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By J. B. Clark, A. S. Yue

The zone-melting technique can be adapted for the de-termination of the eutectic composition in complex metal systerrzs. The application of this method is demonstrated in a simple eutectic system, Mg-AE, in which the eutectic composition is known and in a complex ternary system, Mg-Al-Zn, in which the literature is uncertain as to the composition of the ternary eutectic. The advantages and limitations of this unique approach for the determirution of the eutectic composition are discussed. ThE eutectic composition in phase diagrams is usually determined by thermal analysis of a series of arbitarily selected alloy compositions. The temperatures of the liquidus and eutectic arrests for each alloy are plotted and the eutectic composition is estimated by extrapolation to the entectic temperature of the curve formed by the liquidus arrest temperatures for the series of alloys. Although this approach readily yields the eutectic temperatures, several dekrminations are needed to estimate the eutectic composition, even in a simple system. In a complex ternary system, a great many determinations are often necessary to estimate, even approximately, the ternary eutectic composition. Thus, the conventional method is inherently tedious and time consuming. The application of zone melting provides a relatively efficient method of determining the eutectic composition.' As an illustration, consider the zone melting of an alloy composition C, in the simple eutectic system A-B, shown in Fig. 1, under the ideal conditions of infinitely rapid diffusion in the liquid, no diffusion in the solid, and ease of nucleation of both phases. As the zone moves along the bar, the composition of the zone is enriched by solute rejected during the freezing of the a phase and the zone composition approaches the eutectic composition CE.Once the zone composition attains the lowest melting composition, i.e., the eutectic composition, it remains at this composition as the zone moves along the bar and finally freezes as such at the end of the bar. Chemical analysis of the end of such a zone-melted bar then should yield the eutectic composition CE of the system A-B. A corresponding analysis can be made for a ternary eutectic system. Under the ideal conditions noted above, only one pass of the molten zone is required to yield the eutectic composition. Experimentally, however, a solute-rich layer forms at the solid-liquid interface2 and the composition of the zone does not attain the eutectic composition as rapidly or as uniformly as in the ideal case outlined above. But with agitation of the melt, the ideal conditions can be approximated experimentally. Also, as shown below, zone melting permits a cumulative build-up of the solute at the end of the bar to the eutectic composition. The purpose of this paper is to demonstrate this unique method for determining the eutectic composition. The method is here applied to two systems: first, to the binary Mg-A1 system, in which the composition is well established, and second, to the complex Mg-Al-Zn system in which there is doubt concerning the composition of the ternary eutectic. EXPERIMENTAL PROCEDURE The zone-melting apparatus used in this study is described in detail elsewhere.3 Briefly, the binary alloy rods (5/8 in. in diam and 9 in. long) and the ternary alloy rods (5/8 in. in diam and 6 in. long), with the compositions given in Table I, were zone

Jan 1, 1962

By D. A. Thomas, E. S. Meieran

Tungsten wires were examined by transmission electron microscopy after drawing and after high-temperature annealing. Drawn wire consists of highly elongated grains called fibers, whose long axis is parallel to [110]. Each fiber is ribbon-shaped, with the wide dimension of the ribbon parallel to (001) and the narrow dimension parallel to (110). Furthermore, most fibers are bent about [I10] and twisted along their length. The fibers are divided into cells, which in some cases contain a platelet substructure lying on (110) planes. The misorien-tations of these platelets accumulate to allow the macroscopic twist of the fibers. During annealing, several competing reactions occur, starting at different temperatures and progressing at different rates. Among these processes are fiber-boz~ndary migration, polygonization, dislocation rearrangement, and possibly impurity segregation. The fiber-boundary migration accompanied by the formation of transverse boundaries during polygonization leads to an equiaxed grain structure although recrystal-lization does not occur. There is a relationship between the flow stress of the wires and their average subgrain width in the form sy = s0 + kyd-1/2 . Also, there appears to be a relatio'nship between wire ductility and the formation of transverse boundaries during annealing at about 800°C. THERE have been many investigations of the structures and properties of tungsten wires1-4 due to their commercial importance for use as lamp filaments. The structural studies have so far been limited to optical microscope and replica electron-microscope studies. due to the difficulty of .-me- paring from wires thin foils which can be examined by transmission electron microscopy. However, this difficulty has been recently overcome,5 and it is now possible to examine tungsten wires by transmission electron microscopy as well as by other techniques. In this paper, the structure of drawn tungsten wire is described, as are the changes in the structure during high-temperature annealing. Some discussion of the relationship between structures and properties is also given. EXPERIMENTAL MATERIALS AND PROCEDURES Commercial 0.030-in.-diam doped tungsten wires drawn at progressively decreasing temperatures between about 1400° and about 800°C were examined. The composition, mechanical properties, and optical microstructures are described in detail elsewhere.' All experimental materials were vacuum-annealed for 10 ot 30 min at temperatures at 100°C intervals between 700° and 2000°C. Specimens were thinned for examination in the Siemens Elmiskop I electron microscope by the method of Meieran and Thomas.5 STRUCTURE OF AS-DRAWN WIRE The optical microstructure of as-drawn tungsten wire has been described by Peck and Thomas.7 They observed that wire in longitudinal section consists of highly elongated grains called fibers whose width varies between 1 and 10 µ, while in transverse section the fibers appear to be elliptical in cross section and bent about their common [110] wire axis. They explained this unusual appearance as being due to the drawing of a bcc material with a [110] texture, and predicted that the wide and narrow planes of the fiber cross section would be parallel to (001) and (110), respectively. The fibers apparently bend about the [110] axis during drawing to maintain grain boundary continuity during drawing. Transmission electron microscopy offers a way of checking these predictions as well as providing a more detailed picture of the wire structure. Figs. 1, 2, and 3 are typical electron micrographs of

