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By C. van der Poel

When oil is displaced from a horizontal formation by another fluid of lower density, the latter tends to override the former in the shape of a tongue owing to gravity segregation. This gravity tongue has an adverse influence on the oil recovery. If the fluids are miscible, diffusion (mixing) takes place at the interfacial boundary of the gravity tongue. This mixing should have a favorable effect on oil recovery. The report describes a laboratory study of the magnitude of the mixing zone under various conditions, so as to assess the effect of diffusion on oil recovery both in laboratory experiments and under actual field conditions. The technique used enables visual observation and measurement of the size of the mixing zone in transparent glass-powder packs. The results show that in experiments in small models and cores the width of the mixing zone may well be of the same order of magnitude as the height of the model. In such cases oil recovery is favorably affected by mixing. It can further be concluded that, under conditions prevailing in the field, mixing of the injected fluid with reservoir oil is equal to that caused by molecular diffusion alone, eddy-mixing not taking place to any appreciable extent. A simple calculation, then, shows that molecular diffusion is too small for a beneficial effect to be expected from the injection of miscible fluids in horizontal or nearly horizontal reservoirs unless pay zones are thin. INTRODUCTION This paper gives results of experiments made on the mixing which occurs when a miscible displacement is carried out in a horizontal reservoir. This mixing takes place at the interfacial boundary of the gravity tongue formed when the lighter injected fluid overrides the oil present in the reservoir. The object of the experiments was to simulate the field case where, for example, propane with a viscosity of 0.075 cp under reservoir conditions displaces an oil of viscosity 0.6 cp. In the experiments the lighter fluid had a viscosity of about 1 cp and the heavier one a viscosity of about 8 cp, so as to obtain the same viscosity ratio. In order to enable the results to be compared with those published in the literature, a set of experiments with viscosity ratio equal to one was also performed. EXPERIMENTAL TECHNIQUE The technique developed for the purpose enables the width of the mixing zone to be studied as a function of time and place. A glass-powder pack is saturated with a water-glycerine mixture of suitable viscosity, which represents the reservoir fluid. The pack is then rendered transparent by dissolving sufficient ammonium thiocyanate in the mixture to obtain a solution with a refractive index matching that of the glass powder. Alkaline water to which phenol-phthalein has been added is used as the lighter and less-viscous displacing fluid. In those places where mixing or diffusion of the two liquids occurs, the slightly acidic ammonium-thiocyanate solution neutralizes the alkali in the water, and the glass pack shows up white against the red-colored invading water. If a black cloth is hung over the back of the apparatus, the transparent part of the glass pack appears black. In this way the position of the two phases and the transition zone between them is clearly visible, as shown in Fig. 1 (where the red-colored invading water is the grey-shaded zone lying uppermost). In all experiments the amount of alkali in the water was chosen such that the upper contour corresponded to a concentration of 5 per cent of the dense liquid. The lower contour is determined by the size of the glass grains and the thickness of the pack and, consequently, varies from experiment to experiment. Corresponding concentrations of the dense liquid range from about 97 per cent for packs of small grain size (permeability = 1 darcy) to about 95 per cent for those with large grains

By R. P. Thomas

Secondary fertilizer minerals are the mineral materials used to supply directly and indirectly the secondary and trace plant food nutrient needs of a fertilizer. Since few soils contain sufficient availability of all plant nutrients for their proper growth, man has prepared mixtures of plant food materials to correct these nutrient deficiencies. These mixtures or fertilizers, when added correctly to a soil, make it possible for abundant and economic crop growth. Many kinds of materials are used as sources of these needed nutrients. They come from natural and synthetic materials and minerals including many beneficiated byproduct compounds. A fertilizer consists largely of carriers of one or more of the three major plant foods, namely nitrogen (N), phosphorus-phosphorus pentoxide (P2O5) and potassium-potash (K2O). Many other nutrients are just as essential for plant growth as the three major plant foods. In fact, the efficient use of fertilizers today depends upon an adequate supply of all these other nutrients. Since these additional materials are usually removed from the soil by plants and supplied in fertilizer in less quantities than the major nutrients, they are called secondary and minor nutrients. In the early days these special nutrients were contained as impurities in the primary nutrient carriers. Today, fertilizers are made primarily from concentrated and synthetic materials which carry very few of these other essential nutrients. Consequently, many secondary and trace nutrient carriers, as salts, byproduct compounds and even minerals have to be added to fertilizers. Secondary Nutrient Carriers The secondary plant foods in fertilizer are next to the major nutrients in abundance. They are calcium, magnesium, sulfur, chlorine, silicon and sodium. Although many of these elements are added to a fertilizer as part of the major nutrient carriers, they are also added in special carriers. The large tonnage of these secondary nutrient carriers used in fertilizers represents only a small percentage of the total production of these materials. A fertilizer producer thinks in terms of materials which supply nutrients instead of minerals. Therefore, these materials will be discussed by elements. CALCIUM Soils need calcium to supply the nutrient needs of plants and maintain the desired physical and biological conditions in the soil. The available calcium is usually 40 to 80 pct of the exchangeable bases. (These bases are ones which can be displaced by other cations and determined quantitatively. They are then expressed as milliequivalents per hundred grams of soil-me.) Direct applications of lime materials such as burnt, ground or hydrated limes are the important sources of calcium for the soil. Most crops, especially legumes, have a high requirement for calcium. The average farmer does not use enough lime to maintain the proper level of available calcium. Hence, it is necessary for many fertilizers to contain soluble calcium materials for efficient use of the major nutrients. The following major nutrient carriers supply some calcium: calcium nitrate, ammonium nitrate mixtures and cyanamid, and many of the phosphates. Both synthetic and natural gypsum are used in fertilizer production. Some crops such as peanuts require a large amount of soluble calcium. Gypsum is the important supplier of this soluble calcium. It is not applied with the fertilizer

