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By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-'; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann's and Planck's constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962

By F. W. Jessen, John C. Miller

In many areas where carbonate rocks form important parts of the stratigraphic sequence, stratigraphers have experienced varying degrees of difficulty in differentiating and correlating limestone and dolomite units in both surface and subsurface work. With early Paleozoic rocks of the Mid-Continent, insoluble residues yield a remarkable amount of strati-graphic data and relatively good correlations may be carried over broad distances.' Unfortunately, neither such information nor electric logs and radioactive logs have been particularly helpful in interpreting the limestone sections of the Permian Basin of West Texas. This is because: (1) the variations in the sections may be very slight; (2) no completely satisfactory method of interpretation has been developed; and (3) the measurements themselves are not sensitive enough for small variations. Also, such logs are influenced by the fluid content. Paleontology and micro-paleontology remain the ultimate arbiters. As a routine tool, however, paleontol-ogical examination is slow and tedious. Chemical analysis may be used, but this, too, is extremely slow. Although rocks are not classified according to chemical composition, there is considerable variation with rock types. Correlation by chemical composition has two advantages, first, the characteristics determined are subject to minimum human error and interpretation, and secondly, the lithologic changes are not masked by fluid content as in the case of electric and radioactive logs. Some fossils concentrate certain elements which tentatively might be used to date rock units.' Rapid chemical analysis by spec-trographic means could be used as an adjunct to other means employed in correlation work, or might, in itself, present a suitable method. PURPOSE OF THIS INVESTIGATION Sloss and Cooke' have published data concerning spectrographic analysis of limestone rocks specifically for purposes of direct correlation of a single formation. These authors found satisfactory evidence that differences in percentage of four elements (Mg, Fe, Al, and Sr) in the Mississippian limestones of northern Montana were useful in carrying out correlation of this formation over a distance of approximately 50 miles. It was concluded from the preliminary work that the spectrochemical method offered possibilities of solution of some problems of correlation heretofore not possible. Since the work of Sloss and Cooke' was confined to one particular limestone zone, extension of the use of the method to examine two or more geologic formations would aid materially in the over-all problem of correlation of such rocks. Equipment is now available commercially with which very rapid spectrographic analyses may be made, and hence the problem was to determine whether the variations existing in the minor constituents of limestones were sufficient for use in possible correlation. Qualitative and semi-quantitative investigations were made to determine whether significant changes in the chemical condition occurred. It was a further purpose to investigate the geologic time-boundaries to see whether significant chemical variation could be found corresponding to the paleontological breaks. It was desirable to attempt correlation of a thick section of limestone or dolomite rock and to have as much information as possible on the section. Furthermore, it was felt that examination of formations more difficult to correlate by other means would enhance the value of the method should definite points of correlation be found. Samples were chosen from the Chapman-McFarlin Cogdell No. 25 well in the Cogdell field, Kent County, Tex., and from the General Crude Oil Co., Coleman No. 193-2 well in the Salt Creek field, Kent County, Tex. These fields belong to the famous series of "Canyon" reef fields of West Texas. Cores from the above wells were available from the United States Geological Survey, Austin, Tex. THE SPECTROGRAPHIC METHOD The choice of procedure to be followed in this investigation was based on the anticipated requirements peculiar to the problem. Since the problem was primarily to investigate the possibilities of applying the spec-trograph to problems of correlation in thick carbonate sections, a precise quantitative analysis did not appear necessary. A qualitative analysis to show the possible absence of presence of any element, or a semi-quantitative analysis of the elements present to show the relative changes in magnitude of selected elements was required. Both types of analysis were employed. The two most widely applied methods of semi-quantitative estimates are those of Harvey and of Slavin4,5 though various other procedures have been described.6 while the Harvey method has been modified by Addink,7 this refinement did not seem necessary to the present problem. Essentially, the procedure employed is a variation of the total energy method of Slavin with two exceptions: (1) stressing matrix effect, and (2) using densitometer measurements. As measured by a densito-

Jan 1, 1956

By Bruce Chalmers, D. C. Larson

Aluminum crystals with longitudinal-axis orientations of (111) . (110), and (100) were deforined in tension and annealed. The conditions of deformation were controlled so that the re crystallization nuclei originated in either the heavily deformed regions at saw cuts {artificial nucleation) or in the lightly deformed matrix (spontaneous nucleation). The artificial-nucleatioln experiments showed that in lightly deformed (110) and (100) crystals low-angle twist boundaries are most mobile, while in (111> crystals and heavily deformed (110) and (100) crystals high-angle tilt boundaries with near (111) rotations are favored. The spontaneous-nucleation experiments showed the existence of preferred orientations in the (111) crystals. The nonrandomness of the grain orientations is quantitatively determined through a comparison with the results which would he obtained from a randowl set of grain ovientations. PREVIOUS recrystallization studies have been performed on single crystals deformed in tension.1 7 The crystals used in these studies usually had random tensile-axis orientations and the extent of deformation was not a primary consideration. The present study concerns the recrystallization of single crystals with tensile-axis orientations of (Ill), (110), and (100). The emphasis of this work is on the influence of the tensile-axis orientation and the degree of deformation on both the nucleation and growth processes. The multiple-slip orientations were chosen because secondary slip or slip intersection promotes nucleation.1,5,8 These crystals recrystallize at lower strains than the crystals which are oriented for single slip. Also, the greatest variation in deformation behavior is exhibited by the multiple-slip orientations. The stress-strain curves for crystals with tensile-axis orientations of (111) are higher than the stress-strain curves for poly-crystals, and the stress-strain curves for crystals with tensile-axis orientations of (100) are lower (at large strains) than the stress-strain curves for the crystals which deform initially in single slip.g The recrystallization nuclei originated in either 1) the homogeneously* deformed matrix of the crys- tals or 2) the heavily and inhomogeneously deformed regions at saw cuts. The nuclei will be referred to hereafter as spontaneous and artificial nuclei, respectively. The two terms do not imply a difference in the nature of the nuclei; they imply simply a difference in the mode of introduction of the nuclei. During spontaneous nucleation very few (always less than ten) grains nucleate, while during artificial nucleation large numbers of grains nucleate. Only a fraction of the artificially nucleated grains penetrate very far into the deformed matrix during annealing. The grains that penetrate the farthest into the deformed matrix will be referred to as the dominant grains. EXPERIMENTAL PROCEDURE The thirty-five crystals used in this investigation were grown from the melt in milled graphite boats at a rate of 1.6 cm per hr. The crystals had dimensions of approximately 6 by 12 by 80 or 6 by 6 by 80 mm and the aluminum was of 99.992 pet purity. The as-grown crystals were annealed at 610°C for 24 hr and furnace-cooled. They were then heavily etched and electropolished in a solution of five parts methanol to one part perchloric acid. The crystal orientations were obtained by back-reflection Laue photographs and were accurate to ±2 deg. The tensile-axis orientations were (loo), (110), and (111). Two of the side faces of the (111) crystals were (110) lanes. The (110) crystals had both {100) and {110) side faces and the (100) crystals had (100) side faces. The crystals were deformed at a strain rate of 0.003 per min. Shear stress and shear strain were obtained by multiplying and dividing the tensile stress and strain, respectively, by the Schmid factor, m. For the (111) crystals m = 0.272 and for the (110) and the (100) crystals m = 0.408. The Schmid factor is effectively constant during deformation for all orientations. The deformed crystals were sawed into 1-in.-long specimens while the crystals were totally enclosed in a graphite boat. The sawing was performed very carefully in order to limit the plastic deformation to the sawed regions. The specimens were electropolished in the solution mentioned above to remove the sawed-end deformation as well as controlled amounts of surface material. A special stainless-steel grip was used to hold the specimens during the electropolishing treatment. The gripping faces were flat, with no teeth, to prevent the introduction of extraneous de-

