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By H. N. Treaftis, J. W. Cahn

THE previous determinations of the solvus of tin in solid lead disagree with one another by as much as 40°C or almost 10 at. pct. Even determinations that appear to be careful differ considerably in both the solubility and its temperature coefficient. Recent kinetic workl -3 on the rate of precipitation of tin from lead-tin alloys and thermodynamic work4 on the heat of solution of tin in lead have given some insight into the time necessary to reach equilibrium in this system. As this time is longer than that used in almost all previous determinations of the solvus, these determinations are questionable. Since the interpretation of recent kinetic results requires accurate values of the equilibrium solubility the present work was undertaken. DISCUSSION OF PREVIOUS RESULTS The methods used in previous studies may be placed into three classes: 1) Several alloys covering a range of compositions are allowed to reach "equilibrium" at a certain temperature.5-7 Some property, such as the X-ray lattice parameter of the lead-rich phase or the re- sistivity of the alloy, is then measured as a function of composition. The solubility limit for that temperature is taken to be that composition at which a discontinuity in the property occurs. However, the recent kinetic work has shown that tin precipitates in two stages. The first stage is rapid but leaves the lead still supersaturated. The second stage is very slow, and it seems from the equilibration times quoted by the investigators of the solvus that the end of the first stage of precipitation was usually mistaken for equilibrium. This is especially true at temperatures below 100°C where the first reaction is still quite rapid (from minutes to months), but where the second stage is so slow that very long holding times are required to reach equilibrium. Alternatively micrographic work8 on several alloys of different compositions seems to have given good results if done carefully. 2) The beginning of precipitation in a homogenized alloy is measured as it cools slowly8-10. Since reactions in solids undercool easily, such determinations will always give too low a temperature for the solvus. 3) Some property of an alloy is measured as a function of temperature while the alloy is above the solvus.5,9,11 The range of temperature can usually be extended slightly into the two phase region. Then the alloy is precipitated at a much lower temperature and slowly reheated. The solvus is taken to be the lowest temperature where the property of the reheated alloy is equal to that previously determined for the homogeneous alloy. Usually one also expects a discontinuity at the solvus in the temperature variation of the property for the reheated alloy. The difficulty in this method is the sluggishness of the dissolution process, and this method may give too high a solvus temperature. EXPERIMENTAL The phase boundary or solvus temperature was determined by a modification of method 3 for a series of chemically analyzed high-purity alloys, ranging from 5.1 to 26.4 at. pct Sn. The resistance, as a function of temperature, of a sample of homogenized alloy (which could easily be undercooled) was compared with the equilibrium resistance which that alloy sample attained after precipitation at room temperature followed by long isothermal anneals at various temperatures. Before each anneal the sample was rehomogenized and reprecipitated. The solvus temperature could be located to within 1°C as the intersection of the resistance vs temperature curves for the homogenized and equilibrium alloys. No attempt was made to locate the phase boundary more accurately since the limiting factor was the precision with which the alloys could be analyzed. This precision was ±0.1 wt pct Sn and corresponds to an error of 1 deg in temperature. This use of isothermal anneals differs from some of the previous investigations in which method 3 was used with baths of slowly rising temperatures. It was found early in the investigation that solvus temperatures tended to be high if the latter method was used even at extremely slow heating rates. For example a

Jan 1, 1961

By G. Nabi, W-K. Lu

Cylindrical specimens of natural dense hematite were reduced to magnetite at atmospheric pressure in H2-H2O mixtures of known composition over the temperature range 1084° to 1284°K. The rate of reduction was measured by the rate of movement of the interface between hematite and magnetite. The diffusion of gases through the gaseous boundary layer, the magnetite layer, and the interfacial chemical reaction were all considered in the interpretation of experimental data. The mass transfer coefficient through the boundary layer was calculated using accepted correlations. Values of the chemical reaction rate constant and the diffusivity of hydrogen in the magnetite phase were determined. THE present investigation is concerned with the reduction kinetics of natural hematite to magnetite by H2-H2O mixtures in the temperature range 1084" to 1284°K at atmospheric pressure. This reaction is the first step in the series of topochemical reactions in the process of reducing hematite to iron. Kinetic information of the simple steps such as hematite-magnetite transformation is necessary in order to have a better understanding of the complex processes of hematite reduction in iron-making. It also has direct industrial significance because magnetic roasting is one of the most important methods in benefication of lean ore.&apos; Although many technical papers have been published on the process of magnetic roasting and iron oxide reduction, very little information is available in the literature concerning the fundamental nature of hematite reduction to magnetite by reducing gases. Hansen et al.2 reduced the dense synthetic pellets of high-purity oxide in CO-CO2 mixtures and determined the reaction rate by weight-loss method. They were able to interpret most of their results by applying the interfacial area control theory developed by Mckewan.3 In contrast, Wilhelm and St. Pierre,4 who studied reduction of hematite to magnetite in H2-H2O mixtures by weight-loss method, stressed that the resistance of the porous magnetite layer to the diffusion of gases cannot be neglected in consideration of the overall reaction rate. In the present study the contributions of interfacial chemical reaction, diffusion of gases through the magnetite phase, and the gaseous boundary layer to the overall reaction rate will be considered. APPARATUS AND PROCEDURE Hematite Specimens Preparation. Natural hematite ore from Vermillon range of Northern Minnesota was selected for the present investigation because of its high purity and thermal stability. Chemical analysis of five samples gave the following average values: 67.52 pct total iron (96.62 pct Fe2O3, 0.28 pct FeO, 0.03 pct metallic iron), 2.53 pct SiO2, <0.07 pct MgO, 0.03 pct CaO, 0.05 pct combined mixture, 0.07 pct loss on ignition, and 0.34 pct other. Cylindrical specimens of 0.93 cm in diam and 2.7 cm in length were drilled from slabs of ore with a water-cooled diamond core drill. These specimens were heated to 1000°C and furnace-cooled. Specimens with silica pockets developed large cracks. The uncracked specimens were heated a second time, and their surfaces were carefully examined with a microscope. Those with hairline cracks or surface inhomoaenitv-- were rejected. Preparation of H2-H2O Mixtures. H2-H2O mixtures were prepared by the combustion of H2-O2, mixtures in a pyrex glass chamber in the presence of a catalyst. Alumina pellets coated with palladium, supplied by Englehard Industries, were used as the catalyst. Purified grades of hydrogen and oxygen were used which were repurified by usual techniques. Hydrogen before entering the combustion chamber was passed through an activated alumina H2O absorption bulb, with copper turning at the top. The cover of this bulb was not made pressure-tight so that any pressure development in the hydrogen line would cause the cover to blow off and also the copper turnings would act as a flame arrester in the case of a flashback from the combustion flame. Oxygen flow rates were measured with a bubble flow meter after purification with 1 pct accuracy. Hydrogen flow rates were measured by "precision wet test meter" and the amount of unburnt hydrogen was accurately measured by a bubble flow meter, after condensing water vapor in the gaseous stream. The Pyrex glass bulb contained concentric Vycor glass tubes as shown in Fig. 1. Oxygen was prevented from diffusing into the hydrogen line by threading platinum wire through pores at the combustion end of gas inlet tube. The glass bulb was heated with a Kanthal heating wire pasted in asbestos paper. The surface temperature of the bulb was measured with a thermocouple and adjusted to remain at approximately 350°C. The gaseous reaction chamber also served as a preheater for gases to avoid thermal segregation. The following sequence of operation was adopted. 1) Nitrogen was passed through the outer concentric tube to purge the catalyst bulb of oxygen. 2) Hydrogen was introduced through the inner tube until a steady flow was obtained. 3) Oxygen was then introduced into the nitrogen stream passing through the outer tube. 4) When combustion had commenced and a flame was visible over the platinum wire, the N2 was turned off.

