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By Kenneth R. Hancock

Iron oxides are unique in that they are the only significant colored mineral found in a natural state suitable for use as a pigment after being pulverized to pigmentary size. The current world production of iron oxide pigments is estimated by the author to be between 499 and 590 kt (550,000 and 650,000 st) based on 1979 data. The fact that highly colored natural deposits of iron ore are found throughout the world accounts for its use in prehistoric man's artistic cave paintings. These early artists did not realize that they had established man's first paint test fence which now has some 20,000 years of exposure. In addition to abundance, constituting about 7 % of the earth's crust, iron oxides have the advantages of low cost, permanency, and are not toxic. Through the centuries, succeeding civilizations have utilized iron oxides as a major source for decoration and protection when coloring was desired. In the last century the chemical industry has improved on nature by developing a complete range of synthetic iron oxide pigments which surpass the pigments produced from natural iron ores in uniformity, color quality, and chemical purity. In the United States alone, the combined production of natural and synthetic iron oxides produced sales of over $28,000,000 in 1970 (Stipp, 1970) and increasing to $97 million by 1980 (Spinrad, 1980). Nomenclature With the increasing importance of the synthetic iron oxides it is necessary to make a distinction between the natural or mineral pigments and the synthetic pigments. Natural pigments are those products which are derived from selected ores and should not be confused with iron ores mined for steel production. Iron ores that are mined for steel must be capable of being mined and reduced to iron on a commercial basis. These ores are selected on the basis of iron content and processing economics. It is therefore unusual when iron ores for steel production are suitable for use as mineral pigments. Natural pigment ore sources are selected for their special physical-chemical properties and can command a premium price. Synthetic pigments, and in this instance iron oxides, are those pigments produced from basic chemicals. Through chemical synthesis pigmentary sized particles are produced as opposed to comminution, the major procedure common to all natural iron oxide pigments. Classification An important characteristic of a pigment is its color and, therefore, a logical separation can be made on this basis. A. Yellow Iron Oxide Pigments 1. Natural mineral origin a) Goethite b) Lepidocrocite c) Ochres d) Siennas e) Limonite 2. Synthetic pigments a) Goethite B. Red Iron Oxide Pigments 1. Natural mineral origin a) Hematite b) Siderite (calcined) c) Pyrites (calcined) 2. Synthetic pigments a) Hematite C. Brown Iron Oxide Pigments 1. Natural mineral origin a) Umbers b) Limonite (calcined) c) Siderite (calcined) d) Goethite (bog ore or sulfur mud) 2. Synthetic pigments a) Blends of hematite, goethite, and magnetite

Jan 1, 1983

By Max Hebgen

I. Natural Features of State Affecting Power Development .. 792 II. Early Developments. 1. Big Hole Plant................. 792 2. Canyon Feny Plant............... 793 3. Madison Plant No. 1............... 593 4. Black Eagle Plant................ 795 III. Later Developments. 1. Madison River System .............. 795 2. Missouri River System.............. 797 3. Great Falls System............... 797 4. Missoula River Development............ 797 5. Big Fork Development.............. 802 $ IV. Present Capacity of Power Developments....... 802 V. Transmission System...............: . 802 VI. Character of Load. 1. Lighting and Small Power Uses........... 804 2. Street Railways ................ 804 3. Mining................... 804 4. Railroads.................... 808 5. Irrigation................... 810 VII. Operation of System................. 812 VIII. Increase in Use of Power............... 811 IX. New Power Developments............... 814 X. Undeveloped Powers................. 815 It is estimated that the total stationary power now used in the United States. steam. water and gas. is probably over 30.000.000 h. p. The total developed water power is about 6.000.000 h. p. The water power in the United States now economically capable of development probably exceeds 25.000.000 h. p. The total developed and undeveloped power is

Jan 1, 1914

By Walter E. Hopper

The Caddo oil-field, shown in Fig. 1, is located in Caddo parish, northwestern Louisiana. The known producing territory of oil is covered by townships 19 N, 20 N, 21 N, 22 N, and ranges 15 and 16 W., shown in Fig. 2. The center of the field may be taken as Oil City, 24 miles north of Shreveport, on the Kansas City Southern railway. Shreveport is the second largest city in the State, and is the connecting point of five railroad-lines. Drilling at the present time, however, is going on all over northern Louisiana, especially in Caddo and the neighboring parishes. During the winter of 1908-09 I spent 'four months in the Caddo field, under the direction of the Louisiana Geological Survey and the U. S. Geological Survey. II. History and Development. Natural gas escaping at the surface is found at numerous places in northwestern Louisiana. At Shreveport, the plant of the Shreveport Ice & Refrigerating Co. has been lighted by natural gas for 20 years. The well was drilled for water, but was abandoned on account of the gas. A test well, put down in 1905 near the western limits of Shreveport, was driven to 1,650 ft., and encountered indications of gas and oil at various depths, but did not succeed in finding enough to be profitable. Attention was first attracted to the Caddo field in 1895 by indications in water-wells from 40 to 60 ft. deep, in which the pressure of natural gas was noticeable. This indication of gas in a shallow well led to the drilling of the first well in the Caddo field, the old Savage Brothers & Morricell, or the Caddo Lake Oil and Pipe Line No. 1. The rig for this well was erected in May, 1904, and drilling began in June, 1904. The well was bailed Mar. 23, 1905, with a small amount of oil. It was deepened July, 1905, and converted into a "gasser" Jan. 3, 1906. It was abandoned January, 1907. In consequence of the finding of oil in the Savage well, drilling-operations were pushed with energy; and in April, 1905,

