Search Documents

By S. C. Sircar, B. K. Dhindaw

KINETICS and mechanism of sulfation reactions have been studied extensively. Qualitative and quantitative data are reported for the kinetics and mechanism of sulfation reaction of copper oxide pellets;''2 yet it remains a controversial Subject. The mechanism and kinetics of the sulfation of zinc oxide powder (B.D.H. analar quality) were studied by gravimetric technique. A spring of high-carbon steel wire with accuracy well within 0.2 mg was used for measuring weight change. The sample was taken in a Pyrex glass bucket, hanging freely inside a Pyrex glass tube reactor, with a gold wire attached to the spring, the reactor being surrounded by a movable furnace (double wound type) with a temperature control within *5"C. Flow of oxygen, 60 cu cm per min, and sulfur dioxide, 45 cu cm per min, were measured through calibrated flowmeters and the mixture dried over PZ05 before entering the reactor. The experimental results are presented in Figs. 1 and 2. The plot of weight change of zinc oxide, giving the amount of zinc sulfate formed, was found to be linear over the temperature range of 500" to 700° C and up to a conversion of approximately 60 pct, as beyond it they divert from linearity.' The rate of sulfation was found to be affected by total flow rate of gases at a fixed ratio of SO2/O2, up to 60 cu cm per min, and was found to be linearly dependent on quantity of total powdered sample taken. The plot of rate of sulfation of zinc oxide, 70 mg, with varying amounts of vanadium pentoxide, at a constant ratio of gases as mentioned above, and at a constant temperature of 625"C, was also found to be linear as seen in Fig. 2. Extrapolation to zero V2O5 addition gives the same rate of sulfation, as in case of pure zinc oxide, 70 mg. Vz05 was prepared by heating ammonium vanadate at 600°C for 15 min in a muffle furnace. The available literature points out that the theory of sulfation that has received the maximum support postulates the following mechanism for sulfation of ZnS: 2ZnS + 30, = 2Zn0 + 2SOZ; the ZnO formed acts as a catalyst for the reaction, 2 S02 + O2 = 2S03. This SO3 reacts with ZnO to give zinc sulfate. It is suggested here that the above widely supported mechanism is operative in the sulfation reaction and that the rate-controlling step in the sulfation reaction of ZnO is the formation of SO3 from SO, and 0,. The authors are carrying on further work in this line, and the details will be published later. The authors wish to acknowledge the facilities provided and the help extended by Prof. P. R. Dhar, Head, Department of Metallurgical Engineering, and the permission granted to publish this note by the Director, I. I. T., Kharagpur.

Jan 1, 1969

By J. P. Hammond, C. J. McHargue

The wire textures for cold rolled and recrystallized iodide titanium and the sheet textures for this material produced by cold and hot rolling, and recrystallization at a series of temperatures were determined. &apos;The effect of the a + ß transformation on the sheet texture was noted. UNTIL recently it was believed that all hexagonal close-packed metals deformed by slip on the basal plane, (0001), and that rolling should tend to rotate this slip plane into the plane of the rolled sheet. The pole figures of cold rolled magnesium&apos; are satisfactorily explained on this basis. There is a tendency for the <1120> directions to align parallel to the rolling direction, and the principal scatter is in the rolling direction. Zinc% as a rolling texture in which the hexagonal axis is inclined 20" to 25" toward the rolling direction. Twinning is believed to account for the moving of the basal plane away from parallelism with the rolling plane. The texture of beryllium3 places the basal plane parallel to the rolling plane with the [1010] direction parallel to the rolling direction, and the scatter from this orientation is primarily in the transverse direction. Cold rolled textures reported for zirconium&apos; and titanium5 how the [1010] directions to lie parallel to the rolling direction and the (0001) plane tilted by approximately 25" to 30" to the rolling plane in the transverse direction. Rosi has recently reported that the mechanisms for deformation in titanium are distinctly different from those commonly reported for hexagonal close-packed metals. The principal slip plane is the prismatic plane, {1010), with some slip also occurring on the pyramidal planes, (1011). However, there is no evidence for basal slip. The slip direction is reported to be the close-packed digonal axis, [1120]. In addition to the twin plane commonly reported for metals of this class, {1012), Rosi found the twin planes (1122) and {1121), with the dominant twin plane being (1121). Information regarding the recrystallization and hot rolling textures of hexagonal close-packed metals is limited. Barrett and Smigelskas report that rolling beryllium at temperatures up to 800°C and recrystallization at 700°C produce textures not differing from the cold rolled sheet texture.3 McGeary and Lustman find that hot rolling at 850°C produces the same basic texture in zirconium as rolling at room temperature.&apos; These investigators also report that the texture for sheet zirconium recrystallized at 650 °C differs from the cold rolled orientation inasmuch as the [1120] direction, instead of the [1010] direction, is parallel to the rolling direction. In the case of titanium, it is not possible to deduce which direction is preferred in the recrystallized state from the pole figures presented by Clark." The purpose of this paper is to report an extensive investigation of the preferred orientations in iodide titanium. Since the deformation mechanisms for titanium are different from those commonly given for hexagonal close-packed metals, it is not surprising to find distinct differences between the textures of titanium and other metals of this class. Materials and Methods This investigation was carried out on iodide titanium obtained from the New Jersey Zinc Co. with an analysis as follows: N2, 0.002 pct; Mn, 0.004; Fe, 0.0065; A1, 0.0065; Pb, 0.0025; Cu, 0.01; Sn, 0.002; and Ti, remainder. The crystallities of titanium were broken from the as-deposited bar and melted to form 20 g buttons on a water-cooled copper block in a vacuum arc-furnace. Hardness tests conducted on the material before and after melting differed by only two or three Vickers Pyramid Numbers, indicating no or insignificant contamination. The buttons were hot forged, ground, and etched to sizes and shapes suitable for the rolling schedule, and vacuum annealed at 1300°F. Specimens for determination of the wire textures were reduced 91 pct in diameter to 0.027 in. in 24 steps using grooved rolls. In order for the orientation of the central region to be studied, portions of these wires were electrolytically reduced to a diameter of 0.005 in. using the procedure described by Sutcliffe and Reynolds.&apos; The sheet textures were determined on titanium cold rolled 97 pct to a thickness of 0.005 in. A reduction of approximately 10 pct per pass was used, and the rolling direction was changed 180" after each pass. Specimens used for determination of the recrystallized textures were annealed in evacuated quartz tubes at 1000°, 1300°, and 1500°F. The grain size of the 1000°F specimen was sufficiently small to give satisfactory X-ray patterns with the specimen stationary. However, it was necessary to scan the surface of the other recrystallized specimens. The microstructure of each annealed specimen was that of a recrystallized material. The diffraction rings all showed the break-up into spots typical of recrystallized structures.

