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By Mark S. Childs

FRIEDENSVILLE orebody in Lehigh County, Pennsylvania, lies in the south central part of the USGS Allentown Quadrangle. Physiographically the area is located in a small reentrant-known as Saucon Valley-of the Great Valley Province into the Reading Prong of the New England uplift. Saucon Valley itself is an oval-shaped lowland eight miles long and four miles wide, surrounded by ridges except where connected with the Great Valley through a breach in the rim known as Saucon Gap. These ridges, composed of Pre-Cambrian metamorphic rocks and Cambrian quartzites, rise some 500 ft above the valley floor. They are continuous with the New Jersey Highlands. The valley lowland is immediately underlain by lower Paleozoic dolomites and limestones. This area is one of low relief having a swing of approximately 100 ft, with an average elevation of 375 ft above sea level. The entire valley, which has a water shed of about 58 sq miles, is drained by Saucon Creek. This unit flows in a northeasterly direction to the Saucon Gap, where it discharges into the Lehigh River.

Jan 1, 1957

By Jasper L. Stuckey

PYROPHYLLITE, first identified as soapstone,1 later as agalmatolite,2 and finally as pyrophyllite,3 has been known to occur in North Carolina for more than 130 years and has been produced intermittently in commercial amounts for the past 100 years. Pyrophyllite mining, however, has become a major industry in North Carolina only during the past 25 years. North Carolina and California are the chief producing states. Current annual production averages 125,000 tons, of which slightly more than 90 pct comes from North Carolina. Distribution and Geologic Setting: All known pyrophyllite deposits in North Carolina are associated with rocks of the Carolina Slate Belt,4 which is composed of a vast series of metamorphosed volcanic and sedimentary materials, occurring as two zones extending in a northeast-southwest direction across the state. The larger of these zones, lying in the central Piedmont region, varies from 8 to 50 miles wide. The smaller zone lies along the eastern edge of the Piedmont region and is partly covered by coastal plain sediments.

Jan 1, 1958

By William L. Boyd, Eugene L. McCarthy, Laurance S. Reid

Proper control of the moisture content of natural gas is essential to reliable operation of gas transmission and distribution facilities serving northern markets. The moisture content of natural gas is usually determined by dew point measurement at the existing pressure. For any gas of constant moistrire content. the dew Point varies with the pressure. A correlation of the data of several investigators is prezented in graphical form by the authors. These data were correlated by the authors and F. M. Townsend, C. C. Tsao. M. I). Rogers. Jr.. and J. A. Porter. graduate students in chemi(.a1 engineering at the University of Oklahoma. Of articular interest are the hitherto unpublished low temperature data observed by Wickliffe Skinner. Jr., which are included in this correlation. PRESENTATION OF DATA The problem of interpreting water dew points, or saturation temperatures. of natural gas in terms of specific moisture con-tent has increased in importance during the past decade bec.arl.;e of extensive development.; in the transmission and petro-chemical phases of the natural gas industry. Virtually all gas transported to northern and eastern markets must be dehydrated to a low water vapor content to prevent hydrate formation in transmission and distribution lines and resultant interruption.; in gas deliveries. Complete dehydration is required in certain phases of tile petro-chemical industry involving low-temperature operations. It is a well-known fact that the water vapor content of pure hydrocarbon vapors and their mixtures at superatmospheric pressures cannot be predicted with accuracy by assuming validity of the ideal gas laws." Earlier interest in the general problem was concentrated on the water vapor content of pure hydrocarhons and hydrocarbon mixtures in the pressure and temperature ranges common to gas and oil producing reservoirs in order to obtain fundamental data for the improvement of production techniques and the furtherance of reservoir studies. Excellent data are published for pressures ranging from atmospheric to 10,000 psig and for temperatures ranging from 100° to 460° F4,9,10,11 and are found to be in close agreement. However, experimental data at high pressures and temperatures below 100°F are comparatively limited in scope. Experimental data in the lower temperature range have been reported by Laulhere and Briscoe.8 Deaton, et al,2,3 Hammerscllmidt,5,6 and wade," In general, the pressures employed in these investigations ranged from atmospheric to 1.000 psig while temperatures ranged from 32° to 120°F; i.e., the usual conditions encountered in gas transmission line operations, Additional data were reported by Russell, et al,12 at pressures as high as 2.000 psig and covering a rather narrow atmospheric temperature range. In 1947, Hammerschmidt published a correlation of all available data,' in which the water vapor content of gases at saturation. under high pressure and low temperature. was predicted by extrapolation. In 1948, Wickliffe Skinner. Jr.. presented data on the moisture content of a low nitrogen content gas at low temperature and at pressures ranging upward to 1.500 psia.1-3 Comparison of Skinner's experimental data with the extrapolated data of Hammerscllmidt revealed an appreciable variation in the lower temperature range. emphasizing the need for a new correlation which would rely on Skinner's data at lower temperatures. Careful scrutiny of available data suggested that presence of an appreciable quantity of nitrogen in a gas mixture may affect its saturated moisture content so that data obtained from gases with more than three per cent nitrogen were not used in this correlation. CORRELATION OF DATA Data employed in this correlation are presented in Table I. The data of Dodson and Standing.4 McKetta and Katz,9 and Olds, Sage and Lacey10 were compared and found to be in close agreement so that the data of Olds. et al, re-plotted in a more convenient form by the Humble Oil and Refining Co.,' were used for temperatures of 100°F and above. Skinner's data were used for temperatures below 40°F. Between these intermediate temperature limits, the data of Hammerschmidt.7 Wade" and extrapolated data of Olds. et al.1 were tabulated

Jan 1, 1950

By Strathmore R. B. Cooke, Paul B. Queneau

The kinetics of the dissolution of scheelite in basic solutions of carbonate and fluoride were investigated. Work was also done with solutions of alkali metal chloride, hydroxide, phosphate, and mixtures of phosphate and fluoride. The study was conducted at 90 psig and at temperatures ranging from 100" to 155"C, and both natural and synthetic scheelite single crystals were used. The interaction of scheelite with carbonate solutions generally followed a parabolic rate law, and resulted in the formation of calcite crystals on the attached surface. The transport of the CO3 through the calcite to the scheelite surface was probably rate -controlling between 115" and 135°C. Positive deviations from Parabolic behavior were observed at 100" and 155?C, presumably due to the calcite grain growth, and to the formation of a noncoherent calcite layer, respectively. The leaching of scheelite with alkaline fluoride solution produced a calcium fluoride reaction-product which covered the surface as a sheet-like layer. Below 110°C the dissolution rate was parabolic; at 115" and 135°C it was linear. In the linear region, the periphery of the calcium fluoride layer lifted from the sample. Only the lower layers, braced by the scheelite substratum, remained unbroken. This bound layer, approximately constant in thickness, limited the rate at which the fluoride could attack the scheelite. The phosphate and phosphate-fluoride leaches dissolved scheelite at a linear rate; solid reaction products were respectively hydroxyapatite and fluorapatite. Sodium hydroxide and chloride were not effective leachants, and did not produce observable solid reaction products. THE feasibility of pressure leaching of scheelite pulps with basic solutions containing either carbonate or fluoride ions, as indicated by the following equations, has been established by previous investigators:1-3 200°C CaWO4s + CO37q - CaCO3s+WO4aq [1] 200°C CaWO4s + 2Faq ^ CaF2s+WO4aq [2] It is to be noted that a commercial process employing reaction [I] is in use at Union Carbide's operation near Bishop, Calif. In the earlier work referred to, it was apparent that the precipitation of the solid reaction-product on the scheelite particles sharply reduced contact of the leachant with the scheelite. We have extended this work by studying the kinetics of dissolution employing single crystals of scheelite of known exposed surface area. In addition, the effectiveness of solutions of phosphate, of phosphate with fluoride, and of chloride and hydroxide as leachants for scheelite have been investigated. EXPERIMENTAL Apparatus. The low-pressure autoclave used in this wo (100 psig maximum) is essentially that of J. Halpern4 as modified by F. A. Forward.5 Constructed entirely of 316 stainless steel, its maximum capacity is 4000 ml. The temperature in the autoclave was regulated to *0.5?C by a Wheelco thermocouple controller. A 4-in. diam, three-bladed impeller, circulated solution upward against the sample, and a strobo-scope permitted holding the stirring rate to *15 rpm. A check valve and a "pop" type safety valve were installed, a sample holder was fixed to an externally adjustable rod, and a water-cooled condenser was placed in series with the sampling valve. The stainless steel sample holder, Fig. 1, held the epoxy-mounted sample (f) five mm above the impeller. Tightening the tapered sleeve (d) positioned the epoxy-resin specimen-mount by forcing it back against the spacer (c). The mount (e) was 1 in. diam. Sample Description and Preparation. Both synthetic and natural scheelite crystals were leached. The former were single crystals of 99.95 pct purity which were leached approximately perpendicular to the "c" axis; they were supplied by the Gallard-Schlesinger Chemical Manufacturing Corp. The natural crystals, supplied by Minerals Unlimited, were transparent, analyzed 99.8 pct CaWO4, and in ultraviolet illumination exhibited the characteristic blue glow of substantially molybdenum-free scheelite. To permit exposure of an essentially constant surface area of scheelite to the leachant, the samples were mounted in Scotchcast Brand Resin No. 250 (Minnesota Mining and Manufacturing Co.). The mount-