Jan 1, 1960

By J. Wade Watkins, E. S. Mardock

The accurate evaluation of reservoir-performance characteristics in the secondary recovery of petroleum by water flooding requires use of a water tracer that may be injected into water-input wells and detected at oil-production wells to supplement data obtained from core analyses, wellhead tests, and subsurface measurements. Radioactive iodine has been used successfully as a water tracer in field tests to determine: (I) relative rates and patterns of flow of injected water between water-input and oil-production wells and (2) zones of excessive water entry into oil-production wells. Laboratory evaluations of potential water tracers, previous tracer studies, the value of using a radioactive tracer, general field procedures, and the use of surface and subsurface instruments for the detection of the emitted gamma radiation, are summarized. Data from the field tests are presented graphically and discussed in detail. It is concluded that the radioactive-tracer method, using radioactive iodine, may be used successfully to measure either the relative rates and patterns of flow or zones of excessive water entry into wells under conditions of comparatively rapid transit time between wells. INTRODUCTION Extensive use is made of data obtained from core analyses, wellhead tests, fluid characteristics, and subsurface measurements in evaluating the sweep efficiency of water injected into oil sands for the recovery of oil. Theoretical flow rates and patterns may be calculated from those data using radial-flow formulas, if it is assumed that the physical conditions in the productive formation are homogeneous. Unfortunately, homogeneous conditions rarely, if ever, exist in oil-productive formations. The use of a tracer that may be injected into an oil sand and detected quantitatively, or even qualitatively, at offsetting oil-production wells provides basic data that may be used in determining more accurately the subsurface rates and patterns of flow of injected water between wells than is possible by theoretical calculations based on assumed conditions. Consideration of the data obtained by using a water tracer assists in the application of remedial measures to water-input wells, such as plugging of channels, or selective plugging of highly permeable zones, thereby effecting a more uniform flood and a greater ultimate oil recovery. A water tracer should have the following characteristics: (1) low adsorption on solid reservoir material; (2) high solubility in water; (3) low or negligible solubility in crude petroleum; (4) a wide range of solubility of compounds that may be formed by chemical reactions with ions present in reservoir rocks or waters; (5) high detectability in low concentrations by portable apparatus; and (6) general availability at low cost. Additional desirable characteristics are that the tracer should be nonhazardous in nature under normal working conditions and quantitatively detectable in the well bore, as well as at the surface. Review of Previous Tracer Studies The need for a water tracer has been recognized for many years. As far back as 1906, Dole1 described the use of fluorescein in flow-rate studies made in France in 1901. In 1921, Ambrose" discussed in detail the use of organic and inorganic dyes, chlorides, nitrates, and other anions, lithium salts, and the Slichter electrical

Jan 1, 1955

By C. E. Schwab

A lead-zinc orebody, in fairly strong quartzite and with a dip of 35" to 60°, is block-caved by use of scrams in a stair-step pattern up the ore footwall. Scram linings to handle coarse muck and permit the use of folding scrapers are developed by the use of end-grain wooden blocks to reduce maintenance and keep operating cost to a minimum. THE Bunker Hill mine, since its discovery in 1885, has steadily produced a high grade of lead-silver-zinc ore. By the end of 1952 over 21,000,000 tons of this high-grade ore had been produced by square-set mining, and reserves in the mine continue to be very satisfactory both as to quantity and grade. For many years prior to 1941, mine production and mill capacity had been 1200 tons of feed per day. Closely adjacent to the mill, and stored behind dikes, coarse jig tailings had been impounded during the time preceding the advent of fine grinding and selective flotation. When manpower became short in 1941 and sink-and-float preconcentration was proved successful, mill capacity was increased to 1800 tons per day to treat these jig tailings economically. By 1946, because the supply of jig tailings was limited, underground exploration was started to discover and prove ore reserves of low-grade material which could be mined by an appropriate bulk mining method. During the years of square-set mining many possible areas of low-grade mineralization had been observed. One chosen for the first exploration work was sufficiently remote from active mining areas so that subsidence, if an ore-body were proved, would cause no problem. Also, old adits and workings were still open and in good enough condition so that exploration in the mineralized zone could be started with a minimum of preparatory work. In 1948 an orebody was proved of sufficient tonnage, of a grade about 2 pct Zn, 0.5 oz Ag, and 1.0 pct Pb. It was decided to use block-caving, the only appropriate mining method by which this grade of ore could be economically recovered. Exploration for additional reserves in other areas of the mine is continuing, but ultimate results are not known at this time. With more sink-and-float capacity, larger ball mills, and more flotation machines, mill capacity was increased to 3000 tons per day, permitting the mining of ore in the square-set area at a maximum rate not usually achieved, because of the scarcity of labor. Increased mill capacity also permits block caving and the mining of jig tailings at variable rates to keep mill feed up to 3000 tons per day. Fortunately the three types of feed are amenable to the same mill circuit and reagents for recovery of Pb and Zn. For example, during the first 10 months of 1952 square sets produced 827 tons per day, block-caving 1421 tons per day, and jig tailings 643 tons per day, an average daily production of 2891 tons for all three products. Exploration had proved the existence of an ore-body 1000 ft long and 165 ft wide in horizontal section, see Fig. 1. Company engineers were concerned only with the vertical extension, about 300 ft, from an old level to the surface. Much of this almost outcropped, Fig. 2. The ore lies in the hanging wall of a major fault of the Bunker Hill mine, standing at 65" in one end of the zone and separated from the fault by a wedge of waste, see Fig. 3. This wedge pinches out near the center of the zone, at which point the ore dips 45", lying nearly on the fault, Fig. 4. The remaining portion lies on the fault and conforms to the fault dip of 35", Fig. 5. Open-pit mining for the top of the ore was considered, but since the ore zone dipped into and under the mountains, adverse waste-to-ore ratios precluded use of this method. The ore occurs in massive quartzite of sufficient strength to support untimbered drifts, crosscuts, and raises. Zones of weakness in the quartzite are bedding, jointing, and small faults or slips. The mineralization, which occurs as small stringers of sphalerite and galena as well as pyrite, creates another line of weakness. The mineral veins or veinlets in themselves are high-grade. Their size and regularity and the amount of barren quartzite by which they are separated determined the limits of mineable ore, which are all assay limits except for the one determined by the major fault. Block 1 Without any background of caving in this type of quartzite, engineers selected the first block on the very steep end of the zone. Compelling reasons prompted this decision. The steep portion of the ore in Block 1 was of the lowest grade, so that if difficulties were encountered no very valuable ore would be lost, while the experience gained might be applied in mining the remaining blocks. A block 200x200 ft was laid out, with four scrams spaced 50 ft apart for drawing and placed at a right angle to the strike. Finger raises were placed in a 25-ft interval grid pattern, with flat undercutting done by crosscuts at the undercut level 25 ft above

