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By R. A. Haney, S. J. Gigliotti

Over the past ten years, analysis of the acceptability of face ventilation systems has been based on numerical criteria rather than solely a study of air flow and methane patterns in the face area. This type of analysis has become possible primarily because of the instrumentation and mathematical models developed by the Ventilation Division, Pittsburgh Health Technology Center, Mine Safety and Health Administration (MSHA). To properly use these mathematical models, large amounts of methane and airflow data must be collected in the face area during mining activities. To supplement underground testing of face ventilation systems, a full scale model of a face area was built. This model includes a full scale model continuous miner, a face ventilation system, a gas release system, and a remote methane detection system. The remote methane detection system consists of an array of twelve methane sensors located throughout the face area. Data from the sensors are transmitted to strip chart recorders. Methane, air quantity, and other data collected during a test are entered into a computer for analysis. This paper presents the data entry system, the models used for data analysis, the test results, and the application of these results to a face ventilation system.

Jan 1, 1983

By Edwin B. Wilson, Joseph W. Leonard, Richard W. Borio

preparation of specification coals for the utility industry is approached from the standpoint of a cooperative effort with the power company to assure that the shipped product will be a noncorrosive coal. Selective mining, coal preparation, the use of additives, and coal blending are mine-site techniques proposed as means for upgrading corrosion-retarding constituents of utility coals (CaO and MgO) while, at the same time, reducing the concentration of those constituents of coal (Na20 and K,O) which cause corrosion. Data obtained from large-scale boiler testing in combination with bench-scale physical and chemical tests are used as a basis for the formulation of mine-site procedures to improve coal combustion utilization. Electric power generation remains the greatest market for coal in the United States. A major reason for this strong market has been the ability of the coal industry to supply a superior product for combustion while maintaining competitive prices. Now that the coal industry is engaged in intensive competition with nuclear power for future energy demand, it becomes ever more imperative that superior coal products are produced. One important problem when burning some coals is a liquid phase corrosive attack on boiler tube metal in the superheater and reheater areas of the furnace where steam temperatures may exceed 1050°F. In addition to causing power outages and high maintenance costs, corrosion is a continuing barrier to the future development of more efficient steam cycles which permit lower generation costs when using coal. Research methods of the past which have been directed at finding solutions which could be applied at the power plant site have been only partially successful and are generally costly. This paper contains a suggested --method of corrosion control through investigation of the problem at the source of the trouble—the coal supplier facility. It is proposed that mine-site pre-ventative procedures be considered as an effective means of cooperative corrosion control between the power company and the coal supplier. Economic justification must be applied to the individual situation. This paper is based on recent work by Combustion Engineering, Inc. and the Coal Research Bureau of West Virginia University under a contract from the Department of the Interior Office of Coal Research.',' Results which are of importance to this discussion may be summarized as follows: 1) The alkali minerals of coal (Na2O and K2O), as measured by an acid leaching process, can be related to corrosion rate in utility boilers. As these constituents increase in a coal product, its corrosiveness can be expected to worsen. 2) The alkaline-earth minerals contained in coal, reported as total CaO and MgO reduce corrosiveness 2s their concentration increases. 3) Naturally occuring, alkaline-earth-bearing materials, such as limestone and dolomite, may be added to a coal to reduce its corrosiveness. 4) Coals with very low iron contents tend to be less corrosive. These results provide the groundwork for examination of the system of operations which occur at the supplier facility from the seam face where mining is begun to the point of loading for shipment. The Mining System Fig. 1 is a cross section of one of the typical coal seams (designated coal A) that was boiler tested during this research program. This seam is overlain by material which consists primarily of a gray-black shale. In the lower third of this seam, there exists a thin rock parting of less than 4 in. in thickness which is consistent throughout the seam. The floor material is fireclay. In order to examine mineral distribution throughout this particular seam, the Coal Research Bureau collected a