Jan 1, 1965

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori' molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,' using the data of Parravano and Malquori.' Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

By A. H. Larson, R. J. McClincy

ALTHOUGH arsenic has a very high vapor pressure and vacuum distillation appears to be a likely method for its removal from lead, the published literature contains virtually no information concerning the vacuum removal of arsenic from lead. Caldwell, Spendlove, and St. Claire1 mention arsenic in their investigation of the removal of volatile metals from lead by vacuum distillation. They do not, however, give any data for arsenic removal or refer to any actual experimental work involving arsenic dissolved in lead. Moriyama, Kozuka, and Miura2 have determined the activity of arsenic in dilute As-Pb alloys in the temperature range from 450" to 600°C using a closed galvanic cell. They found that the activities of both arsenic and lead showed a positive deviation from ideality at 600°C. In view of the lack of experimental data regarding the vaporization of arsenic from As-Pb alloys, a limited vapor pressure study was made on liquid alloys containing from 0.5 to 3.3 wt pct As in lead at 703°C. The pressure of As4(v) above the alloys studied was determined from weight-loss data collected by means of the inert-gas saturation method. The experimental apparatus and procedure used were similar to that discussed by Alcock and Hooper9 with modifications as described by the authors., The technique involved was one of passing a known volume of inert gas over the alloy to be studied in a known amount of time and determining the loss in weight of the sample. Because of the low vapor pressure of lead at 703"C, the observed weight loss could be attributed solely to the vaporization of arsenic as the tetratomic molecule AS43 Measurements of the apparent vapor pressure were repeated at different inert-gas flow rates until from three to five values were obtained which were independent of inert-gas flow rate. This value of the apparent vapor pressure was taken to be the equilibrium vapor pressure of the alloy under consideration. The vapor pressures measured in this investigation have been converted to the activities of arsenic in As-Pb alloys, Table I, by use of the data compiled by Elliott and Gleiser5 for the vapor pressure of pure arsenic. The standard state for arsenic was chosen as the pure, hypothetical, supercooled liquid. The activity of arsenic was calculated from the fourth root of the ratio PAs,/PAS,. The low magnitude of the vapor pressures given in Table I explains the difficulty en- countered by earlier workers in successfully vacuum distilling arsenic from very dilute As-Pb alloys. The data shown in Fig. 1 indicate that the As-Pb system behaves ideally. The apparent outlier represented by the alloy containing 1.43 mol pct As is a result of the fact that the pressure of As, above the alloy was barely detectable by the experimental procedure used in this investigation. Because of this, the apparent vapor pressure determined for this alloy could be in considerable error. Moriyama, Kozuka, and ~iura' have reported that arsenic shows a positive deviation from ideality in dilute solution in lead. However, details of their results have not been made available. This research was made possible by a grant from the National Science Foundation (GK-196) for which the authors are very appreciative.