Jan 1, 1954

By Charles E. Lundin

The character of the Er-D system was established by determining pressure-temperature-composition relationships. A Sieuerts&apos; apparatus was employed to make measurements in the temperature range, 473" to 1223"K, the composition range of erbium to ErD3, and the pressure range of 10~s to 760 Torr. The system is characterized by three homogeneous phase regions: the nzetal-rich, the dideuteride, and the trideuteride phases. These phases and their solubility boundaries were deduced from the family of isotherms of the system zchich relate the pressure-temperature-composition variables. The equilibrium plateau decomposition relationships in the two-phase regions were determined from can&apos;t Hoff plots to be: The differential heats of reaction in these two regions are AH = - 53.0 * 0.2 and -20.0 *0.1 kcal per mole of D2, respecticely. The differential entropies of reaction are AS = - 36.3 * 0.2 and - 31.0 * 0.2 cal per mole D2. deg, respectively. Relative partial molal and intepal thermodynamic quantities were calculated from the pure metal to the dideuteride phase. The study of the Er-D system was undertaken as a logical complement to an earlier study of the Er-H system.&apos; The primary interest was to compare the characteristics of the two systems and relate the difference to the isotopic effect. Studies of rare earth-deuterium systems by other investigators have been very limited in number and scope. Furthermore, there is even less information available wherein an investigator has systematically compared a binary rare earth-hydrogen system with the corresponding rare earth-deuterium system. The available information consists primarily of dissociation pressure measurements in the plateau pressure region of a few rare earths. Warf and Korst&apos; determined dissociation pressure relationships for the La- and Ce-D systems in the plateau region and several isotherms for each system in the dideuteride region. They compared these data with those of the corresponding hydrided systems. The study of these systems as a whole was very cursory and did not give sufficient data for a thorough comparison of the effect of the hydrogen vs the deuterium in the respective rare earths. The heat capacities and related thermodynamic functions of the intermediate phases, YH, and YD2, were determined by Flotow, Osborne, and Otto,~ and the investigation was again repeated for YH3 and YD3 by Flotow, Osborne, Otto, and Abraham.4 This investigation studied only these specific phases. Jones, Southall, and Goodhead5 surveyed the hydrides and deu-terides of a series of rare earths for thermal stability including erbium. They experimentally determined isotherms of selected hydrides and plateau dissociation pressures for deuterides. These data allowed comparison of the enthalpy and entropies of formation of the dihydrides and dideuterides. To date, no one rare earth has been selected to thoroughly establish the complete pressure-temperature-composition (PTC) relationships of binary solute additions of hydrogen and deuterium, respectively. The objective in this investigation was to provide the first comparison of a complete family of isotherms of a rare earth-deuterium system with those of a rare earth-hydrogen system. This would allow one to determine what differences exist, if any, in the various phase boundaries and the thermodynamic relationships in various regions of the systems. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure deuterium, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GMl00A and a CVC, GM110). Pure deuterium was obtained by passing deuterium through a heated Pd-Ag thimble. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit deuterium to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to . An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to k0.5 Torr and in the McLeod range (10~4 to 10 Torr) to *3 pct. The deuterium compositions in erbium were calculated in terms of deuterium-to-erbium atomic ratio. These compositions were estimated to be *0.01 D/Er ratio. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9+ pct. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<i vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the PTC relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 gr for each loading of the reaction chamber. The procedure employed to obtain the PTC data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen

Jan 1, 1969

By R. Bainbridge

THE Consolidated Mining and Smelting CO. of Canada Ltd. has operated a lead smelter at Trail, B. C., for many years. In order to take advantage of metallurgical advances, as well as to improve materials handling methods, this company, commonly known as "Cominco," commenced planning a program of smelter revision and modernization some years ago. The first stage of this program involved the design and construction of a new blast furnace gas cleaning system. The selection of equipment, the design of facilities, and preliminary operating details of this system will be dealt with in this paper. The essential problem was to clean and collect 100 tons of dust daily from 153,000 cfm* (12,225 lb per min) of lead blast furnace gas which varied in temperature from 350º to 1100°F. Because it was desired to collect the dust dry, either a Cottrell or a baghouse cleaning plant was to be selected. Comin-co&apos;s many years of experience with both systems provided a background for choosing the most satisfactory installation. All information pertinent to the two methods of dust recovery was carefully investigated, and it was decided to replace the existing equipment with a baghouse. Very briefly, the reasons for this decision were as follows: 1—A baghouse installation would be practical because the SO2 content of the gas was low and corrosion would not be a problem if the baghouse operating temperatures were held sufficiently above the dew point. 2—Variations in the physical characteristics of fume and dust, which are inherent in this blast furnace operation, should not substantially affect the operating efficiency of a baghouse. 3—For the same capital cost, metal losses (stack and water losses) would be appreciably less in a baghouse. 4—A baghouse would be easier to operate, and would not require the use of highly skilled labor. 5—Operating and maintenance costs of a bag-house would be lower. 6—The only available space for reconstruction was relatively small, and not suited to a Cottrell installation. Once the baghouse system was decided upon, detailed design of the installation was begun. Baghouse Design Gas Cooling: Before the required capacity of the baghouse could be determined, the method of cooling the gas to the temperature necessary for bag-house operation had to be chosen. The problem confronting the design engineers was how best to cool 153,000 cfm of gas from a temperature ranging from 350°F to brief peaks of 1100°F, down to 210°F, the maximum safe baghouse inlet temperature. A survey of existing blast furnace gas temperatures in the outlet flue showed that the normal range was as given in Table I. The obvious choices of cooling method were: 1— cool completely by the addition of tempering air; 2—utilize a heat exchanger; 3—cool by radiation; and 4—cool with water spray in conjunction with the admission of tempering air. The advantages and disadvantages of the various cooling methods were: Air Addition: To cool completely by the admission of tempering air involved tremendous volumes, Fig. 1. For example, to cool 1 lb of blast furnace gas at 450°F requires 1.84 lb of air at 80°F or 1.60 lb at 60°F. As it is necessary to design for peak conditions, it can readily be seen that volumes of tempering air in the order of 1,500,000 cfm would have to be handled. Using the normal design figure of 2.5 cu ft per sq ft of bag area, a baghouse installation comprising some 600,000 sq ft of filter cloth would be necessary. Such design requirements would be prohibitive, not only from a standpoint of capital expenditure, but also because of space limitations. Heat Exchanger: The utilization of a heat exchanger was given serious consideration. A horizontal tube unit using air as the medium to cool the required volume of blast furnace gas from 400" to 250°F was investigated. Cooling above 400°F would be done by water spray, and below 250°F by admission of tempering air. The estimated capital cost of such a unit was found to be prohibitive. From an operating standpoint, there was considerable doubt as to whether the soot blowing equipment provided would effectively keep the dust from building up on the tube surface. The performance of heat exchangers operating on dusty gas in other company operations had not been too favorable. Radiation Cooling: Although somewhat cumbersome, gas cooling by radiation from &apos;trombone&apos; tubes or other similar equipment (cyclones) is employed in many metallurgical operations. Such an installation was also considered. However, calculations showed that an installation much larger than the space available would be required to handle the gas volume involved. For example, to cool 153,000 cfm of blast furnace gas from, say, 600&apos; to 250°F (i.e., remove in the order of 58,500,000 Btu per hr with heat transfer rates varying from 1.1 Btu per sq ft per hr per OF for the higher temperature ranges to 0.88 Btu per sq ft per hr per OF for the lower ranges) would need a cooling area of some 175,000 sq ft.

