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By James C. M. Li

The Petch relation between the flow stress and the gain size is derived from a consideration of gain boundary sources of dislocations without the need of dislocation Pile-ups. Three mechanisms for inierpreting the yield stress: the gain boundary strength, the unpinning of Frank-Read source near a grain boundary, and the generation of dislocations from the grain boundary are compared and the condition of their equivalence is shown. The effect of the average angle of misfit of pain boundaries is found to be sma11 and so is that of the average angle of misfit of subboundaries having impurities. The effect of impurities on the ledge density in the grain boundary is treated thermodynamically and a relatwn is proposed for the variation of Petch slope with impurity activity. The effect of temperature on the Petch slope is interpreted as due to the change of ledge structure in the grain boundary. It is indicated that the effect of annealing temperature may be more important than that of the test temperature and therefore should be studied. The effect of plastic strain on the Petch analysis is deduced from a work-hardening equation in which the generation of dislocations has first-order kinetics and the annihilation of dislocations has second-order kinetics. It is concluded that the Petch slope will decrease with plustic strain if the rate of annihilation of dislocations is sufficiently large. Critical experiments which may shed light on the mechanism for the Petch relation are suggested. THE relation between the yield or flow stress, 0, and the grain size, l, was first proposed by all' and later studied more extensively by Petch and co-workers, who also proposed a similar relation for the fracture stress and deduced from these a grain-size effect of the ductile-brittle transition temperature. The microscopic mechanism used by all' and petch2 involves a pile-up of dislocations of like sign generated from a Frank-Read source. The yielding or flow takes place when the pile-up exerts sufficient stress at the grain boundary so that the plastic deformation can propagate from one grain to another. If the average strength of the grain boundary is ai and the average length of the pileup is lp, the Petch slope, k, is given by" where p is the shear modulus, b the Burgers vector, and v the Poisson ratio. This slope will be independent of the grain size if l/lp is a constant. This is possible, since, if the Frank-Reed source is situated near the grain boundary, lp = 1, and if it is situated in the middle of the grain, Ip = 1/2. cottrell,12 also using the pile-up mechanism, proposed that the stress concentration at the grain boundary will initiate Frank-Read sources near the grain boundary and in this manner a Lüders band can propagate from one grain to another. Assuming that the average distance between the Frank-Read sources and the grain boundary is 1, and the unpinning stress of the Frank-Read sources is op, Cottrell obtained the following Petch slope: This slope will be independent of the grain size if ls is independent of the same, which is not as obvious as the condition, Ip = I for Eq. [2]. In addition to this assumption, the direct relation between the Petch slope k and the unpinning stress, up, was recently questioned by Johnsonon grounds that it is inconsistent with the following observations: the independence of k with temperature and strain rate, and the small k in columbium, which, like iron, has a sharp yield point. As pointed out by ohnson," the most important objection both to the Hall-Petch mechanism, in which the strength of the grain boundary plays the role in yielding, and to the Cottrell mechanism, in which the unpinning of Frank-Read sources plays the role in yielding, is the lack of direct observation of the pile-ups. The dislocation structure in deformed iron has been examined recently in the electron microsope.'-' Dislocations appear to be generated from grain boundaries or other interfaces; they form clusters and tangles within the grain at very early stages of deformation, even in the Lüders band, if the deformation is slow or at normal and elevated temperatures. Although it is still too early to interpret bulk properties from thin-film observations, it does seem worthwhile to look for a mechanism for the Petch relation which does not require dislocation pileup. SUBBOUNDARY SOURCES In order to show that a consideration of grain boundary sources can lead to the same Petch relation as does the consideration of the strength of the grain boundary, we shall first discuss the case of a simple tilt boundary whose elastic properties have been studied in detail.17 The strength of a partially

Jan 1, 1963

By J. H. Schulman, M. H. Buckenham

Although much interest has been taken in the use of mixed collectors in flotation, this investigation is probably the first in which oppositely charged collectors have been considered. The results obtained and the techniques used could well be applied in the behavior of other mixe the behavior of other mixed collector systems and could possibly explain the effective flotation results which have been reported when various collector combinations have been used. Collectors conventionally employed in flotation systems are soluble in water, but many of their homologs of longer hydrocarbon chain length are insoluble. The properties and behavior of these insoluble compounds may be conveniently studied when they are spread as monolayers at the air/water interface on the Langmuir-Adam trough. Although some extrapolation is involved in applying effects observed at this interface to the solid/liquid interface where the action of collectors is most important in flotation, the technique nevertheless is most useful for the study and interpretation of flotation phenomena. Of particular interest in this field are investigations on the insoluble monolayers of the fatty acids, alkyl sulfates and alkyl amines; the penetration of these insoluble monolayers by soluble surface active components and their interaction with metal ions from the underlying solution.'-' Unfortunately, the insoluble xanthates and related compounds do not exhibit stable monolayer properties due to rapid oxidation at the air/water interface and, therefore, cannot be studied directly in this way. These approaches have enabled Leja and Schulman8 to suggest mechanisms explaining dynamic attachment of mineral particles to air bubbles involving collector-frother interaction and the adsorption of collectors onto mineral surfaces. In this and other papers 9-12 considerable evidence is presented to support the concept of collector-frother and metal ion-monolayer interaction and to emphasize the value of monolayer techniques in elucidating the flotation system. Molecular interactions resulting from monolayer penetration are determined by the nature of and the association between both the polar and nonpolar groups of the two molecules concerned. Stable complexes are formed on penetration when interaction takes place between both the polar and nonpolar groups, and although the resultant complexes are not necessarily true chemical compounds, the properties of the molecularly associated complexes are very different from those of the individual components. Shortening of, or changes from, a straight hydrocarbon chain in one of the reacting molecules reduces considerably the stability of the associated complex as do changes in temperature, pH and substrate composition. The effect of hydrocarbon chain length becomes most important when observed effects are to be applied in flotation studies where soluble homo-logs and, therefore, much shorter hydrocarbon chain lengths are used. The present investigation is based on Langmuir trough work carried out by Bowcott,l3 who studied the penetration of insoluble amine monolayers by potassium lauryl xanthate. Bowcott observed that cetyl amine monolayers were readily penetrated by xanthate, but found that with time the high film pressures resulting from penetration and association fell off, indicating decomposition and ejection of xanthate from the film. This decomposition was pH dependent. Of particular interest in this work were studies on an equimolecular mixed monolayer of the fully N-substituted ammonium compound, for example, cetyl trimethyl ammonium iodide (CTAI) and potassium cetyl xanthate. Despite the fact that the CTAI is water soluble and the xanthate on its own is incapable of forming a monolayer, the mixed film was stable up to a surface pressure of 67 dynes per cm. In this condensed state the xanthate was stabilized against atmospheric oxidation, although iodine injected beneath the film caused an immediate collapse. The stabilizing of xanthate against oxidation by association with an alkyl trimethyl ammonium bromide (TAB) could be important in flotation, and a study of the performance and behavior of mixed collectors therefore was undertaken. A modified Hallimond tube operated under controlled conditions was used to evaluate flotation. Surface tension measurements were made to investigate the properties of the soluble