Jan 1, 1954

By Anne Nicholson Hird, H. A. Schwartz

Of the outstanding investigators of the system iron-carbon-silicon Gontermann,1 Charpy and Cornu-Thenard,= and Honda,3 only the first touched on the chemical composition of the solid and liquid phases in equilibrium with one another. He concluded that his data did not permit a decision as to which of an indefinitely large number of pairs of compositions of liquid and solid would be found in any given case. If through the three dimensional equilibrium diagram of the iron-carbon-silicon system an isothermal plane is passed in the region of partial solidification, two lines of intersection with the liquidus and solidus, respectively, are obtained, also a point marking the alloys&apos; composition. If, in this plane, a straight line is drawn through the point, and intersecting both the liquidus and solidus isothermals, the two intersections mark a liquid and a solid alloy that may be chemically in equilibrium at the chosen temperature. From thermal data alone, Gontermann could not assign any particular direction to the line and, hence, could not determine which pair of conjugate points to choose, A separation of the liquid and solid for analysis, obviously, presents grave experimental difficulties. During the solidification of white cast iron, austenite of progressively higher carbon will separate as the temperature falls and cementite will appear suddenly at the freezing point of the eutectic. This cementite will be accompanied by a corresponding amount of austenite which, for our purpose, will be chemically inseparable from the primary austenite. We have attempted to decide on the conditions at the end of the freezing by a chemical separation applied to the solid metal.

Jan 1, 1925

NEW MEMBERS The following list comprises the names of those persons who became members during the period May 10 to June 10, 1914. Members ABE, ASAKA, Chief Min. Engr., Yamagano Gold Mine, Satsuma-Gori, Satsuma, Japan. ANDERSON, FRANK M., Geol Cartagena Refining Co., Cartagena, Colombia, S. A. BACON, MAURICE W., Genl. Mgr Stewart Mining Co. Butte, Mont. BACON, RAYMOND F., Chem Director, Mellon Institute, Pittsburg, Pa. BAKER, HAMILTON WALLACE, Min. Engr Fernley, Nev. VON BAYER, AUGUST HECTOR, Supt Kentucky Solvay, Coke Co., Ashland, Ky. BISHOP, WHEELER SCOTT, Research Chem Care Braden Copper Co., Rancagua, Chile, S. A. BOWEN, CHARLES GILMAN, Timekeeper 208 School St., Grass Valley, Cal. BOYER, SAMUEL L., Mine Operator, Mgr., Mike. Horse Min. Co., W. 2808 Boone Ave., Spokane. Wash.

Jan 7, 1914

By T. R. Ingraham

When aluminum sulfate was decomposed in an evacuated apparatus and the sample cooled, Q alumina was found. The thermodynamics of the decomposition reaction were resolved by measurements of the total pressure of SO3, SO2, and O2 generated over the sample at various temperatures. The results were correlated with other published data to calculate the rmges of thermodynamic stability of the various compounds involved. The thermal decomposition of aluminum sulfate was studied by Wijhler, Pluddeman, and Wöhler1 and by Warner and Ingraham.2 The results of both studies were critically reviewed by Kellogg,3 who observed that "each set of data shows considerable scatter and strong curvature on a plot of log pso3 vs 1/T".3 He agreed with Warner and Ingraham2 that both the discrepancy in the two sets of results and their curvature may arise from the indefinite properties of the particular form of A12O3 which is formed during the decomposition. While studying the thermal stability of other sulfate systems, we had noted the presence of nonequilibrium oxide properties in both the cobalt4 and manganese5 systems, but neither had shown any appreciable curvature on a logPSO, vs 1/T relationship, and the data from both systems agreed reasonably well with prior work. It therefore seemed reasonable to reexamine the technique which had been used in our earlier work on aluminum sulfate.2 The principal difference was that a tightly compacted pellet had been used for the earlier aluminum sulfate work, whereas a loose powder, contained in a platinum boat, was used for our work on other sulfate systems. In addition, a better technique had been developed for dehydrating the samples. From work done on the nickel system,6 we had become aware of the highly protective nature of some sulfate layers on their oxjdes, and hence of the necessity of providing a large surface area of P3e sample when equilibrium was to be attained in a reasonable time. That observation suggested that perhaps a steady state, rather than equilibrium, had been reached in the earlier work on aluminum sulfate. This paper reports a repetition of the experimental work with large, finely divided samples of anhydrous aluminum sulfate. APPARATUS AND PROCEDURE The apparatus used in the experimental work was described in earlier papers.2,7 The source material was Anachemia reagent-grade Al2(sO4)3 - 18H2O which was first partly dehydrated by heating at 400°C for 48 hr and then completely dehydrated by repeated baking of an aluminum sulfate-oleum slush to dryness at 450°C. ? Alas was prepared by decomposing some of the sulfate in a muffle furnace at 800° C overnight. Approximately equal amounts of the 7) alumina and aluminum sulfate were used in the experiments. The finely divided samples were handled under dry box conditions, and in addition some of the aluminum sulfate was decomposed in the apparatus while it was under vacuum, to ensure its complete dehydration prior to sealing the apparatus. The samples were heated to a series of constant temperatures on both increasing- and decreasing-tem-perature programs. Two to three days were required to obtain steady readings of the total decomposition pressure on an increasing-temperature program, and 5 to 6 days on a decreasing-temperature program. Three samples were examined on both programs. Within experimental error, the results for each sample and each program could not be distinguished.