Jan 1, 1953

By David Cornell

Back pressure test data on natural gas wells are short time test data of unsteady state nature. Performance curves from which unsteady state effects have been eliminated, called stabilized performance curves, are necessary for understanding the behavior of gas wells and for scheduling gas fields for periods up to 20 years. A calculation procedure has been developed whereby three day, seven day, 30 day, or other duration stabilized performance curves may be calculated from back pressure test data. Such curves are essential for correct gas deliverability calculations and gas field scheduling. I NTRODUCTION The manner in which a back pressure test is made will affect the slope of the back pressure curve because the radius of drainage changes with the length of time that the well is allowed to flow. The reciprocal of the slope of the back pressure curve is defined as n in Equation 1 and varies from 0.5 to 1.0. If the flow is viscous and the radius of drainage constant, n will have a value of 1.0. Because of turbulence in the formation near the wellbore, the pressure drop is usually greater than the viscous flow pressure drop and the exponent n is frequently less than 1.0. In addition, since the radius of drainage moves away from the well-bore during the test, the gas flows a greater and greater distance as the test proceeds, with a resulting increased pressure drop at the high flow rates, and, again, n for the test tends to be less than 1.O. The effect of the changes in the radius of drainage may be calculated and the results used in preparing stabilized performance curves for fixed values of the radius of drainage. Such curves can be made for a defi- nite time period, such as three day, seven day, or 30 day stabilized performance curves. These cukes will show the effect of turbulence near the wellbore and can be used to predict the performance of the gas well at any flow rate or for any production period. In order to discuss the importance of the radius of drainage quantitatively, it should be defined. Muskat" defines the radius of drainage as follows: "... the radius of drainage gives the distance from the well to which the approximately steady state condition has been established ... it being assumed that no gas is removed from any point until the radius of drainage has passed that uoint." An eauivalent definition of the radius of drainage is that radius at which the extrapolated portion of the steady state portion of the pressure gradient gives a pressure equal to the shut-in reservoir pressure. This definition is also implied in the back pressure equation. The radius of drainage is, then, the distance into the reservoir from which the gas appears to originate at any time. It is, however, only a useful concept and does not actually exist. Fig. 1 illustrates the definition of the radius of drainage. At the end of each flow period the radius of drainage may depend on three factors: (1) the duration of each flow period; (2) the rate of gas production; and (3) the rate and duration of the previous flow periods. In general, back pressure tests are conducted with various lengths of production time and at various flow rates. Each individual back pressure test, therefore, requires an individual analysis. The calculations of the change in the radius of drainage have been made, however, for the case of equal flow periods for all four production rates and several sets of increasing flow rates. Fig. 2 illustrates the results of such calculations made by the method of Cornell and Katz2 for the case of 8, = 50,000 and the flow rate increasing in the ratio 1.0:2.0:3.0:4.0 for each flow period. The increase in the radius of drainage during the test is apparent.

Jan 1, 1956

By R. N. Dokken, J. F. Elliott

A high-temperature solution calorimeter was used to measure directly the partial molar heat of mixing of nickel in the Cu-Ni system, 0 to 15 at. pct Ni and 1200°C; of silver in the Cu-Ag system, 0 to 50 at. pct Ag and 1100°C; and of cobalt in the Cu-Co system, 0 to 6 at. pct Co and 1200°C. The heats of fusion of copper and silver were also detervnined directly. The results of these investigations are as follows: Cu-Ni: HM = [2.64 + 0.25Xm JXNiXCy kcal/g-U~OI Cu-Ag: HM =[4.00 + 0.31XAglXAgXCu kcal/g-atom Cu-Co: HF~ = [8- 5X~,]X& kcal/g-atotn Cu, AH, = 3290 * 275 cal/g-atom Ag, AH, = 2890 * 250 cal/g-atom The performance of the calorimeter was enhanced by improving the operational and control procedures, particularly the temperature-wieasuren~ent method and the solute-addition practice. The interpretation of the experimental data was improved by developing machine computational techniques that increased the speed, flexibility, and accuracy of the treatment of the data. THIS paper reports further measurements of the heats of solution of liquid metals with the high-tem- perature solution ca1orimeter.l Measurements were made of the partial molar heats of mixing in the following liquid alloys: Cu-Ni, Cu-Ag, and Cu-Co. In addition the heats of fusion of copper and silver were also determined. The apparatus and the experimental procedure were essentially those of Benz and Elliott.2 Several modifications in the experimental method and the means for interpreting the data were incorporated in this study to improve the results. The operation of the calorimeter and its characteristics will be described only briefly here. The

Jan 1, 1965

By C. M. Tucker, K. R. Van Horn, W. P. Sykes

Recent investigations of the molybdenum-carbon alloys have been reported by Becker and Ebertl,‡ Westgren and Phragmén2, T. Takei3, and H. Tutiya4. Takei3 studied the Mo-C system by employing metal-lographic and X-ray methods, and the other publications described the determination of the crystal structure of the molybdenum carbides. In exploring this system by a technique previously applied to the tungsten-carbon series5, the results of Takei were confirmed with two definite exceptions; i.e., first the composition of the eutectic, and second the nature of the carbon-rich intermediate phase. Consequently, a more thorough examination of the molybdenum-carbon constitution was initiated in an effort to correlate the data supplied by the microstructures, diffraction patterns and chemical analyses. Metallographic Investigation A briquette of molybdenum powder when heated in a carburizing atmosphere at 1500" to 1600" C. for several hours develops the carbon-rich layer shown in Fig. 1. The carburization was accomplished by placing the briquette in a carbon tube, which was heated in the hydrogen atmosphere of an alundum muffle wound with tungsten resistor. While the macrostructure indicates two distinct shells, and suggests the possibility of two carbon-rich phases, no evidence of this condition could be detected by the microscope, which revealed but one high-carbon constituent. This carbide forms next to the molybdenum as a relatively dense, light-colored zone (Fig. 2) which passes abruptly into an outer layer of spongy texture. As will be noted later, only one intermediate phase was observed in the X-ray photograms prepared of different locations in the carburized zone. The metallographic structure at the inner border of the shell, reproduced in Fig. 3, shows a marked porosity accom-

