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By H. H. Stout

IN the early fall of 1025, the writer was conducting, in the Ledoux and Co. labora-tory, New York, experiments directed to-ward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point. The apparatus consisted of a vertical I-in. dia. silica tube about 12 in. long, heated on the outside. The cathodes were broken to pass 3/8-in. mesh, and a current of various differ-ent gases was passed up through a 4-in. long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to 1500° to 1600°F. and the gas treatments lasted from 3 to 6 hr. The writer observed that whenever reducing gas (H2 or CO) was used, these cathode par-ticles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc., had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500°F." Smoot's reaction, after a few moments considera-tion, was, "It looks perfectly all right to me." The writer and his assistants, W. H. Osborn and H. H. Stout, Jr., after confer-ring as to ways and means, decided to go ahead with preliminary laboratory experi-ments, which, it was thought, would move the new process from the possible to the probable. This program followed a course indicated by three basic considerations: I. Since brittle cathodes were often unin-tentionally produced, it seemed probable that the laws controlling this type of deposi-tion could be ascertained. 2. We had already proved the gas-clean-ing feature. 3. There remained to prove: whether a sound, homogeneous metal billet could be produced with crystal growth established over the entire surface of each individual particle in the billet; and, if so, what would be the physical properties? Osborn arranged with Columbia Uni-versity for conducting experiments in its research laboratory to prove or disprove the third item; Columbia assigned C. A. Phillipi, Jr. to assist in the project. A press with a cylinder 2 in. high and of I-in. dia. was used. It was surrounded and heated by a resistance coil of Nichrome wire. Broken tough cathodes were used.

Jan 1, 1940

By C. R. King

Most of the acid volcanic glasses such as obsidian, perlite, pitchstone, pumice, and pumicite (volcanic ash) are susceptible to some expansion if suddenly subjected to a suitably high temperature in a properly designed furnace, and subsequently suddenly cooled. Expansion results from the action of chemically combined or dissolved water expanding as a vapor within the softened heated rock particles. This expansion forms countless minute bubbles within the pasty mass of the natural glass particles. If the particles are cooled before these bubbles can escape, the resulting products are cellular, more or less spherulitized glass froths or hollow glass spheres of many types. Chemically, they are essentially aluminum silicates containing about 70 to 75 pct silica, 10 to 16 pct alumina, and 2 to 7 pct sodium plus potassium oxides. They are relatively resistant to attack by acids or alkalies, are resistant to heat up to over 1000°F, and are completely inert to insect or fungus attack. These products are of great potential value in many branches of industry as insulation materials, aggregates, fillers, abrasives, and additives. By proper selection of the perlite rock type and control of processing conditions, expanded perlite of a bulk density varying from about 2 to 20 Ib per cu ft can be • made. The physical properties of the particles comprising a product of a given bulk density also may be varied within wide limits of porosity, water absorption, and crushing strength. In general, crushing strength of expanded perlite increases in direct relation to increase in bulk density, but insulating value varies in inverse ratio to bulk density. The selection of a particular grade of expanded perlite for a given use as an aggregate is therefore always a compromise between insulating value, lightness, and friability. If porosity and water absorption are factors affecting the use of the material, factors other than bulk density are important. Some types of perlite rock tend to decrepitate excessively during expansion, resulting in a highly porous or even hygroscopic product of high friability relative to the bulk density of material produced. In general, treatment of any good perlite rock below the temperature necessary for maximum expansion, or insufficient time in the hot zone of the furnace for effective heat penetration to the core of the rock particles will result in some decrepitation and high porosity in the expanded product. On the other hand, exposure of the material to the temperature required for optimum expansion for a period of time slightly longer than that necessary for proper heat absorption will result in a slightly heavier product of extremely low porosity, i. e., a glazed surface. It is beyond the scope of this paper to describe in detail the rock types and processing methods used to produce the many types of expanded perlite in present use, or that may be produced to fill the present and future needs of industry. A few phases of the economics involved in processing and selling products made from this abundant and cheap mineral raw material, plentifully distributed in large and relatively accessible deposits in most western states and in other areas within economic shipping distance of large centers of consumption, will be treated with particular reference to the Los Angeles area. Relation of Balk Density to Use and Cost of Production Perlite differs from most other lightweight aggregates and fillers in that the raw material (perlite rock) may be quarried much as rock arid sand is mined, and then shipped into consuming areas as crude rock in open gondola cars at correspondingly low freight rates and handling costs. At processing plants in or near large consuming areas the rock is converted into relatively fragile, very bulky products which in most cases are used within a short haul of the processing plant or enter into a manufactured product made at the site of the perlite processing plant.