Jan 1, 1970

By Josiah Royce

To evaluate chemically the sample of rock obtained by diamond drilling, it has long been recognized that the analyses of the two components of the sample, core and sludge, must be given appropriate influence in computing the average analysis of any unit of depth. The purpose of this investigation is to set forth what means are available for apportioning the effect of core and sludge on the final analysis, what variables affect the problem, and what combination of applied mathematics will closest approximate the truth under each condition as these variables proceed within their limitations. A drill hole is bored in iron ore exploration principally to test variations in rock composition with depth and is usually directed as nearly normal to the bedding of a horizon to be tested as possible. This practice has a tendency to minimize variation in composition laterally which in any event is not likely to be great. It is obvious that the opportunity for change in analysis of a particular rock is not statistically as great radially in a diamond drill hole where the distance in which such a change may occur is from 0.719 in. (EX bit) to 1.469 in. (NX bit) as there would be longitudinally even in a' run as short as 5 ft. Variations in composition of bedded or layered rocks are usually greater normal to the bedding than parallel thereto. Even in massive rocks, like porphyries, variations are functions of distance. Hence. in either case, variations along the hole are of greater effect than across it. Let us examine Fig 1 briefly to observe a cross section of a unit of depth of a typical diamond drill hole. If we neglect radial change in chemical composition, which we have seen is small compared to lengthwise variation, we can see that if core recovery was 100 pct, the core and its surrounding area, which would be recovered as cuttings (assuming 100 pct sludge recovery), must analyze the same if the sampling is perfect. This is the foundation of this paper, namely, that if core recovery is complete we may assume that the core constitutes as nearly as possible a perfect sample of the ground drilled. Now let us pass to the methods of weighting core and sludge in the final analysis and then develop each in turn. One might employ core analyses only, sludge analyses only, or apportion the influence of each by one of several methods. The most common apportionment is by direct proportion to relative theoretical vol- ' ume occupied by each component in the cylinder hollowed out by the drill, known as the Longyear formula. Another logical treatment would be to consider core and sludge in the final analysis according to the weight of each recovered. This procedure was elaborately set forth and refined by R. S. Moeh1man.l Then to be sure that we have embraced all the possibilities, we must admit that some other method or methods may be devised empirically or by mathematical maneuvers. Should a drill machine be capable of recovering 100 pct of the core in all types of rock, certainly core alone need be analyzed and no complicated mathematics are required; but although some companies have had fair success in obtaining high percentages of core in certain homogeneous ores on the Mar-quette Range, their same methods have proved disappointing on the Menominee, Cuyuna, and Gogebic Ranges where the iron formation often varies widely from flinty chert beds interstratified with soft hematite to wholly leached ore material composed of an unpredictable mixture of hematite and limonite with occasional zones of sugary, recrystallized chert. In spite of numerous mechanical improvements in core barrels, few drilling programs can count on complete core recovery. The sludge alone might be analyzed but for practical reasons this is inadvisable when core is obtained due to the numerous opportunities for contaminating or losing portions of the cuttings. The Longyear formula involves a weighting of the core and sludge in proportion to the theoretical volume of each, that is, where the volume of the core recovered is one-third of the total cubic volume of the cylindrical hole made by the drill, the analysis of the core is given one-third of the weight in the final analysis. This approach to

Jan 1, 1950

By O. F. Walker, W. C. Hahn, V. A. Johnson, J. D. Wood

The diffusion coefficients of zinc in single-crystal zinc and carbon in single-crystal and poly crystalline nickel were measured by means of radioactive tracer techniques both with and without the application of ultrasonic vibrations under conditions such that the temperature of the sample was closely controlled. The results of this investigation indicate no enhancement of diffusion in any of the samples. It is suggested that previously reported enhancement may have been due either solely to temperature increases caused by ultrasonic vibrations or in combination with changes in the boundary conditions. A number of observations have been reported in the literature in which it has been implied or inferred that the application of ultrasonics enhances diffusion (see, for example, Refs. 1-5). The present study was undertaken in an attempt to observe this effect under carefully controlled conditions, particularly with regard to measurement and control of the temperature of the sample. Two different types of systems were studied; these were the self-diffusion of zinc and the diffusion of carbon in nickel. EXPERIMENTAL For diffusion with ultrasonic energy applied, the samples were included as part of a resonant ultrasonic system operating at 58.5 kcps. The ultrasonic generators used were rated at 100 and 250 w and could be tuned over a frequency from 10 to 100 kc. A PZT (lead titanate/lead zirconate) ceramic transducer provided the driving vibration. This system requires no metallurgical joining of the specimen to the acoustical transmission line since the ultrasonic driver and the follow-up section clamp the specimen in position by means of a constant pressure of 50 lb developed by an air cylinder. The ultrasonic driver and follow-up section, both made of titanium, were 4 in. in length from clamping point to the end in contact with the specimen. Using the relationship given by Mason,6 A = V/f, the resonant wavelength, A, in titanium is calculated to be 3.3 in. at a frequency, f, of 58.5 kc, taking the velocity of sound in titanium, V, as 1.95 X 105 in. per sec. The 4-in. driver and follow-up section, therefore, are each 4.0/3.3 =1.21 times the resonant wavelength. Clamping pressure must be applied at stress nodes of the transmission line in order to preserve resonance. Therefore, a specimen length of 0.58 times the wavelength in the specimen was required to place the clamping pressure application points at stress nodes exactly three wavelengths apart. A stress antinode was contained in the center 3 in. of the specimen. A small PZT ceramic disc attached to the follow-up section provided an output voltage proportional to the intensity of the standing wave. This output voltage was monitored on an oscilloscope and the ultrasonic system was tuned to resonance by varying the frequency until the output signal was a maximum amplitude. The amplitude of the output signal was maintained constant throughout the diffusion anneal. A split cylindrical stainless-steel chamber, which was purged with argon prior to and during the runs, was placed around the specimen. The chamber in turn was surrounded by a movable furnace whose temperature could be controlled to 7C. Heat exchangers were used to cool the driver, follow-up section, and ultrasonic transducer. Great care was taken to obtain the true specimen temperature in all cases. Several different methods were tried; the most successful was that in which the thermocouple was held in contact with the midlength of the specimen by means of an asbestos insulating pad and wire straps. In the case of zinc, single-crystal specimens of 99.999 pct purity were used. The samples were 0.25 by 0.25 in. square and of the proper length for resonance, that is 1.1 in. long with the c axis parallel to the long dimension of the specimen for the case of diffusion perpendicular to the c axis and ultrasonic motion parallel to the c axis, and 1.9 in. long with the c axis perpendicular to the long dimension of the specimen for the case of diffusion parallel to the c axis and ultrasonic motion perpendicular to the c axis. In each case, one of the rectangular faces was electroplated with a thin film of zinc containing Zn The constant pressure used to clamp the specimen in place in the ultrasonic system caused some deformation in some of the samples. For these samples the deformation was concentrated in either end of the specimen; thus, for all samples (both zinc and nickel) the center in. was cut from the specimen after the diffusion anneal to be used for sectioning and counting. The nickel single-crystal samples, of 99.999 pct purity, were used in the form of rods 0.25 by 0.187 by 2.07 in. long with the (100) direction parallel to the rod axis. The polycrystalline nickel samples of 99.97 pct purity had an average grain diameter of 0.007 in. and were used in the form of rods 0.25 by 0.125 by 1.87 in. long. The direction of ultrasonic motion was parallel to (100) direction (bar axis) for the single-cqstal samples and parallel to the bar axis for the polycrystalline specimens. A thin film of c14 suspended in methanol was applied to the diffusing face of the specimen. Two specimens were butted together lengthwise for each diffusion anneal to minimize oxidation. After diffusion, a precision lapping device similar to the one described by Goldstein7 and a radiation detector were used to obtain a plot of specific activity vs penetration distance for each specimen. (A scintil-

