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By L. H. Sjodahl, J. B. Conway

of each particle on grain boundary movement is proportional to the area it occupies on the grain boundary and this increases with the square of the particle radius. In contrast to the impression gained by Tiwari the effectiveness of a particle, as a grain boundary obstacle, increases rapidly as the particle size increases. The counterbalancing factor in a dispersion of constant volume (e.g., those considered by Zener) is of course the rapidly diminishing number of particles, a situation which does not exist in thoria dispersed materials where the volume fraction of thoria remains constant. Although it has been assumed that the Zener approach is valid for the sake of the above argument, it is open to the following objections: 1) It assumes that the effect of many small particles along a grain boundary is cumulative and does not take into account the possibility of each small particle being overcome separately. In this case the boundary will not be able to move forward until the largest particle on the boundary has been overcome. This means that the rate controlling factor will be the rate at which a few relatively large particles are overcome with the remaining small particles playing a negligible role. 2) When the dispersion consists of very small particles the interparticle spacing is usually small compared to the grain size and most particles are located away from grain boundaries where they can play no part. The most efficient dispersion, from a purely geometrical viewpoint, is one where the particle spacing is equal to the grain size so that all the particles are on grain boundaries. Tiwari's second point that voids cannot prevent re-crystallization seems to be unfounded as several workes20-23 have shown that voids alone can retard grain boundary movement and recrystallization. To further convince Tiwari, Fig. 17 shows a void in deformed TD Nichrome holding back a recrystallization interface. Tiwari's explanation for the effect of voids on recrystallization, i.e., they reduce local strain energy and hence lower the driving force for recrystallization may be valid in itself but is irrelevant to the present case where even complete recrystallization after ONE of the more recently proposed expressions for describing stress-strain behavior is that due to Voce.1,2 This equation is usually written: s =s8 ?(s8?so)e??/?c [l] where s is the true stress, ? is true strain, cC is a constant called the characteristic strain, s8 is the asymptotic stress approached at high strain values, and so is the threshold stress at which the plastic deformation begins. While this expression has not been universally accepted as yet it does contain certain features which are consistent with experimental stress-strain behavior. In a more recent publication Hsu, Davies, and Royles3 employed the concept of generalized strain proposed by seth4 and identified a method for linearizing the stress-strain plot. In this approach the generalized strain was given by: where 7 is the generalized strain, 1 is the instantaneous length, 1, the datum length, and n is a constant called the "coefficient of strain measure". A value of n was said to exist which would yield the linearity: s —s+ S[.-(tf] [3] In recent studies of both these approaches, it has been found that while the Voce equation and the gen-

Jan 1, 1970

By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967

By R. A. Breitrick, J. N. Swinderman, J. J. Cooper, H. L. Bauer Jr.

The Robinson Mining District, near Ely, Nev., is one of the major porphyry copper districts in the world. Within the district is an eight mile long east-trending zone of altered porphyry, metamorphosed sedimentary rocks, and sulphide mineralization surrounded by Paleozoic limestone, dolomite, shale and sandstone, Tertiary volcanics, and Quaternary alluvium. Six major disseminated ore deposits have been exploited in this zone. About 20% of the district production has come from disseminated ore in metamorphosed sedimentary rocks found adjacent to altered quartz-monzonite porphyry. The following brief statements summarize some of the relations between porphyry alteration, metamor-phism, and mineralization: 1) Disseminated copper ore does not occur in unaltered porphyry or in m-metamorphosed sedimentary rocks. 2) Sedimentary rocks have been only weakly metamorphosed where intruded by unaltered porphyry. 3) Intensely metamorphosed sedimentary rocks are found only adjacent to altered porphyry. 4) Many hydrothermal minerals are common to both altered porphyry and adjacent metamorphosed sediments. 5) Disseminated ore is found in altered porphyry and adjacent metamorphosed sedimentary rocks. 6) In general, there is a direct correlation between grade of ore in porphyry and copper content in the adjacent rocks. 7) Chemical changes in the altered porphyry and metamorphosed rocks appear to be related. The foregoing relations support a hypothesis that the porphyry alteration, the metamorphism of the sedimentary rocks, and the ore deposition were all part of a continuous hydrothermal process which probably closely attended the porphyry intrusion. The Robinson Mining District, most often referred to as the Ruth or Ely District, is located in eastern Nev. and is one of the major porphyry copper districts of the world. Production from 1908 through 1962 was nearly 250 million tons of ore averaging a little over one percent copper with a total metal value of nearly one billion dollars. The ore has been produced from six major disseminated-type deposits with the Liberty Pit deposit accounting for 70% of the total district production. Less than one million tons of base metal and gold ores have been produced from the replacement-type deposits of the district. Approximately 20% of the district production has come from underground mining operations; the pit ore has been mined with shovels and removed by train haulage, truck-train haulage combinations, truck haulage, and presently by a combination truck-skip system. Many of the ore deposits formerly worked by underground methods have been and are being exploited by open pit methods. (See Fig. I.) Two co.'s have accounted for virtually the entire production from the district. In 1958 Kennecott Copper Corp. acquired the district assets of Consolidated Coppermines Corp. and is now the sole ore producer in the district. Present operations are confined to the Liberty Pit where 22,500 tons of ore averaging a little less than 0.8% copper is mined per day. Cutoff grade is 0.4% copper, and the stripping ratio is three to one. The ore is hauled by rail 23 miles to the McGill Reduction Plant where it is concentrated to about 20% copper. Molybdenite is recovered as a by-product in the mill. The copper concentrates are smelted in McGill, and the blister copper is shipped for refining to Balt. where gold, silver, platinum and palladium are recovered. The Robinson Mining District has been well known as a porphyry copper district for the past fifty years, but many geologists are unaware of the fact that a large portion of the production has come from disseminated ore found in metamorphosed sedimentary rocks. The scope of this paper describes the occurrences of disseminated ore in the various metamorphosed sedimentary rocks, and presents evidence for the hypothesis that these ores are genetically, spacially, and coevally related to the disseminated ore in the porphyry rocks. Publication of this paper was granted by the management of Kennecott Copper Corp. A. H. James suggested and encouraged the writing of the manuscript. Special mineralogical and spectrographic analyses were performed by the Kennecott Research Center. The deposits of the district have been studied by many geologists since the turn of the century, and