Jan 1, 1950

By Peter M. Fozzard

The San Bartolomt silver deposit was discovered by a United Nations team of geologists working with a counter- part team of staff of the Ecuadorian Government's General Directorate of Geology and Mines (DGGM). The Phase I project over five areas of operation during which this discovery was made was financed through a United Nations Development Program contribution of $860,000 and an Ecuadorian Government participation of about $680,000 equivalent. Existence of mineralization at San Bartolomé was first recognized in 1966 when a reconnaissance geochemical stream-sediment program was carried out over a 10 500 km2 (4,054 sq mile) area centered around the city of Cuenca in southern Ecuador. Over the course of this project more than 10,000 samples of stream-sediment, soil, and rock materials were collected. Average costs per sample were $10.00, as follows: collection, $5; sample preparation, $1.60; assay work, $3.40. Initially in the program (1965-1966) sediments were collected along all motorable roads and tracks. Routine analyses, originally by colorimetry and later by AAS, were for Cu, Pb, Zn and occasionally As, Ni, and Co. Discovery geochemical samples from the San Bartolomé drainage area were among the first to be taken in 1965. As luck would have it, the road along which this traverse was taken passes only some 100 m (328 ft) downstream from the mineralized suboutcrop. The relevant two streams sampled are of inconsequential size, some 1 m (3.3 ft) in width, with a limited flow volume throughout the year. Original anomalies were recognized through cold-extractable Cu/Zn analyses. The pH of all river waters was also recorded at sample sites. Resampling the discovery sediments when AAS became available showed total extractable values of between 150 ppm-300 ppm Zn, 550 ppm Pb, and 10 ppm Ag. In 1967 the first followup was by rough-and-ready means. Dithizone field-kits (THM) were used to rapidly test soils from the surrounding area. The area has no outcrop. This work allowed the definition of an area of interest of some 2 km (1.2 miles) x 500 m (1640 ft). Six approximately 1 km (0.6 mile) to 1.5 km (0.9 miles) lines spaced at approximate 250 m (820 ft) intervals were established and used for IP surveys and soil sampling at 50 m (164 ft) intervals. Where one of the lines crossed the westernmost geochemical discovery creek a first-priority geophysical anomaly coincided with a major Zn/Pb (and later Ag) soil anomaly. A pit was sunk and encountered mineralized vein material at a depth of 1.5 m (5 ft). This lucky glory hole confirmed the geochemical discovery and prompted systematic followup. Immediately, costeaning of the west bank of the discovery creek, the Quebrada Ocashuaico, was carried out and exposed weathered and leached mineralization. Nearly 100 mineralized veinlets ranging in thickness from 0.5 cm (0.2 in.) to 8 cm (3 in.) were exposed across the 180 m (59 1 ft) costean. Sixty mineralized veinlets were determined over a 90 m (295 ft) wide zone. Sampling delineated minable widths averaging between 0.16 and 0.31 kg/t (5 and 10 oz per st) Ag with associated copper (very sporadic) lead and zinc. Over the period 1968- 1972 a considerable amount of detailed work was completed: detailed IP, EM Turam, magnetic and mise-a-la-masse geophysics, very detailed soil- sampling, trenching, drilling and glory-hole drifting, and cross-cutting. Numerous problems were encountered: the area was found to be a most difficult geoelectrical target; zero outcrop; pyrite (nonargentiferous zones) associated with faulting; mineralized groundwater; extensive clay development; loss of diamond drill-core, and no two-dimensional surface information. As the program developed the complexity of the structure was slowly unravelled, using a degree of good guesswork. Apart from photogeological and ground geological mapping at various scales, the following