Jan 1, 1970

By Shiou-Chuan Sun

SHIOU-CHUAN SUN (author's reply).-Thanks are extended to Professor Hassialis for his recognition of the usefulness of a new tool, the cataphoretic cell, as an adjunct to the bubble machine and the abstraction test. His questions concerning adsorption, dielectric constant, floatability, activation, and depression are interesting and worthy of discussion. I According to Mueller,28 it is questionable that any of the present formulas gives absolute values of zeta potentials which are completely accurate. The problem is further complicated by the question" of whether the "dielectric constant" has any meaning at all for such a microscopically thin layer. With these in mind, the results in this paper should be considered in the relative sense as a first approximation and not as absolute quantities. Adsorption Referring to item a of Fig. 8, the dielectric constant and the viscosity of the xanthate solutions are the same for galena, sphalerite and quartz. If dielectric constant and viscosity (but not the adsorption) were the first-order variable of the cataphoretic system, as claimed by Professor Hassialis, then the magnitudes of zeta coefficient of galena, spha)erite and quartz would have been similar to each other. These are not. The big difference of zeta coefficient of these three minerals in the same xanthate solutions is not altogether unjustified to be attributed to their difference in adsorption of xanthate ions. This is supported by the results of chemical abstraction tests reported by Ince.14 Again, the big difference of zeta coefficient between wollastonite, calcite, and fluorite in the same laurylamine hydrochloride solutions (p. 118, Figs. 58, 59, and 60 of ref. r5) also indicates that the cataphoretic system is not governed chiefly by the dielectric constant. Beside the data shown in Fig. 8, other experimental evidences15 which support the idea of correlation between adsorption and zeta coefficient are: (I) there is a qualitative parallelism between the zeta coefficient curve and the chemical abstraction curve of sphalerite in solutions of various concentrations of sodium cyanide, (2) there is a qualitative parallelism between the zeta coefficient curve and the chemical abstraction curve of sphalerite in solutions of constant concentration of copper sulphate at different pH values, and (3) there is a qualitative parallelism between zeta coefficient curve and chemical abstraction curve of quartz in solutions with constant concentration of barium chloride at different pH values. The above mentioned experimental results are generally in agreement with Gouy's double layer theory,1-5 and support this idea that the concentration and the kind of ions adsorbed at the mineral surface and in the adjacent surrounding liquid chiefly govern the electrokinetic phenomena. Dielectric constant and viscosity of the liquid medium may be of somewhat lesser importance. It follows that the correlation between the coefficient and adsorption as claimed in this paper is justified. Dielectric Constant The term "dielectric constant " was first introduced into the electrokinetic equations by Perrin.30 In a footnote of his publication he states that Holmheltz has forgotten to include the dielectric constant. The conversion of the moment29 to the zeta potential involves an additional difficulty and confusion not involved for the moment, namely, assigning a value to the dielectric coefficient. This is conventionally assumed to be constant and equal to the dielectric constant of the bulk liquid. 21 The published literature 10, 12 indicates that the values of dielectric constant for dilute chemical solutions have been assumed as those of pure water.