Jan 1, 1963

By Harry M. Mikami, A. Gene Sidler

Chemistry of the evolution of materials in contact with copper converter tuyeres is delineated by means of analyses of periodic punch rod samples taken during a converter cycle. Lining samples from known peripheral and end locations from three converters were investigated chemically and petrographically. One set of eight specimens representative of all lining parts was removed for study before completion of the campaign. Purely surface removal by slag action is minor. Slag filling of interconnecting cracks extending to the hot face results in a "stoping'' action which shapes the hot face contour and is a significant factor. Major wear mechanism is believed to be copper metal slabbbing caused by metal first penetrating joins and invading fractures or impregnating brick structure laterally from the joints. Importance of lining design and joint fit are emphasized. New laboratory tests are indicated. In the copper converter, molten matte, which is essentially a solution of iron and copper sulfides, is blown with air to produce blister copper. During the first stage of the process the FeS component is oxidized to SOz and FeO, the latter combining with a siliceous flux to form a predominantly ferrous silicate slag. Successive increments of matte and flux are charged, blown, and skimmed of slag until sufficient CuzS ("white metal") has accumulated. This white metal is then blown to copper metal in the final or blister-forming stage by the oxidation of sulfur to SOz and the reduction of combined copper to metal. The reactions of both stages are exothermic so provide the required heat. Temperature is controlled by cold scrap copper, flue dusts, smelter reverts, and so forth. Considerable vari- ation in practices occur depending on the type of converter, grades of the matte and flu, and other factors. Lathe and Hodnett's' survey of world converter practices gives much information on these variations and their effects on the refractories. Principles of converting chemistry are presented by Newton and wilson,' Ruddle,' and schuhmann. Most copper converting occurs within the temperature range 2100" to 2370°F although individual smelters report1 ranges from as low as 1700" to 2240°F to a high of 2200" to 2400°F. Temperature intervals reported from beginning to end of blow varied from 45" to 540°F. Average temperature range was 2030" to 2260°F and the average interval 250°F During the matte-blowing stage varying amounts of magnetite (FeO.Fe,O,) are formed in the slag as suspended crystals and also the liquid portion of the slag will contain, in addition to ferrous silicate, some Fe20s which adds to the potential magnetite formation if the temperature falls. This is a component of the so-called "dissolved magnetite" often referred to in the literature. Although the slag may contain minor amounts of CaO, A1209, MgO, and alkalies, the principal components are Fe0-Fez03-SiO,. The phase equilibria relationships of this system have been elucidated by Muan~ and Schuhmann, et a1.' These data and estimates of converting atmospheres by schuhmann4 are useful tools in studying slag behavior. It would appear that in many cases reported magnetite contents of slags are apparently higher than actually is present at operating temperature. This is probably because much of it is formed during slag solidification. The quaternary systems which have Mg-0,1,0,' and addition to iron oxides and silica are also of interest in considering the reactions of the slags with basic refractories. The formation of magnetite has an important interrelationship throughout the pyrometallurgy of copper (Mossman,' Gronningsater and Drummond," Ruddle,' Elwood and Henderson") but its presence in the converter particularly relates to operating efficiency and lining life in certain instances. Archi-