Jan 1, 1969

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

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

Jan 1, 1995

By Vineet Kumar Yadav, Akshay Dvivedi, Pradeep Kumar

Near-dry electric discharge machining (EDM) is a process variant of EDM, which uses two-phase flow of liquid and gas as dielectric medium. This article reports the results of an investigation pertaining to the drilling of holes on high speed steel (T2 grade) by a rotary tool near-dry EDM. The One-Factor-At-a-Time (OFAT) approach was used for experimentation. The effects of process parameters, viz. tool rotation speed, peak current, pulse duration, gas pressure and liquid flow rate on material removal rate (MRR) and overcut were investigated. The dielectric medium used was a mixture of glycerin-air. The experimental results reveal that rotation of the tool electrode along with high pressure of two-phase dielectric medium contribute in an effective flushing of inter electrode gap (IEG). Further, in rotary tool near-dry EDM process, higher values of current can be used. This improves process economics in terms of MRR. The MRR measured with rotary tool near-dry EDM was three to four times higher in comparison with conventional EDM. Additionally, appreciable surface quality was achieved.

Mar 1, 2017

By W. C. Leslie, R. M. Fisher, K. G. Carroll

A nitride, believed to be Si3N, has been separated from three nitrided silicon steels. Germanium nitride, Ge3N4, has been prepared from pure germanium. Comparison of the diffraction patterns indicates that the two nitrides are isomorphous; on orthorhombic structure is suggested in place of the rhombohedral structure previously reported for Ge3N4. THE possibility that a nitride of silicon may, under appropriate conditions, precipitate in silicon steels or in steels killed with silicon makes it desirable to have some positive means of identifying such a compound. One such means is the X-ray or electron diffraction pattern of the nitride. A review of the meager data in the literature indicates that the nitride most likely to form is Si3N4, a conclusion supported by the results of a study of nitrided silicon steels to be published shortly by L. S. Darken and R. P. Smith, of this Laboratory. Unfortunately, there is available no diffraction pattern for this nitride. Data have been reported, however, for Ge3N4 which, judging from the similarity between germanium and silicon, might be expected to be isomorphous with Si3N4. An effort was made, therefore, to form such a silicon nitride, to determine its composition and diffraction pattern and, if possible, its structure. To this end a series of three silicon steels was nitrided under controlled conditions with the resultant formation of nitride particles which yielded an electron diffraction pattern in situ. The particles were then extracted from the steel and an attempt was made to determine their chemical composition. X-ray and electron diffraction patterns were also obtained from the extracted particles, which indicate that the nitride is isomorphous with Ge3N4, although a complete determination of the structure has not been possible. These results show that a silicon nitride with a well-defined diffraction pattern can form in silicon steels, and they suggest that this nitride is Si3N4. Materials and Procedures The sillicon steels investigated were In the form of thin sheet or strip and had the composition shown in Table I. The 0.58 and 1.21 pct Si steels were nitrided by holding them at 1110°F in an H2-NH3 atmosphere containing 3 pct ammonia for 48 hr. The nitride particle size was increased by subsequent heating at 1500°F for 13 1/2 hr in helium. The resulting microstructure is shown in Fig. 1. The steel containing 3.20 pct Si was nitrided at 1200°F for 16 1/2 hr after which it was held in helium at 1500°F for 4 hr. Its structure as seen under the electron microscope is illustrated by Fig. 2. As would be expected from the higher silicon content and the shorter holding time at 1500 °F, the nitride particles are smaller and more numerous than those in the 1.21 pct Si steel. The ammonia-hydrogen treatment reduced the carbon content of the steels to a very low level, so no interference was encountered from carbon or carbides. In the case of the 3.2 pct Si steel, the carbon was reduced to 0.003 pct before nitriding by heating in dry hydrogen. Attempts to obtain an X-ray diffraction pattern from polished and etched surfaces of the 1.21 and the 3.20 pct Si steels were unsuccessful. However, an electron diffraction pattern was obtained from the surface of the steels. The interplanar spacings obtained from these patterns arc shown in Table 11, col. 5. The nitride particles were then extracted from all three steels by dissolving the ferrite matrix in bromine-methyl acetate, the solution used in the Beeghly method for the extraction of aluminum nitride from steel. X-ray diffraction patterns of these residues, obtained by means of a spectrometer and by a 57 mm Debye-Scherrer powder camera using filtered cobalt or chromium radiation, are given in Table II along with the pattern obtained by