Jan 1, 1969

By PAUL DYER MERICA

PAUL DYER MERICA, who has been awarded the James Douglas Gold Medal for his achievements in non-ferrous metallurgy, is a Hoosier, having been born at Warsaw, Ind., in 1889. His father, a clergyman and educator, was president of the University of Wyoming from 1908 to 1913. After graduating from the University of Wisconsin in 1908, young Merica (not yet twenty years of age) went to China, where he was professor of chemistry in Chekiang Provincial College, Hangchow, until 1911. He then went to Germany to s t u d y and was fortunate enough to receive his Ph.D. from the University of Berlin just a few months before the outbreak of the World War in 1914. Returning to America, his first position was as special investigator at the En¬gineering Experiment Station of the University of Illinois, but before the year was out he joined the staff of the U. S. Bureau of Standards as associate physicist. Since 1918, he has been superintendent of research for the International Nickel Co. His work during those years is excellently summarized in the following quotation from the statement of Zay Jeffries recommending him for the award.

Jan 1, 1929

By E. R. Funk, H. Udin, J. Wulff

The surface tension of solid silver is measured by a refinement of the Udin, Shaler, and Wulff technique. The tests were made in a purified helium atmosphere at four different temperatures and various times. The average of the results is y = 1140 + 90 dynes per cm for the range 875° to 932°C. A SUCCESSFUL measurement of the surface tension of solid copper was reported by Udin, Shaler, and Wulff.&apos; They performed experiments on copper held in vacuum within 100°C of the melting point. At these temperatures, the creep rate in 5 and 3 mil copper wires was sufficient to permit determination of a balance between the contractile force of surface tension and the extending force of small copper weights joined to the end of the wire specimens. By suspending a series of variously weighted specimens and measuring the change in a gage length during the test, the balancing applied load could be found. This point of zero strain is a measure of the surface tension. The mathematical formulation of this gives: w = r y [1] where w is the weight for zero strain; r, the radius of the wire; and y, the surface tension. A subsequent note by Udin pointed out that eq 1 applies only to single-crystal specimens. Since the specimens used revealed a "bamboo" structure upon

Jan 1, 1952

By Leon McCulloch

WIIen clean iron and metallic zinc dust, protected from the air, arc heated below the melting point of zinc, the iron takes on a coating that has excellent protective value. This coating is a brittle alloy of zinc and iron, and the process is called sherardizing. Although the zinc particlcs are covered with oxide and cannot touch the iron, an extremcly small amount of the zinc vaporizes and the vapor, reaching the iron, alloys with it. Other zinc then vaporizes to replace that which has been removed from the atmosphere. This process continues indefinitely at a decreasing rate, for the coating already formed permits zinc to diffuse through it to combine with the iron beneath. In this way, the coating grows outward from the surface of the iron, as the bark grows from a tree. The method of growth was clcarly seen while sherardizing small cubes of cast iron, at about 450" C., in a srnall glass-stoppcrcd bottle enclosed in a rotating drum. The dust contained about 3 per cent. iron, which prevented caking, and coatings % in. thick were grown in a few hours. After a heavy layer had been formed, the cubes mere again treated for a shorter time. The layer last formed was seen to lie next to the iron, instead of at the outer surface, showing that the growth was from the surface of the iron outward. The coatings split at the edges and corners, leaving the iron exposed there. Flakes of graphite from the iron were lifted upward and embedded in the coatings. The composition of sherardized coatings varies from the outer surface inward, as would be expected from the mode of growth. That is, the iron content increases slowly at first, then more rapidly as the iron is approached. At the surface the least amount of iron possible is 6 per cent., as the experiments described below have shown. A study was made of the effect of iron in zinc dust on the proccss and on the resulting coatings. Glass bulbs, holding the small pieces to be sherardized, together with enough zinc dust to make them two-thirds full, were heated in a small, rotating electrically heated and controlled furnacc. The bulbs had 6-in. (15 cm.) necks, of 96-in. (9.Fj mm.) tubing, plugged