Jan 1, 1963

By M. E. Wadsworth, J. S. Cho

Colloidal silica dissolved in aqueous suspensions of high surface area thoria was permitted to adsorb on the thoria surface. Silica in three forms was identified by means of infrared spectroscopy and characterized by Si-O vibrational modes in the 9.0 to 10.5 region. A band at 9. 1 was attributed to free unad-sorbed silica, while adsorbed silica resulted in bands of greatest absorbency at 9.4 or 10.3p, depending upon the character of the surface bonding. Size considerations, the amount of silica adsorbed, and the character of the infrared spectrum for strongly adsorbed silica has been interpreted as evidence of formation of chain or layer silica linkages on the thoria surface. Infrared spectroscopy has been used successfully in recent years for the identification of minerals and synthetic inorganic substances. Unfortunately, infrared studies of silicate minerals have not proceeded to the point that unambiguous assignments may be made for Si-O vibrational modes as affected by lattice substitutions and structures. Several investigators have presented infrared spectra of silicate minerals, 1,7 and their work has pointed to the potential value of infrared to identify minerals as well as to note the sensitivity of various Si-O modes to structural and substitutional environments. The strong infrared absorption of various Si-O vibrational modes makes the infrared method a very useful tool for the study of silica adsorbed on the surface of solids of high surface area. Spaepen et a18 studied the adsorption of silica on thoria surfaces from aqueous solutions of silicic acid up to 300°C. A general review of the application of the infrared method to the study of surface adsorption has been presented by Pliskin and Eischens.9 EXPERIMENTAL Du Pont colloidal silica, Ludox SM (16.36% SiO2) and Ludox HS (30.25% SiO2) in aqueous suspensions were used as the sources of silica for the adsorption studies. The thoria used for this study was supplied by Union Carbide Nuclear Co.* under the preparation *Chemical Technology Div., Union Carbide Nuclear Co., Oak Ridge, Tenn. . number D-16-650. It was fired from the oxalate at 650°C and had a surface area of 32.4 ± 0.6 m2 per g measured by nitrogen adsorption. The chemical analysis of the D-16 thoria in ppm was: CO3= (5500), NO3- (< 4), so4±PO4 (100), and Si (20). The Ludox silica was placed in contact with the thoria in a two-liter autoclave10 between room temperature and 250°C. Slurries were made by placing 1 g of thoria in one liter of distilled water containing various additions of the silica sol. Samples were removed from the autoclave by opening a small stainless steel valve. Extracted samples were centrifuged for 10 min and excess solution was decanted. The sample was then dried for several hours at 80°C. Infrared samples were prepared by thoroughly mixing 10 mg of the thoria with 400 mg KBr in polystyrene vials on a "Wig-L-Bug" amalgamator. Pellets were pressed under vacuum and had final dimensions of 1.2 cm diam and 1.2 mm thick. Infrared spectra were

Jan 1, 1963

By H. H. Hausner, O. V. Roman, F. V. Lenel, G. S. Ansell

The radial shrinkage during sintering of cylindrical compacts and loose aggregates of copper powder was measured. It was found to be nonuni-form from top to bottom of the samples and to depend upon the method of supporting them. The non-uniformity is due to the effect of gravity forces during sintering. Since gravity has an effect in sintering without externally applied stresses, no sharp dividing line can be drawn between conventional sintering and hot pressing. RECENT investigations of the sintering behavior of compacts1 and of loose powder aggregates2 have indicated that forces, other than those arising from surface tension effects, may play a role in shrinkage. In compacts it was shown that residual stresses from the pressing operation influence shrinkage behavior. In loose powder aggregates gravity forces due to the weight of the powder affect the ratio of shrinkage in the vertical and the horizontal direction. The main effort in the work reported here was to show that gravity plays a role also in the sintering of compacts. A few additional experiments were made confirming the effect of gravity in the sintering of loose powder aggregates. EXPERIMENTAL PROCEDURE Compacts and loose powder aggregates were prepared from irregularly shaped, electrolytic copper powder. Prior to use the powders were reduced 30 min at 400°C in dry hydrogen to remove surface oxides. Then the -325 mesh size fraction was separated from the -100 + 325 mesh fraction. The compacts were pressed at a pressure of 10,000 psi from 50 g of powder in a hardened steel die, 1 in. in diam. The height of the compacts was 0.725 i 0.005 in. An effort was made to get as uniform a green density distribution in the compacts as possible. The walls of the die were lubricated with a suspension of 3 pct of zinc stearate in acetone and the compacts were pressed using double action by first pressing the powder at 1200 psi with the die barrel supported, then removing the sup- ports and pressing to final pressure of 10,000 psi with the die barrel floating. The pressure was maintained for 10 sec. The compacts were sintered at a temperature of 925°C, generally for 1 hr. In order to maintain uniform temperature they were sintered in boats made from cylindrical copper blocks. The blocks were 2 in. in diam, either 2 or 2 1/2 in. long and, split to form the body of the boat and a lid. The body of the boat contained a cavity 1 3/8 in. wide, 1 in. deep and either 2 1/8 or 1 3/8 in. long. The longer cavity accomodated two samples, the shorter one only one sample. The uniformity of temperature distribution within the boats was checked with thermocouples welded to the top and bottom of the samples. The maximum variation between top and bottom temperatures was i 1/2°C. The actual sintering temperature was held constant within ±2°C. In order to determine the effect of gravity forces, i.e., the weight of the compacts, upon shrinkage, they were supported in the following ways during sintering: a) Full Bottom Support. The compacts rested either on a flat alundum disk or on alundum powders. b) Partial Bottom Support. The compacts rested on a graphite cylinder, 0.3 in. in diam which formed a projection on a larger graphite disk. It is difficult to balance the compact on the small projection. To avoid having the compact tip, a small hole was drilled through the compact and through the graphite disk and its projection. The graphite disk was then suspended from the lid of the boat by a thin iron wire which passed through the holes in the disk and the compact. c) Top Support, first type. A hole 3/32 in. in diam was drilled diametrically through the green compact 3/16 in. from the top of the compact. The compact was sintered suspended from an alundum rod (thermocouple protection sleeve) inserted into the hole. d) Top Support, second type. A hole was drilled axially through the center of the compact. The upper part of the hole from the top surface of the compact one fourth of the way down was 1/16 in. in diam; the lower part of the hole from the bottom surface three fourth of the way up was 3/32 in. in diam. The compact was suspended from the lid of the boat by an iron wire passing through the upper part of the hole and then tied into a knot. The loose powder aggregates were made by filling l in. deep, l in. diam cylindrical graphite molds with -325 mesh powder. To achieve uniform density in all the loose powder aggregates, the powders were settled in the molds by placing the

