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By Heribert Wiedemeier, Ali Khan

The tetnperature-conposition phase diagram of the syste,n MnS-CdS has been investigated over a range fro)n 600° to 1000° C. The small degree of solid solution on the MnS rich slde cornpared to the large CdS rich single-plzase region could be esplained by the difference in strzrctures of the cotnponents and the relative sizes of the metal ions. The change in lattice parameter as a function of cot)zposition is linear atzd jollous Vegavd's rule within experittzental limits of error. Mns and CdS have gained considerable attention in recent years because of their interesting solid state properties. In order to investigate such properties and thermodynamic quantities of mixed compositions of transition metal chalcogenides, it is necessary to establish their phase diagrams. Two earlier publications are concerned with the MnS-CdS system. Schnaase' found complete miscibility when MnS and CdS were co-precipitated in aqueous solutions at room temperature. However, there is evidence that the mixed crystals were not stable over the entire range of composition. roger's' investigation of the ternary system ZnS-CdS-MnS at 900" C indicates a solution of 48 mole pct MnS in CdS. During the course of this work which covers a temperature range from 600" to 100O° C, emphasis has been placed on the use of high-purity materials and well-defined modifications of starting products. EXPERIMENTAL Starting Materials. The stable green modification of MnS with NaCl structure was prepared by direct fusion of the elements and by chemical transport reaction. Stoichiometric amounts of manganese of 99.99+ pct purity and of sulfur of 99.999 pct purity from Gallard-Schlesinger Corp. were sealed in an evacuated quartz tube at a pressure of 10"5 mm Hg and annealed for 48 to 60 hr at 800°C. The quartz tubes used throughout this work were outgassed under high vacuum at a temperature of 90OU to 1000° C for 12 to 18 hr. For the synthesis of MnS by chemical transport3 stoichiometric ratios of elemental manganese and sulfur and small amounts of iodine were sealed under vacuum in a quartz tube, which was placed in the temperature gradient, 900/800-C, of a two zone furnace. Single crystals of MnS in form of platelets and octahedra were deposited at the cooler end of the tube. The manganese content was determined by EDTA titratin. A typical result of several analyses was 63.05 pct Mn which agreed well with the computed value, 63.14 pct. Commercially available CdS of 99.9+ pct purity, a mixture of the cubic and hexagonal forms, was converted into the hexagonal high-temperature modification by annealing CdS under vacuum in quartz tubes at 700° C for about 36 hr. As a second method, cadmium sulfide was transported in a temperature gradient, 70O° /650" C, with in vacuo sublimed iodine from the hot to the cooler zone of the tube. Large sized crystals in form of hexagonal columns and some platelets were obtained. An average result of the cadmium analysis by EDTA titration4 was 77.93 pct in good agreement with the computed value, 77.81 pct. Only the NaCl modification of MnS and the wurtzite modification of CdS were used for the solid solutions. Preparation of Solid Solutions. Finely powdered MnS and CdS samples were thoroughly mixed in molar ratios and compressed into pellets of about 6 mm diam and 2 mm in height at a pressure of approximately 13,500 atm.

Jan 1, 1969

By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube's rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir' interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir's principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-' with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By E. L. Claridge, K. S. Lee

Areal sweep efficiency of oil displacement by enhanced-viscosity water exhibiting pseudoplastic behavior was measured in a Hele-Shaw model representing one-quarter of a five-spot pattern. The pseudoplasticity of polymer solutions and the velocity distribution in the five-spot pattern produced a condition under which the mobility ratio between the displacing and the displaced fluid could not be assigned a single value. Instead, the movement of the displacement front is governed by local mobility ratios which are also time dependent. The areal sweep at breakthrough with polymer solutions was poorer than the sweep obtained with Newtonian fluids of comparable viscosity. However, the areal sweep at 1 PV throughput was greatly improved as compared to flood water without polymer. It was also demonstrated that, even after the oil-cut had declined to a low value during a regular waterflood, switching to polymer flood efficiently swept out the oil remaining in the model. INTRODUCTION The behavior of fluid displacements in isotropic porous media for various patterns of injection and production wells has been extensively investigated.1-7 These investigations all concerned Newtonian fluids, i.e., the viscosity of each fluid was constant regardless of flow rate. The generally unfavorable influence on areal sweep efficiency of higher mobility of the displacing fluid as compared to the mobility of the displaced fluid has been established for both miscible and immiscible fluids. The principle was also established that a close correspondence exists between miscible and immiscible flood front behavior,2, 3 although oil recovery in a waterflood at unfavorable mobility ratio may be less than that observed in a miscible displacement at the same mobility ratio. This is true even when oil recovery is expressed on the basis of movable oil. The reason is that oil saturation only slowly achieves its final value behind the water-flood front in accordance with the Buckley-Leverett8 simultaneous flow relations. It is convenient to use miscible displacements for laboratory simulation of waterflood frontal advance since the interfacial tension forces which are negligible in proportion to viscous forces on a reservoir scale9 are thus made nonoperative in the laboratory model. For miscible displacements, the Hele-Shaw type of model adequately represents a porous medium so long as the appropriate scaling rules5-10 are observed in its design and operation. During simulation of waterflood front behavior in the laboratory by using miscible displacements, the behavior of connate water may ordinarily be disregarded since it is usually indistinguishable from flood water in this process. However, when the flood water is deliberately thickened to improve the mobility ratio between water and oil. the effect on the sweep efficiency due to generation of a connate water bank during the process must be considered. In a uniform porous medium, such a bank is generated11 and efficiently displaced by injection of thickened water.l2 The oil originally in-place at the start of the waterflood is then displaced by connate water followed by thickened water. If the flood water must be thickened to obtain a favorable mobility ratio, the mobility of the oil phase is appreciably less than that of the connate water. Hence, the oil phase is inefficiently displaced by the connate water bank, and a considerable proportion of the oil comes in contact with and is displaced by the thickened waterflood front' A recent study 12 of five-spot displacements using miscible Newtonian fluids in which connate water banks of various sizes were simulated shows that, for connate water banks as large as 40 percent of 1 PV, major improvements in sweep efficiency resulted from use of a thickened