Jan 1, 1964

By D. J. Brunner, S. Mathur, D. McKinney

With the advent of faster micro-processors, the use of numerical methods to simulate complex fluid dynamic phenomena in three dimensions for use in design has become prevalent in the automotive, and turbo-machinery industries. The Computational Fluid Dynamics (CFD) method divides the region of interest into small control volumes which form the mesh representing the physical characteristics of the problem, and uses the finite volume method to intergrate the equations for the conservation of mass, momentum, energy and species over each control volume. Recent developments in CFD software expedite mesh generation, and enable the use of unstructured grids, comprised of tetrahedral volumes in three dimensions and triangular areas in two. CFD more accurately represents complex geometries and allows for relative movement of meshes enabling simulation of multiple moving bodies. 'ibis paper presents two examples of how CFD simulation can be used to assess mine and tunnel ventilation problems formerly addressed by application of analytical solutions which were developed assuming ideal incompressible conditions. CFD simulation is used to evaluate the impact of varying the airflow in a descentionally ventilated airway on the layering along the roof of smoke and hot gases resulting from a vehicle fire. Control of the smoke layer is required to enable safe egress from the vehicle, particularly if the vehicle is for personnel transport, and to ensure control of the fire contaminants throughout the ventilation system. The airflow required to prevent layering against the ventilation direction, calculated from the Bakke and Leach relations (Bakke and Leach, 1962), is compared with the CFD simulation results. An evaluation of the pressures, generated as a vehicle enters a tunnel portal, using CFD simulation, is also presented for unflared and flared portal configurations. These simulation results are compared with predictions derived using an analytical method which assumes one-dimensional and incompressible flow. Results of the CFD simulation are presented in an animated video format. SIMULATION OF BACKLAYERING In designing a ventilation system for a transit tunnel, the ability of the ventilating air to control and prevent backlayering of smoke and hot gases resulting from a vehicle fire is of prime concern. The buoyant nature of hot smoke causes it to rise relative to the colder, fresh air provided by the ventilation system. If the vehicle fire occurs in a descentionally ventilated tunnel, the smoke may tend to move upgrade in a layer above the incoming ventilation airflow. The layer may become thick enough to engulf a substatntial part of the tunnel cross-section upgrade of the incident that comprises the evacuation route. This effect is termed "backlayering' and it is similar to the development of methane layers in mines for which most studies related to backlayering have been done. Prediction Techniques Analytical A number of studies have been conducted (Bakke and Leach, 1962) to define the characteristics of this phenomena and as a result have produced relations which are used both in the mine and transit ventilation fields to define the air velocities required to control layering. In the transit industry the air velocity required to prevent the backlayering phenomena from occuring during a vehicle fire is called the "critical velocity" (Associated Engineers, 1975) and is dependent upon a number of factors: tunnel height, cross-sectional area and grade; ambient air temperature and density; and the heat release rate of the fire. Common practice in transit ventilation design is to provide an airflow which meets or exceeds the critical velocity. In order to determine whether or not the critical velocity can be achieved with a particular ventilation system, a one-dimensional simulation of the tunnel network is typically performed using programs such as the Subway Environment Simulation program (SES) originally developed in the late 1970's (Associated Engineers, 1980). The results obtained from SES are compared to the critical velocity to determine the adequacy of the ventilation system. Computational Fluid Dynamics For the backlayering simulations, a commercial CFD code which has been used successfully in a wide variety of engineering applications, was used. It provides numerous options for modeling laminar and turbulent flows, multiple turbulence models, definition of multiple species and chemical reactions between them, a variety of boundary conditions (including constant pressure and constant velocity inlets) and the ability to apply user-defined FORTRAN subroutines. It includes the ability to model conductive, convective, and radiative heat transfer. FLUENT also permits the use of "body-fitted coordinates" to match the computational mesh or grid to complex real-world geometries. Computational Fluid Dynamics Model The model developed to simulate the backlayering phenomena is comprised of an airway of rectangular cross-section, 4 meters wide, 4.5 meters high, and 200 meters long. A laterally

Jan 1, 1995

By Susan T. Bagley, Kenneth L. Rubow, David H. Carlson, Bruce K. Cantrell, Winthrop F. Watts

Permissible exposure limits (PELs) have been established for gaseous pollutants, carbon monoxide (CO), carbon dioxide (CO2), nitric oxide (NO), nitrogen dioxide (NO2), and some gas-phase hydrocarbons emitted in diesel exhaust. There is, as yet, no PEL recommended for diesel exhaust aerosol (DEA), nor is there a standard method for sampling this aerosol. The University of Minnesota and the U.S. Bureau of Mines have collaborated to develop a personal diesel exhaust aerosol sampler (PDEAS) which utilizes size-selective inertial impaction and gravimetric analysis. During the field tests of this sampler, numerous air quality measurements were made in underground coal mines that use diesel equipment. The mine mean DEA concentrations for the five mines surveyed, determined with the PDEAS in the haulageway, was 0.89 mg/m3 with a standard deviation of 0.44 mg/m3. DEA contributed 52 % of the respirable aerosol at this location. In three of the mines filter samples were collected for DEAassociated polynuclear aromatic hydrocarbons (PAHs) and biological activity determinations. Two of the mines were also monitored for the major gaseous constituents found in diesel exhaust. In general, the PAH and biological activity levels were similar for all three mines, and indicate that up to 25 % of the haulageway concentrations may be contributed by outby diesel vehicles. Measured concentrations of CO, C02, NO, NO2, and SO2, were well below regulated levels. INTRODUCTION Diesel exhaust contains pollutant gases, such as carbon monoxide, carbon dioxide, nitric oxide, nitrogen dioxide, and gas-phase hydrocarbons, as well as DEA. Much of the health-related concern focuses on DEA and associated organic compounds (Watts, 1992a). A wide variety of these PAHs have been identified and some are known carcinogens and/or mutagens. The U.S. Mine Safety and Health Administration (MSHA) has proposed new PELs for these and other contaminants (MSHA, 1989). MSHA has also published an advance notice of proposed rulemaking to establish a separate PEL for diesel particulate (MSHA, 1992). The U.S. Bureau of Mines has collaborated with the University of Minnesota to develop and field test a PDEAS. The PDEAS is a three stage sampler based on the MSA' personal respirable dust sampler. It utilizes a respirable cyclone preclassifier followed by a 0.8 µm cut point impactor and afterfilter operating at a flow rate of 2 L/min. Respirable aerosol greater than 0.8, µm in size is collected by the impactor while DEA, less than 0.8 µm in size, is collected by the afterfilter. Hence, gravimetric analysis of the afterfilter permits measurement of DEA concentrations. This development and laboratory evaluation of the PDEAS were described previously by Cantrell (1990) and Rubow (1990). During field tests of the sampler, numerous air quality measurements were made in continuous miner sections of five underground coal mines that use diesel haulage equipment. These air quality measurements included levels of selected PAH and biological activity associated with DEA collected in the intake and haulageway areas of three of the five underground mines, and CO, CO2, NO, and NO2 in two of the mines. The objectives of this paper are to present the DEA and associated pollutant concentrations measured in these mines and to assess the impact of diesel face-haulage equipment on underground mine air quality. MINE DESCRIPTIONS The mines used for the PDEAS evaluation were designated J, K, L, N, and 0. Mines K, N, and 0 are located in the Western United States, while mines J and L are located in the East. Each mine produces high volatile, bituminous coal with shift production levels varying from 500 to 2000 tons/section. Seam heights varied from 1.5 to 3.0 m. Mines K and N use continuous mining to develop longwall panels. The others are strictly room-and-pillar operations using continuous miners. The number and types of diesel-powered vehicles used at these mines were described by Watts (1992b). Mines J, K, N, and 0 use diesel power to assist in a wide range of activities in addition to coal haulage. These included road maintenance, personnel and materials transport, lubrication, and welding. Mine L used only three diesel-powered shuttle cars to haul coal. SAMPLING AND ANALYSIS METHODS Aerosol Measurements Aerosol samples were collected in the mine portal area, the clean air intake to the continuous miner section, the haulageway one crosscut inby from the feeder breaker and belt, in the return airway, and on selected personnel. The haulageway sampling site was located near the point where the diesel-powered shuttle cars turn around to dump their loads. Additional respirable and DEA samples were collected and have been reported by Haney (1990).

Jan 1, 1993

By Thomas Foster

One of the most dreaded things which mining men sometimes have to contend with is underground mine fires, which are both dangerous and expensive. In the Reliance mines we have had considerable trouble with mine fires. We have at the present time five different fire zones, three of these zones give us considerable trouble and the other two have not given any trouble since they have been walled off. Fire Zone No. 1 comprises No. 2, 3 and 4 South Entries, about 50 acres are enclosed in this zone. Fire Zone No. 2 comprises the main drift entry from the mouth to the Old Boundary Plane and extends to the crop line, about 10 acres are enclosed in this zone. Fire Zone No. 3 comprises 1 and 2 North Entries from the main slope to the Old Boundary Plane, a distance of about 1,200 feet, about 15 acres are enclosed in this zone. Fire Zone No. 4 comprises 11/2 and 2 North Entries, a distance of 1,100 feet between New Slope and Old Boundary Plane, about 15 acres are enclosed in this zone. Fire Zone No. 5 comprises the inside end of No. 11/2 and 2 North Entries and 3 North Entry from the New Slope to 30 room, a distance of about 2,600 feet along No. 3 North Entry, about 20 acres are enclosed in this zone. The first mine fire started in No. 2 South Entry in No. 1 zone in 1914. Inside of No. 7 room on the high side of the entry, there was a soft piece of coal. There were no rooms driven in this coal and one day a fire was discovered in the solid pillar on the high side of the entry, work was started at once to load out this fire. and several places was driven into the pillar and cribs built where the coal was taken out, but this method proved a failure and a sand pack was put up along the entry between the track and the high rib. This consisted of timber set about 3 feet from the rib and 2-inch boards put behind the timber and sand or adobe put in between the boards and the ribs, and this method gave very good results except that it required close watching as the sand would settle and let the smoke out between the roof and the sand. Fire broke out in No. 3 South Entry in No. 1 zone in the summer of 1919. We sealed this fire off by building 36 fire stoppings, which also enclosed the fire in No. 2 South Entry and we have never had any trouble with fires in this zone since it was walled off. The fire started in No. 2 -zone in 1919 and has been very active ever since. When this fire was first discovered we built new stoppings in front of the old one in the room necks; we also opened up some of the room necks and loaded out part of the burning coal and rock but this did not help any, the fire, would burn out around the stoppings also burn along the roof between the top coal and the roof sometimes nearly across the entry. Several holes were drilled from the surface to the fire area and flushing the fire was tried but this was also a:\, failure, the rock above the coal was so hot that the mud would dry in the hole and fill it. In 1921 we started to take down the top coal along this entry, timber the entry and put 2-inch boards behind the timber and fill in between the coal and the boards with sand or adobe. We have at present over 1,000 feet of this work done and it has given us better results than any other method that we have tried. As the coal burns out behind the timber the weight breaks the timber and it is necessary to renew some of it. Fire broke out in No. 1 North Entry in No. 3 zone in 1922. There was a stopping in this entry that had been put in when the entry was finished some few years before. The fire burned around the stopping on the low rib of the entry, we built another stopping in front of the old one taking down the top coal and extending it up to the roof also digging in both ribs and setting the stoppings into the coal about 18 inches. This fire did not cause any trouble until June, 1924, when we discovered this fire was very active on the inside