Jan 1, 1947

By J. W. Downey, J. B. Darby, L. J. Norton

THE only previous investigation of the phase equilibria in the Ta-Pd system was reported by Greenfield and Beck.1 Their work (actually a portion of a much broader survey) was limited to the composition range 50 to 75 at. pct Ta and to a single temperature, 1000°C. The results indicated that no intermediate phases were present at this temperature. They pointed out that this was an unexpected result in view of the fact that niobium, which belongs to the same group in the periodic table as tantalum and has essentially the same atomic size, forms a o phase with palladium.' Also, tantalum in combination with rhodium,' iridium,' or platinum' stabilizes the s phase. By analogy, the Ta-Pd system would also be expected to contain a s phase. The present investigation was therefore undertaken to explore more fully the phase relationships in this system. Alloys were prepared by arc melting on a water-cooled copper hearth in an argon-helium atmosphere. The purity of the starting materials was greater than 99.9 pct. The weight losses on melting were less than 1 pct and therefore the alloys were not analyzed chemically. Specimens were wrapped in molybdenum foil, encapsulated in quartz capsules under a vacuum of at least 1 x 10-5 mm of Hg, annealed as indicated in Table I, and water quenched. Optical and X-ray metallography were used for identifying the phases present in the annealed and quenched alloys. The alloys were resistant to attack by several acids; however, a sodium cyanide electroetch and an immersion etch containing 1 part HF, 1 part HNO3, 2 parts H2SO4, and 5 parts H2O by volume were found satisfactory. The X-ray diffraction patterns were taken with a Straumanis-type Debye-Scherrer camera and filtered copper or chromium radiation. A summary of the phases found in this investigation is presented in Table I. No attempt was made to determine the composition limits of the various phases. The present results indicate that this system consists of two terminal solid solutions separated by at least four intermediate phases at the approximate compositions Ta3Pd, -TaPd, TaPd,, and TaPd3. The Ta-rich solid solution, containing less than 10 at. pct Pd at 1150°C, is in equilibrium with a o phase which is stable in the vicinity of 25 at. pct Pd. The latter phase is also in equilibrium with a bct phase at the equiatomic composition. At high temperatures it appears that the Pd-rich solid solution extends to at least 66.6 at. pct Pd and is in equilibrium with the bct phase. When annealed at 900°C, a sample containing 66.6 at. pct Pd transformed to an unidentified phase designated as X. An X-ray diffraction pattern of this phase contained sharp low-angle lines while the high-angle lines were characteristically diffuse. The observed d-spacings and relative intensities for lines in the low-angle region are presented in Table 11. In the vicinity of 70 at. pct Pd an intermediate phase having the TiA13-type structure is formed. It is stable to at least 1100°C, and presumably dissolves congruently into the ter-

Jan 1, 1963

By S. L. Couling, D. J-P. Adenis

i2) twinning in poly crystalline magnesium does not usually occur homogeneously but is concentrated in localized regions or bands inclined at about 45 deg to the stress axis. These bands of twinning are in many ways similar to the Luders bands seen in mild steel alzd Al-Mg alloys. Within a hand the percentage of the volume twinned may approach 100 with no twinning outside the band. Bands are not produced in specimens of grain size a3 x 10-= in. or in samples deformed at temperatures 300°F. Annealing of heavily twinned regions leads to re crystallization textures markedly different from those found in the starting material. The exact preferred orientation appears to depend on the starting grain size, the amount of compres-sive strain and the manner in which it is introduced. MAGNESIUM, with its hexagonal crystal structure, deforms plastically at room temperature by a variety of deformation mechanisms, one of the most important of which is (1012) twinning. In single crystals such twinning occurs on compression parallel to the basal plane or tension perpendicular to it. In wrought polycrystalline magnesium, such as rolled sheet, the preferred orientation is such that almost all the grains have their basal planes nearly parallel to the sheet surface. Therefore, if sheet material is deformed by cold rolling or by tension in the plane of the sheet, deformation of the grains by (1012) twinning is not favored. On the other hand, twins form readily on compression parallel to the plane of the sheet as in a compression test, on the compression side of a bent sample, or at the outer rim of a drawn cup. The first part of this paper deals with the morphology of (1012) twinning in polycrystalline magnesium. Some aspects of this subject were covered by Barrett and ~aller.' Of direct bearing on the work to be reported here are the comments of Jetter' in discussion to Ref. 1. He shows that Mg + 1.5 pct Mn alloy sheet when bent about a transverse axis develops a pattern of transverse bands on the surface of compression. A longitudinal section through the sheet shows that the bands are wedge-shaped and inclined to the rolling direction. The bands were identified as "outcrops of regions in which deformation is localized as the result of the reorientation brought about by (1012) twinning". The second part of the paper treats the recrys-tallization texture of the specimens twinned by compression. Magnesium deformed and then annealed generally recrystallizes with no change in orientation.1'3'4 This statement is true provided that the amount of (1012) twinning occurring during deformation is small. In an isolated observation, Anse15 has shown that, when deformation produces much (1072) twinning, annealing causes new maxima to appear in the pole figure. The second part of the paper elaborates on this point. I) MATERIALS AND PROCEDURES All of the experimental work to be reported was done using the commercial sheet and plate alloy AZ31B (nominal composition: 3 pct Al, 1 pct Zn, 0.4 pct Mn, balance magnesium). This alloy is available commercially in two tempers, -0 (fully annealed) and -H24 (partially annealed), and specimens of both tempers were used in various experiments. The average grain. diameter (AGD) for -0 temper 0.125-in. sheet is about 0.5 x 10- in.; where material of larger grain size was desired, anneals at elevated temperature were used to grow the grains. compression tests were made on a screw-driven "hard" machine. The specimens were clamped in a