Jan 1, 1912

By F. S. White, E. L. Kinsella

THE solids fluidization process brought out by the Standard Oil Development Co. in the early forties for catalytic cracking of petroleum enabled rapid transfer of large quantities of heat from gases to solids under closely controlled temperature conditions. As the technique developed, it was natural that applications for the process outside the petroleum industry would be sought. The calcination of limestone to ' quicklime requires the transfer of a large quantity of heat at high and closely controlled temperatures. For these reasons, this possible application was one of the first to be investigated. Laboratory work conducted by the Dorr Co. indicated that lime produced by solids fluidization would be of exceptional quality. Calculation of theoretical heat balances showed that savings in fuel could be expected. Accordingly, a pilot plant of 10 tons per day capacity was erected by the New England Lime Co. at Adams, Mass., to substantiate the process. Operation of the pilot plant, previously described,1 showed that excellent lime could be produced with a saving in fuel. The work also indicated the necessity of preparing feed to remove the finer fractions if dust losses were to be held to a tolerable level. A single-stage fluidized solids drier-stripper was developed to accomplish this sizing.2 Subsequently a commercial lime reactor was erected at Adams, beginning operation in June 1949, followed by air sizer facilities completed in November 1951. This paper will describe these two applications of solids fluidization. The raw material for preparation of lime by the fluidizing process is a high calcium crystalline lime stone having the approximate chemical composition shown in Table I. The stone is first prepared by crushing and grinding in conventional equipment to pass a 6-mesh sieve. After crushing, the material is sent to the FluoDry unit for drying and dedusting. Fluidized Drying and Sizing As shown in Fig. 1, the FluoDry unit consists of a 1/4-in. cylindrical steel shell, 9-ft ID by 22-ft 6-in. overall height. Attached horizontally at the bottom is a 6-ft diam combustion chamber, approximately 7 ft 6 in. long. A refractory constriction dome, consisting of first-quality fire brick shapes, partitions the inside into two sections. The lower section is called the windbox and the upper the bed compartment. The vertical wall of the shell is lined with 6-in. first-quality rotary kiln blocks. In the bottom of the windbox a hoppered section is formed with castable refractory to permit the windbox to be readily cleaned via a 6-in. screw conveyor. The combustion chamber is similarly lined with refractory shapes. On the 6-in. diam section, 4 1/2 in. of insulating brick, HW-26, are used. The inner combustion chamber is lined with 4 1/2-in. Korundal brick to withstand the high flame temperatures encountered. An 8-in. steel feed pipe, entering vertically through the top and fitted with an air-operated cone valve,

Jan 1, 1952

By G. L. Smit

The Buffelsfontein Gold Mining Company is situated in the Klerksdorp district of the Province of the Transvaal in the Republic of South Africa, approximately 100 miles west of Johannesburg. Gold production commenced in January 1957 and Uranium treatment of residue slimes as a by-product started in July 1957. The mining property is 5435 mining claims in extent, the equivalent of 7988 acres or 12.5 sq miles. The mine was initially exploited by the Pioneer Twin Shaft System, consisting of a 26-ft diam down-cast shaft and a 22 ft-diam up-cast shaft, sunk in the north-west area of the mine to cater for the hoisting and ventilation requirements for a milling rate of 150,000 tons per month. To exploit the Eastern zone of the property and assist in increasing production to 200,000 tons milled per month, it was decided to sink a further Twin Shaft System consisting of a 28-ft diam downcast shaft and a ventilation up-cast shaft -22-ft in diam, both monolithic concrete lined — 200 ft apart and 5300 ft deep. This paper deals with the sinking and commissioning of these Eastern Twin Shafts. This was achieved by one sinking crew within a period of 20 months. A) PLANNING 1) Siting: The Eastern Shaft System was sited in the north-east area of the property, 12,000 ft east on strike from the Pioneer System. (Fig. 1). Initially the system was sunk to the 5300 ft elevation to conform with the original Pioneer Shaft System. On completion a sub-vertical main shaft will be sunk to the 8000 ft elevation in the immediate vicinity, and subsequently the surface ventilation shaft will be deepened to this elevation by raising from level to level and sliping to full size. The exact positions of the shafts were chosen after: a) underground development had located certain known water bearing zones, and b) geophysical and topographical surveys had been carried out. The shafts passed through the following geological succession: Surface to 4430 ft - Dolomites of the Transvaal System 4430 to 4470 ft - Quartzites and conglomerates of the Black Reef Series of the Transvaal System. 4470 to 4470 ft - Diabasic Lava of the Venters-dorp System (Ventersdorp Contact Reef at base). 4470 to 5250 ft - Quartzites of the Elsburg Series of the Upper Witwaters-rand System. The shafts were sited to ensure that the least possible water would be encountered during sinking, and this contributed to the rapid rate of sinking. 2) Duties: a) The 22-ft diam ventilation shaft was designed to up-cast 1,400,000 cfm of air (0.060 density) against a resistance of 22 in. water gauge. b) The main shaft was designed to handle 160,000 tons hoisted per month as well as the men, material and down-cast ventilation to serve this tonnage. The 284 diam main shaft is equipped with streamlined buntons spaced at 15 ft centers set in pockets which were left during sinking. There are six compartments, four of which are sewed by two dual purpose hoists, hoisting either, twedeck man cages or 13-ton bottom discharge skips. The other two compartments are served by a single purpose winder hoisting double deck cages accommodating 60 men per deck. (Fig. 2). 3) Timing: Permanent equipment was ordered well in advance to insure continuity in the operation. Development underground reached the shaft positions before the start of sinking operations. From this development, boreholes were drilled into shaft positions to drain off water in the vicinity of the shafts. To ensure complete co-ordination of effort, all relevant data, as well as the allocation of responsibility, were made known to all persons and departments concerned. 4) Models: The extensive use of scale models during the preliminary planning stages proved most useful in deciding on design such as buntons, bunton pockets and guide cleats, and complex layouts concerning loading, spillage and pumping arrangements. (Fig. 3). These models also proved invaluable in determining the walling routine. Normal working conditions could