Jan 1, 1924

By V. Steve Reed, Ed L. Reed

The in situ leach mining process generates a waste stream that is high in sulfates, total dissolved solids, and radium 226. During the mining phase, the volume of the waste stream is relatively low and consists primarily of the bleed stream. During the restoration phase, larger volumes of waste water are generated. These waste streams require environrnentally sound disposal. The low net evaporation rate in the Coastal Bend area precludes pond evaporation as a feasible disposal alternative. Reverse osmosis is a practical method of reducing the volume of the waste water handled, but the concentrated waste stream from the reverse osmosis unit must be disposed properly. Deep well injection into highly saline reservoirs is considered a sound method of disposing of the liquid waste generated by in situ mining in the Gulf Coast uranium district. Thirteen injection wells have been permitted to serve the disposal needs of the leach mining industry in Texas. Of these 13, 11 have actually been drilled. Seven applications are pending. The injection zones for the permitted wells range from depths of 3050 to 6200 feet. Pressure limitations imposed on these wells range from 500 psi to 1350 psi. The following criteria are used to determine the desirability of a disposal well site: 1. A minimal number of nearby, improperly plugged borings which penetrate the disposal zone; 2. Minimal crustal disturbance; 3. Sufficient salinity of the water contained in the disposal zone; 4. Protection of oil and gas producing zones; and 5. Sand of sufficient permeability and areal extent to handle the desired volume without fracturing the reservoir. 1. Improperly plugged borings: During the early part of the century, oil wells, gas wells and test holes were drilled using cable tool equipment, often with a minimum amount of surface casing. Production casing, when it was set, was often partly removed when the holes were abandoned. Thus, wells drilled prior to 1940 frequently have less than 100 feet of surface casing and either no production casing or the upper part of the production casing removed. Additionally, these holes are often plugged only with mud. The close proximity of these holes to an injection well location are a concern in that they can provide an avenue for injection-depth fluids to migrate up the bore hole and jeopardize shallower fresh water reservoirs. Usually, where there are more than 6 or 8 poorly plugged borings in a 2 1/2 mile radius of the well site, it is preferable to examine deeper zones for disposal well potential. The deeper zones are especially attractive where the borings are not in a cluster, which renders monitoring more difficult. Often, even the deeper disposal zones are penetrated by a few improperly plugged borings. When this condition arises, the potential for leakage through the borings can be addressed in the following ways. a. Demonstration that the static head in the boring is higher than the anticipated increase in bottom hole pressure generated at the boring by the disposal well. A 100 psi differential between these two pressures is recommended. The calculated increased pressure at a boring caused by injection should be refined using annual bottom hole pressure measurements in the disposal well. Figure 1 illustrates an injection pressure map which can be overlain on the oil well map to determine the anticipated increase in pressure expected at each oil, gas or abandoned hole. b. Shallow ground water monitoring. A shallow monitor well is drilled next to the boring and both pressure and quality measurements are made periodically in the shallow well. c. Disposal zone monitoring. Recently there has been a tendency for regulators to require disposal depth monitor wells instead of shallow well monitoring. We consider disposal depth monitoring to be a less effective method of monitoring because it provides only indirect evidence of potential problems. Assumptions have to be made for the unplugged borings, such as mud weight, that are not addressed by the disposal zone monitoring program. There is little improvement with this system to that discussed in "a" above. A shallow zone monitoring program, however, yields direct evidence of a developing problem with an unplugged boring. Leakage by the boring will be detected quickly by an abnormal increase in pressure in the shallow well. Quality monitoring will detect upward migration of poor quality fluids. The pressure data provide an early warning of impending leakage; the quality monitoring will detect actual fluid migration.

Jan 1, 1980

By G. M. Schwartz, G. A. Thiel

Dimension stone was first quarried in Minnesota in 1820 and a very active industry has grown up over the years. The main basis of the present industry is a wide variety of igneous rocks sold under the general trade name of "granite." Also of considerable importance is the Ordovician dolomite sold under the locality names, Man kato, Kasota and Winona. THE first record of the quarrying of dimension stone in Minnesota dates back to 1820 when limestone was quarried locally for part of old Fort Snel-ling. Limestone quarries were operated at Stillwater, Mankato, and Winona as early as 1854. Granite was quarried first at St. Cloud in 1868, and within a few years thousands of tons were shipped to widespread points. Rough dimension stone for large buildings furnished the first important market, but beginning in 1886 paving blocks were in demand. The largest shipment was in 1888, when 1925 cars were shipped from the St. Cloud area. Quartzite was quarried first at New Ulm in 1859 and somewhat later at Pipe-stone and elsewhere in southwestern Minnesota. The productive dolomite quarries at Kasota were opened first in 1868 and have continued as large producers of a variety of stone to the present time. At present, the industry is controlled by relatively few operators, and for that reason detailed figures on dimension stone are not released for publication. A general idea may be obtained from the data in the Minerals Yearbook for 1948. The figures for total stone produced in Minnesota are 1,804,000 tons valued at $5,090,652. Probably the largest item in the latter figure is received from dimension stone. A better idea of the situation in relation to the country as a whole may be gained by using the data for 1930 when more companies were operating in Minnesota, and complete figures were published. In that year Minnesota produced granite valued at $2,668,119 and ranked third among the states in value. Minnesota's production of granite was almost exclusively for dimension stone. In the same year Minnesota produced 300,000 tons of limestone (dolomite) valued at $840,860, and this likewise was mainly dimension stone. In finished limestone Minnesota ranked second among the states in 1930. Sandstone and minor amounts of quartzite are the only other dimension stones that have been produced in Minnesota, but the quarries are now inactive. The commercial stones of Minnesota have been described in two reports by Bowlesl and by Thiel and Dutton. The early history of quarrying in Minnesota and extensive notes on the various rocks are given by N. H. Winchell.8 Small limestone and dolomite quarries were numerous throughout the area of Paleozoic rocks in southeastern Minnesota. Early production was largely dimension stone. With the increased use of Portland cement, most of these ceased production, and today only those at Kasota and Winona remain in operation. In recent years many quarries have reopened and new ones started, but these are devoted to the production of crushed rock and agricultural lime. As the application of modern quarrying and finishing methods increased, small companies in the granite business have dropped out, and the remaining companies have modernized their plants, purchased old quarries, and opened up new ones, thus furnishing a wide variety of granites suitable for most of the customary uses. It is the purpose of this review to present notes on the geology and operations of each of the quarries now operating within the state. Granites and Related Igneous Rocks The term granite as used in this report includes granites, gneisses, diorites, gabbros, and other igneous rocks. The granites of greatest economic importance are found in three widely separated regions, see Fig. 1. 1—Central Minnesota in the region of the city of St. Cloud, 2—the upper Minnesota River valley region, 3—the northeastern portion of the state, commonly referred to as the Arrowhead region. The St. Cloud Region: The rocks of the St. Cloud region are mainly granites and related rock types such as monzonites and quartz diorites. The stones may be grouped into three major types, namely, pink granite, red granite and gray granite. Most of the pink granite occurs in the area to the southwest of St. Cloud. The rock is best described as stone with large pink crystals set in a finer grained black and white background. The minerals of the matrix occur in remarkably uniform sizes, and the pink crystals are sufficiently uniform in their dis-