Jan 1, 1953

By David J. Mack, Dennis R. O’Boyle

The mechanical properties of three polycrystalline intermediale Phases that have the y bvass structure were measured in compression between 400° and 900°K. At the lower testing temperatures— termed Region I— no plaslic deformalion occurred prior to brittle fracture. A1 higher temperatuves— lermed Region III—the three phases deformted plaslically for all strain rules from 1.5 to 36.0 x 10-4 sec-1. The homologous temperature for the inilialion of plaslic flow increased in the same order as tile atomic size difference between atoms in each plmse (0.50Tmp for y AgZn, 0.62Tmp for y CuZn, and 0.76 Tmp for y CuCd). The increased flow resistance oj. y CuCd above 0.50Tmp is explaitzed in terms of the more random arrangement of copper and cadmiwn atoms on the laltice sites of&apos; the y bvass slrilctlire. Plaslic deformation of the three intevmiediate phases in the smooth plaslic flow region appears to be controlled by oacancy-induced dislocation climb. RESULTS are reported in this paper on the mechanical properties of three binary intermediate phases having the complex cubic y brass structure (D82, 143m) containing fifty-two atoms in the unit cell. The structure of the prototype y brass phase, y CuZn, was first analyzed by Bradley and Thewlis&apos; based on the X-ray work of Westgren and Phragmen.2 The y brass structure can be visualized as an arrangement of twenty-seven body centered cubes (3 by 3 by 3) into a unit cell containing fifty-four atoms. From this cell the center atom and the four corner atoms are removed and the remaining fifty-two atoms are slightly displaced, resulting in the y brass structure. Approximately thirty-five binary intermediate phases that have an electron to atom ratio of 21:13 have been reported to form the y brass structure. The three y brass intermediate phases selected for this study are formed from elements in groups IB and IIB of the first and second long period. Each compound exists over a composition range that includes the stoi-chiometric composition A5BB (Cu5Zn8, Ag5Zn8, Cu5Cd8). y CuZn (a0 = 9.944A) has solubility limits extending from 57 to 67 at. pct Zn at 500°C apd melts peritecti-cally at 834°C; y AgZn (a0 = 9.326A) has a solubility range from 58 to 63 at. pct Za and melts peritectically at 661°C. y CuCd (a, = 9.596A) melts congruently at 563°C and has a maximum range of solubility extending from 58 to 64 at. pct Cd. In order to minimize coring and microporosity during solidification, the composi- tion of the compounds that form peritectically (y CuZn and y AgZn) was chosen so that the temperature difference between the liquidus and the solidus is only a few degrees centigrade. In selecting y brass compounds for this study, phases were avoided that contained a transition element or that had an electron to atom ratio greater than 1.70. Hume-Rothery et a1.3 has observed that, when the electron to atom ratio of y brass intermediate phases exceeds 1.70, atoms begin to drop out of the unit cell to maintain a constant electron to unit cell ratio. EXPERIMENTAL PROCEDURE Each of the three intermediate phases was prepared from elements having a purity >99.999 pct. Only trace quantities of impurities (<0.0001 pct) were detected by spectrographic analysis of the four elements. A master alloy of each compound weighing approximately 130 g was prepared by melting the elements in evacuated sealed quartz tubes heated in an electric furnace. Specimens having the desired diameter for the mechanical property measurements were obtained by remelting the master alloy in a Vycor tube under argon and drawing specimens from the melt into 4-mm-diam quartz tubes. To obtain a smooth surface on specimens drawn from the melt, the inside of the quartz tube was coated with a thin layer of graphite formed by thermally decompositing acetone. All specimens were imbedded in sealing wax and cut to the proper length with a diamond-impregnated cut-off wheel. The individual specimens (4 mm diam by 8 mm long) were then sealed in evacuated Pyrex tubes and homogenized at 500°C for 72 hr. Chemical composition, variations over the length of the rod (10 cm long) were generally less than 0.2 pct and the analyzed composition differed from the desired composition by less than 0.5 pct.4 Metallographic evaluation of the specimens after homogenization showed no evidence of a second phase in any of the compounds. The average grain size of the specimens after homogenization was 1 to 2 mm. All mechanical property measurements were carried out in an argon atmosphere using a compression apparatus described previously.5 Prior to applying the load to the specimen, the test apparatus was evacuated, back-filled with argon, and heated to the test temperature for 20 min to establish thermal equilibrium. EXPERIMENTAL RESULTS Mechanical properties measured as a function of temperature and strain rate for each of the three y brass phases were similar. From room temperature to the ductile-to-brittle transition temperature, only elastic deformation was observed prior to fracture.