Jan 1, 1964

By M. A. Dayananda, R. E. Grace, P. F. Kirsch

Ternary diffusion experiments were carried out at 750°C with vapor-solid diffusion couples in single-phase copper-rich Cu-Zn-Sn alloys. The Philibert-Guy method was used to calculate intrinsic diffusion coefficients at compositions corresponding to the plane of inert markers imbedded in the diffusion couples. Inter diffusion coefficients were determined at common composition points of intersecting diffusion paths. Intevdiffusion coefficients were also obtained at compositions corresponding to maxima in the tin concentration pvofiles Relations between the interdiffusion coefficients and the expansion of vapor-solid diffusion couples are described in detail. Such relations permit the calculation of constant interdiffusion coefficients in binary couples from expansion data directly. In ternary couples expansion data provide an additional constraint on the interdiffusion coefficzents. ThE phenomenological analysis of diffusion in ternary solid solutions has been developed extensively, and various approaches taken in the determination of diffusion coefficients have been reviewed recently by Guy et al.' Finite,' semi-infinite,3 and infinite4 diffusion couples have been used in studies of ternary diffusion, but most of the work has been done with infinite diffusion couples. Semi-infinite diffusion couples3 (vapor-solid couples) have been used to determine both intrinsic and interdiffusion coefficients in the Cu-Zn-Mn system, in which two diffusing species, zinc and manganese, were supplied from the vapor phase. If only one component has a sufficiently high vapor pressure to be supplied from a vapor source, vapor-solid diffusion couples may still be used. In this case the boundary conditions at the gas/solid interface may be governed by partial equilibria rather than by virtually complete equilibrium between the phases. In the present work diffusion measurements were carried out at 750°C with vapor-solid couples of Cu-Zn-Sn alloys. Only zinc was transported between the vapor source and the diffusion disks, because the vapor pressures of both copper and tin are at least 108 lower than that of zinc. Both intrinsic and interdiffusion measurements were made at several compositions. A secondary objective was to relate expansion of the diffusion couples with the interdiffusion process. Such measurements for binary couples yield average values of the interdiffusion coefficients over composition increments. In ternary diffusion couples ex- pansion data provide an additional constraint on the interdiffusion coefficients. COMPOSITION-DEPENDENT INTRINSIC AND INTERDIFFUSION COEFFICIENTS As shown by Philibert and GUy5 the determination of intrinsic diffusion coefficients in a ternary system requires two independent diffusion couples containing marker planes with identical composition. In the case of vapor-solid couples such a requirement torresponds to two couples set up with the same vapor source exposed to two diffusion disks of different composition. Inert markers placed initially on the disk surfaces become imbedded during diffusion. If the pair of couples exhibits appreciable marker burial with marker planes of virtually the same composition, the intrinsic diffusion coefficient may be evaluated at the composition of the marker planes. Fig. 1 is a schematic diagram of the concentration of of a Cu-Zn-Sn ternary vapor-solid couple after diffusion of zinc from a vapor source into a binary Cu-Sn alloy. The areas, Ai correspond to the cumulative intrinsic fluxes of the three diffusing species across the marker plane:5 where Ji is the intrinsic flux of component i, t is the diffusion time, and D3i are the intrinsic diffusion coefficients. For the determination of interdiffusion coefficients a pair of diffusion couples with intersecting diffusion paths is needed. At the composition point of intersection (C1, C2) the coefficients are evaluated from the equation:3

Jan 1, 1969

By W. N. Poundstone, W. M. Merritts, B. A. Light

A joint investigation by the Bureau of Mines and the Christopher Coal Co. at the Humphrey No. 7 mine, operating in the Pittsburgh coalbed in northern West Virginia, was undertaken to gain more insight concerning the hazardous emission of methane gas in mining. This report describes the equipment, procedure, and results. Horizontal bleeder holes drilled in the faces drained large quantities of methane, eliminating downtime of mining equipment. Also, larger quantities of methane were removed by forcing 14 to 25 g,.p.m. water at 25 to 200 p.s.i. 5 pressure into the bleeder holes. In one infusion test a fluorescein dye was added to the infusion water; in later mining operations, the infusion water was traced for a distance of 1,500 feet. With vacuum pump applied to the horizontal hole the gas-flow rate increased, and the methane content decreased. Tests indicated that methane and water infused in bleeder holes traveled along the bedding planes of the Pittsburgh coalbed at a faster rate than across the planes. Methane associated with coalbeds is produced by the slow decomposition of carbonaceous material in the absence of air and the presence of water. It is lighter than air and, depending on its concentration, forms an inflammable or explosive mixture with air. It is believed that methane is entrapped in and around the pores of the coal and adjacent strata--often under great pressure. In many cases where the strata have been disturbed by geologic movements the