Jan 1, 1964

By Samuel Hoyt

THE writer has long been interested in seeking an explanation of the upper heat effect in the copper-tin alloys over the a + ß range, first described in 1913. These notes are offered, not at all as the final explanation of this heat effect, but rather to indicate certain progress which has been made toward establishing what happens over this temperature interval. While working on the thermal analysis of the copper-rich kalchoids (copper-tin-zinc alloys), it was noted that those alloys containing major portions of tin and minor portions of zinc exhibited two marked heat effects, one at about 520° C. and the other at about 600° C., instead of the single effect which is generally observed in either of the two binary series. This matter was discussed with Dr. Guertler, who suggested that a heat effect at about 600° C. in the pure copper-tin alloys might be expected. This led to a more searching examination of the thermal critical points in the pure copper-tin alloys, with the result that a marked, although somewhat weak, heat effect was located at about 600°. Somewhat later, this upper heat effect was discussed with Dr. Burgess, and it was requested that the Bureau of Standards make heating and cooling curves of one of these alloys for the purpose of removing any possible doubt as to the actual presence of the heat effect. Results obtained by the Bureau are given in Plate I. In an earlier paper1 differential curves were published showing that the heat effect occurred at constant temperature over the a + ß range and increased in magnitude with the amount of a up to a point somewhat above 20 per cent. tin. No heat effect was noticed at this temperature in the eutectoid alloy. The existence of this heat effect seems to require a modification of the present copper-tin diagram in the a + ß field, and it has been the object of the work here presented to secure the evidence upon which such a change should be based.

Jan 12, 1918

By S. Weinig, J. Winter

The grain boundary adsorption of solutes as a function of bulk concentration and solution temperature was studied using internal-frictimz techniques. From the variation of the cor-responding energy of activation for the Phenomenon, the inter-actior2 energy between a solute atom and a high-angle boundary was calculated. Interaction energies in the range of 0.3 ev were obtained, and were used to obtain the actual concentration of solute at the grain boundary. In corroboralory creel, studies the direct grain boundary contribution to the total creep strain was measured. It was found that the interface creep varied with the type and magnitude of the solute adsorbed. Subscribing to the theory of their being energetically favorable sites at the grain boundary for solutes of both Positive and negative size deviations, ternaries were investigated in Which solutes of both types were present. A marked increase in the resistance to grain boundary creep was manifested. THE major difficulty which has been encountered in investigations of the grain boundary segregation of solutes has been the lack of a sufficiently sensitive method of measuring the amount of adsorbed solute at the boundary. For the general case of a high-angle boundary, no direct method of measuring the adsorption at the boundary has been found to date. Internal friction has been used in several studies of grain boundary adsorption1-3 and although it is somewhat indirect, it was demonstrated to have the necessary sensitivity. In this investigation the authors have used internal-friction techniques in conjunction with a study of the grain boundary contribution to the total creep strain. As both parts of the investigation were performed on the same specimens it was possible to combine a highly sensitive technique with a somewhat more direct method in order to obtain information about the adsorption phenomenon. From internal-friction studies the rate of increase of the activation energy was observed to be a function of the difference in size between the solute and solvent atoms. It was proposed that if Gibbs' adsorption isotherm is considered, i.e., where r is the excess solute at the boundary, c is the bulk concentration, and ay/ac is the change in grain boundary energy with bulk concentration, then AH b/ac must vary in the same way as ay/ac and therefore In this way a relative measure of the grain boundary adsorption of solutes is directly obtainable from in-ternal-friction studies. If the previous work in the field of grain boundary adsorption of solutes is examined, certain apparent information is desirable if the phenomenon is to be understood. The most important questions that must be asked are as follows: 1) Is the adsorption of solutes at the grain boundary an equilibrium process? 2) Can the Mott model of the grain boundary be used as a basis of setting up an elastic interaction between the grain boundary and solute atoms? 3) Is it possible to obtain an exact measure of the excess solute at the grain boundary as a function of temperature and bulk concentration rather than merely a relative measure of the adsorption 4) Are the conclusions obtained from an indirect method such as internal-friction studies meaningful in considering gross grain boundary effects such as creep? EXPERIMENTAL PROCEDURE The material used in this investigation was Bureau of Mines "superpurity" titanium (79 Bhn—1500 kg