Jan 1, 1964

By Arthur W. Sheafer

MR. ECKLEY B. COXE, in his able and interesting paper on " The Preparation of Small Sizes of Anthracite,"* read and discussed at the Glen Summit Meeting, October, 1891, refers to the reputed immense amount of coal contained in the culm-banks, which are the unsightly accompaniment of every mining operation in the anthracite coal-regions. Mr. Coxe thinks the available amount and value greatly exaggerated, giving among his reasons (1) the spoiling of the culm by mixing with other refuse; (2) its deterioration; (3) its destruction by fire ; and (4) frequent failures to realize expectations as to the size of the banks. These points are undoubtedly important factors in determining the advisability of working any individual bank, but they have a varying influence in the several regions, some prevailing more in one than in another. Although the amount of fuel lying waste in these banks is still an uncertain and undetermined quantity, yet no one can visit the Schuylkill region without being impressed with the fact that a considerable amount of culm, too valuable to be left merely to the mercy of the elements, surrounds and encumbers each site of an old or present colliery operation. The rapid increase in the number of washeries, and the demand for leases on old culm-banks, shows that, in the Schuylkill region at least, the question of deterioration doès not play an important part. The proportion of coal to refuse, the relative percentage of the sev-

Jan 1, 1895

By D. R. Wieland, A. N. Barron, A. R. Hendrickson

A definite relationship has been found between the reactivity of flowing hydrochloric acid and its shear rate in a carbonate fracture. Both flow velocity and fracture width affect the acid reaction rate. Laboratory studies were conducted on acid reactivity at different flow velocities through horizontal-linear fractures, using 15 per cent hydrochloric acid at 80' F and approximately 1,100 psi. Fracture width varied from 0.02 to 0.20 in. These data provide a new basis from which the spending time and penetration of the acid can be estimated. Equations were derived expressing the relationship between injection rate, fracture width, acid concentration, time and fracture height, for linear and radial fracture systems. Because the penetration of the acid before spending is closely related to the extent of productivity increase resulting from an acidizing treatment, these data provide a valuable insight into some of the controlling factors that must be taken into consideration during treatment preplanning. INTRODUCTION Acidizing of carbonate reservoirs to improve production characteristics has been widely practiced since 1932. Originally, it was assumed that the acid uniformly penetrated natural formation pores and flow channels, enlarging them and thereby increasing their flow capacity. Little consideration was given to the reaction rate of the acid, or how far it would penetrate away from the wellbore into the formation, before spending. It has been shown recently' that, unless fractures are present in the rock, very little penetration is attained before spending, and the benefits of the acidizing treatment are largely confined to the immediate vicinity of the well-bore. Therefore, acid treatments may be classified into two categories: (1) matrix acidizing, in which the acid flows through multiple: formation pores; and (2) fracture acidizing, in which the bulk of the acid travels through fractures in the rock, whether natural or induced. When acidizing treatments are conducted at pressures of sufficient magnitude to open and extend such fractures, it is often desirable to inject a propping agent to hold the fracture open after the treating pressure has been released, thus providing a highly conductive flow channel through the rock. In some cases where acid attack produces surface irregularities, the resulting flow passages can be sufficient to provide high conductivity without use of a propping agent. During injection, the acid dissolves the carbonate rock with which it comes in contact until it is spent. Deeper penetration of the spent acid into the formation produces no appreciable benefit (if no propping agent is used) because the unetched fracture faces will rejoin when treating pressures are released and the fracture will "heal", with negligible resultant conductivity. The spending time of the acid thus becomes important in determining how far from the wellbore the improved-conductivity zone extends. The spending time of acid after injection into carbonate rock depends on the rate at which the acid reacts with the rock. This in turn is controlled by a number of factors, as previously reported. 2-4 These include temperature, pressure, acid concentration, rock composition, injection rate and the area-volume relationship between the acid solution volume and the surface area of the formation flow channels through which it penetrates. Thus, in matrix acidizing, where an extremely large area is exposed to the acid, spending is rapid. In contrast, spending time is prolonged in open fractures, where the area-volume ratio is much lower. Thus, greatest penetration of the acid before spending will be achieved in acid-fracturing treatments where fractures are held open by hydraulic pressure. Perkins and Kern5 have presented equations for fracture-width determinations which, for hard formations such as limestone or dolomite, indicate that high injection rates and viscous fluids are required to create wide fractures. Increasing the injection rate will, in itself, produce faster reaction rates. Because this type of reaction can be considered to be first-order diffusion-controlled, '-' the rate of movement of fluid past the rock surface affects the thickness of the diffusion layer, in turn affecting the reaction rate. Staudt, et al,10 report the results of tests in which a rotating marble cylinder was immersed in acid, and the weight loss at different speeds determined. Such test conditions, however, are not truly indicative of the situation in a formation during an acid-fracturing treatment. This paper reports reaction-rate data obtained under