Jan 1, 1962

By O. J. C. Runnalls, L. M. Pidgeon

Some observations on the kinetics of the iodide process are reported. The deposition rate is geometry-sensitive in a system containing a finely divided titanium charge. Further, results indicate that the iodine diffusion rate influences the velocity of the process. The nonvolatile iodide, Til,, forms in the hot filament zone, thus removing iodine from the cycle. TITANIUM metal of 99.9 pct purity may be prepared using a refining technique originated by Van Arkel and de Boer.' The purity of this metal, commonly called iodide titanium, exceeds that produced by any known process. In a recent application, the method was employed by Gonser et al.² to prepare titanium rods up to 2 to 3 cm in diam. In the Van Arkel-de Boer system, the relative influence of the fundamental mechanisms: l—production of titanium iodides, 2—gaseous countercurrent diffusion, and 3—decomposition, on the deposition rate have not been clearly established. Blocher and Campbell" have indicated that the controlling step in the process under practical conditions of operation may be the reaction rate of iodine with the crude metal. Fast' reported that crude titanium metal reacted with iodine rapidly, even at room temperature, in his apparatus. Little has been reported on the effect of gaseous diffusion or decomposition on the deposition rate. It is these aspects of the process about which this investigation is centered. An attempt has been made to separate these latter effects from those due to the formation of the iodides at the crude metal surface by a division of the experimental program. Reaction of Iodine with Titanium Apparatus: In the investigation of gas-metal reactions of this type, the chemical reactivity of the halogen and halide vapors dictates the use of all-glass apparatus. In such a system standard techniques for measuring reaction rates are difficult to employ. Here, a simple apparatus was devised (Fig. 1) so that some indication of the reactivity of titanium powder with iodine vapor could be obtained. A stream of iodine gas was evolved from a bulb of controlled temperature and passed over a sample of titanium powder heated in a horizontal tube furnace. The product of the reaction, TiI4, volatilized and was condensed outside the furnace in a series of four glass bulbs, each cooled to room temperature in turn. Preliminary experiments indicated that distillation was retarded in a sealed evacuated system due to a pressure build-up in the condensing end of the apparatus. Hence, the system was pumped continuously using a mechanical pump and two oil diffusion pumps in series, through a liquid air trap. The iodine bulb was made large and a capillary restriction was inserted between the titanium bulb and the condensers so that the iodine pressure over the metal would approach the equilibrium pressure over solid iodine crystals. The effect of this restriction on the evaporation rate of TiI4, was determined separately. The iodine bulb was heated in an oil bath controlled to ±2°C. The titanium bulb temperature was automatically controlled to ±5°C. Procedure: About 200 mg of —30 mesh titanium powder, weighed to 0.1 mg, was placed in the reaction bulb after part B had been joined to part A. The powder was tapped into a long (5 cm) shallow mass along the bottom of the tube. Two chromel-alumel thermocouples were inserted into the magnesium radiator which was clamped to the reaction

Jan 1, 1953

By M. D. Schlesinger

As part of the development of processes for producing synthetic fuels from coal, the Bureau of Mines prepared a special jet fuel in a pilot plant for evaluation by the Air Force. This jet fuel had all the required physical properties, including the important specifications of high heating value and high density. However, the finished fuel did not pass the stability test specified by the Air Force and conducted by the Southwest Research Institute in a high-temperature research coker. The cause for this instability is being investigated because pure compounds of the type identified in this fuel are known to be stable. The tar acid oil used was a 230° to 300° C. fraction of low-temperature tar obtained by carbonization of a West Virginia bituminous coal in the pilot plant of the Consolidation Coal Co. Both the desulfurization at 400° C. and saturation at 300" C. were done in the vapor phase at 2,500 p.s.i.g. After catalytic treatment and distillation the final jet fuel had a boiling range of 194° to 247° C., a net heating value of 18,420 B.t.u./lb. and a specific gravity of 0.8463 60° F./60° F. It also had u pour point below -62° C., and at 0° C. its viscosity was 4.5 cs. The oil was virtually all bicyclic, 41 pct. noncondensed and 56 pct. condensed.