Jan 1, 1969

By L. C. Brown, C. St. John, C. C. Sanderson

The diffusion rate in Cu-Te couples is very sensitive to compressive stress, with a load of 20 psi making a significant difference to the width of the diffusion zone. At zero stress, two phases appear in the diffusion zone (Cu4Te3 and CuTe). Under compressive loading the third stable phase (Cuz Te) also appears, and its thickness increases progressively with increasing stress. The results are explained on the basis of an incipient Kirkendall porosity which restricts the transfer of atoms from the copper into the diffusion zone. DURING a study of the Kirkendall effect in Cu-Te couples prepared by clamping together the two components, it was found that the diffusion-zone width and shape in the plane of contact were not reproducible. Although the stresses involved in clamping are not normally sufficiently high to affect diffusion rates, preliminary tests established that the Cu-Te system is particularly stress-sensitive. The phase diagram for the system Cu-Te given in Hanssen1 shows that there is practically no solid solubility at either end of the phase diagram. Many areas of the diagram are not fully substantiated, but there appear to be three intermediate phases: Cu,Te—hexagonal in structure, having a grey luster; Cu4Te3—a tetragonal defect structure, having a red-purple luster; CuTe—orthorhombic in structure and having a golden-green luster. The existence of a fourth phase, the X phase at 37 at. pct Te, is considered doubtful. The composition ranges of the three stable phases are small, and are not accurately known. The phase diagram changes little with temperature up to 305°C, at which temperature a polymorphic transformation takes place in Cu2Te. The nature of the Cu-Te phase diagram indicates that the diffusion zone in a Cu-Te couple would consist of a series of layers of intermediate phases. The relative thickness of any one phase will depend on its diffusion coefficient and composition range.' In this type of diffusion couple it is often found experimentally that some phases are not visible at all in the diffusion zone due either to a small diffusion coefficient or to a restricted composition range.3 Since the composition ranges of the phases in Cu-Te are not known, it is not possible to determine diffusion coefficients in this system from a knowledge of the phase thicknesses. Several investigations have been carried out to determine the effect of compressive stress on diffusion rates in multiphase systems. Diffusion couples of Ni-A1 have been investigated by Storchheim et al.4 and by Castleman and Seigle.5 Two phases (ß and ?) appear in the diffusion zone under zero stress and the thickness of both phases is progressively reduced with increasing stress. According to Storchheim et al.4 a stress of 25,000 psi reduces the thickness of the diffusion zone by 50 pct. In a-brass—?-brass couples the thickness of the 0 phase formed in the diffusion zone was reduced by 20 pct at a stress of 20,000 psi.6 In other investigations the compressive load has been observed to increase the width of the diffusion zone. In A1-U, several investigators3,8 have found the width of the whase UA13 to increase with stress. According to casileman,8 the rate of formation of UA13 at 520°C is 75 pct faster at a stress of 20,000 psi as compared with a stress of 2500 psi. In Cu-Sb the effect of stress is greater than in the other systems described. According to Heumann9,10 only one phase (y) appears in the diffusion zone at a stress of 500 psi, but at a stress of 850 psi two phases (y and k) are present. If a diffusion couple containing both y and k phases is annealed at a low stress level, the y phase grows at the expense of the k phase. EXPERIMENTAL The diffusion couples were prepared from electrolytic copper bar stock with a nominal purity of 99.92 pct and from tellurium of 99.7 pct purity. The tellurium proved difficult to machine because of its brittleness and a technique was developed for casting the tellurium into a graphite slab mold and spark-machining specimens from this slab. Both the copper and tellurium were produced in the form of discs 2 in. diam by approximately 1/4 in. thick with surfaces ground flat to 3/0 emery paper. The diffusion apparatus is shown in Fig. 1. Auni-axial compressive stress was applied to the system through a simple lever system. A stainless-steel rod actuated by the lever arm lay inside a stainless-steel tube. The diffusion couple lay on top of the steel rod, and pressure was applied to the couple between the rod and a plug welded into the center of the tube. To ensure a uniform stress across the couple, a hemispherical boss and cup were used to transmit the load to the diffusion couple. A 400-w tube furnace with a uniform hot zone 3 in. long slid around the stainless-steel tube and maintained the assembly at temperature. A thermocouple situated 3 in. from the specimen operated a proportional temperature controller which maintained the specimen temperature constant to ±2°C. Most diffusion runs were carried out at 250C although a few tests were made at other temperatures in the range 235° to 300°C. The specimens were inserted and removed with the furnace at operating temperature, and took only 2 min to reach diffusion temperature—a time small compared with the total diffusion time. All the diffusion experiments were carried out in a hydrogen atmosphere, since consistent results were obtained in hydrogen and nitrogen atmospheres and in