Jan 1, 1985

By E. D. Gardner, E. M. Sipprelle

The Synthetic Liquid Fuels Act (58 Stat., 190; 30 U.S.C. Sup., Secs. 321-325) was approved by Congress April 5, 1944; it directed the Bureau of Mines to build demonstration plants to produce synthetic liquid fuels from coal, oil shale, and agricultural products. The most important oil-shale deposits in the United States are in the Green River formation of Colorado, Utah, and Wyoming. The oil shale of western Colorado generally is more amenable to exploitation, more persistent, and apparently richer than elsewhere in the Rocky Mountain Region. It occurs at the top of a high plateau surrounded by bold, nearly vertical escarpments 500 to 600 ft in height. The top 400 to 500 ft of these escarpments comprises an oil-shale measure that averages 15 gal of shale oil per ton; the bottom 70 90 100 ft of the measure, called the Mahogany Ledge, averages over 30 gal per ton. The full measure in a 1000-square-mile area is estimated to contain 300 billion barrels of shale oil;' the Mahogany Ledge is estimated to contain 100 billion barrels of oil. These estimates are based on numerous surfac,e samples and on core-drill holes drilled by the Government and by private enterprise. The oil-shale beds are undisturbed and lie nearly horizontal. The name "oil shale" is unfortunate, as the rock is a tough, strong marlstone. Organic matter named "kerogen" is a constituent of the rock. The oil-shale demonstration mine is on Naval Oil-Shale Reserve No. 1; it is about 5 1/2miles by mountain road from the plant site, which, in turn, is 2 miles from U.S. Highway 6 and 10 miles west from Rifle, Colo. The highway parallels the Colorado River, the Denver and Rio Grande Western Railroad, and a 66,000-volt public-utility power line. Early in the program it was realized that an oil-shale enterprise would have to be on a large scale to be commercial, and that unusually low mining costs would be necessary. The physical characteristics of the Mahogany Ledge and an overlying roof stone are unusually favorable both for large-scale operation and low mining costs. Quarry practices largely will be followed underground to mine the Mahogany Ledge. The aim has been toward complete mechanization of all mining operations. A mining unit would comprise a square mile containing 100,000,000 tons of oil shale with allowance for mining losses. An investment of $1,000,000 would be $0.01 a ton; such an expenditure, therefore, could be made to save, say, $0.015 per ton daily operating cost. A goal of a mining cost of $0.50 per ton was set up in 1945. Open-cut mining costs then were about $0.25 per ton of material handled; it was hoped that a cost double this amount could be obtained in mining the Mahogany Ledge. Costs of labor and supplies have increased since 1945 and so has the selling price of petroleum products. To those unacquainted with the character of the Green River deposits, the name "shale" suggested high mining costs. Others assumed that coalmining costs of $2 to $5 per ton would apply. To many, the expected mining costs appeared the principal handicap to the establishment of an oil-shale industry. The purpose of the Bureau of Mines is to demonstrate methods and to establish costs for mining the oil shale on a large scale. It is hoped this work will lead to the establishment of a large-scale, commercial oil-shale enterprise.

Jan 1, 1950

By Edward B. Walker, Michel Grosmangin

The geological and economic conditions peculiar to the Greater Oficina area are presented to demonstrate the necessity of a low-cost, well-site method of distinguishing gas-bearing formations. The method of gas detection with the neutron log is briefly discussed and its limitations are explained. A new method is described which consists in running a second neutron log with a larger source-to-detector spacing. Field data indicate that under favorable conditions the larger spacing response is proportionately more influenced by the virgin gas zone than is the shorter spacing response. One important condition is that the gas sands be invaded, with a diameter of invasion equal to about two to three times the hole diameter. The calibration of the longer spacing log is made so that the two logs read the same deflection in shale and in a known water or oil sand. Under such conditions, gas is indicated by a positive separation, i.e., the curve for the longer device is displaced to the right of the curve for the shorter device. Because of the non-linearity of the long spacing response, low porosity formations also show positive separations. In sands with large porosity variations, the gas sands can no longer he located visually. They can be detected on a plot of shorter spacing vs longer spac-ing deflections. INTRODUCTION In the Greater Oficina area of Eastern Venezuela, the rapid and accurate detection of gas from well logs is of primary importance because of a combination of economic, geologic, and operational conditions. Briefly, these conditions are: economic—there is no market for gas at the present time; geologic—a single well may contain as many as 30 or more oil or gas sands for which intervals -to be tested must be selected; opera-tional—first, once opened to the casing through perforations, gas sands are extremely difficult and expensive to squeeze off, and second, gas detection must be rapid because the geologist must decide immediately, at the well, which sand to perforate. During the early period of exploitation in Greater Ofi-cina, when clay base muds were used, sidewall samples, together with electric logs, gave fairly good distinction between oil and gas sands. When exploitation became concentrated on deep fields of poorer sidewall sample recovery, and after the advent of oil emulsion muds, now the standard drilling fluid in Greater Oficina, the regular neutron log became the most reliable indicator of gas. In 1953, R. Norelius devised the dual-spacing neutron technique for gas detection. The dual-spacing neutron log has proved to be highly successful in detecting gas and has been adopted as a regular survey by all of the oil companies of the area. Several hundred dual-spacing neutron logs have been run in Eastern Venezuela and several tests per well are available for positive evaluation of the logs. The findings outlined below are based upon this extensive field experience. GEOLOGICAL CONDITIONS OF THE GREATER OFICINA AREA The Greater Oficina area lies on the south flank of the Eastern Venezuela Basin (Fig. 1). Nearly all accumulations of oil and gas in the area are trapped, in whole or in part, against normal faults. All known oil and gas reservoirs in Greater Oficina occur in the Ofi-cina formation (Miocene-Oligocene) or in the "U" sands. The U sands are the lithologic equivalent of the Merecure group (Otigocene-Eocene), which contains oil in many fields north of Greater Oficina. Most of the petroleum produced in Eastern Venezuela is from the Oficina formation.