Jan 1, 1935

By C. M. Tucker, K. R. Van Horn, W. P. Sykes

Recent investigations of the molybdenum-carbon alloys have been reported by Becker and Ebertl,‡ Westgren and Phragmén2, T. Takei3, and H. Tutiya4. Takei3 studied the Mo-C system by employing metal-lographic and X-ray methods, and the other publications described the determination of the crystal structure of the molybdenum carbides. In exploring this system by a technique previously applied to the tungsten-carbon series5, the results of Takei were confirmed with two definite exceptions; i.e., first the composition of the eutectic, and second the nature of the carbon-rich intermediate phase. Consequently, a more thorough examination of the molybdenum-carbon constitution was initiated in an effort to correlate the data supplied by the microstructures, diffraction patterns and chemical analyses. Metallographic Investigation A briquette of molybdenum powder when heated in a carburizing atmosphere at 1500" to 1600" C. for several hours develops the carbon-rich layer shown in Fig. 1. The carburization was accomplished by placing the briquette in a carbon tube, which was heated in the hydrogen atmosphere of an alundum muffle wound with tungsten resistor. While the macrostructure indicates two distinct shells, and suggests the possibility of two carbon-rich phases, no evidence of this condition could be detected by the microscope, which revealed but one high-carbon constituent. This carbide forms next to the molybdenum as a relatively dense, light-colored zone (Fig. 2) which passes abruptly into an outer layer of spongy texture. As will be noted later, only one intermediate phase was observed in the X-ray photograms prepared of different locations in the carburized zone. The metallographic structure at the inner border of the shell, reproduced in Fig. 3, shows a marked porosity accom-

Jan 1, 1935

By C. A. Mitke

(Butte Meeting, August, 1913.) 1. Character of Gases which Caused Helmets to Get Out of Order. DURING September, -1911, the fire area in the Lowell mine continually increased and gases resulting from the fire came through the upcast shaft. These gases contained such a large percentage of sulphur dioxide that the men were unable to go up and down on cages, and, within a comparatively short time, repairs in the shaft were found to be necessary. Since the fire was in sulphide ores and extended into certain timbered sections, the gases contained varying amounts of SO2 CO2, and perhaps, at times, CO. The temperature in the shaft was generally about 97°, and the relative humidity from 97 to 99.5 per cent. The corrosive action of the fumes became apparent when the cables had to be changed more often than usual, the heads of lag screws .in the guides of the shaft disappeared, and the cages needed frequent repairs. It also became necessary to repair two compartments of the shaft by putting in 150 ft. of new guides between the 600 and 800 levels and lag screws in nearly all the old guides from the surface to the 800 level. 2. Ordinary Methods of Testing Helmets which were Unsatisfactory. These conditions required all work to be done by men wearing oxygen helmets. The Draeger type was tried, and was used until all repairs were completed. At first the helmets were. tested for air circulation and air tightness and the injector was tested by water gauge according to the methods recommended by the Draeger Oxygen Apparatus Co. Six arrangements, covering .these different tests, are illustrated in the catalogue and circulars of the company.

Jan 7, 1913

By Carl R. Davis, J. L. Willey, S. E. T. Ewing

The first tube-mill on the Rand was put into operation in May. 1904, at the Glen Deep Mine. From that time onwards, tube-mills were added to various plants, although little was known regarding the capacity of a given tube-mill when working on banket ore. Within a few years, however, the so-called standard size (length of shell, 22 ft. 0 in.; diameter, 5 ft. 6 in.) was generally used until the last year or two. Practically the only exceptions were about 30 tube-mills having a length of 16 ft. and a diameter of 6 ft., and a few open-end mills of the roller-supported type. Most of the information obtained during the last 15 years has been obtained with mills of the standard dimensions. The adoption of the tube-mill as an accessory to the stamp mill was rapid; and where 3 tube-mills were working on the Rand at the end of 1904, 244 were in use seven years later.&apos; By 1910, good practice provided 1 tube-mill for 20 stamps of 2000-lb. falling weight. The horsepower of the motors driving the tube-mills had increased from 80 to 100 and then to 125 at this date. Broadly speaking, current practice at that date aimed at a ha1 product of which 60 per cent. was suitable for sand treatment and 40 per cent. for slime. The sand grading was +60 mesh, 6 per cent.; +90 mesh, 25 per cent.; — 90 mesh, 69 per cent.; and the slime grading +200 mesh, 2 per cent.; —200 mesh, 98 per cent. It was recognized comparatively early that the tonnage of — 90-mesh product produced by a tube-mill per 24 hr. was a convenient measure of

Jan 1, 1925

By Charles Barrett

PLASTIC flow in metal crystals and the changes in orientation resulting from it are generally understood to take place by the following funda-mental mechanisms: (1) slip on crystallographic planes, (2) homogeneous crystal rotation resulting from the slip, (3) bending of the lattice between the planes of slip, and, under certain circumstances, (4) twinning. This paper and a preceding one on iron subjected to uniaxial compression1 concern two additional processes that must now be added to this list: (5) the formation of deformation bands, and (6) the bending and rotation of these bands. The present investigation yields a new understanding and definiteness to the common terms so loosely used when speaking of cold-worked metals -"grain fragmentation," "elongated grains," and "deformation twins," "deformation bands," "etch bands," or "X-bands." Bands have been noted on the polished and etched surfaces of cold-worked metals by vari-ous investigators for more than 25 years, ? yet their nature and their significance have been so little understood that they are not treated in the most comprehensive modern texts on the deformation of crystals. The experiments in this series show that they are one of the fundamental processes in the deformation of metals, of importance in the development of preferred orientations, in work-hardening (since they have the effect of reducing the effective grain size and interfering with slip), and in the recrystallization process. The present experiments were performed on the same stock of mate-rial that was used in the earlier compression experiments1-hydrogen-purified mild steel in which the carbon content had been reduced to the limit detectable under the microscope and in which single crystals could be grown by a strain-anneal treatment.2

