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By Richard M. Foose

FIVE miles southwest of Mt. Holly Springs, Cumberland County, Pennsylvania, the Philadelphia Clay Co. has been mining and milling a white clay since 1896; for use in white cement, as a filler in rubber, pigment and paper, in the manufacture of insecticides, and for other minor purposes. Until late in 1942, when the mine was abandoned because of labor shortage, combined underground mining and surface stripping produced approximately 30,000 tons of clay a year, of which 10,000 tons were refined in the mill. GEOLOGY Lower Cambrian Antietam quartzite and the Montalto quartzite, stratigraphically older, trend N.55°E. and make a sharp 1600-ft. anticlinal ridge of the South Mountains. The Tomstown dolomite overlies the Antietam quartzite on the southeast flank of the anticline, which is displaced near its crest by a steeply dipping oblique fault. Erosion of the less resistant Tomstown formation has resulted in a narrow valley at an elevation of 700 ft. Directly on top of the Antietam quartzite and at the base of the Tomstown formation is a zone of sandy white clay, lenticular along the strike of the formations, ranging in thickness from 10 to 300 ft. within a mile. All of the formations dip steeply to the southeast, from 65° to vertical. The clay crops out at an elevation of about 1000 feet. ORIGIN AND CHARACTER The uppermost part of the Antietam formation is sericitic and schistose at many places, and at all these places weathering is in an advanced stage. The clay is the residual product of weathering of this sericitic quartzite or sandy schist. The crude clay has the physical aspect of a sandy kaolin, but there are large areas in the clay formation that are low in free silica, and commonly the 30 ft. adjacent to the Antietam quartzite is notably free of silica. The overlying Tomstown dolomite has been weathered almost completely to a mixed yellow and brown clay, which carries a zone of nodular and chunky limonite and manganese ore, 4 to 12 ft. thick, about l00 ft. from the contact with the white clay. In mining, this zone is an important "marker," indicating where the white clay may be expected in an advancing tunnel. The contact of the white clay formation with the yellow and brown clay of the Tomstown formation is relatively sharp, although the line of contact is irregular and therefore responsible for the lenticular character of the white clay formation. Following is an analysis of the refined clay containing less than one per cent of moisture when dried at 212°F.: Si02, 67.05 per cent; A1203, 22.27; Fe203, 0.40; CaO, 0.00; Ti02, 1.05; MgO, 0.52; Na20, 0.04; K20, 0.88; ignition loss, 7.65; total, 99.86.

Jan 1, 1944

By Robert L. Hoss

The application of Muskat's differential equations for predicting the performance of a solution gas-drive reservoir to the Fullerton field indicates that a recovery may be expected of 14,030 bbl per acre under primary depletion, and 15,910 and I7,190 bbl per acre, respectively, under the two pressure-maintenance programs analyzed. In this analysis it is assumed that fluid properties are the same throughout the reservoir, that the core data used are typical of the Clear Fork limestone in the locality, and that injected gas is completely diffused through the pay zones. The economic study of the three recovery programs considered indicates that the one in which 60 pct of the produced gas is returned to the formation is the most profitable. Introduction The purpose of this paper is to consider the effect of pressure maintenance by gas injection on the ultimate recovery of oil from a solution gas-drive reservoir. This prediction of reservoir behavior is the result of calculations based on the equations presented by M. Muskat in the Journal of Applied Physics, March 1945. Reservoir The reservoir analyzed is the Fullerton field in Andrews County, West Texas. It is situated on a broad anticlinal structure with approximately 330 ft of closure, and extends approximately eight miles north and south and five miles east and west. The areal extent is taken as 16,642 acres. The producing horizon is the Lower Clear Fork limestone of Permian age, occurring at depths from 6650 to 7350 ft. It is divided into four zones. For the purposes of this study, the fluid characteristics in all zones are assumed to be the same. Therefore an equivalent zone is assumed of thickness equal to the sum of the thicknesses of the four zones, or an average of 216 ft. The reservoir contains 3,586,991 acre feet of producing limestone, with an initial volume of stock tank oil in place of 918,-403,100 bbl. The average connate water saturation is 24.0 pct. The permeability ranges from 6.7 md. to 12.6 md., and the porosity ranges from 7.7 pct to 11.4 pct, except for occasional cavernous streaks. Based on these values, the limestone may be considered intergranu1ar.l Production histories and material-balance studies have indicated that the driving mechanism is solution gas. Water levels have been established. Theory It is possible to express mathematically the change in residual oil saturation with pressure decline in a solution gas-drive reservoir as being equal to the change in the physical properties of the fluids present in the reservoir as this pressure decline occurs. Essentially these equations, in differential form as presented by M. Muskat,2 express quantitatively the instantaneous net effect