By E. S. Machlin

An extension of the thermodynamic theory has been made for the case of irreversible growth processes occurring by the motion of an interface. The theory is applicable to such diverse phenomena as diffusion, growth in recrystallization, continuous grain growth, growth of carbides, etc., growth of eutectoid products, growth in solidification, recovery, "slipless" flow, etc. THE publication of a recent book1 has served to focus attention on a very powerful means of treating certain irreversible processes. This method which has been formally described as the thermodynamic theory of irreversible processes is applicable to processes which involve an approach to equilibrium and for which the deviations from equilibrium are small. The irreversible processes can be classified into three groups: chemical reactions, transport processes (diffusion, heat and electrical flows), and relaxation phenomena involving a degradation of internal energy to more stable states. The limits of applicability of the theory can be precisely defined1,2 for each type of irreversible process. For example, in a chemical reaction at constant temperature and pressure, the Gibbs free energy released per mol in the process should be less than the thermal energy, RT. Another type of irreversible process, which sometimes involves a combination of the first two of the above-mentioned groups, is treated in this paper. This process is one characterized by the motion of an interface separating two regions having different values of free energy and may be briefly described as a growth process. Prigogine2 and Herring3 have treated special cases of this type of process. Previous conscious applications of the theory in metallurgy have been limited to the field of diffusion, one of the transport processes. Darken,4 Bardeen,5 Prigogine2 and others have made significant contributions in this respect. Some other applications of the theory are described in this paper. The Theory The thermodynamic theory of irreversible processes is based on the work of Onsager,6 DeDonder,7 Prigogine2 and others. A resume of the theory has been given by Prigogine2 and DeGroot.1 A brief description of the theory follows, although for a complete understanding the reader is urged to read the references. It is first assumed that the change in entropy, even for a system removed from equilibrium, is given by dS = [dU + pdV - Si µi, dn, - Sk Pk dxk]T-1 Using this expression, the irreversible entropy production in the system is calculated by subtracting the contribution to the change in entropy of the system by transfer of heat, work, or matter from the surroundings. Thus, for example, the irreversible entropy production of a system at constant temperature and pressure is given by dtS = — — dG (DeDonder7) Now it has been shown by Prigogine,2 DeDonder,7 and DeGroot1 that the rate of irreversible entropy production diS/dt, when calculated in the manner suggested, can be written as a sum of products of conjugate forces XK and fluxes Jk, i.e., d,s/ = Sk Jk Xk [I-1] dt The assumption is next made that a linear relation exists between a given flux and the forces, obtained from Eq. I-1, i.e., Ji = Sk Lik Xk (i = 1, 2, . . . n) [I-2] Generally, there is a degree of freedom in choice of the fluxes and forces. However, for all the choices consistent with Eq. I-1 the Onsager8 relations, based on the principle of microscopic reversibility, namely, Lik = Lki, are valid. The coefficients Lik, depending upon the choice of the conjugate fluxes and forces, may be more or less dependent upon the parameters defining the state of the system. In general, the proper choice of fluxes and forces utilizing Eq. I-1, makes the coefficients Lik independent of time. Also, because many of the three classes of irreversible phenomena have already been treated,1,2 a proper choice can be made by analogy. In any case, the validity of Eq. 1-2, from whatever choice made using Eq. I-1, must be tested by experimentation. The theory, thus, comprises the following steps: 1—The irreversible entropy production is calculated to yield Eq. I-1. 2—The terms in Eq. I-1 are grouped

Jan 1, 1954

By S. A. Falconer

D. A. Dahlstrom—Mr. Falconer has done an admirable job of proving the adaptability of the cyclone to the beneficiation of a very difficult size range in the preparation of coal. The addition of the cyclone to other coarser size methods makes it economically feasible for the coal operator to rigorously control his marketed products at a high and uniform quality level down to the 48 and 100-mesh size. Furthermore, it should be pointed out that by utilizing the cyclone as a deslimer or classifier the —3 200-mesh fraction, usually containing large percentages of undesirable material, can also be quickly and cheaply removed from the clean coal. Advantages of such a step are several: (1) Reduction of ash content, especially where clays and slimes are serious. (2) lower moisture content of the final coal. (3) easier mechanical and thermal de-watering of the fine coal due to higher cake and bed permeabilities. The author has indicated that adjustable control means should be installed on the cyclone operating on a heavy-media slurry. This also holds true for the cyclone acting as classifier, deslimer or preliminary dewatering agent and is worthy of special emphasis. Such controls, while not necessarily automatic, must be simple, rapidly adjustable, and require a minimum of attention. Three methods available to the operator are (1) throttling valve on the feed line, (2) back pressure valve on the overflow, and (3) adjustable diameter underflow nozzles. The first two, while fulfilling the specifications, suffer the disadvantage of restricting capacity if severe throttling is necessary. The third method has little effect on capacity and easily maintains an underflow of correct moisture content. Several designs are possible, but two find the widest application. The first was developed by Robert Piros of The Truax-Traer Coal Co. and uses a simple casting containing two holders for underflow nozzles which can be rotated about an axis parallel to the cyclone centerline. These holders retain the underflow nozzle flush with the conical section walls. When a change in nozzle diameter is required, the new size is placed in the spare holder and rotated into place. A second design utilizes a soft rubber cylindrical tube which is compressed or released from three sides, causing the inner diameter of the tube to decrease or increase. This is achieved by using a machine-threaded,