Jan 1, 1939

By William L. Fink, Dana W. Smith

Approximately two years ago the authors obtained data that indicated that initial precipitation could not be detected by change of lattice parameter in the aluminum-rich aluminum-magnesium alloys. Some of these data were first published in a brief note in Mining and Metallurgy&apos;. Cast specimens were used at that time and they showed initial precipitation relatively sooner than sheet material of the same composition. For this reason a more thorough investigation has been carried out using a homogenized aluminum-magnesium sheet corltairling approximately 10 per cent magnesium. Materials.—The aluminum used in the preparation of the aluminum-magnesium alloy was of high purity, containing less than 0.01 per cent each of iron, silicon and copper. The magnesium was high-purity sublimed magnesium. Preparation of Alloy.—Approximately 4 kg. of the aluminunl was melted in a plumbago crucible in an electric furnace and the magnesium was added. The melt was thoroughly stirred with a graphite rod and fluxed with chlorine gas before casting. The alloy was cast in the form of a sheet ingot in a cold iron tilting mold (approximately 200 by 165 by 40 mm.) and into small chill-cast slabs for chemical analysis (75 by 40 by 5 mm.). The chemical analyses were made upon drillings from the analysis slabs. The analytical methods were those described in "Chemical Analysis of Aluminum," published by the Aluminum Company of America. The composition of the alloy was found to be: magnesium 10.30, silicon 0.013, iron 0.008 and copper 0.005 per cent. In order to insure homogeneity the alloy was given two intermediate anneals at 430&apos; C. for a total time of 36 hr. The ingot was hot-rolled

Jan 1, 1937

By V. K. Grotzky, F. J. Fraikor

A number of investigators have noted the importance of various precipitation reactions on the properties of commercial-purity beryllium.1-5 Carrabine, for example, has demonstrated the interaction of iron and aluminum on the mechanical properties of hot-pressed polycrystalline beryllium.6 He considered the determining factor on elevated-temperature properties to be a reversible AlFeBe, precipitation reaction which could be directly related to the Fe/Al impurity ratio of the beryllium. Any aluminum in excess of the stoichio-metric amount required to form A1FeBe4 was presumed to remain primarily in the grain boundaries. We have observed, by transmission electron microscopy, such a grain boundary effect after various heat treatments of beryllium sheet. The starting material in this investigation was bare-rolled beryllium ingot sheet (0.001 to 0.005 in. thick), in contrast to the hot-pressed powder utilized by Carra-bine. It should be noted from the ingot sheet analysis shown in Table I that the Fe/Al weight ratio was near unity which would provide some free aluminum although the total aluminum and iron content was still small. Fig. l(a) shows some aluminum or aluminum-rich precipitates in the grain boundaries of a beryllium foil which had been quenched from 1200°C into brine at -TPC. Similar grain boundary precipitates were found, particularly at grain boundary intersections, in other samples quenched from 1100° and 1000°C. The length of annealing time at these elevated temperatures did not appear to substantially alter the amount of grain boundary precipitates, thus attesting to their relative insolubility. No matrix precipitates were observed other than the normal BeO and Be2C inclusions. A microprobe analysis of the larger precipitates at

Jan 1, 1968

By C. A. Mitke

During September, 1911, the fire area in the Lowell mine continually increased and gases resulting from the fire came through the upcast shaft. These gases contained such a large percentage of sulphur dioxide that the men were unable to go up and down on cages, and, within a comparatively short time, repairs in the shaft mere found to be necessary. Since the fire was in sulphide ores and extended into certain timbered sections, the gases contained varying amounts of SO2, CO2, and perhaps, at times, CO. The temperature in the shaft was generally about 97", and the relative humidity from 97 to 99.5 per cent. The corrosive action of the fumes became apparent when the cables had to be changed more often than usual, the heads of lag screws in the guides of the shaft disappeared, and the cages needed frequent repairs. It also became necessary to repair two compartments of the shaft by putting in 150 ft. of new guides between the 600 and 800 levels and lag screws in nearly all the old guides from the surface to the 800 level. 2. Ordinary Methods of Testing Helmets which were Unsatisfactory. These conditions required all work to be done by men wearing oxygen helmets. The Draeger type was tried, and was used until all repairs were completed. At first the helmets were tested for air circulation and air tightness and the injector mas tested by water gauge according to the methods recommended by the Draeger Oxygen Apparatus Co. Six arrangements, covering these different tests, are illustrated in the catalogue and circulars of the company. After the above tests had been made on the oxygen apparatus, the men still complained about leaky helmets. Small quantities of gas entered the helmets and could not be detected by these methods. The

Jan 1, 1914

By J. E. Powers, T. D. Taylor, N. E. Wood

A computer program has been developed to simulate a gas transmission 1ine operating under transient conditions. The program was developed by application of the basic mass and momentum balance equations. The nonlinear equations thus obtained were transformed by the method of characteristics and finite-difference techniques to make them suitable for machine computation. Three tests of the computer program were made. In each of these, the initial condition was assumed to be steady-state flow, the inlet density was held constant at the initial condition, and the outlet mass flow rate was varied with time. One test was theoretical in nature, but the others were made for direct comparison with actual field data. Results of the tests are presented in graphical form. INTRODUCTION Theoretical investigations of the transient flow of gas in long pipelines have been limited in number. In 1951, Olds and Sage4 developed a gaphical method of solving the nonlinear flow equations describing transient gas flow in a long pipeline. Research in this field at the U. of Oklahoma was initiated by Nelson1 in 1956. Nelson utilized a computer to solve numerical equations involving a lengthy trial-and-error procedure, and his results have been reported in the literature? It does not seem likely that Nelson&apos;s method can be extended to the analysis of transient behavior of pipeline networks; therefore, the investigation to be discussed in this paper was undertaken to improve and extend the previous work. The following discussion presents, briefly: (1) the basic differential equations governing transient flow, (2) transformation of these equations into a form suitable for machine computation. (3) role of boundary conditions in the calculations, (4) a very brief description of the computer program which was developed to simulate the pipeline and (5) results of tests of the computer program.