Jan 1, 1971

Cortez Gold Mines operated a conventional 2,100 mtpd (2, 300 stpd) cyanidation plant until the 5 million ton ore body was worked out in 1973. (See Gold and Silver Cyanidation Plant Practice by F. W. McQuiston, Jr. and R. S. Shoemaker, Society of Mining Engineers, AIME 1975.) Sub-grade material was dump leached at the mine -mill location in 1971, and the resulting pregnant solutions were added to the feed in the plant's Merrill-Crowe precipitation unit for gold recovery. In early 1973, however, Cortez put into operation their Gold Acres mine which was located about 13 krn (8 miles) to the west of the 'Cortez mine. Economics at that time dictated the heap leaching of the lower grade portion of the ore body with the higher grade being trucked to the Cortez plant for milling. Leach ore was moved directly from the open pits to prepared leach pads located on a gently sloping terrain of 570 grade. Preliminary pad preparation at the leach site included removal of vegetation which was composed of sagebrush and grading of the base. Pads were comprised of mostly minus 74 micron (200 mesh) materials and were made of clay-silt or slime tailings spread on the pad area in thin 50 to 75 mm (2 to 3 in. ) layers, compacted with a vibrating roller compactor to a depth of about 380 mm (15 in.). This was followed with a 100 mrn (4 in.) layer of coarse rock to prevent erosion on the pad and to allow solutions to move laterally under the heaps. Leach solutions normally traveled the length of the heaps and were collected in plastic-lined ditches from which they flowed by gravity to the pregnant solution storage pond. Both pregnant and barren ponds were constructed in the same manner as the leach pads - being lined with compacted tailings or clay silts. The Gold Acres facility required pregnant solution storage of 6 million liters (1.6 million gal) and barren storage of 3.8 million liters (1.0 million gal) designed to handle two to three days of heap drainage or to retain run-off from a major rainfall. Various heap heights were tried including 3, 6, and 9 meters (10, 20, and 30 ft), with a 6 m (20 ft) height selected. Ore was dumped by trucks in a single 6 m (20 ft) lift using a D8 Caterpillar dozer for

Jan 1, 1981

By O. W. Shimer, D. C. Helms, C. E. Brown

THE early history and progress of anthracite stripping, from the first known operation at Summit Hill in 1821 through 1917, was covered in 1917 in a paper by J. B. Warriner,1 then chief engineer, now president of the Lehigh Navigation Coal Co., and stripping methods between 1917 and 1931 were the subject of a paper in 1931 by H. H. Otto,2 of the Hudson Coal Company. The present paper is confined to methods used today on pitching beds in the western middle and southern anthracite fields. The anthracite industry, not unlike other large industries, had been affected for more than a decade by the adverse economic conditions of the country. High development and operating costs and the competition of other fuels caused some collieries to be closed temporarily, while others were permanently abandoned. In order to obtain a larger tonnage at a lower development cost, a larger stripping program was put into effect by many companies. In 1932, stripping operations accounted for 334 million tons, or 7 per cent of the total anthracite production of the year, and in the next 10 years this increased until more than double that amount, or over 14 per cent of the total production, was from stripping operations. These figures represent the total production of the entire anthracite region; unfortunately, the figures have not been separated from the different fields. There are some operations in the southern and middle western fields where the tonnage obtained from stripping amounts to more than 30 per cent of the total colliery production. Stripping operations on pitching beds present difficult problems. Owing to the various geological formations, a different situation is encountered in nearly every stripping pit; and because of the proximity of an overlying bed, it is very often necessary to load the entire overburden into trucks and haul it out of the pit to the dump area, although back filling and casting is done whenever possible. Beds in the areas described in this paper pitch from 20° to 90° and some are on the invert in, many sharp folds and faults. PLANNING The more successful strippings have had adequate engineering analysis. Some work is being done without much preliminary planning, but many strippings would have failed completely if close supervision by the engineering department had not been maintained. Locations of stripping areas are determined as follows: 1. By constructing cross sections over the areas and drilling sufficient diamond-drill or well drill holes to study the strata and to determine the location, thickness and pitch of the beds.