Jan 1, 1960

By M. H. Forester, John D. Cooner

ANTHRACITE ALTHOUGH the unmined anthracite will last for approximately 150 years, most of the thicker and cleaner coal beds have been almost entirely first-mined and pretty well robbed, leaving much of the present and future production to come from thin and dirtier beds. Herewith is a section of one of the dirty beds being mined in the Wyoming region [ ] This section shows that 45.8 per cent of the bed is made up of impurities and that the 45 in. of coal in the bed is in five benches, the thickest of which is 19 inches. In some localities of the anthracite region there are 14 beds of minable coal. Orderly and proper mining of the coal makes it necessary to rob or second-mine-almost all beds have already been first-mined-in sequence from the top downward. Therefore the robbing of the few remaining portions of the thicker and cleaner beds is in many instances being held up by the mining of the overlying thin and dirtier coal beds. Impurities Impurities consist of fire clay, slate, rock, and bone. The latter, which is black, contains 40 to 60 per cent carbon and often resembles good coal. In some beds there are also bands of "blue" coal, which, as the name implies, is of a bluish slaty color. Although much of this "blue" coal has a carbon content almost as high as the good anthracite, it is not

Jan 1, 1943

By M. G. Corson

INFORMATION regarding the use of manganese alloys has hitherto been incomplete and available only from widely scattered sources. This paper attempts a systematic description of properties and uses of alloys other than manganese bronze, manganin and duralumin, which are probably the only non-ferrous alloys associated with manganese in the minds of most metallurgists.1 PROPERTIES OF MANGANESE Manganese can react either acid or basic; it is hard to obtain in the pure state; it has two different crystalline lattice structures, both of the cubic system, one stable above 850° C. and the other below 650° C., both coexisting in the intermediate range. Although the commercial product is hard and brittle, the pure metal seems to be ductile. In fact Zhemchuzhny, in Russia, was able to obtain ductile manganese and draw it to fine wires by the simple expedient of adding about 3 per cent. copper to the alumino-thermic product. Copper most probably brings the sili-cides, aluminides, nitrides and carbides present in the commercial product into a much less harmful form of distribution. One industrial use that can be foreseen for wrought manganese articles is as anodes for electrolytic processes in sulfate and nitrate solutions, particularly with high voltages. A practically insoluble skin of manganese peroxide is likely to form in such cases and an insoluble and strong anode material will be available.

Jan 5, 1927

By Samuel B. Christy

As is well known, the ore at New Almaden is cinnabar. Native quicksilver occurs also; but, as a rule, in small quantities only. Pyrite occasionally accompanies the ore. Bitumen is quite common,

Jan 1, 1885

By George A. Laird

I. INTRODUCTION. THIS old and once famous district played, through its enormous production of silver and gold, an important part in the history of the State of San Luis Potosi. According to a pamphlet prepared under the direction of the Governor of the State, Sr. Don Blas Escontria, and presented to the visiting members of the Institute during the Mexican meeting of 1901, this district is situated 20 km. east of the city of San Luis Potosi, in a range of mountains of moderate height, extending 135 km. N. and S., and 16 km. E. and W.; and the mineralized area hitherto developed is about 600,000 sq. m. The history of the district,. as given by the record dated 1778, and formerly kept in the San Francisco convent, says that it was discovered in 1575 by Sr. Don Pedro Irarte, and adds that the city of San Luis Rey de Francisco del Potosi received its name (in allusion to the famous Potosi mines in Bolivia) by reason of the remarkable productiveness of its gold- and silver-mines in the first period of their exploration, during which they paid to the Crown, as " quintos " (the fifth part of the product), $97,000,000, as appears from the accounts of the royal treasury. The amount of the quientos paid during the " bonanza period " of 80 years was $72,000,000. The larger sum first mentioned probably represents a longer series of years. But either will suffice to indicate the great wealth of the mines. In 1663, the decadence of the industry began with the caving¬ in of several mines, concerning which the record of 1778, al¬ready cited, says, in substance, that on Good Friday one of the owners in the enterprise, in view of the unfavorable prospect of a lawsuit in which he was engaged, set fire to the timbers supporting the underground galleries and workings of the San