Jan 1, 1951

By J. S. Ll. Leach, L. R. Rubin, M. B. Bever

The energies of formation of ordered and disordered solid solutions of composition CusAu and the energy of ordering in this alloy were determined by tin solution calorimetry. The degree of order was measured by X-ray diffraction and electrical resistance and microhardness measurements were made on ordered and disordered specimens. AMONG the phenomena associated with the order-disorder transformation of a solid solution, the change in internal energy is of special interest because of the part it plays in the various theories of ordering. Published values for the decrease in internal energy accompanying the formation of a superlattice from a disordered solid solution of composition CuAu range from —370 to —2260 cal per gram-atom. Some of these values represent calculations based on theory and others are the results of experimental measurements. The distinction between the change in internal energy, AE, and the change in enthalpy, AH, can here be neglected, because they are approximately equal for solid-state reactions at normal pressure. An analysis of ordering by Bragg and Williams' predicts an energy change of —605 cal per gram-atom for the formation of a superlattice in the alloy Cuau from a completely random solution. Peierls" application to Cuau of Bethe'sb earest-neighbor theory yields —560 cal per gram-atom for the formation of a superlattice from a matrix which initially contains short-range order. Cowley' extended the nearest-neighbor approach to include as many as five shells of neighbors; on this basis a change in energy of —500 cal per gram-atom is expected. Eguchi," using a quantum-mechanical treatment, calculated a value of —2260 cal per gram-atom for the difference in the energy of completely disordered and completely ordered Cu,Au. Sykes and Jones- eated a completely ordered alloy and measured its heat capacity as a function of temperature. This measured heat capacity agrees closely with the corresponding value found by the Kopp-Neumann (or mixture) rule up to about 250°C and above this temperature exceeds it, especially near the critical temperature for ordering. The difference between the integrals with respect to temperature of the observed and the Kopp-Neumann heat capacities was considered to be the energy of ordering. By this method Sykes and Jones found a value of —530 cal per gram-atom. This value is not adjusted for the short-range order remaining above the critical temperature. The pres- ence of such short-range order is suggested by the difference between the measured heat capacity and the extrapolated Kopp-Neumann heat capacity immediately above the critical temperature. Values reported by Weibke and von Quadt' and by Hirabayashi, Nagasaki, and Maniwaa were obtained in the course of investigations primarily aimed at other objectives. Weibke and von Quadt measured the temperature coefficient of the electromotive force of a Cu-CuAu cell. They obtained a value of —1010 cal per gram-atom for the heat of formation of the alloy at 500°C, at which temperature there is no long-range order. They also obtained —1380 cal per gram-atom as the heat of formation of the ordered alloy at 370°C. Considering the heat of formation of the disordered alloy to be independent of temperature, they estimated the energy of ordering at 370°C as —370 cal per gram-atom. At this temperature long-range order is incomplete and the degree of order changes rapidly with temperature. Hirabayashi, Nagasaki, and Maniwa," using an annealing calorimeter, investigated an alloy containing 23.4 rather than 25.0 atomic pct Au and thus could not obtain complete order. Thelr value of the energy of ordering was —490 cal per gram-atom. Orianis has recently investigated the Au-Cu system by the galvanic emf technique. He reports values for the heats of formation of Cu-Au alloys, from which the heat of formation at 427 OC of an alloy of composition CuAu may be found by interpolation. This value is —1080 cal per gram-atom. In the work here reported, disordered and ordered alloys of composition CuAu and corresponding mixtures of gold and copper were dissolved in liquid tin and the heat effects measured. These heat effects are small, since the dissolution of gold in tin is exothermic and the dissolution of copper is endothermic. The method, therefore, yields fairly precise values of the heats of formation of disordered and ordered alloys and of the energy of ordering. Experimental Procedure The calorimeter consisted of a long-necked Dewar flask immersed in a constant temperature salt bath and has been described by Ticknor and Bever." The chief changes in this equipment were an improvement in vacuum and the replacement of the mercury thermoregulator by a resistance thermometer control circuit. The solvent, which was maintained at a constant temperature near 350°C, consisted of 500 grams of 99.99 pct pure tin. The solute samples were mixtures of gold and copper in the proportion corresponding to the composition Cu,Au or solid solutions

Jan 1, 1956

By Frank Foote, Eric R. Jette

In a recent article,1 the authors reported the results of an X-ray investigation on the range of solid solutions that occurs in the iron-oxygen system in the vicinity of the compound FeO, which frequently is called "wüstite." The object of that investigation was primarily to study the unusual type of solid solution phenomena involved in this range. Briefly summarized the results were: 1. The NaCl type of lattice found by earlier workers was confirmed. 2. The lattice dimensions decrease rapidly with decrease in iron content. 3. No alloy that was a homogeneous single phase was ever found at compositions beyond 76.80 per cent Fe, while the theoretical iron content of FeO is 77.73 per cent Fe. 4. Measurements of the densities and lattice constants led to the conclusion that the form of substitution was complex, an FeO group being replaced by oxygen. Such a substitution, of course, is equivalent to removing an iron atom (or ion). The ideal unit cell of FeO can be considered as containing four groups of FeO and, thus, when this type of substitution takes place, there remain in the unit cell three FeO groups and an oxygen, or a total of seven atoms with a gross formula of Fe3O4 instead of the original Fe4O4. 5. This was the only interpretation that would fit the experimental results and at the same time be consistent with (a) the previously determined fact that the FeO lattice is ionic (i, e., consists of Fe++ and O? ions) and (b) the chemical fact that as the oxygen content of the substance increases, ferrous iron becomes oxidized to ferric iron. The experimental results of this investigation are included in Fig. 1. The purpose of the present investigation was to determine the limits of this homogeneity range by means of the X-ray structure analysis. This method has been applied frequently to the study of solid solutions by Westgren and his coworkers as well as by other investigators. The principle is simple: if the change in lattice constant with composition is