Jan 1, 1969

By Forrest F. Craig

Both early and more recent1 laboratory measurements of gas-oil relative permeabilities were made by subjecting oil-saturated cores to external gas drives. In these runs it was generally assumed that the flowing gas/oil ratio was constant at every point throughout the core. Using this assumption, the resulting equation for the gas-oil relative permeability ratio becomes A where Q is the flow rate at the producing end of the system. This relative permeability was then specified for the average saturation of the core. The assumption and resulting equation fail to recognize that in an external drive, the oil flow rate varies from zero at the injection end to a maximum at the producing end. The assumption also fails to consider the existence of a saturation gradient during an external drive. This saturation gradient is due solely to non-steady-state flow. Some authors2,3,4 have used this erroneous method of calculating relative permeability ratios from external drives. Other authors5,6,7 have used relative permeability ratios in calculating expected field performance by external drive, using Equation (1) and making the incorrect assumption that the saturation is uniform within the driven portion of the reservoir. To find the correct relation between the relative permeability. ratio at the average saturation and the produced gas/oil ratio, the insertion in Equation (1) of a factor, F, to adjust it for oil velocity gradient has been considered. The equation then takes the form Assuming that the oil velocity is directly proportional to the distance from the injection point leads to the conclusion that, for a linear system, the average oil velocity is one-half that at the producing end. Thus, the average gas/oil ratio is twice the produced gas/oil ratio, and Equation (2) is transformed into However, here again the existence of a saturation gradient is not recognized. The produced gas/oil ratio is related to the relative permeability ratio at the saturation of the outlet end of the system. It can be shown quite readily that, if the true log k,/k, saturation relationship is linear over small ranges of saturation, then d log kjko Where aaxv and u2 are the average and outlet saturations, respectively. Examination of Equation (3) shows that the factor F cannot have a single value over the whole saturation range. Another method of dealing with external drives is that of Buckley and Leverett.' Their method, which assumes no gas expansion and outlet end effects, considers fully the saturation gradient present due solely to the displacement mechanism during an external drive, and applies Equation (1) to each point along this gradient. The calculation of production history using relative permeability ratio is straightforward. However, the calculation of relative permeability ratios from production history by this method is impractical. In a recent paper, Welge,1 using an approach similar to that of Buckley and Leverett, presents a simplified method for determining the saturation at the producing end of the system. At thi; saturation, the relative permeability ratio calculated by Equation (1) applies exactly, after breakthrough of the stabilizej front. By this method, relative permeability ratios or production history may be calculated with equal ease. Use of this method as a laboratory tool in determination of relative permeability ratios by external drive requires the knowledge of the total injected fluid volume; in addition to the average saturation and producing ratio. As a preliminary test of this method of calculation, laborntory external gas drives were run on a 3% in. diameter, 11 in. long sample of Nellie Bly consolidated sandstone. This core sample had a permeability of 824 md and a porosity of 28.1 per cent. The driving fluid was air. Three different oils were used, having viscosities of 1.4, 9.8, and 125 cp, respectively. The runs were made under identical pressure differentials,