Jan 1, 1963

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).&apos; 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;&apos; 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 Dol Duwez, R. H. Willens

A technique is described by which metastable alloy phases can be obtained by very rapid cooling from the liquid state. The results obtained so far have lead to; 1) extension of solubility limits beyond their equilibrium values, 2) new phases not found under equilibrium conditions, and 3) amorphous alloys. MANY new nonequilibrium phases have been found in alloys rapidly cooled from the liquid state. The technique used in these investigations essentially consisted of propelling a small molten globule of an alloy against the inside surface of a rotating copper cylinder. Since these original experiments were performed, the technique has been greatly improved. The purpose of this paper is to describe in detail, for the first time, a simple and efficient apparatus for producing foils of alloys which are rapidly cooled from the melt and to summarize some of the observations made on these alloys. I) FAST COOLING APPARATUS In the original fast cooling apparatus used by Duwez, Willens, and Klement,&apos; the alloy was melted in a graphite container having the shape shown schematically in Fig. 1. A shock tube was attached to one end of the graphite part to supply the pressure for ejecting the molten globule. The globule was received on the inside of a rotating cylinder located about 0.5 in. from the exit of the graphite container. The globule trajectory made an angle of about 15 to 25 deg with the tangent to the cylinder at the point of

Jan 1, 1963

By A. S. Appleton, M. B. Bever

The stored and expended energies of an Au-Ag alloy deformed in torsion were investigated as functions of strain, strain rate, and temperature. At room temperature, the stored energy, measured by tin solution calorimetry, increased linearly up to an intermediate strain, above which it was nearly constant; at 78 °K the relation was linear up to fracture. Approximate values of the energy stored at 4 OK indicate a rapid increase below 78 OK. The energy stored by specimens deformed successively at 4o and 78oK changed slowly with increasing second strain from the curve for energy stored at 4 OK (measured after annealing at 78oK) to that for deformation at 78°K. The ratios of the stored to the expended energy at room temperature and 78 oK were unusually large. The additional amount of energy stored at the lower temperature is attributed mainly to an increase in the number and energy of dislocations. The stored energy as a function of strain rate at 4oK (measured after annealing at 78oK) increased to a sharp maximum over a narrow range of strain rates, whereas the expended energy changed only slightly. These effects are explained by the generation of point defects resulting from the enforced nonconservative movement of jogs in fast moving screw dislocations. The effect of straining successively at two strain rates at 4oK was also investigated. Stress-strain curves for 4o, 78oK, and room temperature and the results of micro examination of specimens deformed at these temperatures are also reported. THIS investigation is a continuation of a research program primarily concerned with the effects of variables on the energy relations involved in the deformation of metals. The variables investigated in earlier work have included strain, strain rate, temperature of deformation (room temperature and 78oK), and the type of deformation process. Most of this work has been carried out with Au-Ag alloys. In the investigation reported here, the deformation process was torsion, which had not been used previously in the program. The stored and expended energies involved in the deformation process were measured as functions of strain, strain rate and the temperature of deformation in the range 4" to 373" K. The microhardness and microstructure of deformed specimens were also investigated. The relation between stored energy and strain differs for different deformation processes.1,2 In general, the stored energy increases with strain and may attain a nearly constant value at large strains. This value and the rate at which it is reached, however, depend on the process of deformation. This dependence has been attributed, at least in part, to differences in the effective strain rate and rise in temperature of the specimen during deformation. The effects of the temperature of deformation on both the stored energy and the energy expended in the working process have been the subject of only a few investigations.3-6 Values of these quantities at low temperatures are of special interest as they yield information on point defects which, for many metals, is not obtainable at higher temperatures. The effect of the strain rate on the stored and expended energies has received little attention The strain rate has usually been measured only in relative terms, and hence the interpretation of its effect on the stored energy has been mainly comparative.

Jan 1, 1963

By Richard H. Rein, John Chipman

Liquid slags of the system SiO2-Ca0-MgO-A1~03 were equilibrated with liquid Fe-Si-C alloys in graphite or Sic crucibles at 1600°C in pure CO gas at atmospheric pressure, and the silicon content of both phases determined. Ternary slugs of the systern SiO2-CaO-A12O3 were also studied at 1550°C. The silicon content of the metal phase saturated with both graphite and SIC is 22.0pct at 1550°C and In the iron blast furnace, as in nearly all carbon-reduction processes, some silicon is transferred from slag to metal. The importance of this reaction is enhanced by its indirect effect on the transfer of sulfur from metal to slag, and this has stimulated a comprehensive research program on the equilibrium distribution of silicon between slag and metal. Earlier studies&apos;-3 of this same problem provided data for calculation of the thermodynamic activities4 of the components in SiO,-CaO-A1,O3 slags. 22.4 pct at 1600°C. The temperature at which the phases cristobalite, gvaphite, $ SiC, liquid slag, Fe-Si-C alloy, and CO gas at 1 atm pressure can coexist in equilibrium was found to be 1533°C. The results agree well with earlier studies. They are shown graphically as lines of constant silicon cmtent in the metal which also are lines of constant SiO, activity in the slag.