Jan 1, 1948

By N. P. Peterson

The Castle Dome copper deposit is of the porphyry type and occurs in a body of quartz monzonite intruded into the pre-Cambrian formations and possibly into the lower part of Paleozoic limestones. The hypogene sulphide minerals include pyrite, chalcopyrite, and a little molybdenite, sphalerite, and galena. Pyrite and chalcopyrite are disseminated or occur in small closely spaced veins. The hypogene mineralization shows distinct zoning in the distribution of pyrite and chalcopyrite, so that the mineralized area can be subdivided into pyritc and chalcopyrite zones. Supergene enrichment, though not extensive, played an important part in the formation of the ore body, the chalcopyritc zone being the pro-tore. Several thin, gently dipping, diabase sills occur in the mineralized area, and the copper content of the rock in and near these sills is substantially higher than average. The formation of the ore body was caused by the combined effects of three forces: I. Zoning of the hypogene mineralization, 2. Richer copper metallization associated with the diabase sills, and 3. Supergene enrichment. Introduction The Castle Dome copper deposit is about 5 miles west of Miami, Arizona, and about 3 miles west of the Miami-Inspiration ore body. The Castle Dome open-pit mine is on the south flank of Porphyry Mountain, a prominent landmark of the region. In 1941 the deposit was being explored by the Miami Copper Co., but the exploration program was cut short when the decision was made to develop the property as a war project. The Castle Dome Copper Co., Inc., was organized as a wholly owned subsidiary of the Miami Copper Co., and arrangements were made with Defense Plant Corp. for developing and equipping the mine and for construction of a concentrating plant. Construction and development work was begun in January 1942, and milling operations started June so, 1943. Since that date, the mine has been in continuous operation by the Castle Dome Copper Co, under a lease agreement with Defense Plant Corp. producing copper at an average rate of 4,000,000 lb per month. To January I, 1946 the total production amounted to 121,088,000 lb of copper,4,271 oz of gold, and 211,755 oz of silver. A detailed study of the copper deposit and the surrounding area was undertaken by the U. S. Geological Survey in June 1943. Other members of the Survey participating in the work were C. M. Gilbert, G. L. Quick, and J. P. Albers. The results of this work will be published as a comprehensive report by the Geological Survey. General Geology The Globe quadrangle, which includes the Castle Dome area, was studied by F. L. Ransome1 of the Geological Survey in 1901 and 1902. His maps and descriptions were

Jan 1, 1949

By T. P. Meloy

The behavior of slime-sized particles in a flotation cell is neither well documented nor well understood. In general, slimes (or 'fines' as they will be alternatively called in this chapter) have been either ignored, eliminated, or treated empirically. Recently, however, some good experimental and theoretical work has been done that leads qualitatively to a clearer understanding of the problems involved. Fines are small particles that, owing to their smallness, behave differently from larger particles of the same material. The smaller the particle, the larger is its surface-to-mass ratio. The difference in the surface-to-mass ratio for a micron-sized particle and a centimeter-sized particle is 10,000 to 1. For our purposes we shall arbitrarily define any particle less than 10 µ 10-3 cm) as being a fine. This is generally considered the upper limit of colloidal-sized particles. Recently, the field of colloidal chemistry has successfully used the concept of the double layer to explain dispersion and flocculation of fine particles in a static system. Flotation, however, is a dynamic system due both to the turbulence of the liquid and to the coursing of the bubbles through the cell. Further more, a flotation system is a heterogeneous system in which there are a number of different types of particles which interact with one another. A further difficulty is that no two flotation systems are the same for minute quantities of a variety of common chemicals will alter the behavior of the system. These reasons make reproducible experimental results that can ex- plain fine-particle behavior difficult to obtain. In spite of these experimental difficulties, millions of tons of ore containing a large amount of fines are successfully floated every year. For example, at the Morning mill of American Smelting and Refining Co., a galena concentrate that was 42% -6 µ and a sphalerite concentrate that was 33% -9 µ were floated leaving a tailing that was 27% - 9 µ.l Ores that contain fines can generally be divided into two classes. In the first are those in which the valuable mineral tends to slime, such as galena and hematite. In the other class, one or more of the gangue minerals forms the slime; a typical example is barite. Though the problems due to the presence of fines are often the same in handling the two classes of ore, the method of handling them is different because of economic considerations. Nonmetallic mineral flotation is particularly affected by slimes, by either slime-coating effects or excessive reagent consumption. Though a given gangue mineral may not float under the conditions prevailing in the flotation cell, it may still be able to adsorb the collector. I£ it also slimes, a significant

Jan 1, 1962

By H. H

This paper describes the milling practice and operating results of the recently installed heavy-media separation plant of Barton Mines Corporation, the world's largest producer of garnet. This pioneer application of heavy-media separation (sink-float) processes for the beneficiation of a nonmetallic ore is unique in many respects, the details of which will be apparent from the following presentation. Characteristics of the Ore The property is on Gore Mountain, 5 miles west of the village of North Creek, New York, and 11 miles by road. The altitude of the mine is approximately 2800 feet. The valuable mineral, garnet, occurs in a surface deposit, the ore body being about ¾, mile long and varying in width from 50 to 300 ft. The garnet, principally almandite, Fe3Al2 (SiO4)3, occurs in a metamorphic rock of uncertain origin. The gangue mineral is principally hornblende, which constitutes from 40 to 80 per cent of the rock. The remainder of the gangue is divided between plagioclase feldspars and hypersthene, with smaller amounts of biotite, apatite and pyrite. The garnet content of the ore body varies from 5 to 20 per cent of the mass and averages about 10 to I2 per cent. The garnet occurs as crystals, mostly imperfectly developed, known locally as "pockets." These crys- tals vary in size from a fraction of an inch to a foot or more in diameter. Occasionally crystals have been found up to 30 and 36 in. in diameter but they average 4 to 6 inches. Nearly every crystal of garnet is surrounded by a rim of coarsely crystalline hornblende. The quarry faces are striking in appearance, showing crimson-red garnet crystals with their coal black rims scattered over a grayish black background. The specific gravity of the garnet is 3.8 to 4.1 while that of the hornblende ordinarily is 3-07 to 3.24. Some specimens of very dense hornblende have been found with a specific gravity as high as 3.40. The garnet crystals are laminated in structure, and readily cleave into flat, tabular pieces with sharp, chisel-like edges. Even when crushed to a very fine size, the garnet retains this flat, sharp, slivery grain shape. This characteristic, together with its hardness and toughness, gives it its value as an abrasive- Former Operations Mining operations have been carried on for 60 years. Until 1923, only the oxidized (soft rock) section of the ore body was mined. The oxidation, which affected the garnet only slightly, made possible the removal of the garnet from the rock by hand after it was blasted down, using small hand picks. In 1923 a mill was erected on the property, and was rebuilt and redesigned in 1928. Before the adoption of heavy-media separation, concentration was effected by

