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By R. E. Powers, E. H. Kinelski, H. A. Morrissey

A group of 17 American blast-furnace sinters, an American open-hearth sinter, an American iron ore, and a Swedish sinter were used to evaluate testing methods adapted to appraise sinter properties. Statistical calculations were performed on the data to determine correlation coefficients for several sets of sinter properties. Properties of strength and dusting were related to total porosity, slag ratio, and total slag. Reducibility was related to the degree of oxidation of the sinters. THIS report to the American iron and steel industry marks the completion of a 1949 survey of blast-furnace sinter practice sponsored by the Subcommittee on Agglomeration of Fines of the American Iron & Steel Institute. The use of sinter in blast furnaces, sinter properties, raw materials, and sinter plant operation have been reported recently.1,2 After preliminary research and study," test procedures were adapted to appraise the physical and chemical properties of sinter to determine what constitutes a good sinter. During the 1949 to 1950 plant survey each plant submitted a 400-lb grab sample to research personnel at Mellon Institute, Pittsburgh, Pa. A 400-lb sample was also submitted from Sweden. In addition, 2 tons of group 3 fines iron ore were obtained from a Pittsburgh steel plant. The following tests were performed on the iron ore sample and on the 19 sinter samples: chemical analysis; impact test for strength and dusting; reducibility test; surface area measurements, B.E.T. nitrogen adsorption method; S.K. porosity test; Davis tube magnetic analysis; X-ray diffraction analysis for magnetite and hematite; and microstructure. Results of these evaluations are discussed in this paper and supply a critical look at testing procedures used to determine sinter quality. Sinter Tests and Results Each 400-lb grab sample of sinter was secured at a time when it was believed to represent normal production practice at each plant. It was not possible to use the same sampling procedures throughout the survey; consequently samples were taken from blast-furnace bins, cooling tables, and railroad cars. These were very useful for evaluation of test methods, since they were obtained from plants with widely divergent operations. With the exception of Swedish sinter and sinter sample N, which were produced on the Greenawalt type of pans, all survey sinters were produced on the Dwight-Lloyd type of sintering machines. Sinters submitted for test were prepared in identical manner by crushing in a roll crusher (set at 1 in.), mixing, and quartering. To secure specific size fractions for tests, one quarter of the sample was crushed in a jaw crusher and hammer mill to obtain a —10 mesh size. The remainder was screened to obtain specific size fractions. The group 3 fines iron ore was dried and screened and samples were taken from selected screen sizes to be used for various tests. Prior to testing, each ore sample except the —100 mesh fraction was washed with water to remove all fine material and was then dried. This iron ore, a hematitic ore from the Lake Superior region, was used as a base line for comparing results of tests on sinters. The iron ore did not lend itself to impact testing, since it was compacted rather than crushed in the test, and no impact tests are reported. However, the iron ore was subjected to all remaining physical tests to be described. Chemical Analysis: Table I presents chemical analyses performed on the survey sinter samples. Included in this table are data obtained from determination of FeO and the slag relationships: CaO + MgO and total slag (CaO + MgO + SiO, SiO2 + Al2o3 + TiO2). The percentage of FeO was used as an indication of the percentage of magnetite in the sinter. It was believed that slag relationships could be correlated with sinter properties. During initial determination of FeO great disagreement arose among various laboratories, both as to the results and the methods of determining values. Table I lists the values of FeO resulting from the U. S. Steel Corp. method of chemical analysis,' which reports the total FeO soluble in hydrochloric and hydrofluoric acids (metallic iron not removed) with dry ice used to produce the protective atmosphere during digestion. Use of dry ice was a modification required to obtain reproducible results. In this method, the iron silicates and metallic iron are believed to go into solution and are therefore reported as FeO. This is important, for in the study of the microstructure of sinters, glassy constituents suspected of containing FeO as well as crystallized phases of undetermined identity which may also contain FeO have been observed. Strength Test by Impact: In evaluating sinter quality, one of the properties stressed most by blastfurnace operators is strength. This strength may be described as the resistance to breakage during handling of sinter between the sinter plant and the blast-furnace bins. It is also the strength necessary to withstand the burden in the blast-furnace. After