Jan 1, 1967

By W. G. Pfann

A simple method of obtaining multistage batch separations by crystallization was described recently. Known as zone-refining, it comprises passing short molten zones through a long solid charge. This technique can now be used on a continuous basis by means of the zone-void method described in this paper. Feed enters, at an intermediate point, a column down which molten zones travel, and waste and product leave at the ends. Materials move in the column through the agency of voids, which are introduced at the ends and travel toward the feed inlet. The voids and molten zones are moved by external heaters in a simple manner, and the principle of reflux is utilized. ANEW method of obtaining multistage separations by crystallization was described recently.' Named zone-refinina.,-, the method comwrises slowly passing a series of molten zones through a long solid charge. Solute becomes concentrated at one or the other end of the charge, depending on whether it raises or lowers the freezing point of the solvent. The separation increases with the number, P, of zone-passes, approaching a limit as P approaches infinity. Zone-refining has been highly effective in purifying germanium and other substances.2,3 and new applications are steadily increasing. Zone-refining is a batch method and as such it has certain limitations inherent in batch operation. If it could be made continuous, its scope and utility would be greatly broadened. This end has been achieved by the zone-void method described in this paper. In the zone-void method feed is introduced continuously at an intermediate point in a column down which molten zones travel, while impure waste and purified product leave at the ends. Both the flows of feed, waste and product, and also the travels of the zones, are actuated by external moving heaters in a simple manner; and the system utilizes the principle of reflux. The method provides, in the field of crystallization, the counterpart of the continuous fractiona-tion column in the field of distillation. The following will be discussed: apparatus and mode of operation, fundamental nature of the separation, design theory, and practical considerations. The method will be described in terms of a binary solute-solvent system in which the solute is an impurity to be removed and the solvent is the desired product. The distribution coefficient, k, defined as the ratio of solute concentration in the solid freezing out of a molten zone to that in the liquid in the zone, is assumed to be constant and less than one. The process is equally effective for k's greater than one and for ternary or higher order systems. Method and Apparatus The essential features of a continuous zone-refining process are represented in highly generalized form in Fig. 1. A series of molten zones, produced by moving heaters, travels slowly down the column or charge (to the left in Fig. 1). If there were no flows of feed, waste, or product, the process would simply be batch zone-refining, the action of the molten zones being to sweep solute down the column, solvent up the column. For the process to be con- tinuous, with stripping and enriching sections in the column, feed must enter, and waste and product must leave, as indicated. The zone-void process accomplishes both objectives, namely, the indicated movements of zones and the indicated flows of material. Zones are moved by moving heaters, just as in batch zone-refining. Materials are made to flow by creating voids at the waste and product exits and causing these voids to move to the feed inlet. Since there must be a net flow of material from the feed inlet to each of the outlets, the indicated movements of voids are in the desired directions, because movement of a void in a given direction corresponds to flow of material in an opposite direction. In order to produce the desired movements of voids, the column is folded into two vertical sections having the feed inlet in common at their upper ends. Voids are displaced upward by the liquids in the molten zones and their travel is actuated by the motions of the zones. Voids travel with the zones in the enriching section and move continuously. Voids travel opposite to the zones in the stripping section and move intermittently. Creation and travel of voids will now be examined in detail. The enriching section of a column in operation, with its void generator, is shown in Fig. 2. The column section is a vertical tube around which a series of closely fitting, regularly spaced heaters travel slowly upward. Each heater produces a molten region, the temperatures of the heaters and the cooling between heaters being controlled so as to maintain the molten zones approximately constant in size. A void is normally present atop the molten zone in each heater. As the heater rises, it continuously melts solid above it, which drips through the void into the molten zone and continuously freezes out solid below it, of concentration k times that of the liquid in the zone. When a molten zone and void reach the feed inlet, which is kept molten, the void is displaced by an equal volume of feed liquid. Generation of voids of controlled size in the enriching section is shown in Fig. 3. The void generator is a tube of small cross-section, provided with lateral heat-conducting fins which sense the position of the heater. Liquid can escape only when the entire outlet tube is within the heater. If any part of the outlet tube is outside the heater, liquid cannot escape,

Jan 1, 1956

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By F. H. Deily, Jean M. Quets, Milton E. Wadsworth, John R. 222-000-000-012 Lewis, D. S. Rowley, R. J. Howe

Samples of synthetic magnetite were reduced in hydrogen-water vapor atmospheres in the temperature range 450o to 900oC. The reaction was always surface controlled, indicating the final products of reaction are nonfirotective. Three separate cases have been identified from the kinetic results: Case I, reduction of magnetite to iron below 570°C; Case II, reduction of magnetite to iron above 570°C; and Case 111, reduction of magnetite to wustite above 570 oC. In Cases I and 111 the kinetics have been explained by the formation of oxygen anion vacancies in the magnetite surface followed by associated diffusional processes. In Case 11 the observed kinetics have been related to the concentration of iron cation vacancies in the wustite layer formed, followed by associated steady-state diffusional processes. The concentration of cation vacancies in the wustite is maintained constant by the magnetite-wustite equilibrium. THE reduction of the oxides of iron has been a subject of study and interest for many years. However, few attempts have been made to interpret the results in terms of the mechanism of reduction of an iron oxide by either hydrogen or carbon monoxide. Stalhane and Malmberg' using CO, H2, and CO-Hz mixtures, developed the rate expression: where m = mass of oxide reduced, t = time, k = a constant, s = surface area, P = partial pressure of of CO or H,, and P, = partial pressure of the reducing gas at equilibrium. The rate of reaction per unit area was proportional to the difference between the partial pressure of the reducing gas and its pressure at equilibrium. Hansen, Bitsianes, and Joseph2 studied the reduction of pellets of hematite to magnetite with mixtures of CO-CO,. They concluded that below 450°C the reaction proceeded according to a model in which CO reacts with the hematite surface producing an oxygen ion vacancy. The rate controlling step was then assumed to be oxygen ion diffusion through vacancies resulting in the formation of magnetite. They derived an expression giving the rate of reduction proportional to the cO/CO, ratio. Recently McKewan3 published results for the reduction of magnetite spheres in atmospheres below 570°C. He explained his results by an equation of the form where K, is the equilibrium constant for wustite-iron equilibrium attributed to the formation of wustite as an intermediate in the reduction of magnetite. According to McKewan, Kp is an equilibrium constant for H, -HO adsorption in which oxygen is deposited on the surface from the H,Oand subsequently acts as a poison for reduction by hydrogen. Sample Preparation and Experiments. In this work the authors used the same apparatus and experimental procedure employed in the hydrogen reduction of magnetite. Sintered disk samples weighing approximately 1.5 g and measuring 1.2 cm in diameter and 0.25 cm in thickness were prepared by a method described previously.4 Partial pressures of hydrogen and water vapor were controlled by bubbling hydrogen through a series of flasks containing distilled and deionized water maintained at constant temperature in an oil bath. The total flow rate of the reacting gases—hydrogen and water vapor—was approximately 0.5 liter per min. The entire external system was maintained at a temperature above the oil bath to prevent condensation of water vapor. This was accomplished by wrapping electrical resistance elements over all surfaces. The glass column containing the weighing system-a McBain balance suspended from a gold chain-was enclosed in an aluminum tube heated by nichrome resistance wire enclosed in an insulating material. The temperature of the glass column was held constant by means of a series of thermocouples connected in parallel to a Leeds and Northrup temperature controller. This was necessary since variations in temperature resulted in expansion and contraction of the glass column and could be readily observed with the cathetometer. The spring extensions were measured through a window with a gaertner cathe-