Jan 1, 1943

By John E. Miller

Unit Rig & Equipment Co., manufacturer of Lectra Haul trucks, is continually studying methods of reducing the operating costs of large haulage trucks. Reduction of haulage system operating costs is an important goal that equipment operators and equipment manufacturers constantly try to improve on. One of the most variable and important factors affecting operating costs is actual truck operating practices. An examination was centered on methods to optimize truck utilization. It was found that a very effective method of accomplishing this goal would be an automatic truck control (ATC) system to automatically control a fleet of haulage trucks in a predetermined pattern. Economic studies were conducted which showed a very favorable reduction in mine operating costs by use of an ATC system. In 1970, Unit Rig & Equipment Co., in conjunction with SAAB-SCANIA began preliminary development of adapting, for truck use, a proven automated control system, previously used for train systems, small trucks, and military target vehicles. In 1974, the first prototype system was installed on a Lectra Haul M-100 and tested extensively at Unit Rig's test track in Tulsa, OK. This truck and system were then displayed publicly at the 1974 convention in Las Vegas. In 1976, the system was redesigned for production to maximize reliability, ease maintenance, and to accommodate future control and-status reporting developments proposed for haulage trucks. The new design equipment was manufactured, and a full system test will be conducted in an actual open-pit mine for an extended period to evaluate reliability, compile economic data, and obtain application information to evaluate complete mine haulage system conversions to ATC. System Description The ATC system is designed to provide automatic control of all the vehicle functions normally accomplished by the vehicle operator. The basic system consists of the on-board control equipment and the wayside control equipment. The on-board equipment receives commands from the wayside equipment and controls all the truck functions. In addition, on-board sensors monitor all critical truck functions and provide instructions to the truck and system to assure safe operation. The wayside equipment consists of a buried guidewire, block control units and a central controller which provides predetermined signals to the on-board equipment for speed control, steering, and for auxiliary functions (dumping, horn, etc.) through the guidewire located in the truck's path. The wayside equipment also controls vehicle separation, system status, and provides truck location to a central display panel. The central control panel can vary the speed level signals over any segment and can also command an emergency stop to halt all the units. [Fig. 1] illustrates a typical ATC installation. If ATC is used in operations which require flexibility and mobility at the end of the ATC guidance network, the trucks can then be operated by either radio remote control or manually to complete their assigned functions.

Jan 1, 1982

By N. P. Peterson

The Castle Dome copper deposit is of the porphyry type and occurs in a body of quartz monzonite intruded into the pre-Cambrian formations and possibly into the lower part of Paleozoic limestones. The hypogene sulphide minerals include pyrite, chalcopyrite, and a little molybdenite, sphalerite, and galena. Pyrite and chalcopyrite are disseminated or occur in small closely spaced veins. The hypogene mineralization shows distinct zoning in the distribution of pyrite and chalcopyrite, so that the mineralized area can be subdivided into pyritc and chalcopyrite zones. Supergene enrichment, though not extensive, played an important part in the formation of the ore body, the chalcopyritc zone being the pro-tore. Several thin, gently dipping, diabase sills occur in the mineralized area, and the copper content of the rock in and near these sills is substantially higher than average. The formation of the ore body was caused by the combined effects of three forces: I. Zoning of the hypogene mineralization, 2. Richer copper metallization associated with the diabase sills, and 3. Supergene enrichment. Introduction The Castle Dome copper deposit is about 5 miles west of Miami, Arizona, and about 3 miles west of the Miami-Inspiration ore body. The Castle Dome open-pit mine is on the south flank of Porphyry Mountain, a prominent landmark of the region. In 1941 the deposit was being explored by the Miami Copper Co., but the exploration program was cut short when the decision was made to develop the property as a war project. The Castle Dome Copper Co., Inc., was organized as a wholly owned subsidiary of the Miami Copper Co., and arrangements were made with Defense Plant Corp. for developing and equipping the mine and for construction of a concentrating plant. Construction and development work was begun in January 1942, and milling operations started June so, 1943. Since that date, the mine has been in continuous operation by the Castle Dome Copper Co, under a lease agreement with Defense Plant Corp. producing copper at an average rate of 4,000,000 lb per month. To January I, 1946 the total production amounted to 121,088,000 lb of copper,4,271 oz of gold, and 211,755 oz of silver. A detailed study of the copper deposit and the surrounding area was undertaken by the U. S. Geological Survey in June 1943. Other members of the Survey participating in the work were C. M. Gilbert, G. L. Quick, and J. P. Albers. The results of this work will be published as a comprehensive report by the Geological Survey. General Geology The Globe quadrangle, which includes the Castle Dome area, was studied by F. L. Ransome1 of the Geological Survey in 1901 and 1902. His maps and descriptions were