By Carl E. Swartz

In the course of a recent investigation1 to develop a more satisfactory white-metal bearing alloy, a number of alloy systems were studied. The cadmium-nickel system showed characteristics desirable in a bearing alloy, and the system was therefore studied in some detail. Experimental Method Alloying cadmium with nickel offered no serious difficulty. After melting the cadmium, clean sheet nickel was added while the temperature was maintained at 500" to 600" C. A few crystals of ammonium chloride2 served to clean the nickel when the latter did not "wet" readily. In preparing the individual alloys for thermal and microscopic investigation, a "hardener" containing about 10 per cent nickel was used. Thermal Experiments and Apparatus Time-temperature cooling curves were made by standard methods. Globe electrolytic cadmium was added to the hardener to make a melt of the desired composition weighing between 100 and 200 grams. This charge was placed in a Pyrex test tube, 1 by 10 in., closed with a rubber stopper carrying a thermocouple sheath and quartz stirring rod. The assembly was lowered to a depth of about 4½ in. into an electric resistance pot furnace containing a No. 0000 clay-graphite crucible (to catch the melt in case of a break in the test tube). After the tube was clamped in this position, an asbestos-magnesia mixture was loosely packed in the furnace around the tube and a "halved" cover of transite placed on top. This left at least 5 in. of the test tube protruding from the furnace. When the alloy had melted, the thermocouple was adjusted so that the hot junction was l! in. from the bottom of the test tube. The melt was stirred thoroughly for several minutes to insure composition homogeneity and absence of thermal gradients.

Jan 1, 1934

By G. R. Fritterer

Investigators in the field of temperature measurement have long sought a thermoelectric couple fulfilling the following requirements: 1. It should be useful up to and including high industrial temperatures; i. e., 1000 to 1800 C. 2. Its thermoelectric variation with temperature should be linear and be maintained after heating to high temperatures for long periods of time. 3. It should be reproducible; i. e., different couples of the same elements should have similar calibration curves. 4. Its thermoelectric power should be large so as to allow the industrial use of rugged recording instruments. 5. Chemical reactions with, and physical changes within the elements of the couple should not alter its calibration. No thermocouple proposed to date exhibits simultaneously all of these characteristics, whereas the couple about to be described fulfills all requirements to a satisfactory degree. New Thermoelectric Materials A thorough survey of the literature on thermoelectricity revealed that present-day thermocouples could not meet the specifications mentioned above because their thermoelements are metallic. Metals have a marked tendency to deteriorate chemically and their melting points limit their use to low temperatures. Refractory substances, however, are usually resistant to chemical attack and are quite stable at high temperatures. Hence a survey of refractory substances having thermoelectric possibilities was made. One class of thermocouples considered was that in which carbon and a carbide of some metal or nonmetal were the thermoelements. Previous investigators neglected to study this field but certain recommendations were made by them for the use of couples in which carbon served as one element. These proposals are listed in Table 1. The couples suggested are unsatisfactory because of their low thermoelectric powers, the low melting points of their metallic elements, etc. The

Jan 1, 1933

By John T. Popp, Jodi A. Rulli, Anthony T. Iannacchione

Anomalous geological features in the coal and surrounding strata of a mine in northern West Virginia have fractured and deformed an inherently weak roof rock prior to mining. Horizontal stresses, as much as six times greater than overburden related horizontal stresses, have induced cutter roof failure. This failure was distinguishable from rock deformation associated with geological anomalies because it was induced by mining. The characterization of these features has allowed for the prediction of zones of unstable roof rock and the determination of failure trends on gateroad stability. Geological anomalies included clastic dikes and a narrow zone of sandstone roof. Clastic dikes, representing intrusions of shale and claystone, were invariably accompanied by local roof rock instability, and often formed the boundaries of roof falls. Shale was the dominant roof lithology except where a small sandstone occurred in the northwest portion of the longwall mining area. The sandstone occurs in two phases: a sandstone-filled channel, 5-m- thick and 60-m-wide, which eroded and replaced the shale roof and the upper part of the coalbed; and a sheet sandstone unit which was crossbedded to interbedded with the underlying shale. Horizontal stresses are naturally relieved through the initiation of cutter roof failure. This failure may extend from a few meters to several tens of meters horizontally, and from a few centimeters to several meters vertically. Orientations of entries and crosscuts has a greater influence on the direction and total length of cutter roof failure at the rib-roof intersection than does the principal directions of the in situ horizontal stresses. Seventy-four percent of the cutter roof failures occurred along the rib-roof intersection. Orientations of cutter roof failure away from the rib- roof intersection were clustered in the north-south direction and may have been influenced by the horizontal stress field.

Jan 1, 1984