Jan 1, 1933

By S. A. Falconer

D. A. Dahlstrom—Mr. Falconer has done an admirable job of proving the adaptability of the cyclone to the beneficiation of a very difficult size range in the preparation of coal. The addition of the cyclone to other coarser size methods makes it economically feasible for the coal operator to rigorously control his marketed products at a high and uniform quality level down to the 48 and 100-mesh size. Furthermore, it should be pointed out that by utilizing the cyclone as a deslimer or classifier the —3 200-mesh fraction, usually containing large percentages of undesirable material, can also be quickly and cheaply removed from the clean coal. Advantages of such a step are several: (1) Reduction of ash content, especially where clays and slimes are serious. (2) lower moisture content of the final coal. (3) easier mechanical and thermal de-watering of the fine coal due to higher cake and bed permeabilities. The author has indicated that adjustable control means should be installed on the cyclone operating on a heavy-media slurry. This also holds true for the cyclone acting as classifier, deslimer or preliminary dewatering agent and is worthy of special emphasis. Such controls, while not necessarily automatic, must be simple, rapidly adjustable, and require a minimum of attention. Three methods available to the operator are (1) throttling valve on the feed line, (2) back pressure valve on the overflow, and (3) adjustable diameter underflow nozzles. The first two, while fulfilling the specifications, suffer the disadvantage of restricting capacity if severe throttling is necessary. The third method has little effect on capacity and easily maintains an underflow of correct moisture content. Several designs are possible, but two find the widest application. The first was developed by Robert Piros of The Truax-Traer Coal Co. and uses a simple casting containing two holders for underflow nozzles which can be rotated about an axis parallel to the cyclone centerline. These holders retain the underflow nozzle flush with the conical section walls. When a change in nozzle diameter is required, the new size is placed in the spare holder and rotated into place. A second design utilizes a soft rubber cylindrical tube which is compressed or released from three sides, causing the inner diameter of the tube to decrease or increase. This is achieved by using a machine-threaded,

Jan 1, 1951

By W. F. Flanagan, D. H. Polonis, S. D. Dahlgren

Rotation diffraction patterns of Cu-4.84 wt pct Si polymystalline samples were taken during the course of isothel-ma1 affing of the suPersaturated a phase, a diffraction spots were obserzled to streak during the initial stages of aging, and this streaking was similar to the streaking of a spots observed earlier by Barvett with deformed super saturated samples of the same composition. Although it was suggested that stacking faults were the sole cause of styeaking in the deformed samples, the present study has shown that plates with one small crystallite dimension can also contribute to the streaking when there is lattice coherency across close-packed planes. THE decomposition of the supersaturated a phase in Cu-Si alloys has been reported to occur by means of both thermal and stress activation.1-4 According to the Cu-Si phase diagram,3 Fig. 1, the supersaturated a phase (fcc) is expected to transform during aging by the precipitation of the y phase. The results of earlier studies2,4 have indicated that metastable k phase (hcp with nearly ideal close packing) forms initially at temperatures below the eutectoid temperature, after which the k transforms to the a and y phases. Hof-mann et al.4 have proposed a metastable version of the phase diagram, showing the approximate boundaries for k formation below the eutectoid temperature. In view of the close-packed nature of both the a and k phases, it is essential to consider the role assumed by stacking faults in the transformation. Streaking effects have been reported by Barrett 1 in the rotating crystal X-ray patterns of strained Cu-Si alloys and were attributed to stacking faults rather than particle size effects. This deduction was based on the observation that streaks in the diffraction patterns did not occur tangent to the 220fee Debye ring. It is known that the atom movements involved in faulting leave some X-ray reflections unaffected while others are broadened,' and, in particular, it has been shown that faulting will not cause streaking of 220fee reflections tangent to the 220fee Debye ring as would be expected if all the reflections were broadened.' The formation

Jan 1, 1967

By Paul J. Sirkegian

The problem of properly controlling the movements of underground trains in the Emma Nevada and Morris Brooks workings of the Consolidated Coppermines Corporation of Kimberly, Nev., became more complex as the rate of production increased. Ore from these mines, which are connected through a 7000-ft. single-track haulageway (Fig. I), is hoisted through the Emma Nevada shalt. All production to date has been from one level. Because of heavy ground, even on the main haulage horizon, experience has shown that it is necessary to have a minimum cross section in the drifts, thus making it impractical to have a double track system. In 1937, production was 3000 tons per day; in 1938 it was increased to 6000 tons per day and in 1940 to 9000 tons per day. Each increase necessitated a revision in the method of controlling the underground traffic. In 1937 the tramming signal system consisted of a few signal lights in the main haulage drift. These lights were two 100-watt bulbs in a metal box that had one green and one red lens on each side. The box was mounted on the underside of a drift cap timber and could be seen For a considerable distance. The lights were so arranged that all boxes showed either red or green at the same time and all were controlled by a magnetic contactor at the entrance to each lateral drift. When the lights showed green, the main haulage was clear of traffic and a train could enter it. As the motor entered the main haulage drift, the motorman pulled the cord of the magnetic contactor switch, thus changing all the main haulage lights to red, which indicated that no other train could use the main haulage until the first train had turned into a lateral drift. When a train left the main line, its motorman pulled the cord connected with the magnetic contactors, causing the haulage lights to show green again. This arrangement permitted only one train at a time to use the main haulage and thus limited the number of train trips per shift, but it was satisfactory when the ore handled was only 3000 tons per day. Second SystEM Installed With a gradual increase in production it became necessary to place a train dispatcher in charge of all trains. He controlled their movements orally, giving his orders direct or by mine phone, instructing them where to load, when to leave for the station and when to return. His objective was to group several trains traveling in the same direction. Because of the human element involved, some mistakes were made. The danger of a serious collision was always possible. There was a 90° turn and curve in the underground haulageway, therefore travel in this section was always dangerous if mistakes were made in directing traffic. To protect the train crew, particularly the rear switchman who rode the last car or caboose, a two-way push button and flash-signal system was installed on the