Jan 1, 1944

By C. van Dijk

In Sept., 1960, a steam-drive project was started in the solution-gas drive area of the Schoonebeek field. A part(ern of three five-spots and one four-spot was selected covering an area of 65 acres. The pay in the project area has good lateral continuity and dips slightly to the northeut; it is about SO ft thick and permeability increases from 1,000 and at the bottom to approximately 10,000 md at the top. The oil originally in place was 12.6 X 10' bbl. The oil has an in situ viscosity of about 180 cp. At the start of the steam drive the cumulative primary production due to. solution-ga.7 drive amounted id 4 Percent of the oil originally in place. Reservoir pressure had dropped about 120 psi and no significant primary re-.serves remained. Some 11.3 million bbl of steam (all steam quantities are expressed in barrels of water vaporized) have been injected, resulting in production of an additional 4.1 X I0 9bl of oil, or 33 percent of the oil originally in place. This corresponds to a cumulative oil-stearn rario of 0.37 bbllbbl. It appears that the steam preferentially moves r updip while liquids are produced mainly from downdip wells observations indicate that tile steam flows through only the upper part of the formation. The lateral steam distribution in the pattern is satisfacrory since several prodriction wells hardly reacted and, hence, cori tributcd little to the oil production. Production performance and results from material balance calcutlations agree satisfactorily with the results of large-,scale laboratory experiments. On the basis of these experirmental results the .steam drive, together with a cold water follow-up. is expected to bring ultimate recovery to a value of crt leas: 50 percent of the oil originally in place. No serious production problems have been encountered. However, due to mechanical fuilure, two old prodriction wells and one injection well had to be replaced. An extension of the. steam drive in this area is under connstruction. Introduction The Schoonebeek oil field, discovered in 1943 and developed after World War 11, is situated in the eastern part of the Netherlands. The main oil reservoir in this field is the Valanginian sand. A completely sealing fault divides this reservoir into two areas (Fig. 1): the southwestern part of the sand body where primary production is ob- tained by means of a solution-gas drive, and the remain. der where edge-water drive is the production mechanism. In the greater part of the field the reservoir consists of a single, unconsolidated sand body. The net thickness ranges from 30 to 100 ft and the top is between 2,400 and 2,800 ft below sea level. Formation permeability varies from approximately 10,000 md at the top to values of the order of 1,000 md at the bottom, and porosity is about 30 percent. The reservoir contains a paraffinic oil of 25" API gravity with an in situ viscosity of 160 to 180 cp. Initial oil saturation was high (85 to 90 percent). The relatively large quantity of oil in place (more than 10' bbl), and the low ultimate primary recoveries expected from this field — approximately 15 percent stock-tank oil initially in place (STOIIP) for the water-drive area and 5 percent STOIIP for the solution-gas drive area — clearly indicate ample scope for secondary recovery. Because ies-ervoir and crude characteristics made this field suitable for thermal secondary recovery, a hot-water drive project was started in the water-drive area about 10 years ago. A few years later a steam drive and an in situ combustion project were started in the solution-gas drive area. This paper deals with the performance of the steam-drive project, which was started in Sept., 1960, and which is still in operation. Design of Steam-Drive Project, An experimental investigation of the steam-drive process carried out by schenk in 19561 indicated that under schoonebeek conditions steam injection could be an attractive secondary recovery method. the findings and encouraging results of a pilot test in the Mene Grande field in venezuela,i led to the design of a steam-drive project in the schoonebeek field, Pruject Site and Pattern In 1958 the reservoir pressure in the solution-gas drive area had decreased to about 120 psi, and oil production rates of wells in this area had dropped to 7 to 10 B/D. The cumulative primary production was about 4 percent STOIIP, leaving an oil saturation of approximately 85 percent. In view of the large amount of oil left behind in the reservoir, the solution-gas drive area was selected for the planned steam-drive project. The area in the vicinity of Well S1 3 (Fig. 2) was considered to be suitable since it is at least partly isolated from the rest of the field by faults and the sand is relatively thick (about 80 ft).

Jan 1, 1969

By T. R. Cass

THE renewed interest in titanium, resulting from its increasing application as a structural material, has stimulated basic deformation studies on this metal. In the course of our work, we have developed a dislocation etchant and applied it to a perfection study of melt-grown single crystals as well as to a preliminary investigation of plastic deformation in titanium. The etchant, Keller's etch (21 cu cm HF, 64 cu cm HC1, 106 cu cm HNO3, and 160 cu cm H20), reveals the emergence of both grown-in and fresh dislocations on pure titanium and a-phase Ti-Al single crystals. Pits are produced only on surfaces within a few degrees of the basal plane; the more exactly parallel to a basal plane the surface is, the more distinct are the pits. The observed pit density, however, does not appear to depend on the surface orientation; the pits simul- taneously become less distinct as the misorientation from a basal plane increases. Etch times are short, a few seconds, for pure titanium; longer times are necessary for alloy crystals.