Jan 1, 1953

By G. M. Schwartz, G. A. Thiel

Dimension stone was first quarried in Minnesota in 1820 and a very active industry has grown up over the years. The main basis of the present industry is a wide variety of igneous rocks sold under the general trade name of "granite." Also of considerable importance is the Ordovician dolomite sold under the locality names, Man kato, Kasota and Winona. THE first record of the quarrying of dimension stone in Minnesota dates back to 1820 when limestone was quarried locally for part of old Fort Snel-ling. Limestone quarries were operated at Stillwater, Mankato, and Winona as early as 1854. Granite was quarried first at St. Cloud in 1868, and within a few years thousands of tons were shipped to widespread points. Rough dimension stone for large buildings furnished the first important market, but beginning in 1886 paving blocks were in demand. The largest shipment was in 1888, when 1925 cars were shipped from the St. Cloud area. Quartzite was quarried first at New Ulm in 1859 and somewhat later at Pipe-stone and elsewhere in southwestern Minnesota. The productive dolomite quarries at Kasota were opened first in 1868 and have continued as large producers of a variety of stone to the present time. At present, the industry is controlled by relatively few operators, and for that reason detailed figures on dimension stone are not released for publication. A general idea may be obtained from the data in the Minerals Yearbook for 1948. The figures for total stone produced in Minnesota are 1,804,000 tons valued at $5,090,652. Probably the largest item in the latter figure is received from dimension stone. A better idea of the situation in relation to the country as a whole may be gained by using the data for 1930 when more companies were operating in Minnesota, and complete figures were published. In that year Minnesota produced granite valued at $2,668,119 and ranked third among the states in value. Minnesota's production of granite was almost exclusively for dimension stone. In the same year Minnesota produced 300,000 tons of limestone (dolomite) valued at $840,860, and this likewise was mainly dimension stone. In finished limestone Minnesota ranked second among the states in 1930. Sandstone and minor amounts of quartzite are the only other dimension stones that have been produced in Minnesota, but the quarries are now inactive. The commercial stones of Minnesota have been described in two reports by Bowlesl and by Thiel and Dutton. The early history of quarrying in Minnesota and extensive notes on the various rocks are given by N. H. Winchell.8 Small limestone and dolomite quarries were numerous throughout the area of Paleozoic rocks in southeastern Minnesota. Early production was largely dimension stone. With the increased use of Portland cement, most of these ceased production, and today only those at Kasota and Winona remain in operation. In recent years many quarries have reopened and new ones started, but these are devoted to the production of crushed rock and agricultural lime. As the application of modern quarrying and finishing methods increased, small companies in the granite business have dropped out, and the remaining companies have modernized their plants, purchased old quarries, and opened up new ones, thus furnishing a wide variety of granites suitable for most of the customary uses. It is the purpose of this review to present notes on the geology and operations of each of the quarries now operating within the state. Granites and Related Igneous Rocks The term granite as used in this report includes granites, gneisses, diorites, gabbros, and other igneous rocks. The granites of greatest economic importance are found in three widely separated regions, see Fig. 1. 1—Central Minnesota in the region of the city of St. Cloud, 2—the upper Minnesota River valley region, 3—the northeastern portion of the state, commonly referred to as the Arrowhead region. The St. Cloud Region: The rocks of the St. Cloud region are mainly granites and related rock types such as monzonites and quartz diorites. The stones may be grouped into three major types, namely, pink granite, red granite and gray granite. Most of the pink granite occurs in the area to the southwest of St. Cloud. The rock is best described as stone with large pink crystals set in a finer grained black and white background. The minerals of the matrix occur in remarkably uniform sizes, and the pink crystals are sufficiently uniform in their dis-

Jan 1, 1953

By S. L. Craig, C. Orr, H. G. Blocker

WITHIN recent years gas adsorption methods have been developed for measuring the surface area of finely divided materials and have become extremely valuable in research on the corrosion and the catalytic activity of metals. Rather elaborate apparatus is required, and a single determination is so time-consuming that these methods have not been utilized to the fullest extent; the methods are un-suited for most routine control work such as that encountered in powder metallurgical operations and in processes employing metal catalysts. These difficulties are largely eliminated, and surface area is reduced to a routine determination if the liquid-phase adsorption of a surface-active agent such as a fatty acid can be used. When the affinity of the fatty acid carboxyl group for the solid surface is greater than its affinity for the solvent, a unimolec-ular layer of orientated fatty acid molecules will be formed at the solid-liquid interface in a manner similar to that of a compressed fatty acid film on a water surface. The measurement of surface area is then reduced to a measurement of fatty acid adsorption. This propitious circumstance, first investigated by Harkins and Gans,¹ has been employed with somewhat inconclusive results by a number of investigators in evaluating the surface properties of metals, metal catalysts, and metal oxides. The specific surface area values for nickel and platinum catalysts, determined from the adsorption of a number of fatty acids from various solvents, were found by Smith and Fuzek² to agree with values calculated by the gas adsorption technique of Brunauer, Emmett, and Teller," he so-called BET technique. And recently Orr and Bankston4 have also reported good agreement between nitrogen gas and stearic acid adsorption results in the measurement of the surface areas of clay materials. On the other hand, Ries, Johnson, and Melik5 found only order-of-magnitude agreement between these two methods in studying supported, cobalt catalysts having specific surface areas as great as 420 sq m per g; the reason is partially attributable to the very porous nature of the materials. Greenhill,6 investigating the adsorption of long-chain, polar compounds in organic solvents on a number of metal powders, concluded that a uni-molecular layer of stearic acid was formed on exposure of the solid to the acid solution and that the presence of an oxide or another film did not alter this result. Furthermore, the adsorption process appeared to be the same whether or not the sample was degassed prior to exposure to the solution. Greenhill estimated the surface area of one of the powders he investigated from microscopic diameter measurements, and obtained a rough check with surface area evaluation. Russell and Cochran7 found moderate agreement for alumina surface area results by fatty acid and gas adsorption methods. In addition, they also found that the prolonged heating and evacuating pretreatments previously used by investigators were unnecessary. The present work, however, considerably extends these previous investigations, shows that fatty acid adsorption can be used to determine the surface area of a variety of metals and metal compounds, offers further confirmation of the correctness of gas adsorption methods, and presents a simplified technique for the determination of the metal surface area which is suitable for routine work. Experimental Technique Basically, the fatty acid adsorption method is quite simple. It consists of exposing a sample of the material of which the surface area is desired to a fatty acid solution of known concentration. By analysis of an aliquot of the solution, the concentration after adsorption has occurred may be determined. The difference between the initial quantity of acid in solution and the final quantity is that quantity of acid adsorbed by the sample. The specific surface area of the adsorbent material may be calculated from the quantity adsorbed and the weight of the sample. In agreement with the findings of others as outlined above, it was found entirely unnecessary to degas or pretreat the nonporous materials employed other than by drying them thoroughly. However, precaution was necessary so that the dried sample entered the fatty acid solution with little exposure to moisture. The effect of moisture on the interaction of stearic acid with finely divided materials has been thoroughly investigated by Hirst and Lancaster." They found the presence of water merely reduced the amount of acid adsorbed by powders such as TiO2, SiO2, Tic, and Sic. With reactive materials such as Cu, Cu2O, CuO, Zn, and ZnO, however, water was found to initiate chemical reaction. Only with ZnO was reaction observed when the solid and the solu-

Jan 1, 1953

By S. J. Sindeband

Prior to discussing the metallurgy of sintered chromium borides, it is pertinent to outline some of the reasoning behind this investigation and the purposes underlying the work. This study was initiated as an aproach to the ubiquitous problem of a material for service at high temperatures under oxidizing atmospheres, and it was undertaken with a view to raising the 1500°F (816°C) ceiling to 2000°F (1093°C) or better. For the reason that no small, but rather a major, lifting of the high temperature working limit was being attempted, it was felt appropriate that a completely new approach be taken to this problem. A summary of the thinking behind this approach was published recently by Schwarzkopf.' In briefest terms, it was postulated that the following requirements could be set up for a material which would have high strength at high temperatures. 1. The individual crystals of the material must exhibit high strength interatomic bonds. This automatically leads to consideration of highly refractory materials, since their high energy requirements for melting are related to the strength of their atom-to-atom bonds. 2. On the polycrystalline basis, high boundary strength, superimposed on the above consideration, would also be a necessity. Since this implies control of boundary conditions, the powder metallurgy approach would hold considerable promise. Such materials actually had been fabricated for a number of years, and the cemented carbide is the best example of these. Here a highly refractory crystal was carefully bonded and resulted in a material of extremely high strength. That this strength was maintained at high temperature is exhibited by the ability of the cemented carbide tool to hold an edge for extended periods of heavy service. Nowick and Machlin2,3 have analytically approached the problem of creep and stress-rupture properties at high temperature and developed procedures whereby these properties can be approximately predicted from the room temperature physical constants of a material. The most important single constant in the provision of high temperature strength and creep resistance is shown to be the Modulus of Rigidity. On this basis, they proposed that a fertile field for investigation would be that of materials similar to cemented carbides, which have Moduli of Rigidity that are among the highest recorded. The cemented carbide, however, does not have good corrosion resistance in oxidizing atmospheres and without protection could not be used in gas turbines and similar pieces of equipment. It would be necessary then to attempt the fabrication of an allied material based upon a hard crystal which had good corrosion resistance as well. It was upon these premises that the subject study was undertaken and at an early stage it was sponsored by the U.S. Navy, Office of Naval Research. Since then, it has been carried on under contract with this agency. Chromium boride provided a logical starting point for such research, since it was relatively hard, exhibited good corrosion resistance, and, in addition, was commercially available, since it had found application in hard-surfacing alloys with iron and nickel. That chromium boride did not provide a material that met the ultimate aim of the study results from factors which are subsequently discussed. This, however, does not detract from the basis on which the study was conceived, nor from the value of reporting the results which follow. Chromium Boride While work on chromium boride proper dates back to Moissan,4 there has been a dearth of literature on borides since 1906. Subsequent to Moissan, principal investigators of chromium boride were Tucker and Moody,5 Wede-kind and Fetzer,6 du Jassoneix,7,8,9 and Andrieux." These investigators were generally limited to studies of methods of producing chromium boride and detennining its properties. Some study, however, was devoted to the chromium-boron system by du Jassoneix,7 who did this chemically and metal-lographically. This system is not amenable to normal methods of analysis by virtue of the refractory nature of the alloys involved, and the difficulties of measurement and control of temperature conditions in their range. Dilatometric apparatus is nonexistent for operation at these temperatures. Du Jassoneix made use of apparent chemical differences between two phases observed under the microscope and reported the existence of two definite compounds, namely: Cr3B2 and CrB. These two compounds, he reported, had quite similar chemical characteristics, but were sufficiently different to enable him to separate them. The easiest method for producing chromium boride is apparently the thermite process, first applied by Wede-