Jan 1, 1962

By G. H. Kesler, C. E. Dryden, J. H. Oxley

Rates of heat- and mass-transfer from rods to recirculating air were determined within a one-quarter-scale model of a metals deposition bulb. The dependence of local and averaged rates of transfer upon outlet geometry, number of rods, position upon a rod, and airflow rate was established for flow patterns created by radial and tangential air inlets. The results are given a qualitative interpretation in terms of rates and distribution of metal deposition in a prototype deposition bulb. IT is well known that a number of metals can be prepared from volatile compounds containing them by causing dissociation of their compounds to occur at heated surfaces. Examples of such metals include silicon, titanium, zirconium, and aluminum, which can be prepared from their halides. While the ability to prepare high-purity metals by this technique is of importance in itself, the rate of deposition of metal also is important in considering the commercial potential of such a process. If the over-all process of deposition is broken down into separate steps of transport of materials to and from the heated deposition surface and establishment of chemical equilibrium at the surface, as was described in a recent paper,1 then since surface temperatures are usually high and surface equilibrium is attained very rapidly, the rate-controlling step can be considered as either that of transport of reactants to the surface or of transport of products other than deposited metal away from the surface. These two transport steps are related through the reaction stoichiometry. It can be shown1 that the rate and distribution of metal in such a transport-controlled process are determined by the over-all and local mass-transfer coefficients in conjunction with the equilibrium conversions at the hot surfaces. The rate relationship is: w = [KA(y a-y s)] B.E where the bracketed group is the rate of arrival of the reactant at the surface of area A as determined by the mole fraction driving force (y a - y s) and the convective transport constant K. The factor B is the weight fraction of metal in the reactant, and E is the equilibrium fractional conversion to metal. Numerical values of y, and y, are fixed by the vapor composition and the equilibrium compositim of reactant at the surface; and E can be determined by thermodynamic calculations or by experiment. However, values for the convective coefficient K are available generally only for systems of simple geometry, such as cross-flow past a rod or sphere or parallel flow past a flat plate or through a tube. Often it is necessary to work with systems of more complex geometry and in which the vapor flow may not be uniform or exactly parallel or perpendicular to the surface. It is possible, of course, to establish working correlations for these more complex systems by direct experiment; but the experiments usually are costly in both time and money. To circumvent this objection and to aid in arriving at an understanding of the relationships and interactions of the process variables, it is helpful to construct a model of the flow system in which air, water, or other convenient fluids can be substituted for the process vapors and with which mass-transfer measurements or analogous he at-transfer measurements can be made upon a simulated deposition surface. By this means, a large number of measurements can be made in a reasonable time, and the correlation of these results can be applied to the prototype system. Examples of the application of these techniques are to be found in the literature (e.g., Ref. 2). It is the purpose of this paper to illustrate these techniques by description of a model study which was done at Battelle Memorial Institute. The work to be described was of a preliminary nature; the investigation subsequently was extended to develop quantitative relationships among the significant dimensionless transport, geometric, and flow parameters. This more detailed study will be the subject of a future paper.

Jan 1, 1962

By W. F. Domis, F. von Gemmingen, F. Garofalo

The effect of rain size on the creep behavior of an austenitic iron-base alloy has been studied at 1300° F under conditions of constant stress. The average grain diameter varied between 9 and 190 p (ASTM 10.7-2). The subgrain size and apparent activation energy for creep were not found to depend in any systematic manner on gain size. Grain hozmdary serrations were observed in all specimens tested. The variation of the secondary-creep rate, 2,, with the pain diameter, 1, is given by: es = K(213m + 1 )/l.]; 1, is the grain diameter zohere is reaches a minimum. Results in the literature shoujthat 1,increases as the temperature increases. At low creep temperatures is is therefore proportional to 12, at intermediate temperatures <, exhibits a minimum, and at high creep temperatures is is proportional to 1/1. The dependence ofis on the stress, u, is given by: t, = A" (sinh acrln, a and n show little variation with 1. The dependence of A" on 1 is given by: A" = KA[(21k + 13)/1]. For 1 » >>lmn = 4, and at constant values 01- isat lozu stress levels, the steady-state stress is given by the Hall-Petch relation. The variation of c, with grain size is believed to he associated particularly with grain boundary generation of dislocations which becomes more important with increasing temperatures. SEEMINGLY inconsistent experimental findings have led to a certain amount of confusion concerning the effect of grain size on creep behavior. The confusion is attributed to a lack of test results obtained over sufficiently wide ranges in grain size, stress, and temperature. Experimental results presented in this paper and results available in the literature1-5 show a consistent behavior and lead to a unified concept for the dependence of secondary-or steady-state creep rate on grain size. In accordance with this concept, which is substantiated experimentally, secondary-creep rate should increase with increasing grain diameter at low creep temperatures, leading to greater creep strengths for fine-grained materials. At intermediate temperatures the secondary-creep rate should decrease to a minimum and then increase as the grain size is increased. At high creep temperatures the secondary-creep rate should decrease with increasing grain size, leading to greater creep strengths for coarse-grained materials. Whether a temperature is high or low for creep in a metal or alloy depends primarily on its melting temperature. MATERIAL AND TEST PROCEDURES The material tested was an austenitic iron-base alloy of the following composition (wt pct): C, 0.005; N, 0.017; Mn, 1.26; Ni, 14.21; and Cr, 17.18. Two 15 -lb ingots were forged and hot-rolled to 5/8-in.-diam bars which were then cold-rolled and cold-swaged to a diameter of 0.49 in. These were sectioned into 3-in.-long blanks and heat-treated at various temperatures to obtain different grain sizes. The procedures employed and the results obtained are summarized in Table I. The secondary treatment at 1400° F followed the primary treatment without intermediate cooling to room temperature. This final treatment was employed to minimize various effects arising from heating to different temperatures during the primary treatment, particularly differences in intragranular dislocation structure, segregation of interstitial atoms at grain boundaries, and density of grain boundary ledges. The intragranular dislocation structure was examined by electron transmission metallography after each of the treatments described in Table I. Isolated dislocations and a few tangles were observed but no evidence of subgrains was found after any of the treatments. No grain-size effect was evident on the density and distribution of dislocations. Stabilization of grain boundary structure is particularly important because, as will be discussed later, grain boundaries influence high-temperature creep behavior. Magnetic-permeability measurements after each treatment and

Jan 1, 1964

By Edwin B. Wilson, Joseph W. Leonard, Richard W. Borio

preparation of specification coals for the utility industry is approached from the standpoint of a cooperative effort with the power company to assure that the shipped product will be a noncorrosive coal. Selective mining, coal preparation, the use of additives, and coal blending are mine-site techniques proposed as means for upgrading corrosion-retarding constituents of utility coals (CaO and MgO) while, at the same time, reducing the concentration of those constituents of coal (Na20 and K,O) which cause corrosion. Data obtained from large-scale boiler testing in combination with bench-scale physical and chemical tests are used as a basis for the formulation of mine-site procedures to improve coal combustion utilization. Electric power generation remains the greatest market for coal in the United States. A major reason for this strong market has been the ability of the coal industry to supply a superior product for combustion while maintaining competitive prices. Now that the coal industry is engaged in intensive competition with nuclear power for future energy demand, it becomes ever more imperative that superior coal products are produced. One important problem when burning some coals is a liquid phase corrosive attack on boiler tube metal in the superheater and reheater areas of the furnace where steam temperatures may exceed 1050°F. In addition to causing power outages and high maintenance costs, corrosion is a continuing barrier to the future development of more efficient steam cycles which permit lower generation costs when using coal. Research methods of the past which have been directed at finding solutions which could be applied at the power plant site have been only partially successful and are generally costly. This paper contains a suggested --method of corrosion control through investigation of the problem at the source of the trouble—the coal supplier facility. It is proposed that mine-site pre-ventative procedures be considered as an effective means of cooperative corrosion control between the power company and the coal supplier. Economic justification must be applied to the individual situation. This paper is based on recent work by Combustion Engineering, Inc. and the Coal Research Bureau of West Virginia University under a contract from the Department of the Interior Office of Coal Research.&apos;,&apos; Results which are of importance to this discussion may be summarized as follows: 1) The alkali minerals of coal (Na2O and K2O), as measured by an acid leaching process, can be related to corrosion rate in utility boilers. As these constituents increase in a coal product, its corrosiveness can be expected to worsen. 2) The alkaline-earth minerals contained in coal, reported as total CaO and MgO reduce corrosiveness 2s their concentration increases. 3) Naturally occuring, alkaline-earth-bearing materials, such as limestone and dolomite, may be added to a coal to reduce its corrosiveness. 4) Coals with very low iron contents tend to be less corrosive. These results provide the groundwork for examination of the system of operations which occur at the supplier facility from the seam face where mining is begun to the point of loading for shipment. The Mining System Fig. 1 is a cross section of one of the typical coal seams (designated coal A) that was boiler tested during this research program. This seam is overlain by material which consists primarily of a gray-black shale. In the lower third of this seam, there exists a thin rock parting of less than 4 in. in thickness which is consistent throughout the seam. The floor material is fireclay. In order to examine mineral distribution throughout this particular seam, the Coal Research Bureau collected a