Jan 1, 1968

By W. F., Dietrich

THIS paper deals with the- methods of mining the high-grade clays of California. Although the majority of the clay pits in the state are operated on a scale that is small by comparison with most metal mines, this very fact results in a diversity of methods and gives rise to problems of selection of the method best suited to given conditions. Two or three operators in California produce approximately 500 tons per day of a single kind of clay from a single pit. About five varieties of clay are mined on a scale of 200 to 400 tons per day; not over fifteen varieties are mined on a? scale of 50 to 200 tons per day; and more than 50 varieties are mined at a rate of less than 50 tons per day. It is the aim of this paper to delimit, insofar as the data at hand permit, the conditions and scale of operations that favor the selection of each dominant method of mining that is actually being applied at California properties. Details of the occurrence and utilization of the clays of California have been given in a recent bulletin and are not considered here.

Sep 1, 1928

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.&apos;.&apos; It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.&apos; Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,&apos; is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors&apos; sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958

By Douglas E. Hansen

A current trend in blasting of large volumes of rock is to use increasingly larger diameter shot holes. The use of large diameter holes meant; correspondingly large explosive charges will be loaded and detonated, and, if special efforts are not made, will result in more damage and vibration beyond the intended blast area. With the rising awareness of environmental factors, vibration control becomes increasingly important. Equally important is the preservation of intended lines and grades, and in some cases by blasting with care, slopes can be safely steepended. In the past, vibration control was established to prevent damage to man-made structures. The quarry or open pit itself can be regarded as a structure composed of rock. Far too little attention has been given to the effects of blasting on rock walls. The primary purpose of blasting is to break rock. If the integrity of the rock has been destroyed beyond intended lines and grades, the excavation will be more costly than originally anticipated. The increased cost will not only be from in¬creased excavation due to overbreak, but also increased maintenance due to blast induced wall instabilities

Jan 1, 1976

By R. O. Williams

It is shown that Ni3Al precipitates homogeneously from nickel-rich alwminum alloys as plates on the (100) planes. Prior to actual precipitation a process occurs which is believed to be one of increasing short-range order. After precipitating the Ni3Al plates enlarge through competitive growth. Discontinuous precipitation can occur simultaneously with the above processes. Recent ideas of the origin of precipitation strengthening appear adequate to explain the hardness changes. REMARKABLY little appears to be known about the precipitation process in Ni-Al alloys in spite of their technical importance. This investigation originated to supply additional information about precipitation in general, this system in particular. Information on the structures and kinetics have been obtained through the use of hardness, X-rays, microscopy, calorimetry, and resistivity on high-purity alloys. PROCEDURES Six alloys, Table I, were prepared by melting carbonyl nickel and high-purity aluminum in alumina crucibles in vacuum and casting into 1-in. graphite molds. All rods were homogenized at least once at 1300°C for 24 hr prior to swaging and this was repeated on the first three alloys after 75 pct reduction. Alloy 4 could be reduced only 10 pct at 1000°C (probably in two-phase field) prior to fracture but 1/4-in. samples quenched from 1100°C were readily reduced cold. Alloy 5 was reduced 15 pct cold but failed on the next pass while alloy 6 of essentially the same aluminum content failed inter-granularly without apparent flow up to 1000°C. The alloys were heated in hydrogen at the elevated temperatures and formed thin, coherent aluminum oxide coatings which provided excellent oxidation resistance at lower temperatures. However, freshly prepared surfaces showed considerably less resistance at 500"to 700°C in air and apparently resulted in internal oxidation. As a consequence, low-temperature agings were carried out in evacuated tubes. RESULTS The isothermal hardening behavior of these alloys at 500"and 565C is given in Figs. 1 and 2. These results were obtained from samples cold worked 75 pct, recrystallized at 1000°C (1100°C for the 7.8 pct Al) and quenched in water. This recrystallization was used to give smaller grain sizes so as to obtain more uniform hardness values and the points represent an average of five readings. The electrical resistivity was measured on 1/16-in. wires quenched from 1000°C during aging at 495°C to give Fig. 3. The energy release and its rate are given in Fig. 4 for the 6.9 pct Al alloy during aging around 500°C. Inasmuch as this was a single run, its accuracy is not known but certainly the general shape and magnitudes are correct. The method used to obtain these results is described elsewhere.&apos; Data for the aging at 600°, 700°, and 800°C of these alloys cold worked 50 pct are given in Fig. 5. Supplementary information from microscopy and X-ray diffraction have been included to indicate recrystallization, discontinuous precipitation and the appearance of superlattice lines from the Ni3Al. The hardness of these alloys as annealed, aged, cold worked, and cold worked and aged is given vs composition in Fig. 6. Those samples which were isothermally aged, Figs. 1 and 2, were reaged at 532°C and at successively higher temperatures for the indicated times to give the data of Fig. 7. These results as well as certain others, support the idea that the level of hardness reached for temperatures above 600°C are equilibrium values more or less independent of path. This being the case, the breaks in the curves would be the complete solution of the Ni,Al. The electrical resistivity versus temperatures for some of these alloys, both aged and unaged, is given in Fig. 8 along with those data from heating slowly (10 deg per day) to high temperatures. Interesting points include the lowering of the Curie temperature (the change in slope), the lack of any indications of a solubility limit and the large temperature coefficient for the Ni3Al. A slight break for Ni3Al around 100C shows up but this is not a Curie temperature as Ni3Al is not ferromagnetic down to -190°C. Metallographically both the nickel-rich solid solution and the Ni3Al appear very much like pure nickel. Profuse twin boundaries are present both