Jan 1, 1923

By Leon McCulloch

WIIen clean iron and metallic zinc dust, protected from the air, arc heated below the melting point of zinc, the iron takes on a coating that has excellent protective value. This coating is a brittle alloy of zinc and iron, and the process is called sherardizing. Although the zinc particlcs are covered with oxide and cannot touch the iron, an extremcly small amount of the zinc vaporizes and the vapor, reaching the iron, alloys with it. Other zinc then vaporizes to replace that which has been removed from the atmosphere. This process continues indefinitely at a decreasing rate, for the coating already formed permits zinc to diffuse through it to combine with the iron beneath. In this way, the coating grows outward from the surface of the iron, as the bark grows from a tree. The method of growth was clcarly seen while sherardizing small cubes of cast iron, at about 450" C., in a srnall glass-stoppcrcd bottle enclosed in a rotating drum. The dust contained about 3 per cent. iron, which prevented caking, and coatings % in. thick were grown in a few hours. After a heavy layer had been formed, the cubes mere again treated for a shorter time. The layer last formed was seen to lie next to the iron, instead of at the outer surface, showing that the growth was from the surface of the iron outward. The coatings split at the edges and corners, leaving the iron exposed there. Flakes of graphite from the iron were lifted upward and embedded in the coatings. The composition of sherardized coatings varies from the outer surface inward, as would be expected from the mode of growth. That is, the iron content increases slowly at first, then more rapidly as the iron is approached. At the surface the least amount of iron possible is 6 per cent., as the experiments described below have shown. A study was made of the effect of iron in zinc dust on the proccss and on the resulting coatings. Glass bulbs, holding the small pieces to be sherardized, together with enough zinc dust to make them two-thirds full, were heated in a small, rotating electrically heated and controlled furnacc. The bulbs had 6-in. (15 cm.) necks, of 96-in. (9.Fj mm.) tubing, plugged

Jan 1, 1923

By Cyril Wells, Robert F. Mehl

The two earlier papers in this series1,2 presented data on the rate of diffusion of carbon and of manganese in gamma iron. Apart from their scientific interest, these data are needed chiefly in order to treat data on carburization, on rate of formation of pearlite, and on rate of austenit-izing in a quantitative way.1&apos;2&apos;9&apos;10 In the present investigation rates of diffusion of nickel in ?-Fe over wide temperature and concentration ranges have been determined, and the effects of carbon, of im- purities, and of grain size on these rates have been studied. Claussen,3 using the data of Fry,4 has calculated the diffusion coefficient of nickel in y-Fe as 9.2 X 10-11 sq. cm. per sec. at 1200ºC., but had no data from which to calculate the variation of D with concentration, temperature, and percentage of carbon. Method and Materials Method.—Nickel was diffused along the axis of a cylindrical specimen across a concentration gradient, concentration-penetration curves were determined and D values calculated from Grube or Matano solutions.5 Details of the method are given

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The two earlier papers in this series1,2 presented data on the rate of diffusion of carbon and of manganese in gamma iron. Apart from their scientific interest, these data are needed chiefly in order to treat data on carburization, on rate of formation of pearlite, and on rate of austenit-izing in a quantitative way.1&apos;2&apos;9&apos;10 In the present investigation rates of diffusion of nickel in ?-Fe over wide temperature and concentration ranges have been determined, and the effects of carbon, of im- purities, and of grain size on these rates have been studied. Claussen,3 using the data of Fry,4 has calculated the diffusion coefficient of nickel in y-Fe as 9.2 X 10-11 sq. cm. per sec. at 1200ºC., but had no data from which to calculate the variation of D with concentration, temperature, and percentage of carbon. Method and Materials Method.—Nickel was diffused along the axis of a cylindrical specimen across a concentration gradient, concentration-penetration curves were determined and D values calculated from Grube or Matano solutions.5 Details of the method are given

Jan 1, 1941

By O. Schaaber

THE existence of isothermal martensite without the presence of the athermal form thus far has been established only in a 6 pct Mn, 0.6 pct C steel&apos; and a 23 pct Ni, 3.5 pct Mn-Fe alloy.&apos; " Theoretical calculations, moreover, predict this phenomenon to be observable only within narrow composition limits.&apos; In all other steels, it is generally considered that martensite inevitably forms upon cooling below the M, temperature. Even the possibility of isothermal martensite transformation has been questioned for the common steels, although Averbach and Cohen" showed that martensite formation does not stop when the cooling is arrested and that as much as 5 pct retained austenite may transform isothermally to martensite at room temperature. This note presents some observations made on a number of low alloy steels by dilatometric and inductive measurement of isothermal austenite transformation at various temperatures close to the Ms. In the dilatometer studies reported previously, austenitized specimens were immersed in a salt bath maintained at proper temperature and immediately inserted into the dilatometera8&apos; already at thermal equilibrium with the bath. The dilation was read on a dial gage divided into 0.001 mm intervals. Induction measurements were made with a separate excitation source and a test coil, sealed together in a salt-tight case. The increase in the induced voltage caused by the transformation products was recorded at a paper speed of 4 mm per sec. The steels studied are listed in Table I. Specimens prepared from steels 1 and 2 were in the form of hollow cylinders 60 mm long, 10 mm ID, 14 to 16 mm OD, while specimens of steels 3 and 4 were in the form of notched-bar impact test specimens, DVM type. Specimens of steel 5 were in the form of strip, 7x0.3 mm. In the bainitic range, curves representing the amount of transformation vs log time have a single step appearance, as is shown by the curve of isothermal transformation at 320°C in Fig. 1.Y ransformation proceeds in accordance with the Austin-Rickett equationo P -----------= k t" 100-P where P is the percentage of transformed austenite, t is time, and k and n are constants. Near the M, temperature, however, complex curves having two steps are observed. As shown in a previous papera for steel 3 isothermally transformed at 245"C, such complex curves can be separated into two separate transformations or reactions each following the Austin-Rickett equation. The values of n in the equation for a number of such two-step transformations are listed in Table 11 for steel 1. At transformation temperatures of 250" and 235"C, evidence of a second transformation is very