Jan 1, 1963

By F. F. Schmidt, H. R. Ogden, E. S. Bartlett

ThE solubility of carbon in tantalum has been reported to be very low at temperatures below 1500 C,1&apos;2 increasing to at least 0.02 wt pctl at the eutectic temperature of 2800°C. The solubility limits at low temperatures were based on metallo-

Jan 1, 1963

By E. B. Johnson

Cleveland-Cliffs lron Co., which operates Marquette lron Mining Co.&apos;s Republic mine, conducted a test whereby 35,000 tons of self-fluxed pellets were produced in the grate-kiln system from specular hematite flotation concentrates. A brief description of the pelletizing plant is presented along with pertinent operating details. Date is included which compare operating conditions and the chemical and physical properties of the green and fired pellets for the self-fluxing pelletizing test with the normal acid pelletizing operation. The success of self-fluxed sinter in enhancing the operation of the blast furnace during the past few years has reasonably led to the assumption that the use of self-fluxed pellets might result in even greater furnace efficiencies. A great share of development work in agglomeration has been directed towards techniques related to the production of self-fluxed pellets, but only a limited tonnage of self-fluxed pellets had been produced on a commercial scale until this past year when The Cleveland-Cliffs Iron Co. produced 35,000 tons of such pellets by the grate kiln system at the Republic mine during the period May 21-June 5, 1962. REPUBLIC&apos;S GRATE-KILN PLANT The grate-kiln pelletizing process consists of four stages, namely: feed or balling circuit, traveling grate, rotary kiln and annular cooler (Fig. 1). The balling section is conventional and utilizes four 9x30-ft balling drums in closed circuit with 5x14-ft vibrating screens having 3/8-in. rod decks. The traveling grate is 12 ft wide by 126 ft long and has 14 windboxes — six in the drying section and eight in the preheat section. The rotary kiln is 15 ft ID shell and 114 ft long. The annular cooler is 40 ft in diameter and has 12 windboxes. The cooler is divided into two zones by a moveable curtain wall. The high temperature air from the first zone is used as secondary combustion air in the kiln. Normally the only heat supplied is through the burning of No. 6 oil in the single kiln burner. Hot gases pass counter to the pellet flow through the system. The exit gases from the kiln pass down draft through the preheat section through cyclones and are drawn through the drying bed prior to exiting via the stack. The temperatures are normally held within the following ranges: Kiln 2400-2445 °F Preheat 1850-1950°F Drying 480-520°F Exit gas 200°F Pellets 120°F The design capacity of the Republic mine grate-kiln system was 2500 Itpd. Sustained production in excess of 35% over design capacity has been achieved. No screening of the cooler product is practiced. PELLETIZING TEST CONDITIONS When a decision was made to proceed with a test at the Republic mine pelletizing plant to produce 35,000 tons of self-fluxed pellets, several potential failure factors had to be carefully considered. Research work on a batch and pilot plant scale indicated that the grate-kiln system at Republic would require some major changes in order to obtain optimum conditions. In many cases compromises were agreed upon as major equipment changes and revisions were not feasible. The pelletizing conditions which laboratory development tests revealed were required in order to insure successful production of self-fluxed pellets were: 1) Good mixing of limestone and concentrate and proper moisture control; 2) Higher gas flow rates in the preheat section than are normally used; 3) Higher preheat temperatures than normal; 4) Maximum kiln temperature 2350°F. There was just cause for concern about balling problems that might occur. Approximately 10% of dry pulverized limestone was to be added to the specular hematite concentrate just ahead of the Pekay mixers on the belt feeding the balling drum. Large scale

Jan 1, 1963

By D. Hugh Trollope, L. A. Fekete

L.A. Fekete (Project Engineer, Johnson B & Assoc. Engineers, Houston.) - The author tries to classify rock slopes in: a) homogeneous monolith, b) random, c) block-jointed systems. This may be practical at a specific mine, but it does not describe the mechanical behavior of the slopes in general. The difficulty with the problems of earth mechanics is the same, as with other structural problems: To