Jan 1, 1960

By Rafael Fagundes Ferreira

Aços Bake Hardening são aços laminados a frio com envelhecimento controlado. Estes aços caracterizam-se pela boa conformação e por apresentarem aumento de resistência mecânica devido ao envelhecimento, que ocorre por tratamento térmico. Nesse trabalho, corpos de prova de tração do material BH220 foram submetidos à pré-deformações que variam de 0 a 9% por tração uniaxial, posteriormente à tratamento de envelhecimento realizado em temperaturas que variam de 140°C a 210°C em tempos de aquecimento entre 5 minutos a 45 minutos. Foi confirmada que as temperaturas de envelhecimento, na faixa estudada de 140°C a 210°, alteram a variação do limite de escoamento devido ao fenômeno de difusão que é termicamente ativado. Nos resultados encontrados verifica-se que o tempo de aquecimento, dentro do intervalo testado, não é significativo.

Aug 16, 2017

By David W. Cannon, Russell V. Mann

In a dispersion of particles in liquid a net charge will develop at the particle-liquid interface. This surface charge is usually due to the adsorption of charged material from solution. The existence of this surface charge gives rise to the formation of the electric double layer of counter-ions which surrond the charged particle. The particle surface charge and the electrostatic repulsion which exists between similarly charged particles is the primary stabilization mechanism for lyophobic colloids (1). The separation of charge which occurs at the particle-liquid interface gives rise to several dynamic phenomena associated with colloidal systems or with solid-liquid interfaces in general. These phenomena are known as electrokinetic phenomena and the four classic electrokinetic phenomena are; electrophoresis, electroosmosis, streaming potential, and sedimentation or Dorn potential. The actual driving force for electrokinetic phenomena is not the surface charge per se, but the charge at the interface between the liquid which is hydrodynamically bound to the particle surface and the bulk fluid. This interface is known as the slipping plane or the plane of shear and the potential at this interface is the zeta potential (2). The factors linking the electrokinetic phenomena is that they involve a relative motion between the liquid and the charged particle or solid surface and the driving force is the zeta potential of the solid. In addition to the four classic electrokinetic phenomena there are two additional electrokinetic effects in disperse systems; the electro-acoustic effects. When an alternating electric field is applied to a cooloidal dispersion the particles will move in the field due to their net zeta potential. If there is a density difference between the particles and the fluid this motion will result in the development of an acoustic wave. The effect was discovered at Matec and has been termed the Electrokinetic Sonic Amplitude or ESA (3). ESA is the pressure amplitude generated by the colloid per unit applied electric field strength and has SI units of pascals per volt per meter. When an alternating pressure field (acoustic wave) is applied to a colloidal dispersion the inverse of the ESA effects occurs. A density difference between the disperse phase and the continuous phase leads to a relative motion between the particles and the surrounding liquid. This means that there will be a periodic displacement between the charged particle and the oppositely charged counter-ions in the electric double year. This displacement results in the development of an alternating dipole moment at the frequency of the applied field. This effect is termed the Ultrasonic Vibration Potential or UVP and was first predicted for electrolyte solutions by Debye in 1933 (4). UVP is measured in units of volts per unit velocity amplitude of the applied acoustic field or volts per meter per second. In 1938, Rutgers (5) and Hermans (6) pointed out that the effect would also be present in colloidal dispersions. A detailed theory for UVP effects in colloids, also called CVP, was first presented by Enderby in 1951 (7). Extensive studies of the UVP in electrolytes have been carried out by Yeager et al (8). Recently, O&apos;Brien (9) has developed a general theoretical treatment of electro- acoustic effects in colloids and has derived a reciprocal relation linking ESA and CVP effects. The most commonly studied electrokinetic phenomena is electrophoresis. Electrophoresis is the movement of charges particles in an applied electric field. The velocity of the particle divided by the applied electric field strength is the electrophoretic mobility of the particle. The zeta potential can be calculated from this mobility (2). The magnitude of both the ESA and CVP effects are directly proportional to the electrophoretic mobility of the particles. The mobility determined by the two electro-acoustic effects is the dynamic or AC mobility of the particles.