Jan 1, 1968

By Oliver B. Hopkins

Peruvian production for the year 1935 amounted to 17,064,879 bbl., a record amount for any year, bringing the cumulative production of the country up to 188 million barrels. The 1935 figure is an increase of 785,769 bbl. over the 1934 total. The property of the International Petroleum Co. contributed 636,812 bbl. of this increase, and the Lobitos property 158,625 barrels. Exploration work in the country was again active, with attention focused on three areas, the Huallaga River, Lake Titicaca and the Coastal Zone of the Province of Tumbes. It is reported that in the Huallaga River area the Selden Breck Construction Co. has completed geological and engineering studies on its Pachitea River concessions and has ordered a drilling rig. In the Lake Titicaca region further studies in the vicinity of Pusi were made by Government geologists. During the period from 1906 to 1915, the Pirin anticline in this area produced 285,936 bbl. of low-grade crude. The Government holds 120,000 hectares of reserved lands in this area. In the Coastal Zone of the Province of Tumbes explorations by the Government were continued on the National Reserve, and a test location has been selected in the Quebrada Zapotal about 10 miles from the Port of Zorritos. An order has been placed in the United States for drilling equipment. LaBrea-Parinas Estate.—Production on the LeBrea-Parinas Estate reached an all-time high in 1935 of 14,756,914 bbl., an increase of 636,812 bbl. over the 1934 record. The total production from 1890 to 1935 was 148,541,523 bbl. During 1935 a total of 63,021 ft. was drilled in new wells and 5449 ft. in deepening existing wells; 23 wells were deepened and 29 new wells were completed, of which 27 were producers and 2 were dry holes. At the end of the year 2873 wells had been drilled on the Estate, of which 1838 were still productive. The remaining 1035 wells represent abandoned producers or dry holes. Practically all the drilling on the property has been done with cable tools, but during 1934 three strings of rotary tools were introduced. Experience with these outfits has shown that rotary equipment can

Jan 1, 1936

By Oliver B. Hopkins

Peruvian production for the year 1935 amounted to 17,064,879 bbl., a record amount for any year, bringing the cumulative production of the country up to 188 million barrels. The 1935 figure is an increase of 785,769 bbl. over the 1934 total. The property of the International Petroleum Co. contributed 636,812 bbl. of this increase, and the Lobitos property 158,625 barrels. Exploration work in the country was again active, with attention focused on three areas, the Huallaga River, Lake Titicaca and the Coastal Zone of the Province of Tumbes. It is reported that in the Huallaga River area the Selden Breck Construction Co. has completed geological and engineering studies on its Pachitea River concessions and has ordered a drilling rig. In the Lake Titicaca region further studies in the vicinity of Pusi were made by Government geologists. During the period from 1906 to 1915, the Pirin anticline in this area produced 285,936 bbl. of low-grade crude. The Government holds 120,000 hectares of reserved lands in this area. In the Coastal Zone of the Province of Tumbes explorations by the Government were continued on the National Reserve, and a test location has been selected in the Quebrada Zapotal about 10 miles from the Port of Zorritos. An order has been placed in the United States for drilling equipment. LaBrea-Parinas Estate.—Production on the LeBrea-Parinas Estate reached an all-time high in 1935 of 14,756,914 bbl., an increase of 636,812 bbl. over the 1934 record. The total production from 1890 to 1935 was 148,541,523 bbl. During 1935 a total of 63,021 ft. was drilled in new wells and 5449 ft. in deepening existing wells; 23 wells were deepened and 29 new wells were completed, of which 27 were producers and 2 were dry holes. At the end of the year 2873 wells had been drilled on the Estate, of which 1838 were still productive. The remaining 1035 wells represent abandoned producers or dry holes. Practically all the drilling on the property has been done with cable tools, but during 1934 three strings of rotary tools were introduced. Experience with these outfits has shown that rotary equipment can