Jan 1, 1955

THOSE NOT MARKED ARE MEMBERS; MARKED THUS t ARE ASSOCIATES. HEAVY-FACED TYPE SIGNIFIES HONORARY MEMBERSHIP. JUNIOR MEMBERS ARE MARKED II. THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION. AARONS, J. BOYD, Genl. Mgr., Chaffers G. M. Co., Boulder City, West. Australia. '05 ABADIE, EMILE R., Min. Engr Box 291, Porterville, Tulare Co., Cal. '76 ABBOTT, CLARENCE E., Genl. Supt., Iron Mines Div., 1405 Minnesota Ave., Bessemer, Ala. '04 ABBOTT, J. W., Min. Engr., "St. Omer," 123 N. Grand Ave., Los Angeles, Cal. '94 ABBOTT, Louis BENJAMIN, Chief Engr., Consolidation Coal Co., Elkhorn Div., Jenkins, Ky. '15 ABBOTT, ROBERT R., Met. Engr., Peerless Motor Car Co., Cleveland, Ohio. '12 ABE, ASAKA Yamagano G. M., Satsuma-Gori, Satsuma, Japan. '14 || ABRAHAMS, A. I., Student 1391 Madison Ave., New York, N. Y. '14 tACKER, E. O'C., Met Bethlehem Steel Co., Bethlehem, Pa. '86 ACKER, Louis K., JR., Min. Engr 565 Highland Place, Bellevue, Pa. '08 ADACHI, JINZOO 11 Shiba Park, Shiba-ku, Tokyo, Japan. '88 ADAMI, C. J., Min. Engr., St. Joseph and Doe Run Lead Companies, Bonne Terre, Mo. '12

Jan 1, 1917

By M. J. Hordon, M. A. Wright

ReCENT work has indicated that the substantial decrease in the rate of fatigue crack propagation for aluminum observed below a critical vacuum level can be attributed to the depletion of oxygen or water vapor from the vicinity of the fatigue crack opening.' At reduced gas pressures, generally below 10-2 Torr with fatigue strain amplitudes in the range *1 to 2 x 10-3 and cyclic loading rates of 25 to 50 cps, estimated rates of oxide or hydroxide monolayer adsorption on newly formed crack surfaces can fall behind the actual rate of crack extension. Changes in the critical pressure required for the transition in fatigue behavior with changes in temperature, strain amplitude, and cyclic frequency can be interpreted from variations in the adsorption and crack growth rates.'" Although the adsorption model generally appears to explain the enhanced fatigue resistance of reactive metals in vacuum, the specific adsorbing gas species and nature of the adsorption mechanism are uncertain. In addition to the direct dissociation and adsorption of O2 on the metal surfaces,3 the dissociation of H20 and subsequent adsorption of H ions have been advanced for aluminum alloys.4 The present note describes some measurements of the fatigue behavior of 1100 aluminum in reduced partial pressures of specific gases including O2, H2O, and H2 in order to provide additional experimental data. Cantilever-type specimens of 1100-H14 aluminum were fatigued in cyclic reverse bending at constant strain amplitude using a multispecimen vacuum apparatus and procedure described previously.' After initial vacuum evacuation to 1 x 10-7 Torr, the appropriate gas species was bled into the system through a calibrated leak valve. The input rate was adjusted to maintain the desired pressure level under continuous evacuation, thus minimizing possible changes in gas composition during testing. High-purity input gases including 99.9 pct O2, 99.999 pct H 2, and water vapor from triply distilled H 2 O were used to provide residual pressures. Trace amounts of contaminant species were limited by passing the Oz and H 2 input gases through liquid-nitrogen-cooled copper coils prior to entry to the test chamber. Care was taken to repeatedly flush the gas lines and valves before testing to minimize the effect of adsorbed contaminants. Residual gas pressures in the range 10-6 to 5 x x3 Torr were monitored by an NRC ionization gage corrected for each gas species. In the higher-pressure range, 5 x 1CT3 to 5 x 10' Torr, an NRC alphatron gage was used. In operation, eight simultaneous fatigue tests were conducted at a constant strain amplitude of *1.2 x 10 at cyclic bending rates of 25 and 50 cps to give an average fatigue life of 6.5x 105 cycles-to-fracture at standard atmosphere and 3.3 x 106 cycles in 1 x 10"7 Torr vacuum. Representative results for the effect of residual O2, H2O, and H2 contents on the fatigue life are shown in Fig. 1 for tests performed at 50 cps. It is apparent that the presence of either O2 or H2O gas in the system at partial pressures greater than 10"3 Torr was noticeably detrimental to the fatigue life. In contrast, the enhanced fatigue resistance typical of high-vacuum environments was retained with pure H 2 through the pressure range up to 1 Torr. For partial pressures of H2 gas above 1 Torr, the fracture life noticeably decreased. The critical Hz