Jan 1, 1946

By P. Duwez, C. B. Jordan

A. J. SHALER*—I should like to congratulate the authors for having carried out such a precise set of experiments. It has been found useful, in sintering experimental compacts in vacuo, to make certain that the residual gas is not one which reacts with the metal. Since traces of oxygen can be kept away only with great difficulty, the technique is often adopted of using a "getter " of powder in the vicinity of the compacts, and, in addition, of permitting a small hydrogen leak to flow into the vacuum chamber. Did the authors use similar devices? This paper brings up a question concerning the definition of the word ' sintering.' The authors restrict its use to the adhesion between particles. Kuczynski, in a paper presented at this meeting, applies the word to the growth of areas of contact between particles. I have used it to mean both these phenomena and also the dimensional changes which continue to take place after the first two have run their course. May I suggest that we should come to an agreement on the use of these words ? Fig 1 and 2 show an interesting feature: extrapolation of the curves to zero time does not give a densification parameter of zero. The higher the temperature, the higher is the intercept on that axis. These observations agree with the concept of a practically instantaneous densification taking place while the compact is being brought to heat. Such a change may be brought about by plastic deformation and primary creep. The stress pattern causing this first rapid flow is, to my mind, due to the force of attraction between the surfaces of opposite particles in the regions immediately flanking their common areas of contact. The stress is not temperature-sensitive, but at room temperature plastic deformation only proceeds until the metal in the area of contact can support it elastically. As the metal is heated, the elastic limit falls, and further plastic flow occurs. At the higher temperatures, this is followed by primary creep, and finally by the steady-state rate-reaction which the authors are seeking. If they were to recalculate their densification-parameter values, using, not the initial density of the cold compact, but the density after the compacts have been brought to temperature, the systematic deviations from linearity in Fig 3 and 4 might be eliminated. Such initial densities might be obtained by extrapolating the curves of Fig 1 and 2 to zero time. I am naturally pleased to see that such a very well done series of experiments leads to a heat of activation (for the densification process in hydrogen) that is much higher than that for self-diffusion, in confirmation of the less elaborate results reported by Wulff and myself (Ind. and Eng. Chem., (1948) 40, 838). J. T. KEMP*—I would like to comment on Dr. Shaler's remarks. There are apparently different interpretations of the word "sintering." It seems to me that an accurate definition of our word is essential in all metallurgy. May I point out, in this connection, that in practical metallurgy the word "sintering" has been applied to a bonding process in the preparation of ores and flue dust for fur-nacing. It would be unfortunate if in the area of powdered metallurgy we should establish a definition that is essentially different in meaning. F. N. RHINES*—I think that I can answer the question by saying that I see no essential difference between the use of the term "sintering" in extractive metallurgy and in powder metallurgy; physically the same things are going on. I admit sintering is used for different end purposes in the two cases. When we resort to the sintering of lead ore mixture we are doing so to obtain a chemically reactive, loose texture of some rigidity. This is only a difference in use. After all, in powder metallurgy we sometimes deliberately produce a very porous material which has just a little strength, just as in the case of sinter cake. P. DUWEZ (authors' reply)—We agree that it would be helpful to have well-established definitions of such terms as "sintering." Since the question has now been raised, the time might be appropriate for its consideration by some suitable committee of one or more of the metallurgical societies. In answer to Dr. Shaler's first question, no getter nor hydrogen leak was used in our vacuum experiments, except insofar as the guard disks (used to reduce friction between specimens and trays) may have acted as getters. Dr. Shaler's statement that extrapolation of the curves of Fig 1 and 2 does not lead to zero densification at zero time apparently overlooks the logarithmic

Jan 1, 1950

By R. H. Frazier, C. H. Lorig, F. W. Boulger

THERE are both advantages and disadvantages in using semikilled steels in place of killed steels. One advantage of semikilled steels is they provide a higher ingot-to-product yield. This is especially important to shipbuilders in the time of national emergency. By using semikilled steel for hull plates, a greater number of ships can be built from the same ingot tonnage. Consequently, if semikilled steel plates are adequate for the service, the advantage of the higher product yield is of considerable importance. The performance of hull plates is closely associated with the ductile-to-brittle transition temperature, and this, in turn, is strongly dependent on the composition of the steel. A low transition temperature is desirable because it indicates that the steel is less likely to fail at low ambient temperatures. Killed steels are known to have lower transition temperatures than semikilled steels. It is believed that the better qualities of killed steels in this respect are due mainly to the low oxygen contents of the steel. The principal deoxidizers, aluminum, silicon, and manganese, lower the oxygen content. Fundamental studies1-0 have shown that the oxygen content remaining after the addition of one of these three elements is influenced by the residual amounts of the other two present. In the current study, therefore, various amounts of silicon and aluminum were added to steels containing different manganese contents for the purpose of studying the influence of silicon and aluminum on the notched-bar properties of hot-rolled steels. Eleven types of steels were studied. The temperature at which the plates were finish-rolled was care- fully controlled at 1850°F. All plates were rolled to ¾-in. thickness, and tested in the as-rolled condition. The total number of steels prepared in the laboratory for this study was 95. The charge consisting of ingot iron and ferrosilicon equivalent to 0.10 pct Si was melted in a 200-lb induction furnace under an atmosphere of argon to insure low, uniform nitrogen contents. After the charge was melted and the desired temperature was obtained, the melt was partly deoxidized with either silicomanganese or aluminum. Aluminum was used for this purpose in only those steels with very low silicon contents, where the finished steel was to contain some aluminum. This initial deoxidizing addition was made to obtain consistent recoveries of subsequent additions of ferro-manganese, ferrosilicon, and aluminum. Carbon, in the form of graphite, was added, either just prior to tap or to the final aluminum addition. The entire heat of 200 lb was poured directly into a 6x6-in. big-end-up mold. The ingots of semikilled steel were capped with a steel plate. The killed steels, on the other hand, were poured with a hot-top containing 14 pct of the total volume of the ingot. The ingots were processed by heating to 2250°F, followed by forging to slabs 1¾ in. thick and 6 in. wide. After reheating to 2250°F, the slabs were rolled to 0.9-in. gage, using reductions of approximately 1/6 in. per pass. The 0.9-in. thick plates were immediately recharged in a furnace held at 1850°F. After 30 min in the furnace at 1850°F, the plates were rolled to ¾ in. in one pass. Following the final pass, the plates were stacked on edge on a brick floor, with a brick separating one from another, where they were allowed to cool in air. Drillings for chemical analysis were taken from the plates at locations corresponding to the top and bottom of each ingot. Carbon, manganese, silicon, phosphorus, sulfur, and nitrogen contents of each sample were determined. The analysis of each steel was carefully controlled so that the contents of