Jan 1, 1963

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

By E. J. Harris

Mathematical solutions to complex mine ventilation problems are possible, but often the airway network is so complex that the mathematical solution becomes tedious and impractical. A fluid network analyzer, designed and built for analyzing mine ventilation problems has been in service at the Bureau of Mines&apos; Pittsburgh station for approximately nine years. Using this analogue as a model, the mine ventilation network is simulated electrically by a combination of series and parallel circruits laid out to conform with actual mine airways. A tungsten filament lamp, referred to as a Fluistor, is used to simulate mine airway resistance. With the analogue ventilation model established, voltages of the proper amplitude to represent ventilating pressures are impressed across the circuit at points where mine fans and airshafts are located. Comparison of mathematical solutions of complex systems against analogue results showed a maximum variance of 3% for pressures and 2% for quantities. An electrical fluid network analyzer, designed and built especially for analyzing mine ventilation distribution problems, has been in service at the Bureau of Mines, Pittsburgh, for approximately nine years. It is a nonlinear, low voltage, fluid network analyzer of the type developed by the late Malcolm S. McIlroy, Professor of Electrical Engineering, Cornell University, who cooperated with G. E. McElroy, of the Bureau of Mines, in adapting the instrument to mine ventilation systems. Several modifications have been made since the original installation, but a considerable part of this paper is drawn from G. E. McElroy&apos;s original description of the analogue.&apos; The analysis of water or gas distribution systems2,3 led to the development of this type of network analyzer. Several similar units are now employed by utility companies for this purpose; however, the Bureau of Mines unit is the only one designed specifically for mine airflow problems. Other airflow analogues employing a similar principle have been used at the Central Research Station of the Netherlands State Mines,4 in England,5 and in South Africa.6 Information on these devices indicated they were somewhat inflexible because commercial lamps with a sufficient range of resistance are difficult to obtain. Computers for mine ventilation analysis have been developed in Germany which instead of lamps use a variable resistance to adjust for turbulent flow laws. These units are expensive, but excellent results have been reported in their application. THE ANALYZER Theory of Application: As airflow generally follows the law of turbulent fluid flow, resistance to flow is nonlinear; consequently, the problem has been to find a nonlinear resistance element of suitable range that can be used for electrically simulated airflow. Tungsten filament lamps operated on alternating or direct current approximate the square-law resistance characteristics of mine airflow over a large range below maximum or rated voltage; that is, the voltage drop varies approximately as the square of the current. Consequently, the heart of the network analyzer is a nonlinear resistor known as a Fluistor, which is simply a custom-made low voltage, tungsten filament lamp that is available in a progressive series of relative resistance values ranging from 0.05 to 500 in nominal 5% steps. However, variations in manufacturing large groups result in differences of 1 to 3%, but series arrangements required for high-loss branches can be matched within about 1%. Utilizing a combination of Fluistors and load circuits, the mine ventilation system is duplicated electrically. Intake load circuits are connected from power intake to primary points of the circuit network; segments of unregulated flow along intakes and returns are represented by Fluistors, regulated splits and leakage paths are represented by load circuits and Fluistors of proper capacity; and mine exhausts are connected to ground from the last point of the network to complete the circuit. For the special purpose of representing booster fans or natural draft conditions, boosters or separate source circuits are provided that can be inserted between any two points of a network to increase voltage to the required value. Physical Layout: The analyzer consists of three 42

Jan 1, 1963

By Chester T. Sims

RECENTLY, a new type of superalloy material called TD Nickel* has been marketed.&apos; It is a sim- ple, two-phased alloy, consisting of thoria particles dispersed in nickel of rather high purity (Ni-2 pct Thoz). Its mechanical properties appear relatively superior to previous experimental material attempting to use the oxide nonmetallic dispersion concept (except SAP), and superior to conventional nickel-base alloys at high homologous temperatures. This is derived from an interesting method of creating the dispersion, arising during chemical processing of the nickel and thorium salts in solution while reducing the nickel to metal. An evaluation of the thoria phase was conducted at this laboratory. Material and Procedure. TD Nickel was made available, consisting of several inches of 0.470-in. rod, extruded at a ratio of 64: 1, straightened, and centerless ground. Property determinations on this rod by the supplier at 1800°F showed an ultimate tensile strength of 11,400 psi, yield strength of 9600 psi, and 6 pct elongation. Specimens were removed from the rod for as-extruded metallography, and two 1/2-in. lengths supported on high-purity Al2O9 bricks were placed in a laboratory muffle furnace for exposure at 2000° F. The furnace door was left cracked to allow a slight amount of circulation. One specimen was removed at 200 hr for examination; the other was left for 2000 hr. Metallography. The micro structures obtained for the three conditions of exposure are shown in Fig. 1. Elongation of the grain structure in the extrusion direction is readily evident. The grains appear to be up to 0.001 in. (0.003 cm) long, with a length/width ratio of about 10: 1. Allowing for modest local in-homogeneities in structure, no significant change in thoria particle size or nickel alloy grain size occurred during the 2000°F exposure. However, etching depth varies slightly from one specimen to another, changing the number of particles visible. The thoria dispersion appears to be in the order of 0.01 (min) to 0.5 (max) p diam. The minimum diameter is difficult to estimate at X10,000, and may be less. Interparticle spacing appears to be about 0.1 p. Etching effects can be seen, depending upon grain orientation. A cubic etch-pit pattern appears in certain grains, apparently when etching is started by an anodic particle of thoria, Fig. l(c). The cubic pattern appears related to crystallographic orientation, and is prominent when the [ l00 ] direction is perpendicular to the plane of polish. The grains which present a ridged appearance in the photograph appear to be oriented with the [110} direction perpendicular to the plane of polish. Analysis. The thoria particle size was measured by a line intercept method perpendicular to the extrusion direction. Only particle sizes measuring 0.001 in. at X10,000 or larger could be extimated. Within limits of experimental error, particle size distribution appears to be unaffected by exposure, Fig. 2. To check structural stability further, a grain-growth evaluation was made. The number of grain-boundary intersections was counted at X500 on each of several traces normal to the extrusion direction for each condition. It can be seen from Table I that grain diameter appears unchanged by the 2000°F exposure. The slightly finer grain diameter after 200 hr may be attributed to variations in grain size from area to area in the original extrusion. From the present rather limited study of Ni-2 Th on, it appears that: 1) for time-temperature exposure up to 2000 hr at 2000°F (Larsen-Miller parameter = 57, homologous temperature = 0.8) thoria particles of the size studied are highly thermally stable; they do not significantly react, agglomerate, or diffuse; and