Jan 1, 1961

By Whiten WJ, Narayanan S

Data from ball mills of a wide range of sizes are analysed using detailed mathematical models and non-linear least squares fitting techniques. This analysis reveals that the relative power inefficiency of large ball mills is due to inefficient grinding of coarse (plus 4 mm) particles in these mills. A qualitative physical hypothesis is proposed to explain this behaviour. The results of the analysis can be used to scale up ball mill behaviour, using the mathematical models and techniques developed. A simpler ball mill scale-up procedure is also proposed, and its limitations stated. Laboratory experiments are being conducted to determine the average size distributions of single particles of different ores after breaKage. These experiments can distinguish between the different ores, and it is hoped to use their results to model and predict the grinding of different ores in ball Mills.

Jan 1, 1978

By M. Fig, J. Brune, C. Strebinger, G. Bogin

"A fundamental understanding of flame propagation characteristics through and around obstacles is needed to accurately model methane driven longwall coal mine explosions originating or propagating in the gob. Experimental investigations of methane flames in horizontal cylindrical reactors with simulated gob (i.e. rock piles) were carried out alongside coupled Computational Fluid Dynamics (CFD) and combustion simulations. Stoichiometric methane-air mixtures were ignited in semi-open reactor vessels of 5cm, 9.5cm and 71cm diameter, all with a fixed length to diameter (L/D) ratio of 8.6. This was done both with empty reactors and also with a rock pile placed at the open end of the reactor. The rock pile length to reactor length ratio was fixed at 0.3, and the rock pile height to reactor diameter ratio was fixed at 0.33 for all reactors. The smaller two reactor experiments were modeled with ANSYS Fluent in 2D. Experimental results indicate that for this geometry a similar acceleration mode occurs across scales: that the flame speeds up an average of 40% as it passes over a rock pile with this profile. The model is able to capture several important features of the experimental results, including the significant increase in velocity, the speedup ahead of the rock pile, and the leveling off of the empty tube flame front propagation velocity. INTRODUCTION Explosions in underground coal mines are among the largest industrial explosions, known to result in the rapid combustion of 20m3 of fuel gas or more [1,2] Coal beds hold methane gas under pressure, and when the pressure is relieved through mining activity some of this methane is released. The methane then mixes with ventilation air and, if not sufficiently diluted, may form a combustible mixture, which may result in an explosion. Several large coal mine explosions have occurred around the world recently. These include the 2014 Soma Mine disaster in Turkey that killed 301 people [3], and the 2009 Heilongjiang Mine explosion in China that killed 108 [4]. Other recent mine explosions, including the 2010 disaster at the Upper Big Branch mine that caused 29 fatalities [5], have demonstrated that explosive gases can accumulate and ignite within and around the gob area of a longwall coal mine and then expand into the active mining face and nearby areas, endangering workers and equipment. If enough combustible gas is involved, the initial flame can accelerate, eventually transitioning from deflagration to detonation [6]. Researchers are developing a fundamental understanding of the evolution of the explosion process from the laminar kernel to the fully turbulent regime, and its propagation through obstacles such as those found in the gob. Researchers also studied the initial development of methane flames and the potential for the development of a detonation."

Jan 1, 2018

By Andrew Bristow Bevege

El proyecto Guadalupito es el primer depósito de arenas minerales explorado a una etapa avanzada en el Perú y que es controlado por Latin Resources Ltd. La Compañía ha establecido pruebas metalúrgicas que demuestran la capacidad para producir arena de magnetita de alta calidad adecuadas para la exportación directa a mercados específicos o para la fabricación de arrabio.