Jan 1, 1957

By J. H. Swislzer

TWO-LIQUID miscibility gaps have been found to exist in both the CaO-SiO, system above 1705 and the Cr,03 system above 2200"c. Glasser and 0sborn3 studied the extension of these miscibility gaps into the Ca0-Si0,-Crz03 ternary system and reported that the two-liquid region is not present at temperatures below the monotectic temperature of 1705°C in the CaO-SiO, system. The present authors, in connection with other work on surface-tension measurements and foam stabilities in the same ternary system,4 observed that the miscibility gap exists at temperatures as low as 1600°C. A brief experimental study was devoted to deter- mining tie-line positions in the two-phase region. The technique used was to obtain a separation of phases at 1600°C, then to quench-in the high-temperature phases and obtain a chemical analysis of each phase. It was necessary to take special precautions in obtaining a phase separation because of a tendency toward emulsification of the two liquids. The procedure followed is described in the schematic drawing in Fig. 1. A small platinum crucible containing several pinholes on its sides was placed inside a larger platinum crucible. An excess of Crz03 was placed in the outer crucible, together with a prefused binary CaO-Si02 mixture, and the Cr203 was allowed to diffuse through the pinholes and saturate the same binary CaO-SiOl mixture in the smaller crucible. After equilibration at 1600°C, the inner crucible contained only the lighter liquid (liquid A) saturated with Cr203. The outer crucible contained layers of both liquids. Experimental data were obtained by analyzing the entire contents of the inner crucible and only the bottom layer of the larger crucible (liquid B). The upper layer of the outer crucible was not suitable for chemical-analysis purposes because dispersions of the second phase sometimes were found in the samples. The technique is described in more detail in Ref. 4. The same method was used by Grieveson and urkdoan' to study a miscibility gap in sulfate-ferrite melts, where the liquids were difficult to separate because of similarities in density. In addition to the phase-separation experiments, a few others were conducted to obtain information

Jan 1, 1964

By J. E. Wilson, F. P. Lebar

TYPICAL of southwestern Wyoming are coal structures that dip from 4° to 17°. Those at the Reliance and Winton mines of the Union Pacific Coal Co. average 91/2 and 15°, respectively, and dip almost directly to the west. By using a hoist for main haulage, a method of mining has been developed whereby four places are driven on the pitch of the seam. Slightly upgrade from the strike at intervals of 300 ft. a two-entry system is driven to the north and to the south. In both fields, which are nongassy, an exhaust system of ventilation is used. Slope, manway, and lower or haulage entries are placed on the intake. Two air-courses and upper or breaking entries are placed on the return. A retreat system of mining is used exclusively. From the opening of its first coal mine, in the year 1868, until 1923, when the Joy loader was introduced into The Union Pacific Coal Company's operations, slopes, aircourses, and manways were driven by hand. Development work was conducted on the night shift or off shift, and the main hoist was used for haulage. The slope was driven down the pitch with crosscuts turned at intervals of 75 ft. and entries at 230 ft. Connections to the workings above were made by driving up the pitch 75 ft. Mule haulage was used to furnish cars to the hand loaders driving planes up the pitch. A sheave was placed at the upper end of the plane with a I¼-in. hemp rope dou- bling around it and having me end attached to the car and the other to the mule. The mulc, pulling downhill, raised to the working face a small wooden car of one-ton capacity. With the introduction of mechanical loading, mule haulage and small wooden cars disappeared and auxiliary hoists, electric locomotives, and steel cars with a capacity of 4 tons were substituted. Development work was done during two or three shifts of the 24-hr. period. Driving of haulage slopes down the pitch by hand continued. Crosscut intervals were changed to Ioo ft. and the crosscuts were driven with shaking conveyors. With the use of a 90° swivel, aircourses and manways were driven up the pitch. Entry intervals were changed from 230 ft. to 300 feet. Mobile loaders of the Joy type were first employed by this company in the year 1923 at Hanna, Wyo. In 1928, two 4-BU Joy loaders were transferred from Hanna to Winton No. I mine, where they were used in driving slopes and entries. At the time of transfer, the machines were about worn out and were not suited to the steep pitch, therefore frequent breakdowns occurred. However, experience justified the belief that the mobile loader was fitted for driving slopes in this field. During 1937 a unit was installed in Reliance No. 7 mine, and during 1939 one in Winton No. 7½ mine. With the introduction of this type of mobile loader, a new era of development began. Speed undreamed of in hand-loading days became a reality. The cost of development down the pitch has been reduced until it