Jan 1, 1950

By G. C. Van Bever, J. J. Zaluski

Introduction The Surface Mining Control and Reclamation Act (Public Law 9587) (hereinafter the "Act" or "SMCRA") passed by Congress in August 1977 represents a comprehensive federal scheme for controlling surface coal mining and the surface effects of underground mining through permitting requirements, performance guidelines and reclamation planning. While the provisions of the Act have been the subject of numerous legal challenges and court battles over the years, it is difficult to identify a more controversial program within the Act than the provisions for designating lands as unsuitable for surface coal mining operations. The lands unsuitable designation process provides for the acceptance and review of petitions submitted by citizens or organizations seeking to have specified land areas designated unsuitable for all or certain types of surface coal mining activities. In filing these petitions, the interested parties or petitioners are required to make allegations about potential adverse impacts on people or the environment and submit evidence supporting their allegations. In 30 U.S.C. § 1272, Congress provided that "[a]ny person having an interest which is or may be adversely affected shall have the right to petition ... to have an area designated as unsuitable for surface coal mining operations." Under the Act, an area can be designated as unsuitable where the mining operation will (1) be incompatible with existing state or local land use plans, (2) affect fragile or historic lands, (3) affect renewable resource lands where mining operations could result in substantial loss or reduction of long-range productivity, or (4) affect natural hazard lands where such operations could substantially endanger life and property. In enacting SMCRA, Congress mandated that each state establish a process to determine which, if any, lands within the state are unsuitable for all or certain types of surface mining operations. In response to this federal legislation, the Kentucky General Assembly adopted a state regulatory program for surface mining that included provisions direct¬ing the Secretary of the Natural Resources and Environmental Protection Cabinet to establish a program for designating lands as unsuitable for surface mining as required by the Act. In recent litigation in Kentucky, several environmental groups filed a lands unsuitable petition, later joined by the University of Kentucky, challenging a proposal by Arch Mineral Corporation to surface mine over 3 million tons of recoverable coal. The petition sought to designate over 10,000 acres of land adjacent to Arch's proposed operations as unsuitable for surface mining operations, basically alleging that the mining would disturb an outdoor laboratory. The filing of the petition activated Kentucky's regulatory scheme for reviewing lands unsuitable petitions that can result in an absolute prohibition against surface mining on the petitioned land for historical, environmental and other related reasons. The designation process involves vague petition requirements creating a situation that Arch argued is devoid of constitutional due process and subject to abuse by the petitioner on many fronts. Arch maintained that the lands unsuitable regulations do not grant adequate protection to Arch's legitimate property rights under the due process clauses of the United States and Kentucky Constitutions and are thus void and unenforceable. The entire process resulting in a decision on the petition took just under 12 months in the Arch case, and although Arch was ultimately successful in preserving its right to mine, Arch's surface mining permit was held up for this period of time. This delay led to the cessation of mining operations by Arch and the idling of over 250 workers. This paper will review the lands unsuitable designation process and the significant implications the process has for existing surface mining operations, currently proposed operations and even those long-range operations not yet contemplated. Special emphasis will be given to Kentucky's lands unsuitable program. Finally, the recent litigation involving Arch Mineral Corporation and its effort to surface mine 81.5 acres of Arch controlled property will be utilized to illustrate this very unusual regulatory scheme. Regulatory background Chapter 30, Subchapter F of the Code of Federal Regulations (C.F.R.) promulgated to implement the provisions of SMCRA, requires that each state establish procedures under the state's surface mining program for designating non-federal and non-Indian state lands as unsuitable for all or certain types of surface coal mining operations. 30 C.F.R. § 764.1. The C.F.R. establishes minimum standards for state lands unsuitable programs and sets out requirements for filing a Lands Unsuitable Petition (hereinafter "LUP"), processing LUPs, decision-making guidelines and hearing requirements. Kentucky has adopted regulations providing for the implementation of the lands unsuitable process as part of the state's regulatory program under SMCRA. The following discussion summarizes the principle components of the Kentucky lands unsuitable program.

Jan 1, 1993

By W. A. Turcotte, A. D. Paananen

Introduction The large reserve of fine grained oxidized iron-formation at the Tilden mine has been the object of research and development efforts to concentrate the iron oxides as far back as 1949. Due to the nonmagnetic nature of the ore and the fine grinding required to liberate the iron oxide minerals, this crude ore was not amenable to concentration by conventional methods. The iron oxides of the Tilden, ore body have a grain size of less than 25 microns and recovery of the finer, well-liberated iron oxides is essential. Conventional methods of desliming employing cyclones or thickeners were not feasible because of the excessive loss of iron oxides in the finer fractions. Development of selective flocculation-desliming was a key to commercialization of the process. Operations started in late 1974 with Algoma Steel Corp. Ltd., J & L Steel Corp., The Steel Company of Canada Ltd., Wheeling-Pittsburgh Steel Corp., Sharon Steel Corp., and The Cleveland-Cliffs Iron Co. as participants. Cleveland-Cliffs operates and manages the operation. Development of the Tilden Flowsheet The geology and ore reserves of the Tilden mine have been detailed in a paper by Villar and Dawe (1975). A joint program was undertaken in 1961 with the US Bureau of Mines in Minneapolis using the flowsheet developed by the Bureau employing the selective flocculation-desliming and calcium activated anionic silica flotation method (Frommer, et al, 1966; Frommer, 1964; Frommer, Wasson, and Veith, 1973). During this time, parallel testing at Cleveland-Cliffs Research Laboratory and Pilot Plant centered on the same type of desliming but was followed by the cationic flotation of silica with amine collectors (Columbo and Jacobs. 1976). The cationic silica flotation system was eventually chosen for its overall efficiency and simplicity. Regardless of the flotation method chosen, the technique of selective flocculation-desliming prior to flotation is the key to the success of the process. The flowsheet is described in detail by Villar and Dawe (1975). [Figure 1] shows a simplified one-line flowsheet of the Tilden concentrator. A total tailings thickener has been added to the original flowsheet and was placed in operation in 1978. The total-tailings thickener overflow reports to the reuse water pond and the underflow is pumped approximately 8 km (5 miles) to a storage basin. A flowsheet of the reuse water system is shown in [Fig. 2]. Selective Flocculation-Desliming Data have been published on the mechanisms and factors affecting selective flocculation in iron oxide-silica systems. The intent of this paper is not to discuss the theoretical aspects of selective flocculation, but rather to present experience gained from the commercial Tilden operation and from bench and pilot plant testing of fine-grained oxidized iron ores. From the bench and pilot plant testing prior to plant startup, certain reagent combinations and rates for the commercial Tilden plant were established. In the experience gained from three years of plant operation at Tilden, some of these reagent dosage rates have required significant adjustments due to changes in reuse water quality and to meet the requirements of varying ore types. Reuse Water The process water quality is a major concern at the Tilden mine and is constantly being monitored for selected chemical and physical characteristics. This monitoring has continued on a regular basis in order to gain a more thorough understanding of the interactions taking place in a dynamic water system and particularly as water quality is influenced by seasonal variations. Control of the reuse water chemistry is essential to the Tilden process both in the selective flocculation-desliming and flotation stages of concentration. With roughly 75% of the reuse water used in grinding-desliming operations, it is readily apparent that the biggest "reagent" in the selective flocculation-desliming process is water. Not enough can be said about the close control that must be exercised on the overall reuse water system. Control of the chemical treatment of the feed to the total tailings thickener is of utmost importance in order to produce a reuse water for the concentrator that is compatible with all stages of the concentrating process. There are many analyses made which aid in judging the quality of the water. Some of these are shown in [Table 1]. Five are particularly important and are monitored daily so that reagent adjustments can be made as required: suspended solids, calcium hardness, pH, dissolved silica concentration and temperature.

