully machined. The specimens then were electrolytic ally polished to remove the cold-worked metal, mounted in a special fixture and hand-lapped. As a final step, the crystals were annealed in evacuated tubes. Specimens of aluminum crystals, Nos. 24 and 26, were compressed 0.5 and 2 pct, respectively, in the direction of the later impact. The zinc specimens were aged at 50°C for 15 min, In the case of iron, only two specimens could be obtained. To obtain sufficient data, it was necessary to resort to a reaging treatment. After each delay-time test, the specimens were aged at 65° C for 100 min. This treatment, according to Clark,2 is sufficient to restore the original delay time. It is believed that although the specimens were plastically deformed approximately 10-4 pct, after each test the delay-time values are reliable. The delay-time measurements were made in an apparatus similar to that described previously.' Single crystals approximately 1 in. long and having a diameter of 1/2 in. were placed in a pendulum which consisted of a bar 1/2 in. in diam and 8 ft long, designed with a crystal holder to accommodate the specimen at low temperatures. The crystal was held at a position 2 ft from the front part of the pendulum. This portion of the apparatus was supported on a fine molybdenum wire. A projectile bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on

Jan 1, 1962

By M. J. Blackburn

The ordering reaction and its effect on dislocation awangements in alloys based on Mg3Cd has been studied by transmission electron microscopy. Ordering occurs by the growth of ordered domains until they impinge, thus producing an antiphase domain boundary (APB) network. In the disordered alloy, slip is confined to the basal plane while in the ordered condition slip occurs on the basal, prism, and pyramidal planes. Superdislocations have been identuied on these planes and their origin and expected spacings are discussed and compared with the observations. The APBs between the dislocation pairs have been resolved and have proved useful in the identification of superdislocations. Observed slip structures are related to the changes in mechanical properties produced by ordering. At high temperatures magnesium and cadmium form a continuous series of disordered hexagonal solid solutions. At lower temperatures three ordering reactions occur; two based on the compositions Mg3Cd and MgCd3 are transformations to DO19-type superlattices while alloys based on the composition MgCd transform to a B19 lattice. The ordering process in alloys near the composition Mg3Cd has been studied by several workers'-4 and it has been shown to be a first-order type transformation. The variation of mechanical properties with the degree of order and temperature have been reported in some detail by Stoloff and Davies.5 It was shown that the disordered alloy was stronger and less ductile than the ordered alloy, the differences being attributed to changes in the number of active slip planes and to the presence of short-range order in the disordered alloy. In this investigation the ordering reaction has been qualitatively followed by transmission electron microscopy. The effect of this ordering transformation on the dislocation arrangements in deformed specimens has been studied in some detail. EXPERIMENTAL Alloys were melted in a stainless-steel crucible under a flux and chill cast; both melting and casting were performed in an argon atmosphere. The ingots were hot-rolled and tensile specimens cut from the resultant strips. Some large-grained specimens were grown by the strain-anneal method. Heat treatment was carried out in inert atmosphere furnaces and in oil baths at the lower temperatures. Thin foils for transmission electron microscopy were produced by electropolishing in a cooled solution (temp = -40°C) containing 50 cu cm of nitric acid and 180 cu cm of methanol at a potential of 10 v. The ordering reaction was followed by transmission electron microscopy, X-ray, and electrical resistivity measurements but this paper will be concerned chiefly with the electron-microscopy results. Much of the work described in this paper was performed on an alloy containing 26.10 at. pct Cd although two of the micrographs are taken from work on a 25.55 at. pct Cd alloy. RESULTS i) The Quenched Solid Solution. Specimens which were quenched from above the critical temperature showed diffuse superlattice reflections. sark-field analysis on these reflections failed to reveal the presence of ordered domains and thus the superlattice reflections were assumed to arise from regions of short-range order. Quenching from temperatures of 400" to 450°C results in the formation of dislocation loops and helical dislocations. Such defects have been observed and analyzed in detail in several hexagonal metals6-' and as the crystallography and interactions of such loops appear similar in this alloy they will not be reported in detail. Fig. 1 shows a high density of loops