Jan 1, 1969

By M. E. Wadsworth, J. R. Lewis, J. M. Quets

Samples of snythetic magnetite were reduced in hydrogen at various partial pressures and temperatures. The reaction mas found to be surface controlled and directly proportional to hydrogen partial pressure over the temperature range studied (400° to 1000°C). A transition in the mechanism occurred at approxirnately 590°C. This has been attributed to a change in the slow step of the reduction reaction resulting from the presence of stable wüstite at higher temperatures. Below 590°C the heat of activation for the reduction was found to be 14,700 cal per mole and it was 3,200 cal per mole above 590°C. THE reduction of the oxides of iron has been a subject of study and interest for many years. Edstrom1 has reviewed the work up to 1953 and his findings provide much basic information concerning details of the reduction of hematite (Fe2O3 ) and magnetite (Fe3O4) with both H2 and CO. He concluded that below 600°C the reduction of both hematite and magnetite was essentially identical, since the rate was controlled by a surface reaction at a magnetite gas interface and the iron formed was very porous. The decrease in the reduction rate for both hematite and magnetite immediately above 600°C was attributed to the formation of a stable wüstite phase across which diffusion was very slow. The wide difference in reduction kinetics for hematite and magnetite above 600°C was explained in terms of the character of the wüstite formed. The rate of magnetite reduction increased slowly with temperature beyond the minimum immediately above 600°C and rates equivalent to those observed at 550°C were not obtained until the temperature was increased beyond 850oC. Edstrom and Bitsianes2 studied the solid-state reduction of magnetite, the reaction of which can be written (4x-3)Fe + Fe3O4—4 FexO [1] where x is between 0.83 and 0.95. The rate was found to be controlled by the kinetics of transport of iron ions through the wüstite phase. Bogdandy and Riecke3 studied the kinetics of reduction of small grains of iron oxide in hydrogen and qualitatively attributed the slow step in the reduction process to the diffusion of hydrogen and water vapor through pores. McKewan4 has analysed the data of Joseph,5 Stalhane and Malmburg,6 and Lewis7 and has demonstrated that the kinetics of reduction of both hematite and magnetite are controlled by surface reactions and also that the variation in surface area during reduction must be accounted for. McKewan was able to correlate the reduction data by the equation rodo[1-(1-R)1/3] = Kt [2] where ro is the initial particle radius, do is the density of the iron oxide, R is the fraction reduced at time t, and K is a rate constant. The applicability of Eq. [2] for temperatures above 600°C where a stable wüstite phase is present, indicates the slow step in the over-all kinetics does not result from diffusion unless diffusion occurs laterally along the oxide metal interface or through a wüstite layer of constant thickness. Diffusional control through a layer of wüstite is unlikely, however, in view of the pressure effects demonstrated by Tenenbaum and Joseph,' Diepschlag,9 McKewan,10 and the results of the present study. McKewan has demonstrated a linear rate dependence on the hydrogen partial pressure over the temperature range 400" to 1050°C for the reduction of hematite.

Jan 1, 1961

By Gerald Greene

Tan various lead producers have given the subject of lead drosses much attention in recent years but the problem of their economical treatment is yet to be solved. Formerly the copper in the furnace feed was removed from the furnace in the form of matte. The speiss at that time consisted principally of the iron arsenide. The practice today is to roast off most of the sulfur and the copper in the feed forms a dross in the furnace, which is removed from the furnace with the lead. This material is poured into the drossing kettles and allowed to cool down to but slightly above the freezing point of lead. The copper dross, containing almost all of the arsenic and part of the antimony, is skimmed off and treated in a small reverberatory furnace at most plants. This is essentially a liquation process. The skimmed dross contains from 70 to 80 per cent lead, and much of this lead is liquated out. The products from this treatment are: (1) impure lead, (2) speiss and (3) matte. The speiss from the reverberatory furnace was studied in this research. The literature on the subject is of very little assistance, as almost no work has been done on the problem of establishing the exact identity of the various phases present. One author(1) states that speiss consists of a series of isomorphous compounds of the general formula FexAsy in which the Fe may be replaced by Ni, Co, Cu, Pb, Ag, Au, Pt, Zn, Cd and the As replaced by Sb, S and Bi. Hofman(2) states that the iron arsenide present is Fe5As.