Jan 1, 1958

By H. Warlimont

Precipitation of cementite plates from carbon-rich austenite gives rise to localized formation of martensite in the matrix next to the precipitate upon quenching. The growth of this martensite is urmsually restricted. A distinct lattice relationship is found between this martensite and the cementite phase. It is concluded that the martensite is nacleated in the region of lowest carbon concentration at the austenite-cementite integace, with low-energy matching to the cementite lattice. The restriction of the growth of the martensite phase to the vicinity of the cementite plates can be explained by misfit in the austenite -martensite glissile interface and the uphill carbon gradient in the austenite. The investigation was carried out by light- and electron-microscopy and by electron-diffraction of thin foils. THE precipitation of cementite from carbon-rich austenite gives rise to a localized formation of martensite in the matrix next to the precipitate upon quenching. This behavior has been described previously by A. B. Greninger and A. R. Troiano1 for a 1.78 pct C steel ("pseudomorphic martensite"), and by A. Hultgren2 for a Fe-0.99 pct C—5.20 pct Mn steel. By measuring the axial ratio of the martensite phase,' it was found that the carbon content of this martensite was lower than that of the martensite which formed without prior partial transformation to cementite. Therefore, it was concluded that lowering of the carbon concentration in the matrix next to the precipitate raised the M, temperature locally and thus led to nucleation of martensite at the ce-mentite-austenite interface. However, the restriction of the growth of the martensite phase to the vicinity of the cementite plates cannot be explained by localized carbon impoverishment alone. Under ordinary conditions a martensite plate which has been nucleated in a favorable site can continue to grow until it encounters a physical barrier, or until it encounters a compositional barrier in the matrix, where the total free-energy change for the reaction is not negative, since it has been shown by numerous experiments that the activation energy for growth of ordinary martensite is virtually zero.' An investigation was conducted by transmission electron microscopy and electron diffraction to study this extraordinary martensite. It was expected that crystallographic in addition to compo- sitional conditions caused this abnormal mode of martensite formation. MATERIAL AND PROCEDURE An Fe-C-Mn alloy containing 1.15 pct C and 5.1 pct Mn was used for most of the experiments. For metallographic work, specimens 15 by 15 by 3 mm were used. For preparation of thin films, the initial specimen size was 15 by 15 by 0.7 mm. The heat treatment of each specimen consisted of austenitizing for 1/2hr at 1100'~ in an argon atmosphere, subsequent isothermal holding in a lead bath at one of a series of different temperatures, and, finally, quenching into brine at room temperature. For metallographic examination, the specimens were mounted in bakelite (slight tempering effects resulted from the heat in the mounting press) ground, polished, and etched in nital. Thin films for transmission electron microscopy and electron diffraction were obtained by grinding the specimens to approximately 0.2 mm thickness and subsequent electrolytical thinning. The orientation relationships were evaluated from sets of electron micrographs and selected-area electron diffraction patterns of single units of the transformation products and the adjacent matrix. RESULTS In the alloy which was used for the experiments, proeutectoid carbide precipitates over a wide tem-

Jan 1, 1962

By A. P. Pipilen, M. Weintraub, W. F. Hosford, A. A. 230-000-000-006 Orning

In a study of the principal factors affecting the transport of coal-water mixtures through a centrifugal pump and a pipeline, the interrelation between solids concentration, velocity, and pressure drop was established for a minus 2-in. bituminous lump coal in concentrations up to 48% by weight. Optimum concentrations were found to exist for maximum capacity of a given pipeline and for minimum energy requirements per ton of coal. Coal size degradation by particle fracture took place in the pump; abrasion and attrition to form fines took place in both pump and line. A novel system of studying flow of solid-liquid mixtures in pipelines by the determination of relative sound intensities was developed. The hydraulic transport of minerals is in part an established art and in part a relatively new field of industrial technology. The established art developed especially where the mineral was under water, where water was used in hydraulic mining, or where large quantities of water had to be pumped from the mining site to expose the mineral. Power requirements and limited life of pumps and pipelines, under such conditions, were relatively unimportant. Examples may be found in dredging, and in hydraulic mining and transportation of phosphate rock.' In the design of a coal pipeline the most needed information relates to flow characteristics, power requirements, pressure drop, size degradation, and size segregation as a function of solids-water ratio and size distribution of the mineral. A considerable amount of information has become available concerning pressure drop and energy requirements.2'3 These topics were therefore not studied intensively. Coal degradation, however, has not been clearly delineated. Lammers and coworkers4 showed that coal may be severely degraded in size but did not distinguish between degradation produced in the pump and in the line. It is the primary purpose of this paper to outline techniques used to acquire some of the much needed design data. A full report of the investigation is to be published by the Bureau of Mines at a later date. APPARATUS AND PROCEDURE The apparatus for circulation tests (hereafter referred to as Type III tests) consisted essentially of a loop and a centrifugal solids handling pump, with attendant instrumentation, and coal weighing and feeding equipment. It also included an adequate water supply, as shown in Fig. 1. The selection of 6-in., schedule 40, carbon steel pipe was based on the top size of coal to be used. Assuming that the top size of coal should not exceed 1/3 the inside diameter of the pipe, a 6-in. pipe would accommodate 2-in. coal, a realistic size for transport from the mine face. An 872-ft loop was constructed first. Later a few tests were made with a lengthened circuit of 1361 ft by superimposing an additional loop on the original one. All bends used were of 3-ft radius. A noisemeter microphone, taped to the pipe at various points, but generally about 50 ft downstream of the pump, was used to sense segregation of the coal and the length of slugs of coal in water. To measure the stream velocity, radioactive sources were encapsulated in plastic cubes. The specific gravity of the blocks was adjusted to 1.3 and 1.8 to simulate low ash and high ash coal particles. Their passage through the pipeline was detected by a Geiger counter. Because the repeated circuits of the Type III tests did not permit coal degradation in the line to be distinguished from that produced by the pump, the two