Jan 1, 1990

By G. R. Love, C. C. Koch

The changes in superconducting properties with aging time have been studied ,for the pecipitation reaction in a Tc-30 at. pct V alloy. Superconducting critical temperature, upper critical field, and relative critical current density were determined by ac susceptibility techniques. Aging produces changes in critical temperature of both matrix and precipitate which can be rationalized by compositional effects. maximum flux pinning (critical current density) occurs at a time during aging when subgrain boundaries are completely decorated with precipitates and the subgrain centers remain precipitate -free. The particular effectiveness as barriers to flux motion of planar defects which enclose regions of low deject density is discussed. THE precipitation of a second phase can dramatically modify the superconducting properties of type I1 super-conductors. According to Livingston and Schadler1 one might expect changes in the primary, secondary, and tertiary superconducting properties of the material. Changes in matrix chemistry caused by precipitation can alter the fundamental superconducting parameters; critical temperature, Tc, and thermody-namic critical field, Hc. The concimitant changes in electron mean free path (reflected in normal state resistivity) can affect the critical fields Hc 1, IIc2, Hc3. Finally, the presence of precipitate particles may hinder the motion of flux lines and may considerably improve the current-carrying capacity in high-field superconductors. The influence of precipitation on superconducting properties has been studied in a number of systems.2 Magnetization measurements have been used to study the influence of precipitates on flux pinning in lead-base alloys by Livingston3 and Evetts et al4 In these alloys precipitates induced magnetic hysteresis and flux trapping. The amount of hysteresis increased with the volume fraction of precipitate and decreased with coarsening of the precipitate. Jn an Al-Zn alloy5 and an A1-Ag alloy6 the initial precipitate size was presumably smaller than a coherence length and coarsening increased magnetic hysteresis5 and critical current density.6 The influence of precipitation on superconducting properties has also been studied in several of the commercially interesting Ti-Nb7-10 and zr-Nb11 alloys. The maximum in critical current density for these alloys was confined to a narrow range of either isothermal aging time" or isochronal aging temperature7 during the precipitation reaction. Thus, experimental evidence and theoretical considerations suggest there is an optimum precipitate size, spacing, and density, and a critical composition with respect to the matrix for flux pinning. What these "optimum" values might be and the relative importance of each is still not clear, although a few generalizations can be made. It is generally accepted1&apos; that particle sizes smaller than the coherence length or larger than the inter-flux line spacing are poor pinning centers. In high Hc2 materials, precipitate sizes for maximum values of critical current density lie in the range of 50 to 2000Å,9,7 and there are indications that increasing dissimilarity between precipitate and matrix produces increasing pinning force.13 Because of several interesting features of the aging reaction in a Tc-30 pct V alloy, we have chosen to study the influence of precipitation on the superconducting properties of this alloy. The physical metallurgy14 and a survey of the superconducting properties" of the Tc-V alloy system have been reported. The Tc-V phase diagram is presented in Fig. 1. At 1500°C the Tc-30 pct V alloy is in the single phase 6 field. Samples quenched from the 6-phase field have a CsCl structure X-ray diffraction pattern at room temperature and it has been proposed that the 6 structure is closely related to the bcc lattice.14 When held isothermally below the eutectoid temperature, 115O°C, the 6 phase decomposes into the CsCl and hcp phases.

Jan 1, 1970

By O. P. Arora, M. Metzger, G. R. Ramagopal

Single-phase aluminum containing 0.0001 to 0.06 pct Cu was studied in strong acid, mainly through observations of hydrogen evolution. The strong influence of copper was exerted almost entirely through the imposition after a certain delay time of an auto-catalytic localized-corrosiott reaction. Additions of cupric ion to the acid produced lower accelerations. The significance of the quantity and distribution of copper was discussed, and the implications for intergranular corrosion and neutral chloride pitting were indicated. AN investigation of intergranular corrosion in single-phase high purity aluminum exposed to hydrochloric acid indicated the copper content of the metal to have an influence on corrosion at lower levels than previously suspected.&apos; The work reported here was a closer examination of the action of copper but dealt with general corrosion to gain the advantage of having a continuous measure of corrosion through the volume of hydrogen evolved, the reduction of hydrogen ion to hydrogen gas being the principal or only cathode reaction in strong hydrochloric acid. Previous work on the hydrochloric acid corrosion of aluminum was sometimes insufficiently structure-conscious and the need for care in evaluating it arises from the low solubility of the iron impurity,&apos; and of some alloying elements, and the known or possible presence in many of the compositions studied of second phases leading to greatly increased corrosion rates.3 These increases are attributed to the presence of low hydrogen-overvoltage cathodes provided by the second phase.3&apos;4 For the present single-phase work, a few studies which used high-purity base material and small copper additions5-&apos; provide the essential information most unambiguously. The corrosion rate was shown to be increased markedly by the introduction into the acid of small quantities of the ions of copper (and of certain other metals) which cement on the aluminum and provide cathodes of low overvoltage.5 When there was sufficient copper in the aluminum, the same result was produced during the course of corrosion leading to a rate which increased with time as the reaction was stimulated by one of its products (autocatalytic reaction). In 2N (7pct) HC1, an accelerating rate was observed at 0.1 pct Cu but not at 0.01 pct.5,7 The present work dealt with corrosion rate and morphology and their correlation with the quantity and distribution of copper catalyst for copper contents from 0.0001 to 0.06 pct. PROCEDURE A lot of high-purity aluminum containing 0.0021 pct Cu, 0.001 pct Fe and 0.003 pct Si (Alloy A) was alloyed with copper to yield aluminum containing 0.014 pct Cu (B) and 0.06 pct Cu (C). Later it was found necessary to include the lower copper Alloy K which contained 0.0001 pct Cu, 0.0004 pct Fe and 0.0004 pct Si. The upper limit for any other element can be confidently estimated as 0.0005 pct. No element other than copper appears to be present in quantities sufficient to have an effect on general corrosion as great as the observed effect of the copper in A, B, and C. The only other heavy metal detected by spectrographic examination was silver (< 0.0001 pct). The acid was made up from a selected lot of 37 1/2 pct CP hydrochloric acid containing 0.1 ppm heavy metals (mainly Pb), 0.05 ppm Fe, and < 0.008 ppm As and from water distilled from 1 megohm-cm demineralized water and believed to have contained negligible quantities of heavy metals influencing corrosion. Acid strength was adjusted to within 0.05 pct HCl of the stated value by using precision specific gravity measurements. Test blanks 10 by 41 mm were sheared from 1.65-mm cold-rolled sheet. Edges were finished by filing. The blanks were annealed in air at 645°C for 24 hr in alundum boats and rapidly water quenched. The anneal is thought to have produced a substantially homogeneous solid solution—for iron, copper, or silicon, for example, the annealing temperature was 200°C or more above the solvus-and the quench is considered to have preserved the high-temperature structure except for the condensation of lattice vacancies into dislocation loops.&apos; The 0.06 pct Cu alloy did not appear unstable in respect to slow precipitation reactions at room temperature since two pairs of tests failed to show significant differences between specimens heat treated 3 1/2 years earlier and specimens heat treated 1 or 2 days before.