Jan 1, 1935

By D. G. Wilder

D.G. Wilder I found the suggestion that the amount of displacement of a fault can be numerically related to the thickness of gouge or breccia to be both intuitively satisfying and intriguing. I have long agreed that there is some type of relationship between the amount of gouge and the amount of displacement of faults. I congratulate the author for developing a numerical relationship between them. However, I am concerned that the limits for applying this relationship be fully understood. An underlying assumption in this approach is that there is either a uniform thickness of gouge or breccia along a given fault or the thickness does not vary widely. Since it is not always possible to confirm this, the displacements derived by this method should be viewed with caution unless significant fault extent can be observed. At the Nevada Test Site, in drifts constructed in granite for test emplacement of spent nuclear reactor fuel, we found a fault with 0.3 to 0.4 m (12 to 16 in.) of clay gouge. Within a few meters of this location, the fault had no clay gouge, but rather consisted of a highly fractured zone with significantly altered rock and some slickensides. Based on Fig. 1, the 0.3 to 0.4 m (12 to 16 in.) thickness of gouge would indicate a displacement in excess of 30 m (98 ft). However, no gouge thickness would indicate essentially no displacement. Based on a quartz vein that terminated on the fault, and is not identified nearby, an estimated displacement of more than a few meters was made. This estimate is consistent with that obtained using the regression line proposed in the paper if the 0.3 to 0.4 m (12 to 16 in.) thickness for the gouge is used. However, using the regression curves with zero thickness would not yield results consistent with what was observed in the field. Therefore, it is important to recognize that the suggested procedure would properly yield a range of probable displacements. ? *Work performed under the auspices of the US Department of Energy by the Lawrence Livermore National Laboratory under Contract W-7405-Eng-48. Reply by E.C. Robertson It is certainly true that the t (thickness) of gg-bx (gouge and breccia) on a fault does vary along the fault. My observations have been that near the termination of a fault, the displacement d is small and the t is also small, whereas the maximum d and t will usually be found in the central part of the fault. The information on gg-bx and t of the fault found in granite in the NTS tunnel by Mr. Wilder could be interpreted somewhat differently than he does. He speaks of the fault changing within a few meters from 0.3 to 0.4 m (12 to 16 in.) of clay gg to "a highly fractured zone with significantly altered rock and some slickensides," but no gg. The highly fractured rock may be taken to be bx, rock not so finely ground as gg but still crushed by the fault movement, equivalent to the gg in my usage, and probably occupying about the same t. Mr. Wilder's estimates for the fault in the NTS tunnel for t of 0.3 to 0.4 m (12 to 16 in.) and for d of a quartz vein, in excess of "a few meters," would place the point on the low side of the central trend line in my Fig. 1, at the lower limit. There is, of course, a problem with determining d using displacement of only one planar surface. It would be greater or lesser depending on the rake of the movement. Finally, estimating the d of a fault from its t should be made with awareness of our present uncertainties, as pointed out by Mr. Wilder. Although the central trend line in my Fig. 1 has a ratio of d/t of 100, I have put the limiting ratios at 10 and 1000. Understanding of the values of the ratio will be improved only with collection of more data, for which the discussion of Mr. Wilder is much appreciated. ? G.C. Waterman E.C. Robertson's paper provides significant information to a geologist attempting to deduce fault offset by noting the products of structural dislocation. However, considerable mapping in underground and open-pit mines, and examination of structures produced in different geological settings, have convinced me that gouge and breccia thickness are controlled by geological conditions and fault movement. The following paragraphs suggest geological variables that control them. 1. Depth of Loading A near-surface fault resulting from tensional stress has more breccia/gouge than is produced by a similar stress at considerable depth. A deep-loaded compressional stress may produce a linear zone of schist, or structural dislocation may occur along an earlier formed belt of schist. Such "shear zones" are common in Canadian mines in precambrian rocks. In neither case can offset be directly deduced by an analysis of the minimal gouge/breccia in the shistose rocks. At greater depth, stress may be partially to wholly relieved by flowage. I vividly recall first noting the regional "Midas Thrust" in the Lark mine, Bingham Mining District, UT (where we called the structure the North Fault). My recorded notes, as I remember them, showed a narrow gouge streak separated the "Jordan" and "Commercial" limestone units from impure, muddy limestone beds of uncertain stratigraphic position. The visible structure did not indicate the great importance of this premineral fault