Jan 1, 1981

By Werner Schwartz, Wolfgang Haase

Lead sulfide concentrates, which may include other lead concentrates, are sintered on an up-draught sintering machine without the addition of any diluting agents or fluxes. Subsequently they are melted in an oil- or gas-fired rotary furnace. The sintering and melting processes are based upon the following roast-reaction: PbS + 2 PbO = 3 Pb + SO, PbS + PbSO, =2 Pb + 2 SO, For obtaining a lead bullion free from sulfur, the sintering process is carried out in such a way that the sinter product contains a small amount of excess oxygen above that to react with the sulfides. At the end of the melting process, when the reactions are finished, the remaining small amount of oxide residues is reduced with coal to which a certain percentage of soda ash (about 1 pct of the lead bullion) is added. For the lead smelting process described neither coke nor fluxes—except soda ash—are required. This process is being utilized by a European smelter successfully and with a high lead recovery. The consumption figures for the smelting of 100 tons per day of lead concentrates are indicated. The lead content of the lead concentrates from modern ore dressing plants ranges from 65 pct to above 80 pct. In most lead smelters of the world these concentrates are smelted in a blast furnace. For blast-furnace smelting the concentrates have to be desulfurized and agglomerated by sintering. A requirement for the perfect operation of a down-draught sintering machine and of a blast furnace is a maximum lead content in the feed of 40 to 45 pct. For this reason, some lead concentrates have to be diluted by adding return slags, limestone, and possibly iron oxide and sand. As an example, 100 tons of lead concentrate with 72 pct Pb would contain 13.5 tons of gangue (including the zinc). To produce a perfect sinter with 42 pct Pb it would be necessary to add 70 tons of flux and return slag, more than five times the original weight of the gangue, to the sinter mix and blast-furnace charge. A correspondingly large amount of coke would be required in order that all of these materials reach the heat of formation and the melting temperatures of the slag (1200" to 1400°C) inside the blast furnace. The roast-reaction process presents a possibility for lead recovery without dilution of the concentrates. In this process the concentrate mixed with coal is placed upon a Newnam-hearth and air is blown through nozzles into the heated mix. AS a result metalllic lead and a relatively great amount of so-called .'Grey Slag" with a lead content of 25 to 35 pct are formed. The slag is sintered to eliminate sulfur and, after addition of the requisite fluxes, treatt:d in a blast furnace. Owing to the poor recovery of lead from the hearths and to the unavoidable heavy hand-work plus the risk of poisoning this process is utilized in very few 112ad smelters today. Since in mxny countries of the world coke is expensive and difficult to obtain, it appeared feasible to use the principle of the roast-reaction by modern sintering and melting methods with recovery of the lead in electric, or oil, gas, or coal-fired furnaces. Two processes are utilized on an industrial scale: A) Lead smelting in the electric furnace of the Bolidens Gruv A/B in Sweden, as described by S. J. Walldcn, N. E. Lindvall, K.G. Gorling, and S. Lundquist. B) The self-fluxing lead smelting of Lurgi Gesell-schaft fiir Chemie und Huttenwesen m.b. H., Frankfurt a M, Germany, which is described in this paper. In the Boliden process referred to above the sinter mix is pelletized by enveloping return fines with layers of flue dust, limestone powder, and dried galena concentrate. The roasting and agglomeration are carried out on a down-draught machine, and a slight excess of sulfur is left in the sinter product. During the smelting in the electric furnance the roast-reactions occur and a slag poor in lead and a sulfur bearing lead are formed. This latter is subsequently oxidized in a converter to obtain lead bullion and dross. The Lurgi-process achieves the maximum possible extent of the roasting reaction on the sintering machine. The wet flotation concentrates are blended with return fines (lead content 70 to 80 pet), any existing flue dusts and lead slimes—but without the

Jan 1, 1962

By L. H. Munson, D. E. Hadlock, L. F. Munson, R. L. Gilchrist, P. D. Robinson

All uranium mills are required to perform sampling and analysis for radioactive particulates in their gaseous effluent streams and in the environment. Pacific Northwest Laboratory was requested by the U.S. Nuclear Regulatory Commission (NRC) to provide technical assistance to them for their Uranium Mill Health Physics Appraisal Program. In conducting appraisals, air sampling methods used at NRC-licensed mills were reviewed and several deficiencies noted. This paper includes only environmental and effluent particulate sampling although much of the information is applicable to both in-plant and environmental samples. First, the components of a proper sampling program are discussed: program objectives, program design, sampler design, analyses, quality assurance, and data handling. Then the specific deficiencies, or the "pitfalls" from the first 8 mill appraisals are discussed. The first consideration in establishing an air sampling program is defining the objectives of the program. What is air sampling suppose to accomplish? Many of the deficiencies we have observed have resulted because the desired objectives were not clearly established in the minds of the radiation safety staff. PROGRAM OBJECTIVES An environmental air sampling program ought to fulfill the following seven objectives. The first is to: 1) [demonstrate regulatory compliance]. Although a goal of most programs, regulatory compliance, is not well understood. One has not only to comply with the conditions of the source materials licensee, but one must also demonstrate compliance with 10CFR20 and 40CFR190. For example, 10CFR20.106 states: "A licensee shall not possess, use, or transfer licensed material so as to release to an unrestricted area radioactive material in concentrations which exceed the limits specified in Appendix B, Table II of this part .... For purposes of this section, concentrations may be averaged over a period not greater than one year." Even if a mill's license does not require sampling at the site boundary of maximum concentration, a sample may be necessary to demonstrate compliance with 10CFR20. Most mill personnel are painfully familiar with 40CFRl90.10, which states: "Operations.... shall be conducted in such a manner as to provide reasonable assurance that: (a) The annual dose equivalent does not exceed 25 millirems to the whole body.... of any member of the public as the result of exposures to planned discharges of radioactive materials, radon and its daughters excepted... from uranium fuel cycle operations..." This means a licensee's sampling program must give "reasonable assurance" that the member of the general public receiving in the most exposure gets no more than 25 millirems per year. The sampling program necessary to provide that assurance may or may not be a license requirement. However, merely meeting the license requirements and the explicit regulatory requirements does not necessariarly ensure an adequate effluent and environmental air sampling program. The second objective of the environmental air sampling program, is to 2) [identify the source(s) of contaminants]. This will include not only the routine program, but special sampling for verification of sources and nonsources. Only after sampling can a mill operator be assured that roof vents, laboratory hoods, and other localized ventilation systems are not making a significant contribution to environmental releases. An environmental sampling program should also allow the mill operator to fulfill the third objective, to 3) [estimate exposures]. Even before 40CFR190, a sampling program should have provided the mill operator with the information necessary to determine the dose to the "fence post" person, or at least to determine if doses were well below the 10CFR20 limits previously allowed. The program should 4) [detect and measure unplanned releases]. If there is a fire, a scrubber failure, or if a drum of yellowcake breaks open, measured releases will almost always be lower than conservative estimates. Whether or not a system to provide sampling during accidents is needed is almost always a cost-benefit decision. In general, uranium operations do not sample just in case an accident may occur. Yet they may decide on continuous air sampling in lieu of intermittant sampling partially because of the potential for accidents. Another objective of air sampling is 5) [to provide information on the effectiveness of control systems]. This is always a concern with new or modified equipment and may dictate sampling frequency in other situations as well. For instance, if a small leak in a bag filter cannot be detected by other means, then more frequent stack sampling may be indicated. A routine effluent and environmental monitoring program should also fulfill the sixth objective,