Jan 1, 1971

By Michel Elle, John Chipman

The equilibrium of gaseous H20-H2 mixtures with liquid iron-columbium alloys in the range 0.2 to 2.4 pct Cb shows that the activity coefficient of oxygen is strongly diminished by Cb. The oxide in equilibvium with the melt is identified as CbO2. The equi-librium constant at 1600 deg C is [%Cb][fo. % 0]2 = 2.9 x 10-4 where log fo= —0.14 [%Cb]. The deoxidizing power is comparable to that of vanadium, COLUMBIUM (niobium) is finding increasing use as an alloying element in steel. It forms several stable oxides and is removed from the steel bath by oxidizing slags. The specific oxide formed in steel-making is not known although Sazanov snd Shvarts-man,&apos; in their study of its partition between slag and metal, have assumed this to be Cb2O5 It is the purpose of this study to determine its deoxidation equilibrium at 1600°c, the nature of the oxide formed and the interaction between columbium and oxygen in the melt. The investigation was based on the reaction H2 + O=H2O; Kl=ph2o/(pH2[%O]) [1] in which 0 signifies oxygen dissolved in the liquid Fe-Cb alloy. The method and equipment of recent studies2,3 were utilized. In brief, the molten alloy, contained in a small crucible, is held in a controlled mixture of steam, hydrogen, and argon until equilibrium is reached. It is then cooled quickly in a stream of helium and analyzed for columbium and oxygen, the latter by vacuum fusion.4 The solubility of the oxide in liquid iron is determined by visual observation of scum formation on the surface of the melt. Crucibles of MgO proved unsatisfactory because of partial reduction at the metal interface. Pure A12O3 crucibles were heavily blackened by the melt and could not be used at high concentrations of columbium. Silica crucibles were more satisfactory but these introduced some silicon into the melt thus necessitating an uncertain but small correction for its effect on the activities of the other solutes. In silica it was possible to observe the scum formation when the melt became saturated and there was no apparent reaction between scum and crucible. The procedure for saturated melts was as follows. The alloy charge composed of electrolytic iron and columbium grain was melted and held at constant temperature. The gas ratio H2O:H2 was progressively increased by raising the saturator temperature until a point was reached at which a bright film appeared on the surface and covered it completely. This film could be dissolved by raising the temperature of the melt and it reappeared when the temperature was lowered. Under a partial film covering, utilizing bare areas for temperature measurement, the melt was brought to equilibrium with the atmosphere by holding at temperature for about 1 hr as suggested by Dastur.5 INTERACTION IN THE MELT Several experiments were made without columbium to establish a base in silica crucibles. The results are shown in Table I. Except for one run, they agreed well with Floridis1 comparable results in other crucibles. The value of log K1 is taken from Table I as 0.58. This is slightly larger than Floridis&apos; result, probably because of less elaborate safeguards against thermal diffusion. Results obtained in the Fe-Cb-0 series in which no scum formed are shown in Table 11. The equilibrium ratio Kl is defined as ph2o/(ph2[%O]). It is related to the equilibrium constant K1 as follows:

Jan 1, 1962

By H. A. Fisch, A. J. Opinsky, J. L. Bartos

Fort?-six- two-grain bounduries were studied in doped tungsten 1amp wire that had been heated to 3450°K very vapidly. Back-reflection Laue photograms were taken of the grain boundary partners and solved, using a computer. The resulting distribution of large-grain orientations was analyzed. Rotational axes were calculatedfor each grain boundary pair. The axes of least rotation show an anisotropy of rolalional angle. WhILE the orientations of large grains in straight doped tungsten wire have been studied extensively, little has been done to characterize the boundary that separates them. Rosi.1 upon seeing the jagged interlocking boundary in doped tungsten wire. inferred that the grains should have a preferred orientation, and proved it. He interprets his data as indicative of a single ideal orientation—(531)— being parallel to the wire axis. Rieck2, 3 and Mannerkoski&apos; have essentially confirmed this finding. Opinsky, Orehotsky, and Siegle argue that the data suggest that (211)—a plane-is parallel to the wire axis instead. This (211 ) contains the (531). and hence would appear to be a more general case.5 Ahlborn and wasserman6 report that their orientation data stretch from (110) through (531) to (311). This path is the locus of {211 Recently. Opinsky has suggested that the data can be interpreted as a series of ideal orientations that can be related by coincidence relationships to the (110) fiber texture. All these investigators have determined the orientations of the large grains by the back-reflection Laue technique, and they have all obtained similar results. Only Rieck5 as methodically looked at the large grains along a wire. He was apparently not concerned with the relationships of the large grains across their common boundary, but only with their individual orientations. This research was undertaken to fill this gap in the under standing of the mechanical properties of tungsten wire. Only the crystallographic aspects of the problem will be reported here. In addition, the large number of large-grain orientations, which was accumulated in this study. will also be analyzed. EXPERIMENTAL MATERIAL AND TECHNIQUES All of the data were obtained from four pieces of the same 7-mil-diam General Electric tungsten lamp wire. Twelve-inch lengths of the cleaned wire were heated in vacuum by the flick of a switch to 90 pct of the amperes necessary for fusion (a temperature of approximately 3450°K) and held for 1 min. On the basis of other data. it is estimated that the rise time is of the order of 0.5 sec. The four pieces of wire could have come from anywhere within about 18 ft of wire. Consecutive segments of each piece of wire were mounted in bakelite and polished metallographically The polishing procedure followed that described by woods. "nly boundaries between two grains that each occupied the entire cross section of the wire were photographed and X-rayed. The metallographic sample was mounted accurately with respect to the X-ray unit. Steps were taken to read the films as accurately as possible with the conventional Greninger net. The data were then entered into computer programs that solve the Laue film by precisely the same techniques that are used in the solution of the film by means of the stereographic projection. The use of the computer has probably shifted the main source of error from the stereographic plot to the reading of the film. On the basis of several experiments, it is thought that the error associated with the entire process, from mounting the sample through the computer solution, is of the order of about one-half degree. The output of the computer is the direction cosines of the fiducial direction (the wire axis) and the locations of the three cube axes. The former data were used to calculate the differences in orientation between the two grain boundary partners, and the latter were used in the calculation of the rotational axes that could bring the two grains