Jan 1, 1949

By L. C. De Jong, J. F. Shirley, M. L. Campbell

At the Southern Peru Copper operation in Toque-pala, Peru, a new process flowsheet for the recovery of byproduct molybdenite has proved successful in dealing with complex and highly variable ores. This paper describes the process and the functions of each of the chemicals used. The Toquepala concentrator of the Southern Peru Copper Corp., located approximately 720 miles southeast of Lima near the Chilean border, processes a daily 36,500 tons of ore containing between 0.50 and 3.00% copper. The molybdenite content in the ore also varies greatly ranging from essentially nothing to as high as 0.15%. The 1966 yearly averages were approximately 1.20% copper and 0.03% molybdenite. The Toquepala porphyry deposit is a mushroom-shaped ore body consisting of a flat-lying enriched zone of predominant chalcocite with a stem-like extension of hypogene chalcopyrite ore in depth within and around a large breccia pipe.1 The underlying chalcopyrite ore has not been reached; however, due to the presence of a major post orebody fault, predominantly chalcopyrite ore is present in the north side of the pit. Most of the molybdenite occurs either as small, fine granular, pulverulent masses in vugs or empty voids of breccia, or as thin foliated masses and narrow thread-like filling in rock joints and fractures. The normal occurrence of quartz gangue with the molybdenite gives some basis for correlating the molybdenite mineralization to some later periods of silicification. On April 18, 1962, the molybdenite recovery plant at Toquepala went on stream, approximately 27 months after the copper concentrator had been in production. The plant was designed and built by Southern Peru Copper Corp.'s engineering and mechanical departments. The basic method chosen for separating the molybdenite from the copper concentrate was the sodium hypochlorite-sodium ferrocyan-ide process. The selection of this process was based on the results of an extensive testing program performed by the Colorado School of Mines Research Foundation, Inc. and the economic conditions of the area. The originally designed process could never be fully implemented due to a lack of sodium hypo-chlorite and has had to be continually modified to satisfy the requirements of the kaleidoscope of ores from the mine. The three basic problems that plague the operation of any molybdenite recovery plant are all present at Toquepala in large measure. Both the quantity of plant feed and the quantity of molybdenite contained in the plant feed are continuously changing. Even more detrimental to an efficient operation is the fact that the copper mineralization in the feed frequently changes once in every 24 hours and occasionally once a shift. From the point of view of the molyb-

Jan 1, 1968

By H. C. Johnson, J. K. Elliott

One of the primary requirements for successful operation of an enriched gas-drive project is to control the composition of injection gas. This can become a serious and difficult problem, particularly in cases where the enrichment material is being furnished from a number of field -produced gas streams. It is possible to effect control of the injection gas composition through frequent or continuous sampling; however, this can be extremely costly and, in many cases, impractical due to laboratory requirements of time. Another alternative would be to provide a calculation technique which would be flexible and sufficiently accurate to predict composition of the liquid and gas streams of interest at any point in the system. The purpose of this paper is to discuss a technique that was used successfully on an operating enriched gas-drive project for developing information which could be used for controlling composition of the injected gas. FIELD OPERATIONS The particular field (hereafter called Example field) in the example operation being discussed is composed of four oil reservoirs (A. B, C and E) and one gas condensate reservoir (D). Casinghead gas from the oil reservoirs and gas from the gas condensate reservoir are gathered through a field gathering system as shown in Fig. I for injection into Reservoir C. The gas mixture which is recovered from the five reservoirs for injection purposes is composed of gases liberated in 19 individual separators, each operating at a separate temperature and pressure. PROPOSED CALCULATION TECHNIQUE It is well known that vapor-liquid equilibrium calculations in general use throughout the petroleum industry can be used to predict reliably the phase behavior of hydrocarbon mixtures, particularly at pressures less than 1,000 psig. It is then a simple matter to account for the material on a ComPonent basis by m''ing flash and material balance calculations at each separation point in a hydrocarbon system. Accordingly, it was proposed to use vapor-liquid equilibrium and material balance cal- culations with a medium-sized electronic digital computer as a basis for developing a control procedure for use in controlling injection gas composition in the enriched gas-drive project. Although the approach is a simple one, the numerous vapor-liquid equilibrium calculations involved make the problem laborious; in this particular case, it would have been impractical to make sutficiently complete analysis without the aid of digital computing equipment. SAMPLING AND VERIFICATION OF CALCULATION PROCEDURE To obtain representative gas and liquid stream samples and to provide a quantitative measure of overall system Performance for comDarative purpLses, a thorough test of the field and plant system was conducted in the summer of 1957. Oil production at each battery was sta-