Jan 1, 1985

By V. B. Tare, H. Schmalzried

The use of solid electrolytes for determining kinetic paraneters at elevated tevnperatures is pointed out. The reaction rate constant k1 of the phase-boundary reaction during oxidution of iron to wiistite by CO2-CO gas mixtures has been deternined between 850 nnd 975C, using ZrOz(+CaO) as an electrolyte. Values are between 1.4 x 10-a and 5.2 x 10 ole per sq ctn atm. The tzain difficulty is due to mixed potentials arising from side reactions at the electrolyte inteyface. In a number of papers the calcium-doped zirconia electrolyte has been used for the determination of thermodynamic data from measured differences in oxygen activities (or potentials) between two electrodes. The purpose of this note is to suggest the use of this solid electrolyte for kinetic measurements as well. The principle can be seen from Fig. 1. A thin and compact phase II (electron conductor) is fixed on a plate of gas-tight, polished ZrO2(+CaO) (I), which separates two compartments with different oxygen potential. p, is a constant reference pressure of oxygen (1 atm). The electromotive force of this galvanic cell is given by E = RT5 In pep, and pe is the oxygen partial pressure at the interface electrolytephase 11. If phase I1 is in equilibrium with the surrounding gas phase, p, = DR. If pg changes sud- denly to a value pi, p, and therefore the electromotive force, E, change as a function of time according to the phase-boundary reaction rate at the gas phase I1 interface and the transport processes inside phase 11. It is assumed that local equilibrium is established at the boundary electrolytephase 11, that the gas phase shows no concentration gradients, and that the con-

Jan 1, 1967

By R. G. Carlson, F. E. Westermann

HOT pressing of powder particles has gained importance recently, since it affords a method in which high densities are rapidly attained. In a recent study on hot pressing of alumina powders, Mangsen, Lam-bertson, and Best1 have shown within the limits of their experiment, the validity the rate equation for densification in hot pressing, originally proposed by Murray, Livey, and Williams.2 i.e., where D = fraction of theoretical density, t = time, P = pressure and 77 is the viscosity, all in appropriate units. This equation was derived from earlier work of Shuttleworth and Mackenzie3 which is based on the closing of spherical pores under the action of surface tension. The integrated form of this equation yields a straight-line relation between log (1 - D) and t. Such conditions were found by Felten4 to be true only after extended periods of pressing. In an endeavor to quantitatively evaluate the exactitude of this equation in the initial sintering stage, i.e., prior to sealing of the pores, spherical anti-

Jan 1, 1962

By J. W. Spretnak, J. N. Cordea

The gain boundary relaxation in high-purity aluminum, nickel, copper, and silver was studied by means of a low-frequency torsion pendulum. Both internal friction and creep at constant stress tests were conducted. A lognormal distribution in relaxation times was found to account for the relatively wide experimental internal friction peaks and the gradual relaxation behavior during the creep tests. This distribution was separated further into a lognormal distribution of relaxation time constants and a normal distribution in activation energies. A spread of up to ±6 kcal per mole in the activation energies accounted for the major part of the distribution. A "double-peak" internal friction phenomenon was observed in silver. The activation energies in kcal per mole derived from the grain boundary relaxation phenomena are 34.5 for aluminum, 73.5 for nickel, 31.5 for copper, and 41.5 for silver. It was found that the rain boundary relaxation strength in these metals increases with the reported stacking-fault energy. GRAIN boundary relaxation phenomena have been observed in a large number of polycrystalline metals and alloys. Numerous investigations have been conducted to study the structure of the grain boundary through this relaxation process. One of the first investigators was Ke1-4 who observed that the activation energy for grain boundary relaxation in aluminum, a brass, and a iron was about the same as that for volume diffusion. He concluded that the grain boundary behaved as if it were a thin liquid layer with neighboring grains sliding over one another. Leak5 conducted experiments on iron of a higher purity and observed that the grain boundary activation energy is comparable with that of grain boundary diffusion. He suggested that, in metals where this relationship holds, the damping may be caused by a reversible migration of grain boundaries into adjoining grains. Nowick6 has presented an interesting view of inter-facial relaxation with his "sphere of relaxation" model. A relaxed interface is represented as one where the shear stress is greater than the normal value along the edges and zero in the interior of the interface. The region of the stress relaxation is pictured as a sphere surrounding the interface. From his calculations Nowick concluded that the slip along an interface is directly proportional to its length. Therefore, the time of relaxation, T, depends on the size of the relaxation interface. This means that in the Arrhenius relationship, t = TO exp[H/RT], valid for atom movements, the relaxation time T is predicted to be proportional to the grain diameter through the pre-exponential term, TO. Since the internal friction can be given as Q-1 = ?j wt/(1 + w2r2), where ?J is the relaxation strength and w is the angular frequency, an increase in grain size at a constant frequency will shift the peak to a higher temperature. A great deal of work has been done to determine the exact relationship between the internal friction and grain size.1,5,7,8 In metals, the grain boundary peaks are found to be lower and broader than predicted theoretically.' The above model can explain this by a distribution in the size of the interface areas, represented by a distribution in the parameter tO, and an overlap of spheres of relaxation, represented by a distribution in activation energies. Both these phenomena result in an over-all distribution in the relaxation time, which could affect the internal friction peak height, breadth, and also position. This relationship between the experimental data and theoretical calculations appears very promising in the study of interfacial relaxation mechanisms. THEORY A lognormal distribution in t can sometimes be used to adequately describe the spectrum of relaxation times governing an anelastic relaxation. wiechert9 originally suggested such a distribution to explain the elastic after-effect in solids. This choice is particularly applicable to grain boundary relaxation when considering Saltykov's work.'' He found a lognormal distribution in the grain sizes within a metal. Recently Nowick and Berry11 have introduced a log-normal distribution in T into the theoretical internal friction equations. The form of the distribution function is where z = In(r/rm), and Tm is the mean value of t. The parameter ß is a measure of the distribution and is the half-width of the distribution when is l/e of its maximum, IC/(O). Nowick and Berry have described the methods to obtain the parameters Tm, ß, and ?,J from experimental internal friction and creep test data. In the idealized case, where only one relaxation event occurs with one relaxation time, only ?J and T are necessary to completely describe the event, and 0 = 0. For the broader internal friction curves 6 is some positive number greater than zero. The larger the 6, the greater is the half-width of the distribution in In t.