Jan 1, 1970

By G. W. Healy, W. Craft, D. C. Hilty

By means of a theoretical extension of the Cr-C temperature relation in molten chromium steels to low chromium contents and by a correlation of the ratios of chromium to iron in the slag and metal, a method has been developed for estimating the amount of metallic oxidation during the oxidizing period of a chromium steel heat. Application of this method has indicated that due to temperature limitations metallic oxidation may be excessive for very low carbon steels charged with more than a small amount of chromium. IN the melting and refining of chromium steels the oxidation of carbon to a low level is accompanied by the oxidation of chromium and iron in considerable amounts. For the subsequent recovery of chromium and associated iron from the slag, the amounts of metal oxidized must be known for efficient reduction and control of composition. Further, in order to arrive at an accurate understanding of the process, so that chromium-bearing scrap can be used effectively, information is required on the relation between composition of the charge and weight of metal oxidized to reach the desired carbon content. Crafts and Rassbach1 recently developed an empirical relation between chromium, iron, and manganese oxidized per ton of steel charged, and final carbon content and temperature. This relation did not show any dependence on amount of chromium charged. However, it was felt that such a dependence might be present, so a further analysis of the data was undertaken. Cr-C Relation at Low Chromium Levels Crafts and Rassbach&apos;s results were based on temperatures estimated from the Cr-C relation previously established experimentally by Hilty,2 and on a single temperature observation (immersion thermocouple) on a heat made at low temperature from a charge of carbon steel scrap containing only a small amount of residual chromium. The temperatures estimated from the Cr-C relation were for heats charged with chromium-bearing scrap and which contained substantial amounts of chromium (2 to 10 pct) at the end of the oxidizing period. No data, other than that from the low temperature heat just mentioned, were available for the low and intermediate chromium ranges. In order to extend the range in which temperature may be estimated, the Cr-C relation requires further consideration. The Cr-C relation, expressed as suggests that carbon is zero at zero chromium in the bath. This is obviously absurd, because as chromium approaches zero the carbon content must approach the limit established by the Fe-C-O equilibrium. It is evident, therefore, that the Cr-C relation as defined by Eq. 1 is not valid below some minimum chromium content that may vary with temperature. On the other hand, it is probable that any such limiting chromium content is less than 4 pct at 3200°F, since the experimental data from which the Cr-C relation was derived included several observations at that level with no deviation. In any event, it is apparent that further evaluation of the results presented by Crafts and Rassbach is dependent upon a means for estimating the Cr-C temperature relation in the low chromium region. From the observations of Chen and Chipman9 and thermodynamic data given in Basic Open Hearth Steelmaking,4 the following relation can be calculated for melts containing small amounts of chromium and carbon assuming a carbon monoxide pressure of 1 atm: % Cr -21,250 K&apos; = (%C)2; logK1 == —t— +13.88 [2] Moreover, by plotting Eq. 2 for any given temperature on cartesian coordinates, it can be extrapolated graphically to the limiting carbon content at zero chromium for the specified temperature without serious complications. By means of Eq. 2 and its extrapolation, the Cr-C temperature relations originally established experi-

Jan 1, 1954

By C. B. Alcock, R. G. Hudson

Sulfur pressure measurements above FeS in equilibrium with iron have been carried out by the Knudsen orifice method. A comparison is made of the weight loss of the cell per unit time obtained in the above experiments, that calculated from Richardson and Alcock&apos;s measurements of the S2 pressure above FeS in equilibrium with iron, and the dissociation constant for diatomic sulfur from spectroscopic and thermal data. EXTENSIVE equilibrium measurements have been made to determine the sulfur potentials of a great many systems of metallurgical interest.&apos; In order to confirm their reliability, to supply data which may be of use in further thermodynamic calculations, and to establish the reliability of the Knudsen orifice in obtaining accurate thermodynamic values at high temperatures, the present investigation on the pressure of the gaseous species above FeS in equilibrium with iron has been carried out. The Knudsen orifice method has been used for these pressure measurements. Experimental The apparatus and general technique for this investigation are the same as that reported for the determination of the vapor pressure of silver.&apos; To reduce the residual gas pressure in the evacuated chamber, a titanium getter, maintained at run temperature, was introducbed. Several types of Knudsen cells were used—platinum, zircon, and fused silica. The orifice in the zircon cell was fashioned with a small diamond wheel. The same precautions were used in this investigation as were employed in the work on Mo2S2.3 The FeS-Fe mixture was prepared by heating a sample of pure FeS,, supplied by K. K. Kelley of the Bureau of Mines, with excess iron powder, cp grade, obtained from the Fisher Scientific Co. These two substances were heated in a closed Armco iron crucible at 960°C, held in a vacuum of less than 10" mm Hg for 24 hr. The mass was then removed from the cell and ground in an agate mortar. In this form it was charged to the various Knudsen cells. Heating the Knudsen cell for an additional two days was sufficient to obtain constant rates of weight loss of the cell. The data obtained in this investigation are recorded in Table I. To establish whether or not a sulfide of iron is volatile at these temperatures, 0.7646 g of the FeS-Fe mixture, described above and containing 69.2 pet Fe, was placed in the zircon Knudsen cell. Run Nos. 103 to 109 were performed on it. After the completion of these runs, the total amount of iron left in the cell was obtained by chemical analysis. It contained 0.537 g Fe, compared to 0.529 g in the original charge. Thus, there was an apparent gain in iron of 1.5 pet. This is attributed to unknown experimental error, and the conclusion is that no sulfide of iron is volatile. The vapor pressure of pure iron4 is about one thousandth that of the sulfur pressure&apos; at these temperatures. The vapor pressure of iron inside the Knudsen cell will be almost exactly that of pure iron, since in the iron-rich phase the percentage of sulfur is of the order of 0.025 pet.At this low percentage of sulfur Henry&apos;s law is probably obeyed by the sulfur. Thus, the iron will obey Raoult&apos;s law. In any event, the vapor pressure of iron will be lower than that of pure iron and, since the vapor pressure of pure iron is negligible compared to the pressure of sulfur, the weight loss of the cell due to the vaporization of iron should be negligible. Since neither iron nor FeS is volatile to an appreciable extent, the total weight loss of the cell must be due to the vaporization of sulfur. Discussion and Calculations On the assumption that S, is the only gaseous species present in appreciable quantity, its pressure