Jan 1, 1964

By Herbert Kilburn Scott

The information in this paper was collected by the author during a five years' residence in the State of Minas Geraes. Outside the State itself, very little is known of the gold-field. Such accounts as have been published are antiquated and contained in publications mostly out of print. The increased attention now attracted to the natural resources of Brazil, and the probability that American capital will be, in the near future, largely invested there, will make an up-to-date account specially useful at this time. I. Historical and General. Soon after the Jesuits founded what is to-day the city of S?o Paulo, gold was discovered in the streams of the neighborhood; and this incited the natives, known as paulistas, to look for it farther afield. After many expeditions into the interior, gold was found in quantity in placer-deposits in the vicinity of Ouro Preto, in 1699, by a prospecting party headed by Antonio Dias. The name of Ouro Preto (black gold) was given because of the superficial dark coating of the gold, and the inhabitants of the district were known as mineiros (miners). Later on, the placers of Cuiaba, in the State of Matto Grosso, were discovered in 1718, and those of the State of Goyaz in 1724. All this territory was at the time a private colony, but on account of its increasing importance it was taken over by the Crown, and in 1739 a royal governor was appointed, with his nominal capital in S?o Paulo, though for a number of years the real capital was Ouro Preto. In 1711 Ouro Preto was raised to the rank of a city, with the name of Villa Rica de Ouro Preto (" rich city of black gold"); and in 1720, by reason of administrative difficulties, Minas Geraes was constituted a separate colony from S?o Paulo, with Villa Rica as its capital. The site of this city

Jan 1, 1903

By R. A. Burmeister, P. E. Greene

Two methods for the synthesis and growth of single crystals of B6 P are described: a solution-growth process employing nickel as the solvent, and a vapor-growth process employing BBr3 and pH3 as the reac-tants. Relevant portions of the Ni-B-P phase diagram have been examined and liquidus data are presented for an isobaric section at an equivalent P2 pressure of 3.8 Torr, and an isothertnal section at 1300°C. Solution-growth techniques are described and the purity and crystalline perfection of the resulting material is discussed. Epitaxial growth of BeP on &P substrates has been obtained using the vapor-phase system. Evidence is presented which supports the assignment of the stoichioknetry B6P to boron sub-plwsphide. THE B-P system differs from other III-V systems in that it contains two distinct compounds. The existence of the monophosphide (BP) has been known for some time,' whereas the subphosphide (B6P) was reported only recently.' Both of these compounds are large bandgap semiconductors (Eg = 2.0 ev for BP~ and 3.3 ev for B6P4), and are therefore of interest for optoelectronic applications. The crystal structure of B6P is quite different from those of most semiconductors, being derived from that of a-rhombohedral boron by the incorporation of the two phosphorus atoms in the intericosahedral sites of the a-boron unit cell?76 B6P also exhibits a number of unusual characteristics, including a high degree of chemical inertness, hardness, and high-temperature stability. No information concerning other physical properties is available in the literature. The present study is part of a broader investigation of the preparation and properties of B6P. This paper considers methods of growing single crystals of B6P of suitable size and quality for physical-property measurements. A detailed discussion of the electrical and optical properties of B6P will be given elsewhere.' GENERAL CONSIDERATIONS The method first used to synthesize B6P was the disproportionation of BP' according to the reaction The equilibrium P2 pressures corresponding to this reaction were also determined .'" It is therefore possible, in principle, to apply several of the reactions reported for the synthesis of BP to the synthesis of B6P merely by selecting lower phosphorus pressures or higher temperatures, in accordance with the equilibrium data. Other techniques for the direct synthesis of microcry stalline B8P have also been reported.1°

Jan 1, 1968

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria 'Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By Carl J. Christensen