Jan 1, 1967

A comprehensive, systematically structured mineral evaluation system is a prime requirement for objectively assessing mineral supply impacts on the economy. The Minerals Availability System developed by the US Bureau of Mines is a step in the right direction-a well-organized unraveling of the mineral supply network, structured in format to allow quick retrieval for rapid listing, supply analysis, and other uses.

Jan 9, 1977

The surface area that mining requires is a minuscule fraction of the total land mass of the United States, according to the US Bureau of Mines' latest report "Land Utilization and Reclamation in the Mining Industry, 1930-71." During the 42-year period from 1930 to 1971, the mining industry utilized 3.65 million acres-only 0.16% of a total 2.27 billion acres of land-and reclaimed 1.46 mil- lion acres, or 40% of what it used. Which leaves, as still unreclaimed, 0.096% of the nation's total land mass.

Jan 10, 1974

By C. W. Spencer, Che-Yu Li, R. J. Knight

The usual reaction product for the monotectic reaction in the Bi-Se system consists of rod -shaped particles of selenium-rich liquid embedded in a single crystal matrix of At certain crystallo-graphic orientations of the matrix with respect to the reaction interface, more complex shapes are as -sumed by the liquid particles. This reaction has been examined at different growth rates and relative crystallographic orientations of the matrix with respect to the reaction interface. The uhriation in auerage particle size of the liquid phase with reaction rate has been determined at one crystallograpIzic orientation of the matrix. On a plot of logarithm of average particle diameter vs logarithm of reaction rate, data points for crystals grown at rates of 10- to 1.0 cm per hr fall near a curve of slobe -0.4. MONOTECTIC reactions in binary alloy systems are reactions of the eutectic class in which, as the system is cooled through the three-phase reaction isotherm, one liquid phase (L) decomposes to a solid phase and another liquid phase (LII).' A partial phase diagram, as taken from Hansen, showing the monotectic reaction in the Bi-Se system is given in Fig. 1. This diagram specifies the monotectic point at 618°C and 72 at. pct Se, and the monotectic reaction products as the intermetallic Bi Se3 and a liquid (LII) which contains approximately 98 at. pct Se. At a lower temperature, 217°C, this liquid may undergo a eutectic reaction in which the reaction products are BizSe3 and crystalline selenium. However, under conditions of rapid cooling, or quenching, from above 217°C, this selenium-rich liquid may be partially retained to room temperature in an amorphous or glassy state. The intermetallic BizSe3 is rhombohedral, of the space group jm;' however, for convenience it is usually represented by a hexagonal struture. A pronounced plane of cleavage, which lies perpendicular to the main axis of the rhombohedral unit cell or parallel to the basal plane of the hexagonal cell, exists in the structure. The usual monotectic reaction product consists of rod-like particles of LII embedded in a single-crystal matrix of BizSe3, although at certain crystallographic orientations of the matrix BizSe3 other more complex shapes are assumed by LII. A similar rod-like, or cylindrical, morphology for the carbide phase has been reported by westbrook7 in the a Cr-Crz3Ce eutectic structure. In this paper the morphological characteristics of the LII particles, as retained to room temperature, have been examined under conditions of varying growth rate and crystallographic orientation of the matrix BizSe3 with respect to the growth direction. EXPERIMENTAL PROCEDURE Alloy specimens corresponding to the monotectic composition, 72 at. pct, or 50 w pct Se, were prepared from 99.999 pct pure bismuth and selenium obtained from the American Smelting and Refining Co. The two elements, corresponding to a total specimen weight of approximately 30 g, were encapsulated in 13 mm OD Vycor tubing under a vacuum of 5 x X mm of Hg. The capsules were suspended on a fine platinum wire in a Bridgman-type furnace which exhibited a temperature gradient of