Jan 1, 1968

By C. Land, R. Hultgren

Heat contents of four Cr-Ni alloys were determined in a diphenyl ethev calorimeter. Aside from ferromagnetic effects, Kopp's law of additivity of heat capacities is approximately fol-lowed, in disagreement with earlier results of A. W. Foster. In 1934 Foster1 reported heat-capacity measurements of dilute solutions of chromium in nickel, primarily as a study of the effect of alloying on the ferromagnetic Curie temperature. He found that, apart from the Curie temperature effect, the general level of heat capacities was reduced 10 pct by the addition of 1 pct Cr; 20 pct by the addition of 2 pct Cr. His measurements of pure nickel essentially agreed with accepted values. These results indicate that small amounts of dissolved chromium cause an increase in the Debye temperature of nickel, presupposing a change of frequency of interatomic bonding vibrations which is much larger than should be expected. If Foster's results were verified, therefore, they would have important implications for bonding theory. The only other heat-capacity measurements in this system seem to be those of Taylor and Hinton,' who studied anomalies which they attributed to super-lattice formation at 25 at. pct Cr. At temperatures above the anomaly, Taylor and Hinton found heat capacities at this composition were quite normal, approximately obeying Kopp's law of additivity. EXPERIMENTAL WORK In order to verify or disprove the remarkable results of Foster, the heat contents of four dilute solid solutions of chromiunn in nickel were measured in a diphenyl ether calorimeter. This instrument, described elsewhere,, operates on the principle of the Bunsen ice calorimeter, but uses diphenyl ether as the working substance. Diphenyl ether melts at the convenient temperature of 26.S°C and supplies a more sensitive measure of heat than ice. The hot sample, in an atmosphere of argon, is dropped from a furnace at a measured temperature into a chamber which is surrounded by a mixture of solid and liquid diphenyl ether. The heat from the hot specimen melts some of the solid without chang- ing the temperature of the calorimeter. The amount of solid melted, and therefore the number of calories released by the specimen, is measured from the increase of volume of the mixture, which pushes mercury down a graduated capillary tube. The apparatus has been standardized against the known heat content of pure platinum. Heat loss during the dropping of the specimen was estimated by comparing the heat content of an empty platinum capsule with a solid platinum ball of the same radius and degree of polish of the surface. Repeated tests demonstrate the precision of measurement to be closer than *0.3 pct. Smoothed experimental results are listed in Table I. The tabulated values for pure nickel are taken from kelley, several measurements were made which agreed closely with this tabulation. For chromium, however, no similar agreement was found. The values tabulated were taken from a thorough study of chromium with the diphenyl ether calorimeter which will be published elsewhere.= Suitable plots of the data showed the expected ferromagnetic anomalies in the low-chromium alloys, while the 11 pct alloy shows no ferromagnetic anomaly, but a different, small anomaly below 900°K. This is perhaps the same anomaly found in CrNi, which was once attributed to superlattice formation,' but is probably due to some other cause, such as antifer-

Jan 1, 1960

By Arthur S. Huey

AS the end of the collegiate year approaches, the problem of student employment again becomes acute. This subject divides itself into two phases: (1) employment prior to graduation and (2) employment following graduation. "Experience is the best teacher," according to the old adage, and the student needs all that he can get. He is afforded every opportunity to reap from his books the theories and principles of scientific and engineering practice, and occasionally he is privileged to make field trips to observe the practical side of the subject. But it is not enough for one to know the theory and to observe its application; it is also desirable for the student to get the feel of the tools during his training Such opportunities can only be afforded the student if the major companies cooperate with the universities in giving the student part-time and vacation work.