Jan 1, 1963

By J. A. Harrison

The physical composition of coal and the distribution of its physical constituents will partially determine the efficiency of the process chosen for coal preparation. Distribution and concentration of coal macerals will, to a degree, be controlled by preparation processes. A number of preparation processes have been evaluated to determine this interrelation. These evaluations will help provide information needed for the production of coal that meets definite petrographic composition specifications. etrographic composition and degree of coalifica-tion of coal can determine the choice of cleaning processes and equipment used in coal preparation. The purpose of this paper is to present data on studies of the preparation processes of breakage, sizing, cleaning, and blending and to show the effect coal&apos;s petrographic composition has on these processes. Herrin (No. 6) and Danville (No. 7) Coals from Illinois were used in these tests. Nomenclature used herein is that approved in the Glossary of the International Committee for Coal Petrology,&apos; based primarily on the Stopes-Heerlen system of classification2 and used in coal petrography laboratories throughout the world. BREAKAGE TESTS Breakage tests of Illinois coals related to petrographic composition have been conducted at various times at the Illinois State Geological Survey. These tests have been classified under two headings -impact tests and compression tests. Impact tests, as the name implies, consisted of breaking the coal by a sharp, sudden force. Impact tests were further divided into fall tests and block tests. Compression tests consisted of applying a constant pressure on a piece of coal until the coal fractured.

Jan 1, 1963

By E. F. Bradley, R. I. Jaffee, H. R. Ogden, E. S. Bartlett, D. N. Williams

The mechanical properties of solid-solution-strengthened columbium alloys have been assessed as a function of alloying additions. Studies included the effects of tungsten, tantalum, molybdenum, and vanadium. Elevated temperature fabrication was required at alloying levels above about 15 pct W or 10 pct Mo. Tungsten, molybdenum, and vanadium additions increase tensile strength at room temperature and 2200°F, but tantalum additions exert little strengthening. Similarly, tungsten, molybdenum, and probably vanadium additions increase the ductile-to-brittle transition temperature, and tantalum additions decrease this parameter. The 2200°F stress-rupture strength is increased by tungsten and molybdenum additions; with 20 to 25 at. pct additions, 100-hr rupture strengths of 30,000 psi are obtainable. Small vanadium additions exhibit mild stress-rupture strengthening, and tantalum additions are innocuous. At 2500°F, tungsten additions retain stress-rutpure strengthening capability, but molybdenum additions are much less effective. Tantalum additions augment the stress-rupture strengthening of tungsten plus molybdenum additions at 2500°F. Of the refractory metals, columbium possesses specific potential for structural use in the temperature range from 2000" to about 2500°F. Desirable features of columbium are its good low-temperature ductility, ease of fabrication, oxidation mechanics (lack of a volatile oxide at moderate temperatures), good availability and reserves, and relatively low density. However, alloying is required to provide attractive strength at elevated temperatures. Published information concerning alloying be- havior of columbium relative to mechanical properties is sketchy, particularly in consideration for long-time applications at temperatures in excess of 2000°F. Only a few stress-rupture data at temperatures from 2000" to 2500°F have been reported;&apos;-&apos; these are too meager to allow rationalization of the effects of various alloying additions on creep or stress-rupture properties. Additional published data do, however, give some insight toward understanding of systematic alloying behavior for columbium relative to low-temperature strength4-&apos; and ductility,&apos; and elevated temperature tensile behavior.4,6 This paper is intended to augment previous knowledge, and to promote understanding of the alloying behavior of columbium for long-time structural service at elevated temperature. BASIC CONSIDERATIONS Solid-solution strengthening is recognized to be of prime importance in improving strength in columbium-base alloys. Other strengthening mechanisms may be (and are, in current alloys) used to augment solid-solution strengthening. As strengthening results primarily from lattice distortion, the strengthening effectiveness per atom depends upon atomic size mismatch between solvent and solute. Another factor in this regard is conformance to ideal solution behavior in the solid solution. Thus, for example, despite appreciable differences in the degree of mismatch between tungsten (5 pct), molybdenum (5 1/2 pct), and vanadium (7 1/2 pct) in solution in columbium, all are about equally effective in straining the columbium lattice at room temperature.&apos;-&apos; Similarly, tantalum additions do not strain the columbium lattice, and little strengthening is expected. Size effects being equal, maximum solution strengthening at high temperatures is anticipated to result from the addition of elements that increase the melting temperature of columbium. This expectation is based on an increase in the electronic bonding forces exhibited in the transition metal series as electronic structures approach those of the Group Vl metals. Of the metals that exhibit ex-

Jan 1, 1963

By D. T. Novick, M. B. Bever, B. Roessler

Ordered and disordered specimens of the alloy CusAu were cold worked and then annealed at 2880, 310°, and 340°C, together with disordered unworked specimens. me resistivity decreased during annealing mainly as a result of ordering; the resistivity measurements suggest that in cold-worked specimens the growth of antiphase domains is impeded. The strength properties increased during annealing at 288 "C; in cold-worked specimens this increase was lo a level above that for cold-worked specimens which had not been annealed. X-ray diffraction showed that after annealing for a few hours at 288ºC, the long-range order increased to a constant value; additional annealing at 288ºC resulted in the growth of antiphase domains in which the degree of order was constant. Changes in peak breadth and particle size confirmed that in cold-worked specimens the major effects of cold work were not eliminated during annealing at 288 "C, although a slight recovery process occurred. When a specimen of the alloy Cu3Au is heated to a temperature below the critical temperature (388ºC), long-range ordering tends to occur in a specimen containing less than the equilibrium amount of order characteristic of that temperature Ideally, a specimen of Cu3Au contains no long-range order if it has been quenched from above the critical temperature. Long-range order is reduced by cold work. If cold-worked specimens are heated, restoration processes such as recovery and recrystallization may occur,