Jan 1, 1963

By Robert M. Yonco, Irving Johnson, Martin G. Chasanov

The thermodynamics of the cadmium-rich portion of the Pu-Cd system has been studied with a high-temperature galvanic-cell method. The partial phase diagram of the Pu-Cd system was determined. The existence of the intermediate phases PuCd11 (cubic BaHg11 structure, ao= 9.282) and PuCd6 (cubic, CeCd6 structure, a, = 15.59) was established. The existence of at least one other intermediate phase richer in plutonium was indicated. PuCd11 was found to peritectically decompose into PuCd6 and liquid at 406" * 2°C. The solubility of plutonium in liquid cadmium may be represented by the equations: (355' to 399°C) log (at. pct Pu) = 6.223 -4282T-1 (399° to 632°C) log (al. pct Pu) - 5.148 - 5277T-1 > 1.156 x 106 T-2 The free energy of formation values (kcal per mole) of the two intermetallic phases are given by the equations: (PuCd11), ?Gf= -45.9 + 35.7 x 10-3 T (PuCd6), ?Gf0- -39.27 + 25.86 X 10-3T The excess free energy (kcal per mole) of plutonium in liquid cadmium may be represented by the equation: -(-16.72 * 29.54 NPu) 10-3T in which Npu and Ned are the atom fractions of plutonium and cadmium. The thermodyanamics of the U- Cd and Pu-Cd systems are compared. THERMODYNAMIC information on systems of the actinide metals with low-melting metals, such as zinc and cadmium, is useful in the design of pyro-metallurgical processes for the purification of nuclear reactor fuels. The thermodynamics of the Pu-Zn,1 Th-Zn.2,3 U-Zn,4-5 and U-Cd6 systems have been reported. The present report on the Pu-Cd system concerns the liquidus composition in the cadmium-rich region, the characterization of the two most cadmium-rich intermetallic phases, and the thermodynamic properties of these intermetallic phases and dilute liquid solutions of plutonium in cadmium. EXPERIMENTAL Phase Studies. The liquidus composition was determined by analysis of filtered samples of the liquid phase withdrawn at a series of temperatures. The apparatus and procedure were identical to that used in the previous study of the Pu-Zn system.' Briefly. a sample of the melt was withdrawn into a tantalum tube fitted with a porous tantalum filter (30-µ pore). the entire sample dissolved in hydrochloric acid (to avoid errors due to segregation

Jan 1, 1965

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

RECENT investigations of the molybdenum-carbon alloys have been reported by Becker and Ebert1‡, Westgren and Phragmén2, T. Takei3, and H. Tutiya4. Takei3 studied the Mo-C system by employing metallographic and X-ray methods, and the other publications described the determination of the crystal structure of the molybdenum carbides. In exploring this system by a technique previously applied to the tungsten-carbon series5, the results of Takei were confirmed with two definite exceptions; i.e., first the composition of the eutectic, and second the nature of the carbon-fish intermediate phase. Consequently, a more thorough examination of the molybdenum-carbon constitution was initiated in an effort to correlate the data supplied by the microstructures, diffraction patterns and chemical analyses. METALLOGRAPHIC INVESTIGATION A briquette of molybdenum powder when heated in a carburizing atmosphere at 1500° to 1600° C. for several hours develops the carbon-rich layer shown in Fig. 1. The carburization was accomplished by placing the briquette in a carbon tube, which was heated in the hydrogen atmosphere of an alundum muffle wound with tungsten resistor. While the macrostructure indicates two distinct shells, and suggests the possibility of two carbon-rich phases, no evidence of this condition could be detected by the microscope, which revealed but one high-carbon constituent. This carbide forms next to the molybdenum as a relatively