Jan 1, 1905

By J. Gordon Parr, D. H. Polonis

The formation and subsequent decomposition of metastable phases in Ti-Ni alloys containing up to 11 pet (atomic) Ni have been studied. The decomposition of a completely retained ß phase and of a completely transformed 8 phase in a 6 pet alloy has been followed by X-ray diffraction and metallographic methods and by hardness determinations made during the process. The possible mechanisms of the reactions are discussed. PREVIOUS investigations of the Ti-Ni system have usually been limited to phase diagram studies; but little attention has been given to metastable phases and tempering processes. These are important, however, since equilibrium conditions are rarely achieved—nor, perhaps, are they desired—in practice. Up to the present time the available transformation data for titanium alloys appear to be restricted to isothermal transformation curves for selected binary and ternary systems. No quantitative studies have been made of the mechanism by which equilibrium is approached. Several independent investigations have been carried out to determine the Ti-Ni phase diagram. Early work by Wallbaum' and later by Long et al.' produced tentative phase diagrams which were not representative of true binary conditions, since the alloys were contaminated with oxygen and nitrogen. The most recent diagram (Fig. 1) is due to Margolin et al.," and a slight modification of the a + ß/ß boundary (shown dotted) has been proposed by McQuillan.' The structure of the phase Ti,Ni was shown by Duwez and Taylor" to be face-centered-cubic, with 96 atoms per structure cell. The formation of a martensitic ß phase (close-packed-hexagonal) in Ti-Ni alloys has generally been observed when specimens of low nickel content are rapidly cooled from the 0 (body-centered-cubic) range. Margolin et al. reported an increasing tendency for P to be retained in lump specimens as the nickel content increases. McQuillan' has studied the effect on the microstructure of delay time in quenching, and has reported the formation of pro- eutectoid a precipitate in a quenched hypoeutectoid alloy. In a previous study of Ti-Fe alloys," experiments were made on powder specimens produced by filing alloy ingots. Techniques were devised for the preparation and heat treatment of alloys, and X-ray diffraction methods were used both for structure determinations and phase ratio estimations. A similar approach has been made in this study of Ti-Ni alloys. Experimental Methods Ten alloys ranging from 0.25 pet to 18 pet Ni* * All compositions are in atomic percentages unless otherwise stated. were prepared from iodide titanium bar stock (hardness Rf 72) and Johnson-Matthey spectrographic standard nickel by levitation melting.' As a check

Jan 1, 1957

By Henry Mulryan

DIATOMS are microscopic aquatic plants of the order Bacillariaceae. They are unicellular plants with skeletons made up of amorphous opaline silica. The skeletons show highly ornate, complicated geometrical designs. Diatoms live in water virtually everywhere. They are found in clean sea water, brackish water, and fresh-water lakes and ponds. When conditions are right, diatoms propagate by subdivision in huge numbers. Alkalinity, temperature, and the presence of high concentrations of silica in the water largely control diatom life. When the diatoms die the skeletons drop to the bottom of their habitat to form oozes of vary-ing thicknesses. DIATOMITES Diatomite, or diatomaceous earth, is composed essentially of the siliceous remains of the diatoms, although other organic skeletons are also present, especially in sea-water deposits where radiolaria, sponges and silico-flagellates are common. Impurities are generally carbonaceous material, fine-grained silt, volcanic ash and dust, and occasional coarse grains of sand. Diatomites are marine, brackish, or fresh-water, depending upon types of diatoms and their method of deposition.

Jan 1, 1939

By Robert M. Weidenhammer

For years before the war, Coal had the reputation of being a sick industry. Currently it is operating at peak production and succeeding pretty well in keeping out of the red. But, says Mr. Weidenhammer, it will have a relapse as soon as the war ends unless (1) working capital can be built up; (2) it gets the support of the people and Congress; and (3) a truly long-range national fuel policy is formulated.

Jan 1, 1943

By G. M. Ault, G. C. Deutsch

The paper reviews the efforts made to utilize powder metallurgy to solve problems encountered when using alloys at high temperatures. The following subjects are discussed: comparison of wrought and sintered super alloys, sintered aluminum powder, porous materials for transpiration cooling, molybdenum, and cermets. TODAY, powder-metallurgy techniques are be-JL coming increasingly important, producing materials which at the present time cannot be made by any other method. Among these materials are high melting-point metals such as tantalum and tungsten, porous metals for filters and lubricant-containing bearings, electrical contacts and electrodes (i.e., tungsten-copper), cutting tools of the cemented carbides, and magnet alloys. In addition, the powder-metallurgy industry has grown because, through the application of its methods, shaped parts, such as gears, can be produced at tremendous rates with a low scrap loss in comparison with manufacture by casting or forging and machining. In the past few years, by utilizing powder metallurgy, several approaches to the problem of high temperature materials have been investigated. In this paper the authors will review some of the studies on application of materials having properties above 1350°F. Since their experience lies in the aeronautical field, possible uses of powder-metallurgy techniques in the production of aircraft en- gines will be emphasized. A large portion of the work is classified, but such a restriction has not eliminated any field from discussion, although limiting the amount of detail it is possible to present. The development of high temperature alloys from powders and porous metals for cooling will be discussed as well as research done on molybdenum and molybdenum alloys, cermets, and intermetallics. Some studies on the utilization of cermets will be considered along with special problems that have been revealed through these investigations. Special interest in certain factors of sintered aluminum powder (SAP) makes it desirable to discuss this material although its use temperature is below the 1350°F limitation set for this paper. High Temperature Alloys from Powders In general, components made from powders for room-temperature application have been investigated with the primary purpose of taking advantage of the high production rates and economies made possible by powder metallurgy. From the standpoint of properties, the ojective of the powder metallurgist has been to obtain a product comparable to the cast or wrought product that is to be replaced. Comparisons of the properties of alloys made by powder-metallurgy methods with those of similar compositions made by casting and forging are reported in the literature.12 In many cases equivalent