By Robert L. Hoss

The application of Muskat's differential equations for predicting the performance of a solution gas-drive reservoir to the Fullerton field indicates that a recovery may be expected of 14,030 bbl per acre under primary depletion, and 15,910 and I7,190 bbl per acre, respectively, under the two pressure-maintenance programs analyzed. In this analysis it is assumed that fluid properties are the same throughout the reservoir, that the core data used are typical of the Clear Fork limestone in the locality, and that injected gas is completely diffused through the pay zones. The economic study of the three recovery programs considered indicates that the one in which 60 pct of the produced gas is returned to the formation is the most profitable. Introduction The purpose of this paper is to consider the effect of pressure maintenance by gas injection on the ultimate recovery of oil from a solution gas-drive reservoir. This prediction of reservoir behavior is the result of calculations based on the equations presented by M. Muskat in the Journal of Applied Physics, March 1945. Reservoir The reservoir analyzed is the Fullerton field in Andrews County, West Texas. It is situated on a broad anticlinal structure with approximately 330 ft of closure, and extends approximately eight miles north and south and five miles east and west. The areal extent is taken as 16,642 acres. The producing horizon is the Lower Clear Fork limestone of Permian age, occurring at depths from 6650 to 7350 ft. It is divided into four zones. For the purposes of this study, the fluid characteristics in all zones are assumed to be the same. Therefore an equivalent zone is assumed of thickness equal to the sum of the thicknesses of the four zones, or an average of 216 ft. The reservoir contains 3,586,991 acre feet of producing limestone, with an initial volume of stock tank oil in place of 918,-403,100 bbl. The average connate water saturation is 24.0 pct. The permeability ranges from 6.7 md. to 12.6 md., and the porosity ranges from 7.7 pct to 11.4 pct, except for occasional cavernous streaks. Based on these values, the limestone may be considered intergranu1ar.l Production histories and material-balance studies have indicated that the driving mechanism is solution gas. Water levels have been established. Theory It is possible to express mathematically the change in residual oil saturation with pressure decline in a solution gas-drive reservoir as being equal to the change in the physical properties of the fluids present in the reservoir as this pressure decline occurs. Essentially these equations, in differential form as presented by M. Muskat,2 express quantitatively the instantaneous net effect

Jan 1, 1948

By E. A. Gulbransen, W. S. Wysong

THE behavior of molybdenum and its surface oxides in oxidizing and reducing gas atmospheres and in high vacua at elevated temperatures is a question of scientific and technical importance The use of molybdenum as a metal or as an important component in alloys in oxidizing atmospheres at elevated temperatures has been limited because of the unprotective nature of its oxide film and the volatility of this oxide at moderate temperatures. This communication will present results of a vacuum microbalance study 1,2 of the following problems. (11) the oxidation kinetics in the temperature range of 250° to 450°C; (2) the reduction with pure hydrogen of thin oxide films formed on molybdenum; (3) the volatility of the thin oxide films, and (4) the vacuum oxidation of molybdenum at high temperatures. Molybdenum is an interesting metal to study for the following reasons: (I) although the oxide-to-metal-volume ratio is greater than one, the metal is not considered protective; (2) the metal oxidizes readily at temperatures of 250°C and higher; (3) the oxides of the metal are reduced at temperatures as low as 500°C by pure hydrogen; (4) the oxide MoO3 melts at 795°C; and (5) the oxides of molybdenum are volatile at moderate temperatures. The following variables are studied in the oxidation kinetics. time, temperature, pressure, surface preparation, surface area, concentration of inert gas in the lattice, cycling procedures in temperature, vacuum effect and high temperature vacuum oxidation The general interpretation of many of these factors has been previously discussed. LITERATURE The oxidation of molybdenum has not been studied critically. Although" many studies have probably been made on the kinetics of the oxidation process, none has been reported in the literature available to us. The crystal structures found in the oxidation of molybdenum have been studied by Hickman and Culbransen 4 Their results showed that MoO2 is the oxide which is stable in contact with the metallic subgtrate throughout the temperature range 300 to 700°C. As the film thickens in the low temperature range, MoO3 becomes predominant on the surface. Above 400°C, Mo03 is no longer observed, Mo02 being the only oxide found. Hagg and Magneli5 have shown from an X ray study that the a-phase, orthorhombic MoO3 is stable up to 1050°C. Two other phases, ß and ß', with compositions close to Mo02 90 are also obtained The formula for the ß phase is not given but that of the ß' phase is defined as Mo9026. The ß' phase is found to be built upon a monoclinic unit cell. A -?-phase is isolated from a preparation M00275 heated for 17 hrs at 670°C. This phase is