Jun 1, 2013

By Max W. Ball

YOU have been kind enough to ask me to speak to you on "The War and Anglo-American Relations." A speaker always takes the liberty of putting his own interpretation on the scope of his subject. I am going to exercise that privilege, and try to look back over a generation of Anglo-American relationships and forward beyond the present war. I should like particularly to consider responsibilities as well as relationships. A more accurate caption for what I am going to say would be "Anglo-American Responsibilities.?? THE WAR WILL BE WON I am assuming that sooner or later we shall win this war. History and economics point to the same conclusion, that Germany has attempted the impossible and that the seeds of defeat are already sown. As to one ecof1:omic factor, I am already on public record as believing that Germany's oil supply is inadequate for the war she has launched. That opinion is unchanged. Aside from such tangible factors, moreover, I am convinced that the spirit of freedom is unquenchable, and that no combination of powers will be able to rout it from the British Commonwealth of Nations and the United States. Stronger even than this conviction is my faith in a God who will not suffer the defeat of man's aspiration to be master of his own soul. I am sure that all of you share that faith, and that we need not argue it. We can start with the assumption that the war will end in victory. The subject we are to consider, then, is the relationship of the English-thinking peoples during the conflict, and their joint responsibilities in the difficult days that will follow it. A CANADIAN-AMERICAN No talk on such a subject is worth listening to unless the audience knows the background and fundamental beliefs of the speaker. No human statement stands alone; behind and beside and within it are the ideals and the bias of the man who makes it. Because I am a stranger to most of you, I am constrained to talk about myself before I talk about more important matters. The review may be profitable, not because of the subject, but because it may illustrate the evolution of an attitude toward England.

Jan 1, 1941

By R. V. Ramani

In this paper, the application of the concepts of reliability engineering to the evaluation of longwall system performance is illustrated with data from an operating longwall face. A number of cases are analyzed to highlight the impacts of longwall equipment, geological conditions and outby haulage on systems reliability and availability.

Jan 1, 1988

By F. W. H. Dean

A very sensitive sensor for the detection and measurement of hydrogen in solid steel is described. This technique is non-invasive and uses a collector to sweep the hydrogen emanating from a steel surface and feed to it sensor. This method is particularly sensitive, resolving fluxes to < 2 pI cm?2 S?I, with a linear measurement up to 1000 pI cm&apos;2 S?I, The collector is held on the steel substrate by magnets and it is shown that emanation of hydrogen from the steel is controlled by bulk diffusion of the hydrogen through the steel. The technique is demonstrated to have an excellent response time and reproducibility.

Jan 1, 2001

By W. S. CAYPLESS, H. O. Hofman, E. E. HARRINGTON

I. INTRODUCTION. LIME-ROASTING is a term proposed by Ingalls 1 for the operation of forcing air under pressure through a mixture of galena and lime at the kindling-temperature with the object of oxidizing lead and sulphur and of fritting or fusing the charge. If, finely-divided galena were treated in this manner without the addition of lime, the heat set free by the oxidation of part of the lead and the sulphur would be sufficiently great to fuse undecomposed sulphide, and thus stop desulphurization. Besides the chemical action that the addition of lime, limestone or gypsum to the charge may have, the admixture has the physical effect that it keeps the particles of galena separated from one another and accessible to the oxidizing effect of the air. At present, three methods of lime-roasting are carried out on a working-scale, the Huntington-Heberlein, the Carmichael-Bradford and the Savelsberg2 processes. In the last, which interests us here, an 8-ton charge is made up of galena, limestone and perhaps some siliceous or ferruginous flux; the whole is crushed to pass a screen with 3-mm. holes and moistened with 5 per cent of water. It is fed gradually into a bowl-shaped converter, 6.56 ft. in diameter, supported by trunnions attached to a truck. On the .bottom the converter has a grate with blast-inlet beneath. In starting, the truck with the converter

Jan 1, 1907

By Ron Woolf, Corry Goumans

This paper describes rock slope remediation performed along America’s first Superhighway, the Pennsylvania Turnpike and in particular, the specialized drilling equipment designed and built by Pacific Blasting to complete this work. This S-month project was performed on an existing rock cut slope within the Bedford Narrows, a gap formed by the Juniata River through Evitts Mountain. These rocks are in the folded Juniata and Tuscarora Formations within the Valley and Ridge Province and strike northeast with near vertical to slightly overturned bedding.

Jan 1, 2001

By J. Bouchard, A. Desbiens, M. Maldonado, R. del Villar

ABSTRACT: Despite many years of practical applications in mineral processing plants, the potential of column flotation has still not been fully exploited. The challenge in measuring some key variables is certainly an important contributing factor to this situation. Reliable online measurement of variables, such as the froth depth, bias, gas hold-up, frother concentration, bubble surface area flux, and bubble size distribution, provides opportunities for the application of various advanced control strategies and real-time optimization based on an economic criterion. For several years, Université Laval’sLaboratoire d’observation et d’optimisation des procédés researchers have been working on these opportunities. This paper describes the most recent advances and current research trends.

Jan 1, 2011