Jan 1, 1932

By Paul L. Russell

THIS is a progress report of an experiment being undertaken in cooperation with the Bethlehem Steel Corp., the Crucible Steel Co., and the Rock Bit Sales and Service Co., involving heat treatment of the shank ends of drill steel. This experiment is being conducted by the U. S. Bureau of Mines in its experimental mine, Mining Research Branch, Bluemont, Va. The purpose of the experiment is to determine the effect of an increase in the time the steel soaks in the furnace during the hardening heat. It has been thought that increasing this time produces a soft zone below the lugs resulting in a metallurgical notch that causes early failure. Each of the steel companies furnished enough 11/4 - in. straight carbon, hollow, round steel to make up 10 sets of drill steel, in each instance the steel bars were from the same heat. These sets of drill steel, consisting of 2-ft, 4-ft, 6-ft, and 8-ft lengths were fabricated by the Rock Bit Sales and Service Co. Special attention was given to the forging of the steel to produce the best rods possible. The heat treatment of all thread ends was identical and followed the best practice. The heat treatment of the shank ends of five sets of steel from each company produced a soft zone 2 to 4 in. in front of the lugs. It was decided that possibly the best way to obtain this effect was not to overlap the hardening heat but to let the steel soak for an additional 30 min before quenching. Therefore the only variable in the test steels is the length of time the shank ends were in the furnace. The remaining drill steel shanks were treated as follows: Heat treatment in pyrometer-controlled furnace at 1550°F. Quenching oil at 105°F to 125°F temperature. Areas for heat treatment were; shanks, 11 in.; threads, 9 in. Time at heat, standard practice, 20 min for 11/4-in. steel. Actual drilling tests were made in greenstone, (a metamorphosed basaltic rock), and in epidosite. Greenstone has a specific gravity of 2.96 and a compressive strength of 44,200 psi. Epidosite has a specific gravity of 3.26 and a compressive strength of 63,100 psi. All drilling tests were made using a 31/2-in. column-mounted, automatic feed drifter, with a controlled air pressure of 90 psi at the throttle. Tungsten-carbide bits of 2 in. diameter were used for all drilling. Contrary to expectations the drill steels that were allowed to soak for the additional 30 min before quenching performed better than the steels that were heat treated according to standard practice. This performance, as shown in Table I, was especially noticeable in the drilling of epidosite. The "longheat" drill steels furnished by Company "A" drilled 154 pct more minutes than the "standard-heat" steel. Expressed in feet, the "long-heat" steel drilled 114.60 ft more before failure than the "standard-heat" steel. The "long-heat" steel furnished by Company "B" drilled 37 pet more minutes or 60.39 ft more before failure than the "standard-heat" drill steel. The effect of the long heat treatment was not as evident when the steels were drilling in greenstone (Table II). In greenstone, the increase in minutes drilled by the "long-heat" steel over the "standard-heat" steel was 47 pet and 1 pet, respectively, for Companies "A" and "B."

Jan 1, 1952

By Ottey M. Bishop, William G. Peryam, Fred E. Johnson

THE Lepanto Consolidated Mining Company is the largest copper producer in the Philippines, and the only one that makes a concentrate valuable principally for its copper; also, it has the only productive copper mine situated at considerable distance from the sea, and is the only one in the islands operating its own smelter. The Lepanto mine is in the Municipal District of Mankayan, sub-province of Benguet, near the heart of the Mountain Province of Northern Luzon. It is 165 km. from its shipping point at San Fernando, Province of La Union, on the shore of the China Sea. Elevations at the property range from 3200 to 4500 ft. The climate is very mild; temperatures are seldom below 50° or above 80°F. Annual rainfall approaches 170 in. and is mainly confined to a rainy season lasting from May to October. The months from December to April, inclusive, are usually extremely dry. This climatic pecularity entails the problems of landslides on the roads during the rainy season and water shortage during the dry season. The Mountain Trail, an improved rocksurfaced toll road maintained by the Commonwealth Government, gives access to the property. The 105 km. over this road may be traveled in about 4 ½ hr. during the dry season. Very few sections of the road are straight for more than 100 meters, and about one third of it is a one-way road controlled by gates. All freight for the property is delivered by the Manila Railroad Company to Bauang, La Union, 45 km. west of Baguio and at sea level, where it is picked up by freight trucks and hauled via Baguio to Lepanto. Granulated matte is hauled in bulk from Lepanto in four-ton lots on freight trucks to the storage bins at San Fernando. Freight rates from Bauang to the property amount to [P]8.oo per ton, and from the property to San Fernando the rate is [P]16.00 per ton. The company pays the road toll, [P] 1.00 per truck, each way. THE CAMP The company maintains a modern camp, well separated from the mine and reduction plant. Comfortable and sanitary living quarters, water, and light, as well as free medical service are provided all employees. A hospital staffed by a doctor and two nurses takes care of all medical treatment. Considering recreational facilities of great importance, the company has provided two tennis courts, two basketball courts, and badminton courts for employees. Bowling alleys and a motion picture theater are operated by the company, the profits being expended for other recreational purposes. A moderate sized recreation hall serves for barrio dances, meetings,