Jan 1, 1981

By R. D. Daniels, T. W. Wood

The tensile properties of columbium and Cb-H alloys containing up to 455 ppm H were studied as a function of temperature and strain rate. Hydrogen, introduced into columbium at elevated temperatures, using a thermal -equilibrium technique, embrittled columbium most severely at about —77°C. This elnbrittle ment occurred even at hydrogen concentrations of an order of 20 ppm. At higher temperatures, the hydrogen tolerance of columbium increased in relation to the increased solubility of hydrogen in tile metal. Below this temperature hydrogen tolerance, as determined by ductility and fracture stress, increased slightly. Strain rate had little effect on the tensile results for cross-head speeds over the range 0.002 to 2.0 in. per min. Strain aging during the tensile test appears to explain the ductility mininmum at —77°C. The apparent increase in hydrogen tolerance at lower temperatures is attributed to the low mobility of hyhogen. Experiments were performed in which samples were prestrained in tension at room temperature and tested to failure at —196°C. Results suggest that hydrogetz segregation to preformed crack nuclei can cause subsequent embrittlement even at temperatures where hydrogen mobility is too low to cause embrittlement in a normal tensile test. COLUMBIUM is an example of the class of bcc metals with ductile-brittle transition temperatures sensitive to the presence of interstitial atom contaminants. Hydrogen is one of these embrittling contaminants. The embrittling effect of hydrogen is less potent, perhaps, in columbium than in some of the other bcc refractory metals, but it is still a problem of both theoretical and practical interest. Unlike hydrogen in iron and steels, hydrogen in columbium is exothermically rather than endo-thermically occluded. The embrittlement process in exothermic systems has not been studied as extensively as that in endothermic systems, especially at hydrogen concentrations below the limit of solubility. The purpose of this investigation was to evaluate the embrittlement process in initially pure columbium as a function of hydrogen content, temperature, and strain rate. The Cb-H phase diagram, according to Albrecht et al.,1 is shown in Fig. 1. Columbium reacts exothermically with hydrogen producing a solid solution at concentrations of less than about 250 ppm (parts per million by weight) H at room temperature. At concentrations above the highly temperature-dependent solvus a second phase is formed. Like many similar hydrogen-metal systems,2 his system exhibits a miscibility gap with respect to hydrogen solution. Albrecht found the critical temperature of the miscibility gap to be about 140°C, the critical concentration to be 0.23 atom fraction hydrogen, and the critical pressure to be 0.01 mm Hg. Above 140°C there is a solid solution of increasing lattice constant extending across the phase diagram. Hydrogen concentrations of particular interest in this investigation were those below the limit of solubility in columbium. At hydrogen concentrations above the limit of solubility, columbium will contain the hydrogen-rich second phase and will be brittle under most testing conditions because the hydride generally precipitates as platelets with coincident matrix lattice strains.1'3 At hydrogen concentrations below the limit of solubility, the tensile behavior of columbium is expected to be more sensitive to the interrelationships between hydrogen concentration and mobility and the testing variables such as temperature and strain rate. Literature references to the hydrogen embrittlement of metals, especially ferrous alloys and titanium alloys, are too voluminous to mention. It is only recently, however, that detailed studies of the hydrogen embrittlement of columbium have been undertaken. Wilcox et a1.4 studied the strain rate and temperature dependences of the low-temperature deformation behavior of fine-grained are-melted columbium (1 ppm H) and the effect of hydrogen content (1,9, and 30 ppm H) on the mechanical behavior of columbium at a series of temperatures for a single strain rate. A strain-aging peak was ob-served at about -50°C which was attributed to the presence of hydrogen in the metal. Eustice and carlson5 studied the effect of hydrogen on the ductility of V-Cb alloys at a series of temperatures over the range -196° to 25°C. Pure columbium was embrittled by 20 ppm H which produced a ductility transition at approximately -70°C. Ingram et al.6 studied the effect of oxygen and hydrogen on the tensile properties of columbium and tantalum. A minimum in the notched-to-unnotched tensile ratio of hydrogenated columbium was obtained at about -75°C, but because of the relatively large hydrogen content employed (200 and 390 ppm) the ductility

Jan 1, 1965

By Aladar B. Dory

INTRODUCTION Practical experience in mines with known presence of radon daughters in the mine atmosphere in Canada and elsewhere shows that a very high concentration builds up in an unventilated dead end heading. As Holaday et al1 observed, even a minimal air movement results in a drastic reduction in radon daughter concentration. It is therefore obvious that the main objective of radon daughter control in the working environment is to design the ventilation system providing an optimized flow of fresh air into the workplace, resulting in acceptable climatic conditions and achieving radon daughter concentrations resulting in exposures as low as reasonably achievable. BASIC OBJECTIVES Large mining companies, having extensive material resources and professional expertise, have utilized elaborate electrical modelling in the design of mine ventilation systems as early as 1950 (coal mining industry in Europe) and with the advance of computer modelling techniques, their utilization in ventilation systems design is on the increase. Unfortunately, these methods are usually not available to small mining companies and even the large companies might not achieve the fullest benefit from utilizing them, if proper limiting factors are not considered in the modelling. When an evaluation of a ventilation system of a mine is undertaken in literature, a measure of the amount of air supplied underground per one ton of ore mined is used as an indicator of the efficiency of the ventilation system. Yet, even the greatest amount of air forced into the mine might not result in an acceptable working environment if a proper distribution of this air into individual working places is not achieved. The volume and the age of the air are probably the two most important factors in achieving acceptable radon daughter concentrations in the workplace, but other factors also have to be considered. DIRECTOR MINE - ALCAN, NEWFOUNDLAND FLUORSPAR WORKS ST. LAWRENCE, NEWFOUNDLAND, CANADA Ventilation To illustrate the effects of the design of the ventilation system on the control of radon daughter concentration, let us review the gradual development of the ventilation system of this mine from the earlier years of its development up until its final years of operation. This mine, located near the community of St. Lawrence on the south coast of Burin Peninsula was developed in the late thirties and reached full production by 1942. Unfortunately as was customary at that time, the only source of ventilation was a natural draft. The mine was extremely wet, and no significant attention was initially given to possible health effects of dust. It was not until the mid-fifties, when a number of cases of silicosis had surfaced, that de Villiers and Windish2 observed a significant increase of lung cancer incidence among the miners in comparison to its incidence among the general population of Newfoundland. Suspicions regarding radiation as a cause of the lung cancer were expressed, but it was only in surveys taken in late 1959 and early 1960 that Windish3 and Little4 established the presence of radon daughters in the mine atmosphere in very high concentrations. Windish, de Villiers and Hurley suggested that the most likely source of the radon in the mine was the mine water which dissolved radon during its passage through the granitic country rock in the surrounding geological area. This conclusion was confirmed by analyses of water from various areas of the mine by the Atomic Energy Canada Limited laboratories. The radon values in the samples varied from 4,240 to 12,850 pCi/L5. Following the discovery of the presence of radon daughters in the mine, the company took speedy action to install mechanical ventilation for the mine. The system was not designed as a total unit, but fans were installed rather on a trial and error basis. The basic system installation began in March 1960 and was completed by 1962. It remained basically unchanged with only minor modifications until August 1973 when a wholly new, redesigned ventilation system was implemented. A schematic section of the mine and its ventilation system for the period prior to March 1960 is given in Figure "A", for the period 1960-1973 in Figure "B", and for the period after August 1973 in Figure "C". The ventilation system prior to 1960 is not known. All workings of the mine were ventilated only by natural ventilation. If any measurements of airflows at different or any times of the year ever existed, no records have been preserved. The very minimal natural ventilation was augmented by "blowing" air from compressed air supply lines and exhaust air from drills. It is known that the compressor capacities of the mine were limited and therefore no significant air movement was probably created by the "blowing".

Jan 1, 1981

By A. Steiner, K. L. Komarek

Activities of aluminum in solid Ni-A1 alloys have been determined between 20 and 60 at. pet Al and 1200" and 1400°K by an isopiestic method in which nickel specimens, heated in a temperature gradient, are equilibrated with aluminum vabor in a closed all-alumina system. The activity of aluminum shows a strong negative deviation from Raoult's law at low concentrations but increases by three orders of magnitude within the ß(NiAl) phase. The partial molar enthalpy and entropy of mixing are negative. Using Wagner and Schottky's theory of ordered compounds, a degree of disorder of 4 x 10 -4 for NiAl and 1.25 X 10-2 for FeAl has been calculated THE Ni-A1 system has been studied by a great number of investigators, and the results, as far as the phase diagram is concerned, have been compiled by Hansen.1 The phase boundaries from 0 to 50 at. pet Ni are well-established. At higher nickel contents the boundaries are still in dispute and an additional phase, A12Ni3, has been reported.' The phase diagram is dominated by a very stable high-melting compound, NiA1, with a relatively wide range of homogeneity. Heats of formation of solid alloys have been determined calorimetrically by Oelsen and Middel3 from 20 to 95 at. pet Ni and by Kubaschewski4 from 25 to 80 at. pet Ni. According to the most recent compilation5 no other thermodynamic investigations have been reported for the Ni-A1 system. Due to the corrosive nature and the low vapor pressure of aluminum, a method has been employed for determining activities of aluminum which was previously developed for the Fe-A1 system.= Nickel specimens, heated in a closed evacuated alumina system in a temperature gradient, were equilibrated with aluminum vapor from a source within the system kept at constant temperature. After complete equilibration the specimens were analyzed and activities calculated from the known vapor pressure of aluminum. APPARATUS AND EXPERIMENTAL PROCEDURE Materials. The nickel specimens were made from wafers of electrolytic nickel (International Nickel Corp.) of 99.99 pet purity which were rolled to a 0.001-in.-thick foil by Driver-Harris Co. and to a 0.005-in.-thick sheet in our laboratory. The aluminum (Aluminum Corp. of America) had a purity of 99.99+ pct. The alumina tubes and crucibles were made of impervious recrystallized alumina with an alumina content of 99.7 pet (Triangle RR, Mor-ganite Inc.). Experimental Procedure. Annular specimens were punched from the sheet, the punching burrs removed, and the specimens degreased in carbon tetrachloride and acetone and weighed on a micro-balance to within an accuracy of ±0.01 mg. The specimens were positioned with alumina spacers along an alumina tube, and the positions measured. Aluminum metal was machined into cylindrical shape, and placed into an alumina crucible. The tube with the specimens was then inserted into a hole drilled into the aluminum metal. An alumina tube with its closed end at the top was slipped over the specimens so that its lower end fitted snugly into the alumina crucible. The assembled reaction tube was inserted into a mullite tube with a water-cooled brass head which had an opening for a quartz thermocouple protection tube and a metal-to-glass connection to a conventional vacuum system. A Pt-Pt 10 pet Rh thermocouple could be raised and lowered in the quartz tube which was placed along the outside of the alumina reaction tube. The mullite tube was heated by two separately controlled resistance-tube furnaces so that in the experimental temperature range an over-all temperature gradient of approximately 150o to 250°C could be imposed on the reaction tube. The position of the mullite tube was adjusted so that the surface of the aluminum metal was always at the temperature minimum. The reaction tube was thoroughly evacuated before and during slowly heating the assembly up to the melting point of aluminum. A pressure of less than 2 µ (Hg) was maintained during an experiment. Once the aluminum had melted, it isolated the contents of the alumina tube from the surroundings. Several times during an experiment the temperature gradient was carefully measured. An experiment lasted from 3 to 6 weeks and it was terminated by air cooling the evacuated mullite tube. For further details of the experimental procedure the paper on the Fe-A1 system6 should be consulted.