This paper presents the development of diamond coring of the Weber sand section in the Rangely Field, Colorado. The description and operation of the diamond-coring equipment is included as well as the economics and results obtained by its use. Diamond coring is compared with the other methods used for drilling the Weber sand. Two types of diamond coring are discussed. The first and the one used most extensively is the regular 6 ?x 3¾-in. diamond bit and bottom hole 50-ft barrel. The second type, which has also been used successfully by Stanolind, consists of a 4 13/16 x 2 11/32-in. cutting bit and reverse circulation coring equipment. The first type will be referred to as regular or conventional diamond coring while the latter type will be referred to as reverse circulation diamond coring. Introduction Diamond coring has been used for many years in mines, quarries, surface coring at dam sites, laboratory work, and so on, but, until recently, had never been used very extensively in coring oil sands and other oil-bearing strata. It was demonstrated early in its development that hard forma-tions could be cut rapidly and that core recoveries far exceeded those obtained with conventional hard rock bits and quite often 100 pet recovery was obtained. However, the poorly constructed diamond-coring equipment and resulting high costs of early diamond coring slowed down its progress. Early in the development Of the Rangely Weber field, Rio Blanco County, Colorado, the Rangely Engineering Committee selected key wells that were to core the Weber section in its entirety. These cores were to be analyzed and various sections tested to gather sufficient information so that accurate reservoir studies could be made. The number of wells selected were kept at a minimum inasmuch as the productive Weber section, which is found at an approximate depth of 6000 ft, is thick, being as much as 600 to 700 ft on top of the structure. The Weber section is also comparatively hard to drill. For instance, one well took 60 days to core 490 ft of Weber sand with conventional coring equipment. It was noticed, however, that Core Labora-verse diamond plug cutter could quickly cut a plug from. one of these hard cores. This fact led to the serious consideration of diamond coring the Weber sand. The first diamond coring at Randy was performed by Stanolind in August 1946 andl although we experienced some difficulties, the results definitely indicated that diamond coring would be successful at Rangely for .coring the Weber sand. As more wells were cored and the equipment improved somewhat, diamond coring became less expensive than drilling the Weber sand with the conventional rock bit. In less than one Year diamond coring has definitely Proved its usefulness in oil-field drilling operations in the Rocky Mountain area where formations quite often drill very hard. The practice of spot coring in hard oil-bearing formations with conventional coring equipment is giving way diaimond coring of the entire sections, thus givng an operator the complete picture.

Jan 1, 1948

By A. D. Hughes

A relatively small area in Malaya, about 200 miles long by 40 miles wide, is the most important source of tin in the world. Some tin is recovered in other parts of the peninsula. Of the tin mined, 98 pct is recovered from alluvial deposits. From 1935 to 1941 the average annual world production of tin was 190,000 tons. The average annual production from Malaya during the same period was 62,000 tons or about one third of the total. Other producing countries, in order of importance, were the Netherlands East Indies 34,000 tons, Bolivia 30,000, Belgian Congo, Nigeria, Siam, Burma, China, and a few others with smaller amounts. The serious shortage of tin during the war period was due to the fact that the Japanese were occupying Malaya, Netherlands East Indies, Siam, Burma, and China which, together, formerly were producing 65 pct of the world supply. Because of the importance of tin in the world economy, and because of the fact that little is generally known in this country regarding the methods of recovering the tin in Malaya, it is believed that a short description of the industry, as carried on there, may be of interest to many of the readers. In addition you may be interested in the effect of the Japanese occupation, subsequent recovery of the properties and conditions existing at that time. The Malay Peninsula lies at the southeast tip of Asia. Singapore, a British colony, is situated on a small island at the southern end of the peninsula. It is a city of nearly a million population, an important world port, the site of a large British naval base and of one of the tin smelters. The Federation of Malaya consists of nine states, plus Penang, Malacca, and other small areas formerly part of the Straits Settlements, and it now covers the entire peninsula. The civil administration is controlled by the British. A constitution was adopted recently after reaching agreement with the Malay Sultans of the various states, who retain control of religious matters. The Capital is at Kuala Lumpur, a city of about 200,000 population, 250 miles north of Singapore and about half way to Penang. The country covers an area of 51,000 square miles, an area about equal to that of Florida and about one third that of California. It has a population of about seven million consisting of Malays, Chinese, East Indians, and a relatively small number of Europeans. The principal products are tin and rubber. There are over three million acres of planted rubber. The country is not self-supporting agriculturally as about one third of the necessary food supplies is imported. Rice is the principal food of the Asiatic population and some of the recent unrest is caused by a shortage of rice and the consequent high price. Good highways have been built through the settled part of the country. A railway, Government owned, extends from Singapore northward through the entire peninsula. The climate is tropical but health conditions are good for a tropical country. I was in Malaya from 1939 until January 1942, during the time of the simultaneous air attacks on Pearl Harbor, Manila, Hongkong, and Singa-