Jan 1, 1963

By J. F. Pierce, S. M. Enterline

Since January 1959 a zinc refiner of novel design has been in operation at Blackwell, Okla., producing 99.995+ zinc from the output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyro-metallurgical unit with principal dimensions horizonhl permitting one floor operation. It is very ruggedly constructed. Furthermore it is not subjected to deterioration from high concentrations of iron in the feed metal because the boiling units are separate from the rectification columns and constructed with silicon carbide brick arches through which the heat is transferred radiantly to the zinc. A zinc refiner of novel design has been in operation since January 1959 at the Blackwell, Okla. plant of the Blackwell Zinc Co., Inc., a wholly owned subsidiary of American Metal Climax, Inc. Developed by the company&apos;s technical and operating staffs, the new refiner produces special high-grade zinc (nominally 99.995+ pct Zn) from the prime western1 slab output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyromet-allurgical, high-capacity unit employing fractional distillation to separate zinc from its impurities, consisting principally of lead, cadmium, and iron. In prime western slab, these elements may vary in concentration from 0.005 to 1.6 pct. Table I shows the impurities usually encountered in the Blackwell prime western metal fed to the refiner together with their boiling points and vapor pressures at 907oC. The commercial pyrometallurgical smelting processes for extracting zinc from ore include distillation from retorts and a limited degree of refining can be accomplished by redistillation in similar retorts. To achieve special high-grade purity, an impractical number of batch redistillations would be required, however, with an accompanying loss of much metal. A continuously operated and integrated unit is required in which fractional vaporization and condensation can take place in a large number of stages. The first commercial continuously operated unit was developed by the New Jersey Zinc Co.4 In the separation of any two substances the degree of separation is limited if a mixture exists having a constant boiling point. The Zn-cd5 and Zn-pb6 systems contain no constant boiling points and hence these metals may be separated to any degree of purity. Basically, the pyrometallurgical refining of zinc involves three steps: a) iron, copper, and other metals having no appreciable vapor pressures at 907ºC concentrate in the bath when the impure zinc is boiled, b) lead, bismuth, antimony, and other metals having boiling points above but closer to that of zinc are selectively condensed from the vapor boiled from the bath, and c) cadmium and other metals having lower boiling points than zinc are fractionally distilled by reboiling and subsequent condensation of the zinc from the vapor. The boiling and condensation of zinc must be conducted in vessels constructed of materials which are refractory at the temperature involved (907 ºC) and it is highly desirable that they also be resistant to attack by the various metals. This requirement dictates construction from relatively small, simply shaped pieces which limits the pressures which may be employed to avoid leakage through the numerous joints. Stresses induced must be limited essentially to compressive ones and suitable provision must be made to permit thermal expansion of the components in order to minimize these stresses. Where heat is to be added for boiling or removed for condensation, refractory material through which the heat flows must have a high thermal conductivity. Silicon carbide is highly conductive but is subject to attack by iron and is expensive compared to other commonly employed refractories. A hard, dense aluminous fireclay is well suited to contain these metals where high thermal conductivity is not required. Zinc will penetrate the pores of fireclay brick but only to a limited depth in an exterior wall and has little effect other than an increase in weight and conductivity. The design objectives of the Amax refiner were: a) to achieve a long life by heavy, rugged construction and by employing silicon carbide refractories only where required for heat conductivity and not in contact with liquids of high iron concentrations, b) to simplify operation, manning and control by essentially horizontal construction, and c) to obtain high capacity in a single unit. DESCRIPTION Flow of metal through the Amax refiner is shown diagrammatically in Fig. 1 and schematically in Fig. 2.

Jan 1, 1963

By R. M. Hudson

A study has been made of the decarburization of low-carbon sheet steels at temperatures from 1100" to 1475°F in mixtures containing hydrogen, nitrogen, water vapor, and in some instances carbon monoxide. Decarburization occurs principally by the reaction C (in steel) + H20 = CO + H2 and follows a first-order rate law. The decarburization rate appreciably increases with an increase in temperature up to about 1325°F, but the increase in rate is small with fur- Use of a dry hydrogen atmosphere results in a relatively slow decarburization of steel and use of a wet hydrogen atmosphere results in relatively rapid decarburization. It is now generally recognized&apos; that the reaction C (in steel) + H2O = H2 + CO [l] accounts for most of the decarburization that occurs in wet hydrogen-containing atmospheres. The present article is concerned with the decarburization of low-carbon sheet steel in H2-N2 atmospheres ther increase in temperature. The limiting rate of decarburization can be predicted from a knowledge of the solid solubility and diffusivity of carbon and this rate is approached as the water-vapor content of an atmosphere is increased. Hydrogen contents above about 8 pct are beneficial only in that they permit higher levels of water vapor to be used without oxidation of the steel. A buildup of CO in the atmosphere lowers the rate of decarburization. containing various amounts of water vapor and carbon monoxide. The effectiveness of these atmospheres and the influence of temperature on decarburization rate will be considered. EXPERIMENTAL WORK The chemical compositions of the three steels used in decarburization-rate studies are listed in Table I. Steel A was a commercially hot-rolled rimmed steel that was cold-reduced at the Laboratory to furnish specimens 0.025, 0.041, and 0.059 in. thick. Most of the experiments in which this steel was used were made on the 0.041-in.-thick material. Steel B and Steel C were cut from 0.010-in.-thick commercially cold-reduced coils that were

Jan 1, 1963