Jan 1, 1964

By A. B. Cook

Gas cycling is generally considered a much less efficient oil recovery mechanism than water flooding. HOWever, recoveries from some fields have been exceptionally high as a result of gas cycling. Recovery from the Pick-ton field, for example, was calculated to be 73.5 perceni of the stock-tank oil originally in place. In evaluating pressure maintenance projects, determining how much of the recovery is due to displacement by gas and determining how much is due to vaporization of the imrnohile oil in the flow path of the cycled gas is very difficrilt. Even though most of the oil is recovered by displacetr~ent, the success of a project may depend on the amount of oil vaporized. A limited number of experiments have heen performed with a rotating model oil reservoir that simulates gas cycling operations and allows a separation of the oil from, tile free gas flowing into the laboratory wellbore at reservoir conditions, thus revealing which is displaced oil and which is vaporized oil. It Iras been determined that the amount of varporizatio'n is .significant if proper conditions exist These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized. Data from six experiments affecting vaporization are presented to illustrate reservoir condition that range from favorable to unfavorable. 111 these eaperitnenis recovery by vaporization ranged from 73.6 to 15.3 percent of /he immobile oil (oil not produced by gas displacerrlt). INTRODUCTION Between 1930 and 1950, gas cycling was a popular. oil recovery practice. especially for the deeper reservoirs. Later, with many case history-type studies published for both gas cycling and waterflooding, it was generally believed that waterflooding was far superior to gas cycling, even when gas cycling was conducted as a primary production procedure by complete pressure maintenance. A good example illustrating the advantage of water-flooding over gas cycling is given in a paper by Matthews' on the South Burbank unit where gas injection was followed by waterflooding. The author concluded in part that "Early application of water injection, without the intervening period of gas injection, would have recovered as much total oil as ultimately will be recovered by waterflooding following the gas injection, and total operating life would have been shortened". This appears to be a logical conclusion. However, it should not be applied to all fields. Pressure maintenance with gas in the Pickton field, as reported by McGraw and Lohec;' will result in a much larger percentage of oil recovery than was obtained in the South Burbank unit. The great success in the Pickton field resulted partly from vaporization of the immobile oil in the flow path of the cycled gas. The amount of vaporization is related to the following conditions: volatility of the oil as reflected by the APT gravity of the stock-tank oil; reservoir temperature; reservoir pressure during gas cycling; and the amount of gas cycled. Therefore, the U. S. Bureau of Mines is investigating these effects on vaporization in a research project using a model oil reservoir. Three different stock-tank oils having 22, 35 and 45" API gravities are being used as base stock to synthesize reservoir oils. Experiments are being performcd to determine vaporization at 100, 175 and 250F and at 1,100, 2,600 and 4,100 psia. This is a progress report showing the results from six experiments. Other Bureau of Mines reports"- concerning vaporization are listed. LABORATORY EQUIPMENT AND PROCEDURES The equipment ' consists of an internally chromium-plated steel tube packed with finely sifted Wilcox sand. The tube is approximately 44 in. long and has an ID of 13/4 in. The sand section contains approximately 570 ml of voids, has a porosity of 32 percent, and a permeability to air of 4.3 darcies. A unique feature of the laboratory reservoir (Fig. 1) permits the tube part to rotate at 1 rpm while the outlet and inlet heads are held stationary. The outlet end contains diametrically opposed windows to permit observatlon of the flowing fluids, and two valves, one on the top and the other at the bottom. Oil and free gas. when being produced simultaneously, can be separated by manipulating the two valves to keep a gas-oil interface in view through the windows. Thus, only gas is produced through the top valve and only oil flows through the bottom valve. The laboratory equipment was designed to study vaporization. Therefore, a uniform reservoir was made using dry sifted sand as opposcd to using a consolidated sand core with interstitial water. Furthermore. the reservoir was tilted to minimize fingering of gas. This tilting also in-

By J. P. Zannaras

Referring to the article by R. J. Charles and P. L. de Bruyn, let us assume that W = weight of glass bar; P = weight of hammer; e = total deformation; K = unit of deformation; K = potential stress energy; E = modulus of elasticity; L = length of the bar; 7 = coefficient of inertia; h = height, ft; V = velocity, fps; and a = cross section area. The portion of kinetic energy which is effective in producing stress energy in a fixed bar struck horizontally is given by the formula" 1 + 1/3 W/P K =1+1/3w/p/(1+1/2w/p)2 P.V2/2g = Ph where 1 + 1/3 W/P ? (1 + 3W/P/(1=1/2w/p)2 [8] Putting e e = W/P =------------ From the above equation it can be seen that the maximum transfer of kinetic energy to stress energy is when e = 0 or W/P = 0 which indicates that the weight of the hammer must be very large as compared with the weight of the impacted rod. Eq. 8 diametrically opposes the conclusions reached by the authors of this article. In fact, if their suggestions were followed to the extreme when e = co when P = 0, there would be no transfer of kinetic energy to stress energy at all, as 7, becomes zero. Eq. 8 presumes that the velocity with which the stress is propagated through the bar is infinite, whereas the authors claim that the compression waves reflected are reaching the struck end of the bar prior to the complete transfer of the kinetic energy to cause such modification of the conditions there as to make them reach the reverse conclusions demonstrated by the above formula. That such interference exists is unquestionably demonstrated by the authors and others. However, if my observations are correct, such interference for this specific experiment and also for practical comminu- tion is insignificant, and the conclusions of the authors are in error and must be reversed to comply with Eq. 8. Eq. 5, w. = AE 2/2, given by the authors on page 51, is derived from the following equation (Eq. 9): K = 1/2Pe, where P = Sa, S = ?E, e = EL, and L = 1. The above formula, Eq. 9, cannot be applied in this case. This formula is applicable for static loads where the load increases from zero up to its final value, P, in such a way that the deformation at different instants is proportional to the loads acting at those instants and actually represents the area of a right triangle in the strain load diagram of base e and height P. The typical photographs shown in Figs. 3 and 4 represent the familiar strain load diagrams, and since the line of the wave marks the existence and intensity of the strain with the unquestionable conclusion that such strain has been caused by the action of a load acting continuously all along the wave until it reached the horizontal axis, the work stored at this point is represented by the area under the wave line and the horizontal axis and not by the area of the fictitious triangle given by the authors. Then if this is correct, even visual estimation of these areas at gage stations given in the typical photographs of Figs. 3 and 4 suffice to contradict the authors' calculation given in Figs. 6a and 6b and Figs. 7a and 7b. The typical photographs presented by Charles and de Bruyn show a considerable variation of the intensity of the strain at different stations but very small variation of areas which actually represent the stress energy at the corresponding stations. And, apparently, by squaring the small quantities, the authors magnified their error tenfold. J. M. Frankland's paperV iscusses the relative strain intensity and not the total energy for different types of impact loading. He states in his paper, "The reader is explicitly warned not to confuse the results in this report with those obtained when the load is applied by a blow as from a hammer. In this case the peak load rises to very large but mostly unknown values. The accompanying large deflections and stresses are the result of high values of P, not of the dynamic load factor n. According to Frankland "the dynamic load factor" is the numerical maximum of the response factor. It therefore appears that the authors followed the same procedure in obtaining the relative strain energy ab-

Jan 1, 1957