Jan 1, 1957

By C. R. Simcoe, T. J. Koppenaal

The effect of direct and alternating currents on the quench aging behavior in an Al-4 pct Cu alloy has been investigated by use of resistivity measurements. The reaction rate increases with direct current density in the investigated range of 1000 to 3000 amps per sq cm. Alternating current of a specific frequency is observed to decrease the reaction rate by a factor of about two. ErDMANN-JESNITZER et al.,1,2 investigated the effect of direct and alternating current on the quench and strain aging behavior of low-carbon iron. In both cases they observed that direct current accelerates the aging reaction and that an alternating current can completely inhibit the aging process. The purpose of the present research was to investigate these phenomena in the quench aging behavior of an Al-4 pct Cu alloy and to determine the correlation, if any, between the increase in the observed reaction rate and possible heating effects accompanying the aging with direct current. EXPERIMENTAL PROCEDURE The aluminum-base alloy used in this investigation contained 3.98 wt pct Cu (1.72 at. pct) with impurities of 0.003 pct Si, 0.002 pct Fe, and 0.001 pct Mg. The alloy was rolled into a ribbon about 0.36 mm thick and 3.7 mm wide. The ribbon was split end from end with the ends being used as electrical contacts and the central unsplit section, about 5.3 cm in length, serving as the specimen. Solution treatment was accomplished by quenching from a salt bath at 520° ± 2°C into water at 25° ±0.5°C; the specimen was immediately transferred to a liquid nitrogen bath. All aging was done at 75° ± 0.2°C in a rapidly stirred ethylene glycol bath. Resistivity measurements were made by the double potentio-metric method employing a standard resistor; for purposes of convenience, the resistance measurements were made at 77°K. The transfer of the specimen from the aging bath to a liquid nitrogen dewar was accomplished in less than 1 sec. The aging kinteics were studied with the specimen being aged under the influence of direct current, alternating current, and without any type of current. The amount of heating caused by direct currents was investigated by soldering a thermocouple on the specimen surface and measuring the temperature change after applying various current densities. The temperature was observed to increase (from 75°C, the aging temperature) about 0.8°, 3.0°, and 8.5°C with direct currents of 1000, 2000, and 3000 amp per sq cm, respectively. When employing alternating current, the circuit was monitored with an oscilloscope and adjustments made to produce a normal sine-wave pattern. RESULTS Prior investigations3&apos;4 in the aging characteristics of A1-4 wt pct Cu have shown that the resistivity initially increases, reaches a maximum, and then decreases to values significantly lower than the as-quenched resistivity. This type of behavior is seen in Fig. 1 which shows the resistivity at 77°K as a function of aging time at 75°C observed in this investigation. At this aging temperature, the resistivity maximum is seen to occur in about 1 to 1-1/2 min and it further decreases to the as-quenched value in about 24 min. The behavior observed with the application of direct currents of 1000, 2000, and 3000 amp per sq cm during aging is shown in Fig. 2. With increasing current densities, (+) ?pmax decreases and the rate of the aging process increases. The time necessary to reach the as-quenched resistivity value decreases from 24 min for aging without current to about 16, 10, and 7 min for aging with 1000, 2000, and 3000 amp per sq cm direct current, respectively. Fig. 3 shows the results obtained when two changes were made during the aging with 2000 amp per sq cm

Jan 1, 1963

By D. J. Freeh, W. E. Horst, R. C. Kellner

This paper is concerned with the description of grinding characteristics in a batch grinding system. A mathematical model was developed and used for simulating the system on an analog computer. A general equation describing the change of selected size fractions with respect to time is presented. The empirical verification of the model is discussed. In order to understand the performance of a grinding system, it would be desirable to have a mathematical description of the system&apos;s behavior. The development of a mathematical model to describe the performance of a batch dry-grinding operation was investigated. This is the first step toward reaching the objective of a practical mathematical description of a grinding system that could be employed for process control and optimization of a simple or complex grinding circuit. Although this article is concerned only with batch grinding performance, experimental work is being conducted to extend the model to continuous grinding systems. BASIC PROCESS CONSIDERATIONS In a paper dealing with the probability theory of wet ball milling, Roberts1 correlated the rate of change of oversize material, C, with energy input, E, as follows where the energy input is expressed in power/unit mass and k is a constant for each particle size. Experimental grinding studies were made by Bowdish2 to extend the previous work of Roberts. The work of Bowdish also showed that the rate of breaking of oversize particles in a ball mill is proportional to the concentration of oversize particles present. He further demonstrated that breaking of oversize particles is proportional to the surface area of the balls used for grinding. Rate equations were presented and it was concluded that grinding could be considered as a first order phenomenon according to the rate equation [2] di which is in accordance with Eq. 1. In Eq. 2, the effect of ball area is included in the constant k,. Other rate equations were reported to show the effect of a change in ball area and removal of fines during grinding. Correlation studies made by Arbiter and BhranY indicate a first-order rate equation for quartz; however, their data showed less than first-order rates existed for some of the other materials evaluated. More recently Kelsall4 has shown that the rate of breakage of any narrow size range of quartz could be described by a first-order rate equation. Several other investigators5-7 have described grinding behavior in terms of rate equations or kinetics. In general, the rate equations have been described for each particle size; however, the interactions between sizes and the overall relationships that exist have not been considered, at least not in the form of solving a group of simultaneous differential equations. Extensive work has been conducted by various investigators using a probabilistic approach which has expanded stein&apos;s&apos; earlier work. Selection and breakage matrices are incorporated in the probabilistic model as contrasted with the deterministic method presented here. A batch grinding operation may be considered as an unsteady-state process from the standpoint that the conditions within the mill are a function of time. Therefore, a plot of mass fraction of the i-th size versus time would give a set of curves as shown in Fig. 1. In these curves X , represents the mass fraction of large size material, X2 intermediate size, and X3 small size material. An examination of these curves shows a strong similarity to the curves that would be obtained from a chemical reaction of the type9 A?B?C, [3] where A would be comparable to the largest size material being broken to an intermediate size, 3, and

Jan 1, 1968

By C. Gatlin, C. E. Nemir

A common cure of lost circulation is the introduction of granular bridging agents into the mud system. Many materials, such as ground nut shells, are used for this purpose. If the trouble causing void (fracture, fissure, vug, etc.) is not too large, the granular agent forms a "bridge" across or within the opening. Successively smaller particles in the mud stream then accumulate on and/or within this bridge until normal filtration is finally established. The efficiency of many bridging agents has been studied in the laboratory using various slot testers.&apos;,&apos; Many investigators have remarked that a granular bridging material should have the proper particle size distribution. With the exception of the broad range specified in the patent of Goins and Nash,3 here is apparently no definition as to what this distribution should be. A bridge may be initiated when several particles of lost circulation material lodge against each other in a fracture or other void. Smaller particles then may bridge the openings between the larger, previously bridged particles. This process continues until the voids become quite small and the problem becomes one of filtration. It would seem logical that an optimum particle size distribution exists, i.e., one containing the proper quantity of properly sized material to fill the successively smaller voids of the bridge. The filtration characteristics of drilling fluids may be subject to a similar analysis. It has been clearly demonstrated by many workers that the filtration behavior of various muds can be altered by particle size control.&apos;.&apos; Slusser, et al, divided filtration into three periods and showed that particle sizes affecting a given period did not necessarily affect other portions of the filtration curve. An analagous problem is the proper sizing of gravel, liner slots and screen sizes in various sand-exclusion problems. Here the situation is reversed in that a proper "void" size, rather than the size of the bridging agent, is sought. The classic work of Coberly 9 forms the quantitative basis for most sand-exclusion processes. It is interesting to note that, in general, Coberly&apos;s work has been overlooked by most drilling-mud researchers. Other investigators have made various studies of the effect of particle size distribution .on drilling-mud properties. As a part of their studies, Fancher and Oliphant reported 30-minute filtration loss of a variety of mixtures of particle sizes.&apos;&apos; Gates and Bowie noted an effect of particle size distribution on filtration, as well as on other physical properties.&apos; MAXIMUM DENSITY THEORY A maximum density mixture has been mentioned as the possible solution for both lost circulation and mud filtration problems. Furnas 12 derived mathematically a method for obtaining maximum density of beds of packed solids, having either a given number of component sizes or a continuous gradation of sizes. This work was verified experimentally by Anderegg.13 or mixtures having a continuous grading of sizes, the interval between sizes is taken as successive screen sizes of interval 2 The ratio of the quantity of each size and the next smaller size is given by the equation Fig. I, number of size intervals of ratio 2 taken from Furnas&apos; paper, gives the value of n + 1 for any given values of + and K, where K is the ratio of the diameter of the smallest particles to the diameter of the largest particles. Measurement by weight assumes, of course, constant density for all particle sizes. Choosing the quantity of the smallest particle size as a unit weight, the required weights of the successively larger interials are then r1 r2 r3 . ®1,2,3. Thus, the grading curve of a maximum density mixture represents a geometric pro gression of ratio r.