Jan 1, 1956

By Fritz Wald, Martin Weinstein, Herbert E. Bates

ONE of the methods for preparing a fiber-reinforced composite is that of directional solidification of a eutectic melt. Its major drawback lies in the fact that the matrix in this case is a pure constituent (or a terminal solid solution of fixed concentration) and the ratio of fiber to matrix volume is fixed. Only very few, if any, pure metal matrices possess technically useful properties, and the necessity for alloying is the inevitable consequence of this fact. Nevertheless, structures similar to binary eutectic ones can be obtained in higher-order systems by pseudoeutectic reactions of a type where crystallites and a solid-solution matrix are simultaneously precipitated from a liquid.1"3 Trials to solidify such alloys directionally—the matrix consisting of a solid solution of chromium, nickel, and silicon and the reinforcing phase being Cr3C2— will be reported elsewhere.4 This note describes constitutional studies carried out primarily to determine -the position of the pseudoeutectic and further to insure that no undesirable reactions between the reinforcing phase and components of the matrix occur in the solid state at elevated temperatures. In the investigation it was specifically desired to reinforce a matrix which is as close as possible to the 80/20 Nichrome composition with Cr3C2 to insure good oxidation resistance and improve the strength at high temperatures. No konstitutional information on the quaternary C-Cr-Ni-Si svstem in the range of interest was found in the literature. Nevertheless, the two most important ternaries c-cr-Ni5 and have been completely investigated. On C-Cr-Si some investigations have been conducted,7"9 and C-Ni-Si was studied with a few alloys in the course of the present investination 9 Eight alloys were prepared to investigate the changes in the constitution of the ternary C-Cr3Ce-yNi eutectic5 with silicon contents up to 10 wt pct. Five alloys were made with varying chromium and carbon contents around compositions containing -60 to 70 wt pct Ni and 5 to 6 wt pct Si. The latter alloys were designed to locate the y(Ni-Cr-Si-C)-Cr3C2 pseudoeutectic reaction and to determine the maximum chromium content in solid solution compatible with a two-phase equilibrium between y and Cr3C2 only. The alloys were prepared from electrolyte nickel, semiconductor-grade silicon, high-purity chromium (99.999 pct pellets), and semiconductor-grade graphite. They were melted inductively in high-purity alumina crucibles under flowing argon. Twenty-gram charges were prepared and investigated by optical microscopy (including hot-stage investigations), X-ray powder methods, and electronmicroprobe analysis. The alloys were studied in the as-cast condition and also after a homogenization annealing treatment of 48 days at 900°C in evacuated quartz ampoules. The structures of all alloys based on the ternary eutectic plus silicon in the as-cast state consisted generally of an inhomogeneous solid solution and at least two other phases. Annealing of the alloys showed that the solid solution was homogenized but that an incomplete solid-state reaction had taken place in all alloys with silicon contents over 5 wt pct. This reaction is clearly visible in Fig. 1 around the large Cr3C2 crystals (gray areas). Below this concentration, the alloys consisted of a homogeneous matrix and precipitates of Cr3C2 plus graphite, Fig. 2. The Cr3C2 was entirely unreacted here. From these observations and subsequent X-ray and microprobe investigations, it was deduced that the

Jan 1, 1969

By Walter Miller

Hundred-octane aviation gasoiine, toluene for T.N.T. production, high-quality lubricating oils for the needs of aviation and the armed forces, and synthetic chemicals for rubber manufacture again commanded the top priorities of the petroleum refining industry in 1944, the third year of America&apos;s active participation in the war. The objective continued to be to produce more and more of these materials—to keep up with increasingly greater requirements. By the end of the year all of the new installations projected before 1944, with the exception of possibly two or three that will tail over into January or February of 1945, had been completed and put into operation. And with the completion and putting into operation of these various units and the consequent lessening of construction responsibilities and problems, the industry was put into position to concentrate on the new operations and devote much more of its time and effort looking toward maximum output, both as to quantity and quality from the new facilities. Aviation Gasoline Making high-octane aviation gasoline continued to be the prime requisite of refining activities during 1944 as it was in the two previous war years, with the sights at the end of the year set to still higher figures than those which had been previously projected. About July I the daily output had been raised to 400,000 bbl., with some few large plant installations still to be completed and put into operation. Indications were that by December production would be up to all requirements, with good inventories. However, although by the end of the year the industry was turning out something over 500,000 bbl. a day, the estimated requirements of the armed services had been raised by a considerable figure, owing to the greatly increased aerial activities both in the European and Far Eastern combat areas. By the end of the year, therefore, the picture had changed, with the prospect for a much longer continuation of the European war, so that even with the completion and putting into operation in the United States by January 1945 of the last two or three 100-octane units authorized prior to 1944, it was evident it would be necessary to make still greater efforts to increase output of existing facilities to keep safely ahead of the game. Efforts of the industry and the Petroleum Administration for War as well as the Technical Advisory Committee and other research and development groups are concentrated therefore on methods and means of further augmenting the produc. tion of all existing refinery facilities engaged in making 100-octane aviation gasoline and components entering into it. The goal will be reached.