Jan 1, 1936

By Julien F. Phillips, Donald E. Garrett

The production of soda ash from natural sources is one of the United States' oldest industries. The London Company, which financed the settlement of Jamestown, in the fall of 1608 exported in its first cargo from Virginia " . . . trials of pitch, tar, glass, frankincense, and soap-ashes."1 This last product, a crude mixture of sodium and potassium carbonates obtained by the burning of wood in iron pots, was the commercial soda ash of its day, used in the infant soap, glass, and bleaching industries. Besides having a good cash value, its production helped to clear the land, and it was a compact, easily shipped commodity. The extra high potassium content of these American "pot-ashes" gave them an added market as a fertilizer, a field that they dominated until the opening of the Strassfurt deposits in 1860. This form of natural soda ash disappeared forever from commercial importance with the introduction of the Le Blanc process (1791), and later the Solvay process for manufacturing soda ash. The Solvay process was rapidly accepted in the United States, and has accounted for most of the country's soda ash production since 1884. It was not until the western part of the country began to be developed that natural soda ash was again produced. A number of lakes, playas, and springs west of the Rocky Mountains were found to be rich in this mineral, and climatic conditions were ideal for its easy recovery by solar evaporation. The production of natural soda ash from these deposits has become a steadily growing industry in the United States. Production A summary of the production and value of natural sodium carbonates in the United States is presented in Table 1. Prior to 1927 the principal output came from several different companies at Owens Lake, California. Then production at Searles Lake, California, began to [ ] increase until it became the most important source. In 1948 the sale of crude trona from Green River, Wyoming, commenced and since that time production from these latter two areas has been about equal. Table 2 lists the four

Jan 1, 1960

By C. K. Gupta, P. K. Jena

Niobium (columbium) metal in the form of a button has been produced by calciothermic reduction of niobium pentoxide using sulfur as the heat booster. In these experiments with 50 g of niobium pentoxide per batch, the influence of percentage of calcium in excess of the stoichiometric, the percentage of sulfur by weight of the niobium oxide, and the outer-wall temperature of the bomb on the quality and yield of the metal has been studied. The maximum yield on this scale was 78 pct using 50 pct excess Ca and 20 pct of S and at a bomb-wall temperature of 600°C. In experiments conducted on 500 g of niobium pentoxide, reduction with 40 pct excess Ca and 20 pct of S, and at a bomb-wall temperature of 500°C, the.yield of the metal improved to 82 to 84 pct. Some of the reduced-metal samples have been electron-beam melted and the button melts thus obtained have been observed to be extremely ductile and capable of cold reduction to 98 pct without intermediate annealing. NIOBIUM, because of its high melting point (2468oC), its ductility, its resistance to corrosion especially in liquid metals, its high-temperature mechanical properties, and its relatively low capture cross section (1.1 barns) for thermal neutrons, has potentialities as a structural material in the field of nuclear engineering. Niobium and its alloys are also gaining importance in high-temperature technology as components in aircrafts, jet engines, and missiles, electronics, chemical engineering, and surgery. In 1904 Weiss and Aichel 1 produced niobium by reduction of its pentoxide by misch-metal. Since then a large number of investigations have been carried out for the extraction of niobium from its compounds. The various routes through which the metal niobium has been extracted from its compounds can broadely be classified into the following groups: a) reduction of its halides, oxides, and fluo-salts with metals like calcium, magnesium, sodium, and aluminum;2-10 b) reduction of its halides with hydrogen and oxides with carbon or carbides;11-18 c) electrolytic winning from its halides and fluo salts;19-25 and d) thermal decomposition and disproportion ion of its halides26-30 Among the processes in commercial use at present are sodium reduction or fused-salt electrolysis of potassium niobium fluoride, carbide or carbon reduction of the oxide, and hydrogen or metallothermic reduction of the chlorides. In 1907 Von Bolton2 prepared niobium by reducing niobium pentoxide with aluminum. Dennis and Adam-sona attempted reducing the oxide with magnesium powder in argon atmosphere and the resulting metal contained as much as 5 pct O. Mondolfo8 claimed a method for the reduction of the oxides with aluminum. In the case of both magnesium and aluminum reduction, it has been stated31 that by-product oxides such as MgO or A12O3 would involve a major separation problem. Further, in the case of alumino-thermic reduction, the solubility of aluminum in niobium and intermetallic formation have to be reckoned with. In 1922 Bridge3 produced niobium by calcium reduction of niobium pentoxide. Dennis and pdamson' obtained the metal by a similar method with an oxygen content of 0.2 pct. In most of the cases of metallothermic reduction of niobium oxides mentioned above, the metal niobium is obtained in the form of powder. In an attempt to produce massive niobium metal, lock' used iodine as the thermal booster in the bomb reduction of niobium pentoxide by calcium. Massive niobium metal was obtained with a maximum yield of 75 pct containing 0.1 pct 0. Joly32 carried out experiments on calcium reduction of niobium pentoxide on a 2-kg scale using sulfur as the heat booster in a sealed bomb filled with argon. In his experiments, the reaction was initiated by passing a current through niobium spiral wire embedded in the charge. In a typical run consisting of 2000 g of niobium pentoxide, 3100 g of calcium, and 800 g of sulfur (S/Nb2O5 = 3.3), he obtained massive metal in the form of a very uneven mass with a yield of -57 pct. With lower amounts of sulfur and calcium, powder niobium mixed with small metal globules was obtained and the yield was also poor. From these experiments he concluded that this method is not a suitable one for industrial development considering the quality and yield of metal obtainable and the possible hazards with higher ratios of sulfur to niobium pentoxide in the -~charere. In the present work, a detailed investigation on the calciothermic reduction of niobium pentoxide in a stainless-steel bomb in presence of sulfur as the heat booster was undertaken on a laboratory scale.