Jan 1, 1950

By Carl J. Christensen

This paper presents the development of diamond coring of the Weber sand section in the Rangely Field, Colorado. The description and operation of the diamond-coring equipment is included as well as the economics and results obtained by its use. Diamond coring is compared with the other methods used for drilling the Weber sand. Two types of diamond coring are discussed. The first and the one used most extensively is the regular 6 ?x 3¾-in. diamond bit and bottom hole 50-ft barrel. The second type, which has also been used successfully by Stanolind, consists of a 4 13/16 x 2 11/32-in. cutting bit and reverse circulation coring equipment. The first type will be referred to as regular or conventional diamond coring while the latter type will be referred to as reverse circulation diamond coring. Introduction Diamond coring has been used for many years in mines, quarries, surface coring at dam sites, laboratory work, and so on, but, until recently, had never been used very extensively in coring oil sands and other oil-bearing strata. It was demonstrated early in its development that hard forma-tions could be cut rapidly and that core recoveries far exceeded those obtained with conventional hard rock bits and quite often 100 pet recovery was obtained. However, the poorly constructed diamond-coring equipment and resulting high costs of early diamond coring slowed down its progress. Early in the development Of the Rangely Weber field, Rio Blanco County, Colorado, the Rangely Engineering Committee selected key wells that were to core the Weber section in its entirety. These cores were to be analyzed and various sections tested to gather sufficient information so that accurate reservoir studies could be made. The number of wells selected were kept at a minimum inasmuch as the productive Weber section, which is found at an approximate depth of 6000 ft, is thick, being as much as 600 to 700 ft on top of the structure. The Weber section is also comparatively hard to drill. For instance, one well took 60 days to core 490 ft of Weber sand with conventional coring equipment. It was noticed, however, that Core Labora-verse diamond plug cutter could quickly cut a plug from. one of these hard cores. This fact led to the serious consideration of diamond coring the Weber sand. The first diamond coring at Randy was performed by Stanolind in August 1946 andl although we experienced some difficulties, the results definitely indicated that diamond coring would be successful at Rangely for .coring the Weber sand. As more wells were cored and the equipment improved somewhat, diamond coring became less expensive than drilling the Weber sand with the conventional rock bit. In less than one Year diamond coring has definitely Proved its usefulness in oil-field drilling operations in the Rocky Mountain area where formations quite often drill very hard. The practice of spot coring in hard oil-bearing formations with conventional coring equipment is giving way diaimond coring of the entire sections, thus givng an operator the complete picture.

Jan 1, 1948

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By J. W. Pamplin

Some 40 miles east of Tampa is the center of the Florida pebble phosphate deposits. These are of Pliocene age and consist of several members of the Bone Valley formation.1 Physically the phosphate-bearing formation, locally called the "matrix," varies in thickness from nothing to about 25 ft., usually averages 10 ft., and consists mainly of clay, quartz and phosphate pebble, the latter particles varying in size from colloidal to one inch diameter. The pebbles range in color from dark gray, through white, to cream, and in hardness from that which must be broken with a hammer to that which can be scratched with the fingernail. They assay from 66 to 80 per cent bone phosphate of lime (called "B.P.L." in the trade) or tricalcium phosphate (Ca³P2O8) and are secondary apatites. They form from 15 to 50 per cent by weight of the matrix. Over the matrix lies a varying thickness (5 to 40 ft.) of overburden composed of quartz and clay. Briefly, mining consists of two operations2 in open pits about 200 ft. wide by 1/2 mile or more in length. In the first step overburden is removed by large electric draglines at the rate of about 700 cu. yd. per hour. This is followed closely by hydraulic mining of the matrix at the rate of about 300 cu. yd. per hour. This matrix yardage is moved from an improvised sump in the floor of the pit to an ore-dressing plant, sometimes a mile distant, by one, two or three "pit-cars" (pumping units) working on a 12-in. pipe line called the "rock line" to distinguish it from the high-pressure water line feeding the hydraulic giants, which is known as the "hydraulic line." This 700 yd. of overburden and 300 yd. of matrix—1000 yd. in all-amounts to about 1500 tons of material moved each hour. The overburden is dumped into the mined-out pit alongside the pit being mined. The matrix moves to the ore-dressing plant at the rate of about 7% long tons in 4000 gal. of water per minute—a ratio of approximately one to two by weight, or one to six by volume. This constitutes the "mill heads," but in the pebble district it is called the "matrix."