Jan 1, 1955

By S. T. Wlodek

The scale md subscale reaction products were identified and their rates of formation were studied in air over the range 1600" to 2000°F (871 " to 1149°C) for periods of up to 400 hr and for hoth the solution-annealed and aged conditions. The effect of prior sltrface preparation on suhscale oxidation was also studied The general oxidation behavior of both Ni-Cr-Mo-Al-Ti type alloys was similar. A surface film of a, Al2O3, forms immediately on exposure Subsequent oxidation continued at a linear rate (QL = 55 * 5 kcal per mole) as colonies of Cr2O3 nucleated at the A12O3/gas interface Further oxidation proceeded at a paraholic rate zvhiclz could he fitted to two successive rate constants. During paraholic oxidation, and depending on temperature, the scale consisted of Cr2O3, NiCr2O4 , and TiO2 with traces of NiO. In the case of Rene 41, the activation energy of both paraholic processes was 66 * 3 kcal per mole suggesting that diffusion of cations tlzrozrgh Cr2O3 was the rate -determining process. An unusual decrease in the oxidation of Udimet 700 at 1900°F where a spinel of Ni(A1,Crh0, zuas the predominant reaction product prevented the accurate assignment of activation energies for this composition. In both alloys internal oxidation of Al2O3 commenced shortly after parabolic scaling was observed. Prolonged exposure prod7tced intemal oxidation of TiN, and in Udimet 700 a complex Mo-Ni nitride was also found. At 1900oF, the subscale reactions in Udimet 700 undergo an inversion which parallels the decrease in surface oxidation; internal oxidation ceases hut is replaced by the formation of "spherodized" 3.' colonies. Surface-preparation techniqtles which introduce appreciable working, such as coarse surface grinding or grit blasting. increase the amount of alloy depletion and internal oxidation in Reni 41. The reverse is true of Udimet 700 for which electropolished or mechanically polished specimens show much more subscale oxidation than strongly worked stirfaces. The strongest commercial nickel-base alloys presently available are generic to the Ni-Cr-Mo-A1-Ti base which exploits the precipitation of Ni3(A1,Ti) as the main strengthening mechanism, while relying on solid-solution strengthening by molybdenum and chromium reinforced by the pre- cipitation of carbides to attain maximum properties. This study characterizes the oxidation behavior of Rene 41, the strongest alloy of the Ni-Cr-A1-Ti type commercially available in sheet form, and Udimet 700, whose higher aluminum and titanium content allows it to exhibit one of the more attractive combinations of high-temperature properties available in a wrought product. The scaling processes of complex, type nickel-base alloys have received relatively little attention. Malamand and vidal as well as Poulignier et al.2'3 have determined the composition gradients across the metal/oxide interface produced by high-temperature oxidation and considered the effect of surface perature, Limited weight-gain data has also been published by Fere 5 for alloys of this type and Radavich6 has identified the reaction products on Udimet 500 and Inco 702 after oxidation at 1832°F. Reference can, of course, be made to the excellent reviews of Kubaschewski and Hopkins7 or Ignatov and Shamgunova8 for a summary of the data available on the oxidation of binary and ternary alloy systems which are related to the more complex alloys considered here. EXPERIMENTAL The analyses of the different commercial heats studied are given in Table I. Using the experimental procedures previously established,9 continuous weight-gain data were obtained on both heats of Rene 41 sheet (A and B) and 150-mil-thick slices of cast Udimet 700. Subscale oxidation reactions were followed by static exposure of cylindrical specimens obtained from swaged Rene 41 (Heat C) and Udimet 700 (Heats E and F). In brief, continuous weight-gain tests were performed on specimens with a surface area of 10 to 12 sq cm. These were abraded through 600 grit Sic paper, electropolished to 2p rms in an electrolyte of 10 pct H2So4 in ethanol, and lightly etched in 10 pct HCl in ethanol before final washing and rinsing in ethanol. All continuous weight-gain data were obtained in dried (-70°F dew point) flowing (1 liter per min) air to an accuracy of +0.1 mg. Subscale oxidation processes were followed by the metallographic examination of 0.5-in-diam by 1.0-in.-long specimens. After an initial center-less grinding, various additional surface treatments were employed to determine the effect of surface preparation on subscale oxidation processes. Before exposure in zirconia crucibles, all samples were lightly etched in 10 pct HCl-ethanol, washed in ethanol, and dried. The depth of internal oxidation was measured to ±0.00025 in. on unetched specimens mounted so as to provide a taper mag-