Jan 1, 1964

By Robert :H. . Lesemann

I recently gave a talk at a seminar on mine development in the Eighties. I had to present CRU' s long-range market outlook for copper, lead, zinc, nickel, molybdenum and silver. In reviewing the recent history of each metal, and our projections, I tried to find some common pattern of behavior that could prove a guide in projecting future market behavior. When you sweep aside your input-output models and econometric equations, what you seem to be left with is this: "When a market goes through a prolonged period of price weakness, you can usually look forward to a period of considerable improvement. " "When a market goes through a prolonged period of price strength, you can always anticipate a prolonged period of price weakness." Stated another way, "The better things are, the worse they will get."

Jan 1, 1982

L. K. ARMSTRONG H. L. NORTON SECRETARY-TREASURER of SECRETARY-TREASURER Of COLUMBIA SECTION ARIZONA SECTION PERCY E. WRIGHT A. B. CARPENTER SECRETARY-TREASURER Of SECRETARY-TREASURER Of PUGET SOUND SECTION SOUTHERN CALIFORNIA SECTION

Jan 8, 1919

PRESIDENT WILLIAM KELLY, District 5 IRON MOUNTAIN, MICh PAST PRESIDENTS E P MATHEWSON, District 0 NEW YORK, N Y ARTHUR S DWIGHT, District 0 NEW YORK, N Y FIRST VICE-PRESIDENT J V W REYNDERS, NEW YORK, N Y TREASURER CHARLES F RAND, NEW YORK, N Y

Jan 1, 1923

By Clyde E. Williams

THROUGHOUT its history the American iron and steel industry has constantly striven to improve the quality and reduce the cost of its products. No one needs to be told how well it has succeeded. Its success in making steel products at such a low cost has been achieved mainly through large-scale production. While costs have gone down as the rate of production and the degree of mechanization increased, quality of product has been actually improved. Thus high-tonnage records are important only in the light of high quality of the steel. Quality is the watchword! Continual improvement in quality has come as a result of research, not only in the laboratory but in the large commercial units in the plant. In fact, so many operations of the industry are on such a huge scale that experimental work must be done under commercial operating conditions so every progressive steel plant is a research laboratory.

Jan 1, 1938

By Charles T. Holland

This discussion is concerned with those comparatively infrequent bumps that eject material from the failed mass with enough energy to wreck heavy machinery and seriously injure or kill people. In such cases there is a loud report, and the pressure waves set up in the mine atmosphere wreck ventilation controls several hundred feet from the site of the failure. Vibrations are induced in the earth's crust which may be detected several miles from the point of origin, and explosive gases may be released in large quantities.* Usually a dense suspension of dust is produced from the failed mass, together with dust placed in suspension by the resulting air blast. These rock bursts or bumps have also been called mountain shots, bounces, pillar bursts, and crumps. Such occurrences, when extensive, are serious catastrophes, and may force abandonment of the mine.1