Jan 1, 1945

By Paul M. Tyler

Higher freight rates and better methods of beneficiation now may make it more economical to open inferior deposits closer to a glass factory than to work higher-grade deposits farther away. Nature of impurities and special treatments as well as common practice of sulphuric acid leaching are described. HISTORICAL concepts of the economics of the glass-sand industry are changing rapidly. The greatly expanded demand for glass containers combined with higher freight rates on raw materials and manufactured products have induced a migration of glass factories toward densely populated centers and the creation of new standards of place value for substandard sand deposits. This migration has been facilitated by the construction of pipelines to bring cheaper natural gas and liquid fuel to large cities and may be further speeded by the adoption of modern mineral dressing methods to permit economical utilization of local raw materials. Our national resources of naturally high-grade silica sand are abundant, but most of the best deposits are situated so far from large centers of population that it now costs $3.00 to $5.00 a ton to carry the sand from the mine to the optimum site for a factory making beverage bottles, scientific and electrical glassware, and miscellaneous blown and pressed ware for local markets. It follows that on the basis of freight savings alone it may be economical to use material from inferior deposits closer to the factory even though the f.O.b. cost of mining and treatment may be much higher than at a higher grade deposit farther away. Particle-size distribution is a feature of glass-sand specifications. As long as glassmakers insisted upon having their sand principally coarser than 100-mesh, any material was automatically excluded from consideration that could not be purified without fine grinding or other drastic treatment which greatly reduces the size of the quartz grains. However, re- cent large-scale tests in Norway&apos; showed that finely-crushed quartz used in a soda-lime-silica glass batch caused it to melt and become refined appreciably faster than when ordinary coarse (Belgian) sand was employed. Dust losses were negligible. Since the pre-war cost of sand was only 3 pct of the manufacturing cost of the glass, it was deemed economical to pay twice as much for crushed quartz because of the saving in wear and tear on the furnace walls. In the author&apos;s unverified opinion, sand ranging in size between 150 and 400-mesh would probably be superior to that in the more usual range of 20 to 100-mesh. Former objections to fine sand (other than dust) were doubtless fostered by the natural concentration of impurities in the finer sizes. Ordinarily the most objectionable, as well as the commonest, impurity from the standpoint of the manufacturer of any but the cheaper qualities of colored glass is iron. No natural sands are really pure silica. Even water-clear quartz crystals are likely to contain impurities in the form of solid solution as well as inclusions which cannot be eliminated except by chemical treatment that will break down the silica lattice. Pure white pegmatite quartz will usually analyze 0.01 pct or more of iron oxide, and ordinary vein quartz and the quartz grains in most

Jan 1, 1951

By Paul M. Tyler

Higher freight rates and better methods of beneficiation now may make it more economical to open inferior deposits closer to a glass factory than to work higher-grade deposits farther away. Nature of impurities and special treatments as well as common practice of sulphuric acid leaching are described. HISTORICAL concepts of the economics of the glass-sand industry are changing rapidly. The greatly expanded demand for glass containers combined with higher freight rates on raw materials and manufactured products have induced a migration of glass factories toward densely populated centers and the creation of new standards of place value for substandard sand deposits. This migration has been facilitated by the construction of pipelines to bring cheaper natural gas and liquid fuel to large cities and may be further speeded by the adoption of modern mineral dressing methods to permit economical utilization of local raw materials. Our national resources of naturally high-grade silica sand are abundant, but most of the best deposits are situated so far from large centers of population that it now costs $3.00 to $5.00 a ton to carry the sand from the mine to the optimum site for a factory making beverage bottles, scientific and electrical glassware, and miscellaneous blown and pressed ware for local markets. It follows that on the basis of freight savings alone it may be economical to use material from inferior deposits closer to the factory even though the f.O.b. cost of mining and treatment may be much higher than at a higher grade deposit farther away. Particle-size distribution is a feature of glass-sand specifications. As long as glassmakers insisted upon having their sand principally coarser than 100-mesh, any material was automatically excluded from consideration that could not be purified without fine grinding or other drastic treatment which greatly reduces the size of the quartz grains. However, re- cent large-scale tests in Norway&apos; showed that finely-crushed quartz used in a soda-lime-silica glass batch caused it to melt and become refined appreciably faster than when ordinary coarse (Belgian) sand was employed. Dust losses were negligible. Since the pre-war cost of sand was only 3 pct of the manufacturing cost of the glass, it was deemed economical to pay twice as much for crushed quartz because of the saving in wear and tear on the furnace walls. In the author&apos;s unverified opinion, sand ranging in size between 150 and 400-mesh would probably be superior to that in the more usual range of 20 to 100-mesh. Former objections to fine sand (other than dust) were doubtless fostered by the natural concentration of impurities in the finer sizes. Ordinarily the most objectionable, as well as the commonest, impurity from the standpoint of the manufacturer of any but the cheaper qualities of colored glass is iron. No natural sands are really pure silica. Even water-clear quartz crystals are likely to contain impurities in the form of solid solution as well as inclusions which cannot be eliminated except by chemical treatment that will break down the silica lattice. Pure white pegmatite quartz will usually analyze 0.01 pct or more of iron oxide, and ordinary vein quartz and the quartz grains in most