Jan 1, 1964

By Carl Swartz

METALLURGISTS differ considerably in their opinions regarding the effect, if any, of small amounts of iron pyrites, or other iron compounds on zinc sulfide ores during the roasting operation. As a result, the literature on this subject expresses many conflicting ideas. The ore, previously crushed to pass through a one-millimeter screen, dries in the roasting kiln, losing water up to 200° to 300° C. At 150° C. iron pyrites begin to lose sulfur. As the temperature increases, while the ore is passing to the hotter part of the furnace, the sulfur burns to sulfur dioxide, leaving the metals as zinc oxide and ferric oxide. These two substances then interact to form zinc ferrite, a compound, yellow brown in, color, having the general characteristics of a spinet Like magnetite, another spinel, zinc ferrite is insoluble in alkalis and dilute acids. As a result, when leached with 10 per cent. sulfuric acid solution zinc values tied up in this compound remain behind. HISTORY In the electrolytic recovery of zinc from its ores, the roasted ores are usually leached with a 10 per cent. sulfuric acid solution. When the zinc ore contains iron pyrites as an impurity in an appreciable amount, the actual yield of metallic zinc is much lower than a theoretical calculation would indicate. Further, losses of zinc are, in a rough way, directly proportional to the amount of iron pyrites or other iron compounds present. When the iron is present in the ore in an isomorphous relation to the zinc, as in the case of a marmatite, a greater amount of zinc remains insoluble than when present as a true pyrite or marcasite. Work on the insoluble residues obtained from leaching of the calcines shows that the zinc lost is intimately tied up in this residue. Some investigators have suggested a definite compound, such as zinc ferrite, others merely a mixture of zinc and iron compounds.

Jan 1, 1927

By R. Ehrlich, F. E. Crane

A consolidated porous medium is mathematically modeled by networks of irregularly shaped, interconnected pore channels. Mechanisms are described that form residual saturations during immiscible displacement both by entire pore channels being bypassed and by fluids being isolated by the movement of an interface within individual pore channels. This latter mechanism is shown to depend strongly on pore channel irregularity. Together, these mechanisms provide an explanation for the drainage-imbibition-hysteresis effect. The calculation of steady-state relative permeabilities, based on a pore-size distribution obtained from a Berea sandstone, is described. These relative permeability curves agree qualitatively with curves that are generally accepted to be typical for highly consolidated materials. In situations where interfacial effects predominate over viscous and gravitational effects, the following conclusions are reached. 1. Relative permeability at a given saturation is everywhere independent of flow rate. 2. Relative permeability is independent of viscosity ratio everywhere except at very low values of wetting-phase relative permeability. 3. Irreducible wetting-phase saturation following steady-state drainage decreases with increasing ratio of nonwetting- to wetting-phase viscosity. 4. lrreducible wetting-phase saturation following unsteady-state drainage is lower than fir steady-state drainage. 5. Irreducible nonwetting-phase saturation 101lowing imbibition is independent of viscosity ratio, whether or not the imbibition is carried out under steady- or unsteady-state conditions. Experiments qualithtiveIy verify the conclusions regarding unsteady-state residual wetting-phase saturation. Implications of these conclusions are discussed. INTRODUCTION Natural and artificial porous materials are generally composed of matrix substance brought together in a more or less random manner. This leads to the creation of a network of interconnected pore spaces of highly irregular shape. Since the geometry of such a network is impossible to describe, we can never obtain a complete description of its flow behavior. We can, however, abstract those properties of the porous medium pertinent to the type of flow under consideration, and thus obtain an adequate description of that flow. Thus, the Kozeny-Carmen equation, by considering a porous medium as a bundle of noninterconnecting capillary tubes, provides an adequate description of single-phase flow. With the addition of a saturation-dependent tortuosity parameter in two-phase flow to account for flow path elongation, the Kozeny-Carmen equation has been used to predict relative permeabilities for the displacement of a wetting liquid by a gas. 1-5 It has long been recognized that relative permeability depends not only on saturation but also on saturation history as we11.6,7 Naar and Henderson8 described a mathematical model in which differences between drainage and imbibition behavior are explained in terms of a bypassing mechanism by which oil is trapped during imbibition. Fatt9 proposed a model for a porous medium that consisted of regular networks of cylindrical tubes of randomly distributed radii. From this he calculated the drainage relative permeability curves. Moore and slobod,10 Rose and Witherspoon,11 and Rose and Cleary12 each considered flow in a pore doublet (a parallel arrangement of a small and large diameter cylindrical capillary tube). They concluded that, because of the different rates of flow in each tube, trapping would occur in one of the tubes; the extent of which would depend upon viscosity ratio and capillary pressure. They limited