Jan 9, 1958

By R. G. Charles, E. A. Gulbransen, S. Barnartt

KINETICS of the reaction of zirconium with pure oxygen at elevated temperatures have been studied by several workers for periods of time up to 6 hr.1-1 In two cases,3-4 . the experimental values of oxygen uptake, w, as a function of time, t, were best fitted to the parabolic rate law w2 = kPt + constant. In others,3,4 the cubic rate law w3 = kot + constant, showed better agreement. The most recent data of Gulbransen and Andrew4 indicate that the choice between the parabolic and cubic laws for empirical representation of the data will often be arbitrary. This is particularly true if the first few minutes of the reaction with a clean zirconium surface is attributed to a different oxidation mechanism, for deviations from either rate law were found primarily during the initial period. Thus, the kinetics of this reaction have been too uncertain to permit safe extrapolation to oxidation periods of practical interest (many hundreds of hours). The data to be described are of interest, for they indicate that the cubic rate law applies over long oxidation times. The reaction of zirconium with oxygen at 1 atm pressure was followed at 350" and 450°C for 500 and 200 hr, respectively. Abraded test specimens of pure zirconium sheet' 3.0 X 2.0 X 0.012 cm in size were oxidized by the procedure previously described,3 which included periodic cooling to room temperature for weighing. The surfaces were polished to a 4/0 finish using polishing paper wet with kerosene, then wiped with petroleum ether and washed in redistilled acetone. Fig. 1 shows plots of log ? vs log t. Each curve represents the average of duplicate measurements, and deviations from the average were generally less than 3 pet. The cubic rate law (slope = 1/3) is closely followed. The rate constants, 5.2, x 10 -6 and 2.4, X 10- (mg cm-2)3 per hr at 350" and 450 oC, respectively, are plotted as log k, vs 1/T in Fig. 2, together with cubic constants calculated from the data of Gulbransen and Andrew4 for abraded specimens from the same lot of zirconium. Their data refer to runs of 6-hr duration at a pressure of 0.1 atm 0 and under conditions of uninterrupted heating. In spite of these differences, the latter data yield a straight line which appears to apply equally well to the new extended time data. The energy of activation for the oxidation process, calculated from the slope of this line, i.s 38 keal per mole. This may be compared with the value of 47 keal per mole found by Belle and Mallett3 at higher temperatures. It may be concluded tentatively that extrapolation of short-term oxidation data for zirconium to obtain the long-term behavior is best done through the cubic equation ?3 = kpt + constant. References ' E. A. Gulbransen and K. F. Andrew: AIME Trans., 1949, vol. 185, p. A.515; JouRNal OF Metals, August 1949. 'D.p. Cubicciotti Journal Amer Chemical August1949.Soc., 1950, Vol. 72, P. 3 V. Belle and M. W. Mallett: Joulnal Electro chemical Soc., 1954, ' E. A. Gulbransen 339.and K. F. Andrew: Oxidation of Zirconium Between 400" Gulbransenand 800'C.and AIME Trarzs.. 1957, vol. 209, p. 394; JOUR-Nal of Metals, April 1957. IS Barnartt, B G. Charles, and E. A. Gulbransen: Oxidation of 50 weight pet uranium-zirconium alloy, Journul Electrochemical SOC., 1957, vol. 104, p. 218.

Jan 1, 1959

By Louis E. Reber

Jan 1, 1922

By W. E. Brigham, P. W. Reed, J. N. Dew

By L. F. Coffin

Monotonic tension and controlled cyclic-strain tests have been conducted on an annealed steel at various strain rates and temperatures in the weep range. Evidence of a strain-induced precipitate reaction abozle 500°C was determined from pronounced cyclic-hardening effects, increase inflow stress, inter granular fracture, drastic decrease in low-cycle fatigue resistance, and loss in tensile fracture ductility, as well as through electron-microscopy examination. It was found that strain rate as well as temperature had a pronounced effect on these observations. A parameter of the form P = T(7.95 - log ip) was determined, which was directly related to the ductility, defined either as the true strain at fracture in the case of simple tension, or as 2N 1/2 ? E p in the case of cyclic plastic strain. A highly satisfactory comparison of the cyclic life as measured and as computed from the ductility predicted by this parameter was obtained for a range of temperatures from 400° to 650°C and for crosshead speeds of 0.002 to 0.2 in. per min. MANY metals subjected to sustained loading at elevated temperatures derive resistance to creep from solid-state reactions of various alloying constituents. These reactions can be many and varied, and occur as a consequence of time and temperature according to reaction-rate principles. Strong evidence exists that many of these reactions are influenced by plastic strain, the argument being put forth that dislocations act as sites for nucleation and growth for the new phase.' Many examples can be cited where plastic strain during transformation influences the structure, and as a consequence affects the properties.2 The low-alloy steels serve as particularly good examples for investigating the effect which aging reactions have on resulting properties. Alloying elements such as carbon and nitrogen, and carbide formers such as manganese, chromium, molybdenum, and so forth, can, by the particular aging reaction which occurs, produce strengthening effects at various temperatures, and so endow strength to the alloy over a broad range of temperatures. These effects have been systematically studied by Glen both during creep3 and for constant strain-rate tension testing.4,5 The work of Glen is of considerable interest in connection with the present study, particularly in regard to the effect of various alloying additions on the true stress-strain curve and on fracture ductility at various elevated temperatures. He has shown that strain-age hardening occurred during plastic straining, which was quite specific both to the temperature of the test and to the alloying element involved. When strain-age hardening was noted at a particular temperature, a .minimum in reduction of area was also obtained. Provided the temperature for the minimum reduction of area exceeded 300°C, all minimum ductility fractures were found to be inter-crystalline in nature. For carbon steels containing molybdenum, two minima in reduction of area were noted, one occurring at 200° to 250°C, the precise temperature depending on the percentage of molyb-