Jan 1, 1951

By T. J. Neil, C. B. Manula, O&apos

This paper describes a simulation model developed to analyze truck haulage problems as they are found in the open pit mining and construction industries. The model, using a computer, cycles trucks between their assigned loading and discharge points over a measured haulage route. Required parameters for model operation include the number and type of operating trucks and loading units, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each origin. Equipment performance characteristics, system profile characteristics, and service time distributions are also included. Records are kept of all waiting times at the loading and discharge points and of any truck interference on the haulroads (moving queues), and a current journal of ore and waste production is maintained. In the pursuit of reduced truck haulage costs, management is confronted with three particular problems in truck and shovel mines. 1) What is the best assignment of trucks to shovels in the system? 2) If new equipment is needed, which new shovels and trucks will operate most effectively in the system? 3) Are any physical changes in the haulage layout warranted to increase productivity? For small open-pit mines the answers to these questions may be obvious. However, for larger operations complex problems are encountered with production and system configuration relationships usually being unknown. The mining simulator discussed here was developed to aid management in evaluating alternative pit-haulage schemes to reduce the risk involved in the selection and assignment of equipment in open-pit truck and shovel mining systems. There are two fundamental differences between this model and other truck haulage simulators: one is a difference of degree, the other a difference of kind. This model can simulate more complex systems than previous models by allowing transportation of material from multiple mine faces to multiple mine destinations and by being readily adaptable to a wide variety of mine layouts. The second difference that characterizes the model is the standard simulation of truck movements. This technique enables each vehicle to perform according to its mechanical capabilities and the physical profile of the haul road. Among the similarities between other truck haulage simulators and this model are the recognition of the probabilistic nature of certain service times in the system and the use of a digital computer to operate the model. The computer inherits the staggering computational and bookkeeping work loads and provides a means for compressing the time scale by allowing several days&apos; operations to be simulated in a matter of minutes. DISTRIBUTION SYSTEM Basic aspects of the system analyzed here may be brought into focus by referring to Fig. 1, a schematic of the typical open pit truck-shovel operation programmed into the simulation model. A single stage materials handling scheme is employed to transport both ore and waste. Loaded trucks are directed to a crusher or stockpile if ore is being mined, while overburden is conveyed to a waste dump. Each shovel has a given number of assigned trucks and has two associated haulage routes, one for waste and one for ore. Up to 5 shovels and as many as 10 trucks per shovel (or a total of 50 trucks) can be operated in the model. Essentially the model, using a computer, cycles trucks between their assigned shovels and the proper discharge points over measured haulage routes. Required input parameters for model operation include the number of shifts to be simulated, operating time per shift, number and type of operating trucks and shovels, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each shovel. Equipment performance characteristics, system profile characteristics, and service time distributions are

Jan 1, 1968

The Climax Molybdenum Company&apos; s newest operation is the Henderson project, which is located on the east side of the Continental Divide. Ore reserves are estimated at more than 300 million tons at a grade of 0.49% MoS2. For mining the ore a modified panel caving system is used. The ore is transported to the Henderson mill on the west side of the Continental Divide on a 42 in. (1.07 m) gauge railroad through 9.6 miles (15.4 km) of tunnel and 4. 8 miles (7.7 km) of surface track, a total distance of 14.4 miles (23. 2 km). Each train consists of 30 ore cars with capacity of 22 st (20 mt) of ore or 660 st (599 mt) per train. The unmanned trains operate completely automatically. At the 54 in. by 84 in. primary gyratory crusher, the bottom dump ore cars pass over a dump scroll to discharge at a maximum rate of 100 st (91 mt) per minute. Dumped ore falls onto a rock box before passing over a 17 ft long by 46 ft wide (5. 2 m by 14 m) grizzly set at a 40° angle with bar spacings of 7 ½ and 8 ½ in. (191 mm and 216 mm) openings. An estimated 30 to 50% of the ore (which at times is wet and sticky) passes through the grizzly. The operators report that a shallower angle on the grizzly, perhaps 35º to 37º, would have been sufficient and would have prevented impact on the back of the crusher pocket by large boulders. This pocket as well as the crushed ore pocket under the crusher is lined with AR plate. The accompanying drawings show a "future splitter" and the operators are planning the installation of this unit to prevent impact and subsequent damage to the crusher spider. Crushed ore at an 8 to 9 in. (203 mm to 229 mm) size joins the grizzly undersize in the pocket beneath the crusher. This pocket is sized at 660 live st (599 mt) so that it will accept an entire trainload of ore. Crushed ore is removed from the pocket by a four-speed, 84 in. (2. 1 m) apron feeder operating at 9.6 to 29. 3 fpm (2.9 to 8.9 mpm). A 60 in. (1.5 m) takeaway conveyor operating at 480 fpm (146 mpm) delivers the crushed ore to a 58,000 st live and 193,000 st total (52,600 and 175, 100 mt) open stockpile under an A -frame supported tripper gallery. Impact idlers on the takeaway conveyor under the apron feeder discharge are mounted on wood blocks for a cushioning effect and ripped belt detecting bars are located behind each impact idler. The conveyor tunnel is of corrugated and galvanized steel construction rather than concrete. The concrete crusher enclosure is circular in design from its lowest level at elevation minus 110 ft 4 in. (minus 33. 6 m) to elevation