Jan 1, 1942

By J. E. Wilson, F. P. Lebar

TYPICAL of southwestern Wyoming are coal structures that dip from 4° to 17°. Those at the Reliance and Winton mines of the Union Pacific Coal Co. average 91/2 and 15°, respectively, and dip almost directly to the west. By using a hoist for main haulage, a method of mining has been developed whereby four places are driven on the pitch of the seam. Slightly upgrade from the strike at intervals of 300 ft. a two-entry system is driven to the north and to the south. In both fields, which are nongassy, an exhaust system of ventilation is used. Slope, manway, and lower or haulage entries are placed on the intake. Two air-courses and upper or breaking entries are placed on the return. A retreat system of mining is used exclusively. From the opening of its first coal mine, in the year 1868, until 1923, when the Joy loader was introduced into The Union Pacific Coal Company's operations, slopes, aircourses, and manways were driven by hand. Development work was conducted on the night shift or off shift, and the main hoist was used for haulage. The slope was driven down the pitch with crosscuts turned at intervals of 75 ft. and entries at 230 ft. Connections to the workings above were made by driving up the pitch 75 ft. Mule haulage was used to furnish cars to the hand loaders driving planes up the pitch. A sheave was placed at the upper end of the plane with a I¼-in. hemp rope dou- bling around it and having me end attached to the car and the other to the mule. The mulc, pulling downhill, raised to the working face a small wooden car of one-ton capacity. With the introduction of mechanical loading, mule haulage and small wooden cars disappeared and auxiliary hoists, electric locomotives, and steel cars with a capacity of 4 tons were substituted. Development work was done during two or three shifts of the 24-hr. period. Driving of haulage slopes down the pitch by hand continued. Crosscut intervals were changed to Ioo ft. and the crosscuts were driven with shaking conveyors. With the use of a 90° swivel, aircourses and manways were driven up the pitch. Entry intervals were changed from 230 ft. to 300 feet. Mobile loaders of the Joy type were first employed by this company in the year 1923 at Hanna, Wyo. In 1928, two 4-BU Joy loaders were transferred from Hanna to Winton No. I mine, where they were used in driving slopes and entries. At the time of transfer, the machines were about worn out and were not suited to the steep pitch, therefore frequent breakdowns occurred. However, experience justified the belief that the mobile loader was fitted for driving slopes in this field. During 1937 a unit was installed in Reliance No. 7 mine, and during 1939 one in Winton No. 7½ mine. With the introduction of this type of mobile loader, a new era of development began. Speed undreamed of in hand-loading days became a reality. The cost of development down the pitch has been reduced until it

Jan 1, 1942

By James P. Roe

Steel has occupied such a prominent position in most minds during the last thirty years, particularly since the introduction of the basic open-hearth process (by which the field from which the raw material could be obtained has been so widened), that little attention has been made to improvements in puddling iron. In fact, the general tendency seems to have been to accept the prediction that puddled iron is doomed. Events have in a measure justified such a forecast, due in large part to the introduction of mechanical appliances and operations with large units in the manufacture of steel, from which much lower costs have resulted. But this general tendency has met checks in certain directions. This is notably the case where the finished product is a welded one, or is subject to oxidation, to shock or to vibration; and, as far as the writer's observation goes, the bond (which is largely a mechanical one) is not as close and lasting between steel and tin or zinc as between iron and the same materials. The field still open for puddled iron is, therefore, a large one, provided the low costs of steel-manufacture can be approached. The process of puddling is one of the most interesting in the metallurgy of iron, as the reactions and the changes effected are apparent. The subject has had the strongest fascination to the writer from boyhood, and has led, not unnaturally, to a close study, which long ago resulted in the conviction that it could be successfully carried out with large units and by mechanical means. That others have also drawn these conclusions is shown by many undertakings, though there have been few such attempts during the last twenty-five or thirty years. Puddling cousists, essentially, in the removal of most of the carbon and silicon, and part of the phosphorus and sulphur

Jan 1, 1903

By C. B. Murray

"OUR experience from time immemorial has been that the furnace sampler and analyst usually find one or two, and sometimes more, points less iron than the Lake Superior shippers, but, fortunately, their contracts are `iron bound'; and, generally speaking, analyses at this end are practically useless, for we are obliged to settle on basis figured out to a half dozen decimals, and, as a rule, without recourse in the event of flagrant discrepancies between the two analysts." The above is an extract from a letter received by the writer of this paper from the President of an iron company, discussing the question of sampling. It so well expresses the opinion of many blast-furnace owners and managers that it seems a suitable text for a discussion concerning the need of uniform methods of sampling. If all railroad cars were loaded the same, if all stock piles were the same shape, and if ore was received regularly each day, the problem of sampling would be comparatively simple. The conditions, however, vary widely at different places, and at the same place from day to day, and it is probably impossible to determine upon any one method of sampling which will apply at all times and in all cases. However, it would seem as though some general principles might be suggested which would tend to overcome these wide differences in samples of the same thing. The sampling of a cargo of iron ore begins at the breast of ore in the mine. The ore is sampled from the mine cars, from the stock piles, and from the railroad cars at the mines. At the lower Lake ports the ore is practically all sampled from the boat, occasionally from railroad cars. At the furnaces, the ore is nearly all sampled from railroad cars and occasionally from stock piles.

Jan 1, 1914

By D. L. Martin, E. R. Parker

IN a previous paper, one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with, and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a strengthening, so that a longer life at a given stress and temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver .2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. EXPERIMENTAL PROCEDURE Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1943