Jan 1, 1942

The State Mining Experiment Station, Missouri School of Mines and Metallurgy, Rolla, Mo Charles H. Fulton, Director of the School of Mines Martin H. Thornberry, Director of the Mining Experiment Station. From the State Mining Experiment Station are issued all the general and technical bulletins of the School of Mines The latest bulletin containing a complete list of publications will be sent upon application to the Director of the Station Residents of the state may obtain bulletins as issued without charge, or may ask to be placed on the mailing list. Nonresidents should write to the Director for further information concerning specific bulletins. From the long list of bulletins the following have been care¬fully selected as being most likely to interest the geologist and the mining engineer. Vol 8, No. 1 (1916), Bibliography of concentrating ores by flotation, by J Cunningham, vol 1, No 3 (1912), Some apparatus and methods for demonstrating rock drilling and the loading of drill holes in tunneling, by L E Young, vol 2, No 1 (1915), Comparative tests of piston drill bits, by C R Forbes and L M Cummings; vol 2, No 3 (1916), Cupellation losses in assaying, by H. T Mann and C. Y Clayton; vol 4, No 1 (1917), The hydrometallurgy and electrolytic precipitation of zinc, by F D. James; vol 4, No 2 (1917), The effect of additional agents in flotation, pt 1, by M. H. Thornberry and H T. Mann, vol 5, No 1 (1919), The carbonization of Missouri cannel coals, by H L. Dunlap, K. K. Kershner and V. X Smiley. Vol 5, No. 4 (1921), Coal mining methods in Missouri, by W W Weigel, vol 6, No 1 (1921), The problem of the St Peter sand¬stone, by C L Dake, 50 cents, vol 6, No. 2 (1922), Bibliography on the electrothermic metallurgy of zinc, by B M. O'Harra, vol 6, No. 4 (1923), Experiments on the distillation of zinc from complex zinc-lead-silver ores, by B M. O'Harra and E S. Wheeler, vol 7, No 3 (1924), Underground loading devices, by C. E. van Barneveld, 81; vol 7, No. 4 (1924), Briquetting of zinc ores, by B. M. O'Harra; vol. 8, No 2 (1925), A treatise of Missouri clays, by M. H. Thornberry.

Jan 1, 1933

By D. H. Newland

New York has a small but not insignificant place in the oil and natural gas industries of the United States. It has had a continuous record as an oil producer since 1872, with an aggregate yield of about 104,000,000 bbl. The reported output for 1935 was 4,237,000 bbl., a gain of more than 10 per cent for the year and a total that has been exceeded only in the early period of flush production half a century ago. The industry has been steadily building up since 1920 with the successful practice of the water drive, which has given a new lease of life to pools that had been practically drained of oil recoverable by pumping. An additional output of 2000 bbl. or more per acre is being procured by this method. Altogether the fields in New York State cover about 55,000 acres. Their limits are well defined and it is unlikely that they will be extended in the future, although there is some prospect of finding additional supplies by deeper drilling. The oil from New York is all classed as Pennsylvania grade, for which the recent price has been about $2.50 a barrel. It is refined at Olean, Wellsville and Bolivar, in the oil district, and partly in Pennsylvania refineries. Exploration for natural gas, outside of the established districts, was considerable during the year. Altogether 59 wells were drilled, distributed over 13 counties, of which 33 were listed as producers and 26 were dry. At the close of the year, 13 wells were in process of drilling. The 33 producing wells had a combined estimated flow of 278 million cubic feet per day. The best results were obtained from exploration in Allegany County, where out of eight wells drilled to the Oriskany sandstone five were successful and showed a combined open-flow capacity of 107 million cubic feet. The Oriskany sandstone was encountered at a depth of 4500 to 4900 ft. In Steuben County, next east of Allegany County, two out of seven wells to the Oriskany proved productive, and one of these, in the town of Greenwood, on the Watkins structure, was probably the largest that has so far been opened in the state, with a reported yield of 35 million a day. In the central part of New York interest was awakened by the activity shown in exploring for gas in the Trenton limestone, in Camden, Florence and Rome townships, Oneida

Jan 1, 1936