Jan 1, 1962

By C. C. Herrick

The vapor pressure of indium has been measured by the torque-effusion technique, as a function of temperature between 1102o and 1422oK. For liquid indium, the vapor pressure (in atmospheres) can be represented by the equation -R In P = 5.782 x104/T - 25.29from 1000o to 1422oK. Extrapolation yields a calculated normal boiling point of 2329°K and a heat of vaporization at 298 oK of 58.09 kcal per mole by the third-law method and of 58.39 kcal per mole by the second-law method. Calculations indicate that the free-energy functions of Hultgren are to be preferred to those of Guruich. BECAUSE of the potential uses of liquid metals, it is important that convenient experimental methods be developed which will lead to a sufficient body of thermodynamic data so that reasonable estimates of properties of liquid metals can be made. Indium is particularly well-suited to investigation, since it remains liquid over a long temperature interval, it alloys readily, suitable containers for it are easily procured, and relatively few investigations of its thermodynamic properties in the region above 1000°K have been made. PREVIOUS RESEARCH The first determination of the vapor pressure of indium was made by Anderson,&apos; using the Knudsen method and silica-lines stainless-steel cells. Kohlmeyer and spandau2 determined the normal boiling point, and a mass-spectroscopic investigation has been made by Lyubimov and Lyubitov.3 (Unfortunately, only an equation representing the data of the latter investigators has been available to us.) Hultgren et al.4 and Gurvich5 have published discordant tables of the free-energy functions for indium. EXPERIMENTAL METHOD The torsion-effusion principle has been described amply in the literature.8,7 With this method, one observes the angular deflection induced by effusion of vapor from a multihole effusion cell which is suspended from a filament producing a small rotational restoring force. The pressure within the effusion cell can be computed from the relation ziaifiai where k is the torsion constant of the filament, 6 is the observed angular deflection, and ai, fi, and qi are the area, force factor, and moment arm of the ith effusion orifice. The force factor f is analogous to the Clausing factor,&apos; and corrects for the reduction in effusive force attributable to the finite geometry of the effusion orifice. Schultz and Searcy&apos; have tabulated the force factors for various tube geometries. EXPERIMENTAL APPARATUS The physical arrangement employed in this study is shown in Fig. 1. The furnace elements are six Globar heat rods with 15-in. hot zones. Temperature is maintained to * 1°K by a Beck mechanism driving two 26-amp Powerstats in parallel. A Pt (Pt, Rh 10 pct) thermocouple serves as the sensing element. Four inner tubes act as vibration isolators; the air pressure required for maximum isolation was determined empirically, and is maintained by a solenoid valve. The tungsten fiber, 9 by 0.002 in., is joined to an 0.008-in. tungsten wire or graphite rod via a machined lightweight chuck.

Jan 1, 1964

By Paul L. Russell

Introduction As the US and world population increases, so does the problem of supplying expanding energy needs. Early requirements worldwide were mostly met by abundant forest vegetation. Man&apos;s large scale use of minerals-energy resources is a fairly recent development. It occurred only during the past 200 years. Coal was the first mineral fuel to be used extensively. It was not a large factor in US energy production until the beginning of the 19th century. Petroleum and natural gas use is about 125-years-old. Electricity generation by falling water is about a century old. Atomic energy is only about 30-years-old. Extensive use of it is still in the future. Solar energy is in its infancy. Other energy sources such as wind, peat, and geothermal energy are minor and primarily of local importance. There were three main features of the fuel supply picture during the past 125 years. By 1900 coal replaced wood as the principal energy source. Since 1900, oil and gas have captured many coal markets. And after the mid-1970s, there was a resurgence of coal usage. (Figs. 1 and 2). Wood Until the advent of mineral fuels for energy, the major global energy source was wood. But populations increased and became centered in towns and cities. The problem of a sufficient energy supply first developed as nearby, easily obtained wood was exhausted. This problem became more acute as industries such as shipbuilding, smelting, and pottery making, became more widespread. Results of wood use as an energy source and building material are starkly evident in areas of the world where civilization is oldest. Entire forests were consumed and have never been replaced. In the US, wood supplied 90% of all fuel requirements until about 1850; and more than 50% until after 1880. By 1900, wood still supplied 20% of all energy uses. In the mid-1970s, energy costs increased, due largely to the oil embargo. This increase resulted in an increased wood demand for domestic heating. While large quantities of wood were being used, its share of the total energy market was still less than 3%. By 1983, wood was becoming increasingly scarce and more costly near most large US cities. Wind Wind powered ocean vessels for many centuries. Sailing ships were still common in 1900. Windmills provided an early, cheap energy source and continue to be used today on farms. Design and development of windmills for electricity generation is being conducted. Interest in wind power is growing worldwide where availability of wind currents warrants the investment. Also, US regulation requires power companies to "buy back" electricity generated by windpower in excess of that used by the windmill owner. Coal By the 1600s, England was producing, 900 kt/a (1 million stpy) of coal for heating and other uses. The first coal-fired blast furnace for iron smelting was developed in 1621. Coke-making was developed in 1755, and Watt invented the steam engine in 1769. Illuminating gas made from coal was introduced in London in 1800. During this same 200-year period, France and Germany developed coal production, but on a smaller scale than England. US, bituminous coal was mined near Richmond, VA, as early as 1748. Major bituminous coal-producing states in the early period were Pennsylvania, Virginia, Ohio, Kentucky, Illinois, and Maryland. West Virginia replaced Virginia as a major producer, when that state was formed in 1863. As the US expanded west, new coal deposits were found and exploited. Indiana, Alabama, Tennessee, Iowa, Kansas, Missouri, Washington, Colorado, Wyoming, Arkansas, Oklahoma (Indian Territory), Montana, New Mexico, and Texas had significant coal mining operations by 1900. Today the eight major coal producing states are Kentucky, West Virginia, Pennsylvania, Illinois, Ohio, Virginia, Wyoming, and Montana. These states accounted for about 80% of all coal (lignite, bituminous, and anthracite) produced in the US during the past several years.