Jan 1, 1964

By G. S. Tint, M. Herman, V. V. Damiano

Dislocation arrays and substructures were studied in cadmium doped zinc crystals using a newly devised etching technique. Cadmium precipitates delineating the dislocations were revealed by etching a surface closely parallel to the (0001) slip plane. Cinephotomicrography of the continuous etching process revealed the three-dimensional aspects of dislocations in the bulk crystal. Dislocation etch patterns were studied in both deformed and annealed crystals after suitable aging at room temperature. The effect of annealing was evidenced by a rearrangement of the dislocations into low-angle boundaries and hexagonal networks. ETCH pit techniques have been used extensively to study dislocations in both deformed and annealed bulk metal crystals. Ideally one hopes to obtain a one-to-one correspondence between the etch pits and the points of emergence of the dislocations at the surface. One then attempts to deduce the way in which dislocations are arranged in the bulk crystal from the arrangement of etch pits on the surface. It is clear that one can obtain only limited information of the dislocation configurations inside the crystal from etch pit studies of single surfaces. Considerably more information is obtained if one is able to follow the course of the dislocations through the crystal using progressive etching technique. Techniques of this sort were used by Gilmanl to study dislocations on the slip planes of NaCl crystals and by Damiano and Tint2 to study dislocation arrangement in zinc crystals grown from the melt. The present paper makes use of a technique first described by Tint and Damiano3 to observe and continuously record the dislocation structures which appear while a crystal surface was being progressively etched. Studies were made on cleaved (0001) surfaces to reveal the dislocations along their length on the surface closely parallel to the slip plane. The technique for revealing segments of dislocations along their length by etching is well known. Wilsdorf and Kuhlmann-wilsdorf4 revealed disloca- tions along their length in aluminum containing a few percent copper, when precipitates segregated along the dislocations. The technique was used by Low and Guard5 to study dislocation configurations on the slip plane in Fe-Si alloys containing carbon. In the present work the technique was applied to zinc containing cadmium since it was shown by Gil-man6 that a cadmium-rich phase could be made to precipitate from supersaturated solutions along dislocations in zinc. Segments of dislocations delineated by the precipitates were revealed by etching a surface prepared by cleaving the crystal. The three-dimensional nature of dislocations and substructures was thus studied from the cinephotomicro-graphic record of the continuous etching process. EXPERIMENTAL Single crystals of zinc containing the order of 0.1 pct Cd were prepared by slowly lowering a graphite crucible containing the melt through a temperature gradient of 15°C per cm at a rate of 1.5 X 10-3 cm per sec. "As grown" crystals were aged for periods of 1 month at room temperature, then cleaved in liquid nitrogen, and etched according to the procedure used by Gilman.' The etchant containing 32 g of CrO3, 6 g of hydrated Na2SO3 in 100 ml of water behaved as a chemical polish for zinc and etch pits were produced at the site of precipitates or inclusions. After the precipitates or inclusions were removed from the surface, the etch pits left behind were eventually polished smooth. This behavior enabled one to continuously observe the surface while the specimen was immersed in the etchant. Best results were obtained when the specimen surface was vertical and the reaction products of polishing were continuously removed by gravitational convection. Some crystals were heavily deformed in excess of 25 pct strain, others were lightly deformed the order of a few pct by compression such that the deformation occurred essentially by basal glide. Some crystals were etched immediately after deformation, others were allowed to age at room temperature for several weeks prior to etching. Heavily deformed crystals were annealed at various temperatures and etched on the cleavage plane immediately after annealing, others were allowed to age at room temperature for several weeks prior to etching. The etched structures of deformed and annealed structures were studied. Similar experiments were conducted on 99.9999 pct pure zone refined Tadanac zinc crystals which

Jan 1, 1963