Jan 1, 1947

By A. G. Guy

IN the course of a research on steady-state diffusion it became necessary to make diffusion calculations for a finite solid. This problem was found to be sufficiently different from the corresponding problem for the semi-infinite solid for an entirely new approach to be necessary in obtaining a useful solution. The assumption of an exponential variation of the diffusion coefficient with concentration' was no longer a practical necessity, so that the new solution offered the possibility of handling diffusion in semi-infinite solids for arbitrary variations of the diffusion coefficient with concentration. In discussing the principle on which this method of calculation is based, it is convenient to consider the relatively simple problem of one dimensional diffusion into a matrix that initially contains none of the diffusing substance. The solution of the set- ond Fick Law,?C/?t=D0?2C/?x2, for diffusion into a semi-infinite solid is3 C/C=1-F(x/2vD0t [1] where C is the concentration of the diffusing substance at a depth x cm below the surface after dif- A. G. GUY, Member AIME, and M. GOLOMB are Professor of Metollurgicol Engineering and Professor of Mathematics, respectively, Purdue University, Lafayette, Ind., A. S. YUE, formerly with Purdue University, is now with the Research Laboratory, Dow Chemical Co., Midland, Mich. TP 4505E. Manuscript, July 18,1956. fusion has occurred for t seconds; C, is the concentration of the diffusing substance at the surface of the matrix; Do is the diffusion constant, expressed in sq cm per sec; and + represents the Gauss error function. The corresponding solution for diffusion into a finite solid of thickness, 1, is conveniently written for the change in concentration, C+, at a point midway through the matrix and for times, t, great enough for the following equation to be used4 c1/2/C1=(1/2-2/?e-?2D0t/l2) [2] In Eqs. 1 and 2 the diffusion coefficient is represented by the symbol Do (rather than by D) to emphasize that these equations are valid only for constant values of D. To understand how these equations can be modified to take account of actual variations of D, such as that shown in Fig. 1, first consider the fact that for a given time of diffusion theconcentration at a given point is determined, not by the D value alone, but by the ratio x/vD0 in Eq. 1 and by a similar ratio, l2/D0 in Eq. 2. Even though in fact D varies, it is possible to keep this ratio constant by using a special coordinate system, x,, that varies with D in the appropriate manner. The necessary character of this special coordinate system can be easily visualized by imagining that

Jan 1, 1958

By John A. Brown

Granules are used primarily as roofing material. From the earliest times, man has been faced with the basic problem of providing protection for himself, his family, and his property against the ravages of the weather. Basically, this problem is no different today than in the past, except that today the trend is to demand shelter which is also colorful and distinctive. There has been a gradual evolution from the thatched roof to the modem ranchstyle home. In his search for a more permanent and more attractive roof, the home owner has utilized many mineral materials. All granules, whether slate or colored granules, are referred to by the asphalt roofing industry as "Slate Granules." Early Roofing Materials The development of mineral roofing in the United States followed two trends: first, the slate industry, and second, the bituminous products. The early colonists were familiar with slab slate construction from Europe and it was natural for them to continue with this type of roofing. As early as 1780, the forerunners of the present bituminous products were finding favor. Those early products consisted of saturating burlap or similar material with crude tar or pitch. This type of roofing was soon improved by dusting a variety of materials on the surface of the roofing to prevent adhesion while in rolls. Such factors as fire resistance and protection from the actinic rays of the sun soon followed. This started the general pattern which is still followed today, that is, saturating felt materials and supplying a uniform grade of crushed mineral to the surface. In commercial and public buildings, metal roofs found early favor. The attractive green color of verdigris-coated copper became a symbol of churches and institutions of learning. Aluminum roofing has become economical for large structures and is finding limited popularity in rural areas. Tile, asbestos, and cement materials, being weather resistant, found early acclaim and are still popular. Today, by far the most widely used roofing materials in the United States are asphalt products. Two important characteristics-economy and weatherability-account for their popularity. Influence of Building Trends on Roofing The postwar building boom in 1947 had many attractive features for the American people. The ranch-style one story type of home seemed well suited for suburban developments which sprang up in such profusion. As the roof in modern home construction is one of the most conspicuous aspects of its architecture, the home owner could now express his tastes not only in paint and landscaping, but could also select an attractive and harmonious roof color. Variety of Minerals Used Many naturally occurring minerals are used today in the roofing industry. Most widely used (and most noticeable to the public) is the granulated mineral surfacing applied to asphalt products. Selected natural colored granules as well as artificially colored granules are

Jan 1, 1960

By A. L. Marshall, F. J. Norton

THE object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel, iron and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760°C.oin a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and subsequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove. APPARATUS AND TECHNIQUE The apparatus is shown in Figs. I and 2. It consisted of two units, a degassing system and an analytical system. Each had a bake-out oven, as shown surrounding the systems in the sketches. The system will be traced, starting from the sample in the degassing system. A water-cooled quartz chamber surrounded the sample. The high-frequency coil, which heated the sample, extended only around this chamber and was cooled by an air blast. High-frequency power of 0800-meter wave length was obtained from a self-rectifying oscillator circuit with a maximum power input of 20 kw. A graded seal connected the quartz to the rest of the apparatus, which was of hard' glass. The temperature of the molybdenum sample was observed by an optical pyrometer through an optical window about 40 cm. distant from the sample. Since the object viewed under these conditions was not 'a black body, true temperature was not observed, but the so-called "brightness temperature." The correction of this to true temperature is discussed in a later section. The apparatus was taken apart just above the graded seal; the quartz chamber was slipped off, washed with nitric acid, water and alcohol, and dried by an air stream. The old sample was removed by