Jan 1, 1978

By D. G. Swarthout, J. W. Savage, R. W. Guard

The Nb-N constitution diagvam has been examined from 1100° to 1450°C at 1 atm N2 pressure. On the basis of- our work plus that of Brauer and coworkers the stable nitvide Phases are: a) a solid solutlion, basic niobium (bcc) with nitrogen contained interstitially; NbN,, x = <0.40; b) ß NhNx,x = 0.39 to 0.45; hexagonal (W2C type) (NbzN); a =3.058A,c = 4.961 + 0.001A c) y NbNx x = 0.75 to 0.80; tetragonal (distorted NaCl type) (Nb4N3); a = 4.386A,c = 4.332 + 0.001A; d) 6 NbN,, x = 0.88 to 0.91; cubic (NaCl type); a = 4.3885 + 0.0007A; e) E NbNx x = 0.92 to 1.00; hexagonal (Tip type); a = 2.958A, c = 11.272 * 0.0015A. In addition, a metastuble transition phase 6&apos; has been observed and occurs only during the transition 6 — E. 6&apos; NbN has these distinguishing parameters: NbNx,x = 0.96; hexagonal (anti-NiAs type); a = 2.94A, c = 5 .46A. The high-temperature phase fields in the system are governed by two reactions: a) 6 + Y + E, a entectoid reaction occurring at 1270" ± 20° C; b) o + N2 = E, a 2 012 1 reaction occurring at 1370" ± 20° C. As part of a study of the electronic low-temperature. properties of transition metal nitrides, a number of specimens of niobium nitride were prepared. Preliminary observations on these specimens showed several points of disagreement with data already in the literature. It was, therefore, decided to determine the constitution diagram for the Nb-N system between 1100" and 1450°C. The objective of this research was to define the temperature and composition regions of stability of the various phases and to explain the differences among previously proposed diagrams. Review of Previous Literature. The research on the Nb-N system to 1964 has been summarized by storms.&apos; Although he does not present a phase diagram, his review covers the research on the system thoroughly. One of the earliest works on NbN is that of Ascher-mann and coworkers2 who studied the superconductivity of the cubic 6 NbN. Subsequent work by Horn and ziegler,3 Cook, Zemansky, and Boorse,1 Rögener:5 Schroder6 and sellmaier7 has qualitatively confirmed the first results on superconductivity, although their methods of preparation differed considerably. The constitution diagrams proposed for the system by Brauer and Esselborn8 and Elliott9 are shown in Fig. l(a)and (b). The diagram in l(a) has been modified by more recent results in Brauer&apos;s laboratory (private communication). Although 6&apos; is shown on this diagram, Brauer has indicated that he now believes 6&apos; to be a metastable phase in the temperature range shown. The diagram of Elliott, Fig. l(b), is based primarily on the results of Elliott and Komjathy10 on ni-trided niobium strip or rod specimens examined by X-ray diffraction and metallography. It will be noted that these proposed diagrams are in conflict with respect to the temperature and composition ranges of

Jan 1, 1968

By E. Miller, J. M. Eldridge, K. L. Komarek

The liquidus curve of the Mg-Pb system was accurately redetermined. The compound Mg2Pb decomposes peritectically at 538.2° ± 0.3°C to liquid and to a compound p&apos; which melts congruently at 35.0 at. pct Pb and 549.0° ± 0.3°C. The solidus curve of ß&apos; was determined. X-ray diffraction studies indicate that 4&apos; has an orthorhombic structure. Activity values of magnesium calculated from the phase diagram agree with those published in the literature. EXPERIMENTAL thermodynamic properties of binary metallic systems have to be consistent with values calculated from the phase diagram. In systems forming intermetallic compounds the shape of the liquidus curve near a compound is determined by the thermodynamic properties of the coexisting solid and liquid phases. Hauffe and Wagner&apos; neglected the temperature dependence of the chemical potentials and obtained the potential differences of the components of the liquid alloys, relative to stoichiometric liquid. Their calculations were based on the liquidus curve and on the heat of fusion of the compound, and were only valid near the congruent melting point. Steiner, Miller, and Komarek2 developed equations which account for the temperature dependence and obtained the chemical potentials of liquid Mg-Sn alloys over the entire phase diagram from the liquidus and solidus curves and from enthalpy values with the pure components as the standard states. The Mg-Pb phase diagram has been studied by several investigators whose results have been compiled and critically evaluated by Hansen.3 Although the liquidus curve was poorly defined, the general features of the diagram, i.e., one congruent melting compound, Mg2Pb, of essentially stoichiometric composition, two eutectics, and limited terminal solid solubilities, seemed to be suitable for a similar thermodynamic analysis. A careful redeter-mination of the liquidus by thermal analysis revealed, however, the existence of another compound. The liquidus curve between the two eutectics was precisely delineated and the structure and solidus curve of the new compound were investigated. The revised phase diagram was thermodynamic ally analyzed to evaluate the activity of magnesium in the liquid alloys. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) had a purity of 99.99+ pct; lead (American Smelting and Refining Co.) contained 99.999 pct Pb. Most experiments were carried out in graphite crucibles. Several experiments were made in high-purity alumina (Triangle R.R., Mor-ganite, Inc.) and in Armco iron crucibles to test the inertness of the graphite crucibles. Chemical analysis of magnesium and detailed description of the procedure for thermal analysis have been given previously. For the determination of the solidus curve of the compounds, specimens of initial composition Mg2Pb were equilibrated in a closed isothermal system with magnesium vapor. The source of the magnesium vapor was an alloy which had a gross composition lying in the 0&apos; + L field at the temperature of equilibration. As equilibrium was approached, the specimens lost magnesium to the two-phase reservoir thereby lowering the activity of magnesium in the specimens until activity and composition equaled that of the ß&apos;/ß&apos; + L boundary. Crucibles (1.9 cm ID by 2.2 cm OD by 4.1 cm high) and tightly fitting lids were machined from a molybdenum rod; small, shallow trays were fashioned from thin (0.005 in.) molybdenum sheet, and all the molybdenum components were degreased in hot carbon tetrachloride and then dried. The pieces were then degassed in vacuum at 950°C for about 6 hr. The two-phase alloy was placed at the bottom of the crucible and small specimens of the Mg2Pb compound, weighed on an analytical balance, were placed in two molybdenum trays above the two-phase alloy. The crucible was closed by forcing its lid on and then inserted in a titanium crucible. This crucible was evacuated, flushed twice with argon, and welded under argon. The specimens were equilibrated for about 1 week in a resistance furnace regulated by a Celectray controller, and the runs were terminated by water quenching. The specimens were again weighed and the equilibrium compositions were calculated on the basis that the weight losses were solely due to a loss of magnesium to the two-phase alloy. The structure of the B&apos; phase was investigated by the Debye-Scherrer X-ray diffraction technique. Selected ingots from thermal-analysis experiments containing about 35 at. pct Pb were re-melted, slowly cooled, and crushed in an argon-filled glovebox until the entire ingot passed through a 50-mesh sieve. The powder was thoroughly

Jan 1, 1965