Jan 1, 1970

By L. A. Norman

ANOTHER chapter in the history of Mother Lode mining is being written by operations in the Old Eureka mine near Sutter Creek, Amador County, California. During a two-year period (1938-1939), 85,517 tons of ore averaging 0.62 oz. gold per ton were mined and milled, as compared to the production of approximately 210,000 tons of 0.315-oz. gold ore during the preceding seven years. This is a repetition of mining history in the Mother Lode, where a period of prosperity has followed a long period of lean production. The location of this new ore in the hitherto unproductive hanging-wall greenstones and its mining and geological developments are most interesting. HISTORY OF THE OLD EUREKA MINE The Old Eureka mine, also known as the Hayward, Eureka, Hetty Green and Amador Consolidated, is in the most productive 10-mile length of the 120-mile long Mother Lode of California. The mine was first opened in 1852 with operations more or less continuous for the next 30 years. Production during this period amounted to $12,000,000 from an ore shoot 500 ft. long, which bottomed 1700 ft. below the surface. The shaft was continued as a prospect to 2065 ft. on the incline, where work was stopped in 1881. The mine was sold in 1916 by Hetty Green and the shaft deepened to the 3500-ft. level (3212 ft. vertically) by the new owners. Drifts were run on the 1700, 2100, 3000 and 3500-ft. levels, together with approximately 1500 ft. of crosscuts. No ore was found and work was abandoned in 1921. The present owners, the Central Eureka Mining Co., purchased the mine in 1924 after threatened litigation over rights to the rich ore shoot being mined from the lower levels of the Central Eureka mine on the south. Rehabilitation of the shaft commenced in 1926 and in 1930 mining on the old 2100-ft. level was started. While efforts of the previous owners had been directed for the most part toward the area south of the Old Eureka shaft and adjacent to the productive Central Eureka mine, the present owners started drifting northward on the old 2100-ft. level. On the 2000-ft., 2100 and 2300-ft. levels, drifts were run in part along the

Jan 1, 1939

By J. W. Pugh, J. D. Nisbet

THIS study of the ternary has been made as one phase of a metallurgical investigation which began nearly four years ago in the General Electric Company's Research Laboratory in Schenectady, N. Y. The objective of this program is the discovery of new metallurgical information which will lead to the development of better high-temperature materials. Combinations of the four pure base elements—iron, chromium, nickel, and cobalt—are being studied at the present time. It is essential in an investigation such as this to know as much as possible about the constitutional diagrams involved. The study of the iron-chromium-nickel system has been made to this end. Preliminary Explanation of Experimental Procedure: In all, fifty-five alloys at steps of 10 at. pct were made for the investigation of this ternary. Several ternary alloys in the chromium rich corner had to be omitted because their extreme brittleness made testing impractical. All alloys were vacuum melted with hydrogen reduction and centrifugally cast. The apparatus and technique of this process has been described in detail by Nisbet.1,2 The purity of the alloys prepared in this way is considered to be quite good. Impurities are listed as follows: Pct Carbon.............................0.02 Oxygen................................0.02 Nitrogen.........................0.005 Magnesium..................0.03-0.05 Sulphur...........................trace Hydrogen....................trace Phosphorous..................trace Silicon........................ trace After casting, all samples were given a homo-genization treatment which consisted of holding them for 15 hr at 1150°C (2100°F) and water quenching. Testing was begun with the samples in this condition. The tests employed in the study of this system were (1) dilatometer, (2) hardness versus aging temperature, (3) tensile strength and elongation versus temperature, (4) microstructure analysis, and (5) electrical resistance versus temperature. Dilatometer tests were made at the rather rapid heating rate of 1093°C (2000°F) in one hour on a Bristol-Rockwell type instrument. Hardness data were taken on specimens cooled from 204", 427", 649°, 760°, 871°, 982°, and 1093°C under conditions which are thought sufficient to bring the specimens to equilibrium in all but the cases of the very sluggish transformations. Electrical resistance data for several specimens were taken for both heating and cooling conditions in a vacuum furnace especially designed for this work by D. W. Bainbridge, formerly of this laboratory. Provisions were made for heating and cooling standard specimens at a constant rate, while autographic records of resistance and temperature were made simultaneously. Micrographs of all the alloys were made in the quenched condition. Some question may exist as to how such physical values as hardness, tensile strength, and elongation were interpreted to indicate a change in phase. Original data were recorded on physical property versus temperature graphs, each of which was made from the data of a single alloy (fig. la). From these, another series of graphs were plotted with the physical property as a function of composition for constant temperatures (fig. 1b). Sharp deviations in the slope of these composition versus hardness curves often indicate a change in phase. The example of fig. 1 will serve to describe this experimental technique. The plotting of a single point from graph "a" to graph "b," and finally to the phase diagram "c," is illustrated. The location of the point on graph "b" is indicated as point (1). If all the alloys of the A-B binary system were solid solutions at temperature X, the hardness in this curve would be expected to rise at a fairly even rate as A is diluted with B to a maximum at some intermediate value between A and B, as

Jan 1, 1951