Jan 1, 1944

By N. K. Chen, R. Maddin, K. T. Aust

Lattice rotations occurring on the tension and compression sides during the bending of molybdenum single crystals at room temperature were followed in detail. Observations were also made concerning crystallite rotations and slip traces. &apos;The results indicated the participation of (110) as slip planes and the<111>as slip directions. Crystallite fragmentation during bending was also noted. EVERAL investigations have been conducted on pure bending of face-centered cubic metals.&apos;-" Structural changes as a result of "bend-gliding," and the importance of bending and constraints during conditions of axial stressing, have been noted.&apos;," It was evident that the mechanism by which the bending deformation occurs is more complex than the case of simple shear. Studies of the bending of body-centered cubic metals from the aspect of the crystallographic mechanism appear to be lacking. Molybdenum single crystals therefore were subjected to deformation by bending in order to determine the reaction of the body-centered cubic lattice to bending stresses. It might be expected for the bending of single crystals that lattice rotation as represented by the axis of compression would proceed toward the pole of the active slip plane and that rotation of the tensile stress axis should indicate the slip direction.&apos; It was believed therefore that a study of the tension and compression sides of bent molybdenum single crystals should give data concerning the operative slip system. Specific problems which are pertinent to the overall picture of plastic deformation were also investigated, e.g., whether the constraints offered by pure bending give rise to the deformation band, and also the nature of the asterism occurring on the tension and compression sides during the stages of deformation. Experimental Procedure Eight single crystal specimens were grown from sintered molybdenum rods 143 in. diameter using the method described previously.6 The purity of this material was reported as 99.9 pct as described elsewhere.&apos; The specimens were % to 1/10 in. in diameter x 7 in. long, with single crystals approximately 1 to 2 in. in length occupying the entire center sections of each specimen. The specimens were elec-trolytically polished using an electrolyte of 300 cc methyl alcohol, 60 cc H2SO4, 130 cc HCl, and a current density of 4 amp per sq in. Each specimen was then loaded in a bending apparatus similar to that used by Yen and Hibbard,&apos; as shown in Fig. 1. The load was applied by means of a spring and screw arrangement through four ball-bearing surfaces set 1.5 in. apart. Either the inner two bearings or the outer two (A, B, Fig. 1) were attached to a movable steel plate (D) through which the load was transmitted. Since the apparatus was mounted on a track of the X-ray apparatus, the tension or compression side of the specimen could

Jan 1, 1954

By Fred Bond

THERE is acute need for a method that will measure the size distribution of finely di-vided materials, particularly when the par-ticle sizes are smaller than the openings of the finest screen cloth regularly available for testing. Several methods and types of apparatus are in common use, but none are entirely satisfactory for all purposes. The commonest methods are microscopic grain counts, elutriation by liquids or air, and sedimentation. Valuable results have been secured by air elutriating devices, typified by the Haultain Infra-Sizer and the Pearson Air Analyzer. These are especially useful in obtaining sized fractions that can be examined and analyzed separately. They are particularly advantageous because the sizes of the sam-ples produced are adequate for a consider-able amount of subsequent manipulation and testing. The sedimentation methods, such as the Wagner and Klein turbidimeters, and the sedimentation balance, do not deliver sized fractions, but they do provide a means for reasonably rapid comparative determina-tions of fineness and surface area, which are important in many industries. The sedimentation balance consists essen-tially of a balance pan suspended in a liquid that contains falling particles. These are weighed as they settle onto the pan, and the time rate of settling is determined. The size distribution is computed from the set-tling rate. The balance appears to be in-herently more accurate than any of the other methods, and it has served a useful purpose in the study of numerous problems, but there have been limitations which have re-stricted its scope of application. Because of the essential simplicity of the method, it was felt that intensive investiga-tion might lead to modifications that would make it a valuable tool for the operators in industries that require precise information regarding the results secured from grinding equipment. A large number of size-distribu-tion determinations below 200 mesh were required in connection with a particular research problem in fine grinding. The sedimentation balance was used, in this investigation, and a technique was gradually developed that ultimately gave good results. A serious difficulty appeared, early in the work. It was discovered that less material always settled on the sedimentation pan and more on the bottom of the containing jar than could he accounted for by calculation, and also that the material that settled to the bottom of the jar outside the edges of the pan was considerably finer than that on the pan. This segregation was so great that the dis-tribution obtained for the finer sizes was obviously very much in error; material ground to about the degree of comminution of cement might have only 60 per cent of the calculated weight actually settling on the pan, and the error increased with the fine-

Jan 1, 1939

By H. L. Couch, J. D. Lubahn

In decarburized mild steel, the strain hardening arising from 1/2 pct strain can he partly recovered by subsequent heating, even though re crystallization or grain growth does not occur. This recovery varies from 5 pct in an hour at room temperature to 70 pct at 800°C. The variation with temperature was qualitatively similar to that reported for copper, but occurred at lower temperatures. Except for the initial portion (Bazdschinger effect), the stress-strain curve following recovery can be superimposed on the original curve by shifting it to the left. In other words, the tensile behavior is essentially the same after straining and heating as if there had been less strain and no heating. The importance of this observation in understanding simultaneous deformation and recouery is explained. AN earlier investigation1 on copper showed that strengthening due to strain hardening was augmented by heating at moderate temperatures, but was diminished by heating at higher temperatures, Fig. 1. Auxiliary experiments1 indicated that recovery and strain aging are independent processes, which may proceed simultaneously, and whose effects are additive as indicated in Fig. 1. In order to study recovery by itself, similar tests were made on decarburized mild steel, where strain-aging effects are known2 to be absent. MATERIAL, TESTING PROCEDURE The specimens were made from rimmed, hot-rolled SAE 1020 steel 0.040 in. thick, by stamping out rectangular blanks and end holes, Fig. 2, and pack milling the reduced section. These were wet-hydrogen treated2 for 16 hr at 720°C to remove carbon and nitrogen completely and then heated 1 hr at 850°C in vacuum to stabilize the grain size. Auxiliary ex- periments showed that heating up to 800°C will not cause grain growth. They were prestrained 5 to 7.5 mils per in. using the special grips shown in Fig. 2. Such small strains are less than the "critical" strain for recrystallization and, therefore, will not cause recrystallization, even at high temperature. The recovery treatment after prestraining and before the retesting consisted of heating for 1 hr in wet hydrogen at the desired temperature. In one test, Huggenberger gages were used to define more accurately the loading and unloading curves. Fig. 3 illustrates the creep during the early stages of unloading, the hysteresis due to cold stretching, and removal of hysteresis by heating.3 RESULTS The load-deflection curves had ratner widely differing shapes for different specimens, both before and after the recovery treatment. Some specimens showed perfectly smooth curves, Fig. 4, while others exhibited an inflection more or less suggestive of a yield point (Fig. 4 shows all extreme case). Some curves were much steeper than others; Fig. 5 shows two extremes. Some additional ex-