Jan 8, 1984

By S. S. Lisnyak, B. D. Lichter

An important question in the study of the "hot corrosion" phenomenon (i.e., accelerated oxidation of Ni-Cr-base and Co-Cr-base "superalloys" in the presence of sulfur) is the condition of formation and physico-chemical properties of different sulfides in the system Ni-Co-Cr-S. seyboltl has observed the presence of ((chromium-rich" sulfides of compositions M3S4, and M2S3 in the scales of superalloys after hot corrosion; however, as he points out, much confusion exists as to the identity of sulfides found on Ni-Cr and Co-Cr alloys. According to the literature,&apos; ternary sulfides, e.g., NiCr2S4, (monoclinic structure) and CoCr2S4 (spinel structure) exist in these systems. Therefore, it is likely that these compounds are found in the scale of alloys undergoing hot corrosion. At present this possibility has not been discussed in the literature. Accordingly, we have begun investigation on the properties of ternary sulfides and their mutual interaction. The magnetic and electrical properties of pure NiCr2S4 and pure CoCr2S2 have been previously determined."-&apos; In the present work we have studied the interaction between these sulfides at high temperatures by means of X-ray diffraction and magnetic susceptibility. The measurements were carried out at room temperature after appropriate thermai treatment of samples at high temperatures. For alloys containing the three elements nickel, chromium, and cobalt this interaction may be of importance in the study of the hot corrosion phenomenon. The compounds NiCr2S4 and CoCr2S4 were prepared from stoichiometric amounts of the elements and CoS in the case of CoCr2S4. Samples were mixed and sealed in evacuated silica tubes, slowly heated to 900&apos; to 100O°C, and held at temperature for a total of 120 hr (NiCr2S4) or 80 hr (CoCr2S4) with intermediate re-grinding~. X-ray diffraction showed a pure spinel structure for CoCr2S4 and a monoclinic structure for NiCr2S4. Samples of mixtures of the two ternary sulfides were prepared with different compositions, see Table I. Samples were heated for a total of 80 hr at 900&apos;C in evacuated silica tubes, with one intermediate regrind-ing. The capsules were slow-cooled to room temperature in the furnace. Samples for X-ray diffraction were prepared by placing powder on a glass slide with vaseline. Dif- fractometer traces were obtained on a G.E. XRD-5 diffractometer using a chromium tube and vanadium filter (40 kv and 31 ma). The size of the spinel unit cell was determined from the eight highest angle peaks (80 deg < 2b < 160 deg). Calculated lattice parameters were plotted vs cos B . ctn 0 and extrapolated to 6 = 90 deg. Measurements of the magnetic susceptibility were carried out at room temperature using the Faraday method in a magnetic field of 3000 G and using a Cahn RG automatic microbalance. The system was calibrated from the well-established susceptibilities of platinum and palladium: (Xpt = 0.968 x 10-6 g-1 and Xpd 7 5.04 x 10~6 g-1). The weight of samples were approximately 0.200 g. X-ray diffraction patterns for unsintered mixtures showed Bragg peaks from both the spinel (CoCr2S4) and monoclinic (NiCr2S4) structures. After sintering no monoclinic peaks were observed in samples containing up to 40 mol pct NiCr2S4. However, the spinel peaks were displaced to higher angles with increasing

Jan 1, 1970

By Kenneth L. Cashdollar

While underground coal technology has progressed over time, regulations on coal dust have not kept up ? the most recent rules are more than 80 years old. The National Institute for Occupational Safety and Health and the Mine Safety and Health Administration conducted a joint survey recently on coal particle ranges as measured in US coal mine samples. In underground coal mines, dust explosions are prevented by the addition of enough rock dust (usually limestone) to make the total dust mixture inert. The rock dust acts as a heat sink for the dispersed dust mixture by reducing the temperature below the value needed to propagate an explosion. Federal regulations require 65% in combustible content in intake airways and 80% incombustible content in return airways, where the coal dust is assumed to be finer in size. The regulations also require an additional 1% incombustible for each 0.1% methane in the ventilating air in intakes and 0.4% additional incombustible for each 0.1% methane in returns.

Jan 1, 2008

By Shouci Lu, Sun. Keji

Most phosphate ores in China are characterized by fine dissemination of the intergrown minerals and high content of carbonates. Therefore, in order to recover phosphorus minerals by flotation, some technological problems must be solved, such as fine particle flotation and separation of phosphate from carbonates. For effective flotation of finely ground phosphate ores and selective separation of phosphorus minerals from carbonates, S-series and L339 modifiers have been developed. A series of combined collectors with improved collector ability and selectivity have been developed and applied in several flotation plants in China. In this paper, CCLS, a combined collector for phosphates and PA-31 and a collector for reverse flotation of carbonates, are described. It has been found that some surfactants added with fatty acids function well in flotation at lower temperature, hence heating pulp in winter may be excluded. It is important for energy savings. The synergy mechanism of these additives in fatty acid flotation is discussed in this paper.

Jan 1, 1999