Jan 1, 1935

By Peter R. Morris, Alan J. Heckler

THREE angles are required to specify the orientation of a crystallite with respect to a physical reference frame. The distribution of crystallite orientations in a polycrystal is thus a function of three angular variables. The most widely used experimental techniques for studying orientation in polycrystals lead directly to the pole figure representation, i.e., the distribution of the poles of certain crystallographic planes in terms of two angular variables. In recent years1-5 methods have been developed which permit determination of the (three-angle) crystallite orientation distribution from several (two-angle) pole figure distributions. In this work Roe's method has been applied to the study of orientation in hcp materials. The method is illustrated for commercial purity titanium sheet (Ti-70) which was cold rolled (65 pct reduction), annealed at 1450°F for 3 min, and air cooled. The grain shape was observed to be equiaxed after this treatment. EFFECTS OF PHYSICAL, CRYSTALLOGRAPHIC SYMMETRY In Roe's method the crystallite orientation distribution, w(?,?,F), is expanded in a series of generalized spherical harmonics 11(?,?,F) = E E E W^Zirmtye-tote-in* [l] 1=o ,,,=-I ,,=-I where { = cos 8. The set of Euler angles employed here is illustrated in Fig. 1. The axis for each rotation is denoted by a double arrowhead. The positive sense of each rotation is that of a right-handed screw advancing in the direction of the double arrowhead. The X, Y, and Z directions correspond to the rolling direction, cross direction, and normal direction, respectively. In the initial orientation (10.O), (12.O), and (00 . 1) planes are perpendicular to the X, Y, and Z directions, respectively. The IC/ rotation about the Z axis is carried out first by rotating X into X', Y into Y', and leaving 2 unchanged, i.e., Z' = Z. The 8 rotation about the Y' axis is carried out second by rotating X' into X", 2' into Z", and leaving Y' unchanged, i.e., Y" = Y'. The I$ rotation about the Z" axis is carried out last by rotating X" into X"', Y into Y"', and leaving 2" unchanged, i.e., 2"' = 2". Any specified orientation of the X'", Y'", and Z'" crystal-fixed axis system relative to the X. Y, and Z physical axes (rolling direction, transverse direction, and sheet normal direction, respectively) can be obtained by appropriate IC/, 8, and (F rotations. The Zl,, of Eq. [l] are the Jacobi polynomials, augmented by the square root of the weight function. The Zl,, are symmetric in m,n, i.e., Zl,,= Zlnm. For orthotropic physical symmetry and hexagonal crystallographic symmetry, the coefficients, W!,,, of the series are all real, W!mn = Wzfi, = Wlm~ = Wlfi~, 1 and m are even and n is restricted to 6k, where k = ...,-2,-1, 0, 1, 2, .-.. The determination of the Wlmn from pole figure data has been previously described.'~~ The Zl,, may be written in multiple angle form

Jan 1, 1970

By P. L. Hofmann

The National Waste Terminal Storage (NWTS) Program was established in 1976. The objective of this program is to develop the technology and provide the facilities for the safe, environmentally acceptable isolation of civilian- and defense-related, high-level and transuranic nuclear wastes, including spent fuel elements, for which the federal government is responsible. The principal emphasis of this program is on disposal in mined geologic repositories. Technology development in support of the NWST program includes the formulation and management of a strong basic science and engineering program to generate an appropriate data base to aid in understanding of the key geological processes and major engineering structures involved. The current status, problems, and future plans of the technology program will be summarized.

Jan 1, 1984

By Ta M. Li, John D. Wiebmer

Record high prices, burgeoning exploration programs, mine-mill openings, and plant expansions have all characterized a dramatic: resurgence of the US uranium industry in recent years. But while the bull is leading the way on the production side of the nuclear fuel cycle, there is reason for caution from the end-users' viewpoint. How fast will electrical demand grow in the years to come, and what portion of that will nuclear generators supply? How do utilities play their cards when the government holds two of the largest jokers in the deck-a policy on spent fuel reprocessing and a timetable for the fast breeder reactor? Is there a shortfall in domestic uranium supplies on the horizon?

Jan 10, 1978

By R. E. Hucko

Introduction The principal thrust of the US Department of Energy (DOE) coal preparation R&D program is to develop technology to reduce ash and sulfur content of US coals to levels where the resultant product can be formulated into a high quality solid or slurry fuel that could replace oil or natural gas in both new and retrofit applications. The coal preparation program is implemented by the Pittsburgh Energy Technology Center (PETC) and is conducted both in house and by a cross section of industrial organizations, universities, and national laboratories. Research is subdivided into three areas - coal characterization, beneficiation, and ancillary unit operations.

Jan 1, 1985

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By Duk-Won Park, Syd S. Peng

INTRODUCTION More than five years have elapsed since the first shortwall panel was installed in a US mine in 1972. By the latest count, 11 mines have tried the shortwall method on 34 panels. Potentially, the shortwall method (see Figure 1) offers the combined advantages of longwall and continuous mlning. But just like any other mining method, shortwall is not a panacea. It is only applicable under a set of stringent conditions. Coal operators at eight of the eleven mines are satisfied with shortwall mining, though there are only five mines presently producing coal from shortwall panels.

Jan 1, 1981