Jan 1, 1938

By Orville R. Lyons

This paper presents a method whereby the amount of misplaced material and the difficulty of the separation can be used to compare coal cleaning equipment of all types, from effectiveness and capacity standpoints. The correlations presented do not include all types of equipment currently available, but the method can be used to evaluate any make or type of coal cleaning equipment, both old and new. THE relative performance of coal washing equipment, or the effectiveness with which any type or make of equipment removes impurities from coal, has been most difficult to evaluate in the past. The most widely used yardstick is the Frazer and Yancey efficiency formula developed in 1922,' but Yancey in a later article states that "washers treating coals of different density composition or operating at different densities of separation cannot be compared directly on the basis of this criterion."' Prior to and since 1922, a variety of other methods has been used for comparison purposes, including the distribution curve, the error area, and the "ecart probable" or probable error. Yancey and Geer in discussing these methods conclude, "Performance can be evaluated in a number of different ways, with the choice of the proper method to use being dictated by the objectives of the investigation and the data available."' It is true that performance can be evaluated in a variety of ways, but if the equipment is to be evaluated on an effectiveness basis, there should be only one universal comparison method. Varying methods have been used because one universal comparison method has not been found or developed. In the article previously quoted, Yancey and Geer state in clear terms the primary concept for a universal comparison method: "One of the simplest, and certainly one of the most obvious evaluations of washery performance is the quantity of sink material in the washed coal and the float material in the refuse. If the washery products are tested at the density at which the washing unit is operated, the sink in the washed coal and the float in the refuse represent material that has been misplaced." The quantity of misplaced material was used as a criterion of washery performance by Lincoln in 1913," by the United States Bureau of Mines in 1938,' by Hancock in 1947," and by the national French research agency Cerchar in recent years.' In 1950 Andersone proposed the use of this criterion as an efficiency value to replace the Frazer and Yancey formula. However, none of the above-mentioned investigators used the misplaced material concept in a manner that would provide universal coal-cleaning equipment comparisons. The Correlation Theory The ideal coal cleaning process would treat all sizes and would make a perfect separation at any given specific gravity. All material lower in density than the desired value would report in the coal product and all material higher in density would report in the refuse product. Unfortunately, no known cleaning process achieves this goal and there seems little likelihood that any process yet to be invented will do more than approach it. When coal is treated in volume under operating conditions, it is impossible to avoid mechanical entrapment, fluctuations in throughput and effective gravity of separation, and the creation of turbulent currents, even when a true heavy-liquid bath is used and the feed is closely sized and contains little intermediate gravity material. This being so, it is possible to appreciate the difficulties inherent in trying to obtain a perfect separation when treating a wide range of sizes and a feed containing high percentages of intermediate material, using turbulent currents to help create the effective separation gravity, under operating conditions which normally tend to be on the overload side. When coal is separated from refuse in any coal cleaning equipment, some refuse always reports to the coal and some coal to the refuse; the writer therefore assumed that there should be a relationship between the total amount of misplaced material produced by any given piece of equipment and the difficulty of separation as represented by the percentage of near gravity material in the feed. With small amounts of near gravity or k0.1 material in the feed there should be less misplacement of material than would occur with large amounts of near

Jan 1, 1953

By Leslie W. Austen

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, peri-clase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks. These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. I—The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2—As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3—If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4—Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a. problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spa11 being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1953

By Robert B. Sosman

The chance that a Howe Memorial Lecturer will be able to refer back to a personal contact with the distinguished metallurgist for whom this lectureship is named grows steadily I I did not have the pleasure of his personal acquaintance, but I did receive from him in 1916, quite unexpectedly, a letter commenting On a paper that I had recently published27 On "Types of Prismatic Structure in Igneous Rocks." The paper was written for geologists and petrologists, but it had an application, naturally, to the crystallization of iron and steel in a mold. The letter impressed me at the time, and still does, with the breadth of of Howe's interests and his perseverance in keeping up with the progress of any branch of knowledge that had metallurgical connotations. Scope of the Lecture During several years preceding the date mentioned I had worked in collaboration with Arthur L. Day and E. T. Allen8 at the Geophysical Laboratory, Carnegie Institution of Washington, on the temperature scale as defined by the nitrogen thermometer at high temperatures. Later (1928-1947) I had the opportunity of helping to apply this experience to the pyro-metric problems of the steel industry. Because of the range of its temperatures, the multiplicity of the methods used, and the variety of its purposes, pyrometry in the open-hearth process has always offered a fertile field for both research and development. I am therefore devoting an hour to the subject of temperatures in the basic open-hearth furnace, the furnace that makes most of our steel in the united States. I would direct your attention particularly to the choice of the first two words in the title of the Lecture. One sometimes hears or reads of the ((temperature of such-and-such a furnace," as if it were a single, measurable, characteristic quantity. I need hardly emphasize to any one who has ever operated a furnace or a kiln that " temperature of the furnace " is a meaningless phrase. Even if we confine our attention to the space enclosed by the roof, walls, and hearth of an open-hearth furnace, it is doubtful whether any such space has ever been so uniform in temperature that the phrase would have a meaning. In any furnace, there are many different temperatures, capable of being measured at many different places, and actually being measured for several different purposes. These pyrometric purposes, methods, and results, if given in detail, would expand this lecture into a book on the basic open-hearth process. I must therefore confine myself to a statement of the range of temperatures as they have been observed in various parts of the furnace, indicating in a general way why they are measured, and mentioning the methods that are available without attempting to describe these

Jan 1, 1949