Jan 1, 1960

By Fred C. Bond

The process of comminution by grinding is properly classified as an art, rather than as a science. Like most other operations concerned in ore dressing, or in the treatment of nonmetallic minerals, the mathematical relationships of rock breaking are still obscure, and much disputed. If some basic formula exists, comparable for instance to E = RI in electricity, it has not yet been placed in common use. The absence of such a comprehensive mathematical background undoubtedly is the cause of many inefficient designs and installations, as well as of much poorly oriented experimental work. On the other hand, the mathematical immaturity of the process constitutes an opportunity for a real contribution on the part of those who enjoy mental pioneering. Some of the statements made in any such exploratory work may be little more than opinions, and it is to be expected that some will later be proved untrue; but such an evolutionary development is necessary if we are ever to arrive at the fundamental laws, the discovery of which can change the empirical art into a mathematically exact science. The most significant principle of comminution that we possess is probably Rittinger&apos;s law, which states that the work done in crushing or grinding is proportional to the area of the new surface produced. There is an alternative theory, known as Kick&apos;s law, which formerly was preferred to Rittinger&apos;s but which now is rather discredited. According to Kick, the work done in comminution is proportional to the volume, or weight, of the pieces broken, or to the cube of their diameters, while according to Rittinger it is proportional to the square of the diameters. Careful determinations of size distribution below the limit of sieve sizes1 indicate strongly that under ordinary grinding conditions the amount of new surface area produced is directly proportional to the net power input. Changes in the size ratio between the balls and the particles cause important differences in the proportion of the product that passes a given mesh size, but do not affect the total amount of new surface area; they merely change the distribution of the surface among mesh sizes. The principle of constant surface area is the logical result of Rittinger&apos;s law, and it may well have an important bearing on the comminution theories of the future. Formula for Ball Wear Grinding tests have been made in the Allis-Chalmers laboratory for more than 9 years, using a standard charge of mixed balls of different sizes; and a continuous record has been kept of the rates of wear of each size. These results have been combined and plotted in various ways in order to discover the relationship that exists

Jan 1, 1943

By R. Casting, J. Philibert, and C. Crussard

APPARATUS described in this paper uses the properties of X-radiation, emitted by substances under electron bombardment, as a means of rapid chemical point analysis. The method is based upon the principles of emission X-ray spectrography pioneered by Moseley in 1913. A very finely focused beam of electrons—the electron probe—is projected on the surface of a sample, which has a very large area compared with the beam diameter, at the point where it is desired to know the chemical composition. The minute volume of the sample which is thus irradiated emits a complex X-ray spectrum consisting principally of the characteristic radiations of the elements present in the volume. Measurement of the wavelength and intensity of each component of this spectrum thus affords a simple method of determining the chemical identity and concentration of these elements. The volume of sample which is analyzed at each position of the beam is limited by the diffusion of electrons in the sample. For an accelerating potential of the electron beam of about 30 kv, which is a convenient value for producing the characteristic radiation, this diffusion extends over a diameter of about 1 µ normal to the beam, and about 2 µ in the direction of the beam. Thus a beam of 1 µ in diameter leads to a volume of about 2 µ in diameter being irradiated. The limits of the analyzed region are thus considerably smaller than those obtained by using spark or arc emission spectrometry, which must extend to about 50 µ at right angles to the beam, and those obtained in X-ray fluorescence analysis, where the penetration of the specimen is considerably greater. The apparatus itself consists of three main parts: an electron optical system. an X-ray spectrograph and an optical microscope. The electron opticai system consists of a tungsten cathode emitting the electrow and a pair of magnetic lenses which focus the electron beam on the specimen to be analyzed. The specimen is prepared in the usual way, as in optical micrography. The X-radiation, emitted at the focal spot where the electrons strike the sample, is analyzed with a curved crystal, Geiger-Müller counter, vacuum spectrograph. The light microscope, designed to observe the surface of the sample in the region to be analyzed, is provided with a reflecting objective placed on the axis of the second magnetic lens. Its magnification is X450. The quantitative determination of an element A in the analyzed region is made by measuring the intensity I, of a strong characteristic line of the element, as emitted from the sample, and then the intensity I (A) of this same line as emitted from a

Jan 1, 1958

By J. W. Hickman, E. A Gulbransen

The physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,¹ if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth¹ is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn&apos;s6 0xidation measurements from 700°to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow WO a with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors7 presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947