Jan 1, 1952

By R. S. Wagner, H. Brown

Criteria for nucleation with the aid of twin planes during crystal growth from the melt are discussed. It is shown experimentally that bismuth crystals can grow from a subercooled melt in a twinned bismdtic form. A mechanism of growth based on the presence of at least me twin plane is proposed. It is well known that faceted growth can be observed in crystals grown from the vapor phase, dilute solutions, or from the melt. Faceted growth, in which the crystal is bounded by its slowest growing faces, will occur if the growth rate is strongly orientation dependent. The addition of atom layers on a facet plane can only occur by two-dimensional surface nucleation or with the aid of an imperfection. Nucleation with the aid of dislocations was proposed by rank' and observed to be of particular importance in crystal growth from the vapor phase. Nucleation with the aid of two-dimensional imperfections, notably twin planes, was suggested by stranski2,3 and Frank.4 A twin plane, terminating at the growth interface, can form a reentrant step at which nucleation can occur at a much smaller super-saturation (or supercooling) than required for two-dimensional surface nucleation. Nucleation by a twin plane usually results in a fast growth rate along a crystallographic direction parallel to the twin plane. Such a nucleation mechanism, based on the presence of a twin plane, has been used by Dawson5 to explain the growth and morphology of sheet-like crystals of paraffin n-hectane. In recent years more evidence was found that nucleation by twin planes occurs frequently in crystal growth from the vapor phase and from dilute solutions, for example, in cadmium,' barium titanate,7 silver,8 silicon9 and gallium arsenide.10 In crystal growth from a supercooled melt, however, nucleation by twin planes has so far only been observed in materials with the diamond or zinc blende structure. Bennett and Longini11 were the first to recognize the important role a single twin plane plays in the growth of germanium dendrites. Subsequently, it was found that a prerequisite for continued propagation of germanium dendrites is the presence of two parallel twin planes which form a self-perpetuating system of nucleation sites.12 Sili- con and some III-V compounds such as InSb also grow dendritically by twin plane nucleation. It appears that the following criteria must be satisfied in order that nucleation with the aid of twin planes can occur: A) The growth form of the material must be faceted." B) The formation of twin boundaries, by a fault in layer sequence during growth, by plastic deformation, or by an accidental meeting of properly oriented crystals, must be possible. C) Twinning must form a reentrant step where the twin boundary terminates at the faceted growth interface. D) These three conditions are necessary, but in certain cases not sufficient for continued crystal growth with the aid of a twin plane. Depending on interface morphology, a combination of more twin planes is sometimes required to form a self-perpetuating system of nucleation sites. This investigation was carried out with the idea in mind that nucleation with the aid of twin planes is a more general phenomenon and should occur in those materials, grown from a supercooled melt, which satisfy the criteria outlined above. It has been found that crystals of high-purity bismuth grown from a supercooled melt can grow by the aid of a twin plane. In the first two sections the faceted growth form and the twinning elements of bismuth are discussed. In the last section prismatic crystals of bismuth, which appear to grow with the aid of a deformation twin are discussed.

Jan 1, 1962

By H. M. Strong

Nickel and carbon form a metastable nickel-nickel carbide eutectic system which was ohsen)able by freezing latent-heat arvests at pressures 210 khars. The eutectic freezing temperature Is pressure had a slope of -0.9°Cper kbar. At 50 khars, the nickel-nickel carbide eutectic was at 1297° * 5°C and 0.34 mole fraction Ni3C. The composition of the eutectic increased at an initial rate of 0.004 mol fraction per kbar. The carbon content of the a phase also increased with pressure. Seveval illustrations of nickel carbide microstruc-tures are given and data on the lattice expansion of nickel in terms of carbon content are included. IRON, cobalt, and nickel form a variety of carbides with compositions varying between MeC and MC. Of the three, the carbides of iron are most easily recovered. The nickel carbides are so unstable at temperatures above 900°C that their occurrence in Ni-C alloys is unusual. Under sufficient pressure, however, the temperature range for the stability of the ferrous metal carbides is likely to be increased, or their decomposition suppressed (e.g., see Hilliard' on FesC), providing an opportunity to study the unstable carbides more closely. This was found to be true for nickel carbide which, under pressure, formed a eutectic with nickel. This paper describes the conditions of formation of nickel-nickel carbide eutectic compositions and their subsequent recovery. Despite the comparative instability of the nickel carbides, something is already known about them through various chemical reactions at temperatures not exceeding a few hundred degrees, and from their recovery by the very rapid quenching of molten Ni-C alloys from temperatures of about 1450°C or above. At least four carbides of nickel have been reported: A discussion of the state of knowledge about Ni3C is given by ansen.' The studies of Morrogh and williams7 who obtained Widmanstatten nickel carbide structures and of sidorenko8 who first obtained nickel carbide eutectic structures are also of interest. Sidorenko used short heating times for molten nickel in a graphite crucible followed by very rapid quenching to obtain the eutectic structures. Long heating times produced only the nickel-graphite eutectic probably due to the presence of graphite crystals in the melt which nucleated graphite crystallization. According to the early work summarized by anssen,' nickel carbide may form at temperatures far above the melting point and may be recovered by very rapid quenching. More recently, Giardini and Tydings, working on diamond synthesis, found evidence for "free nickel carbide'' in high-pressure reactions carried to temperatures far in excess of the limit for diamond growth, followed by rapid thermal quench. They stated that nickel carbide was not found in association with diamond growth. In the present work, observations were made on the melting and solidification temperatures of Ni-C alloys as a function of composition, temperature, and pressure. The nickel-nickel carbide eutectic was found at pressures above 10 kbar and its variation with pressure followed up to 60 kbar. Nickel-nickel carbide microstructures were recovered by quenching under pressure from temperatures of about 1400°C and higher. The formation of nickel carbide structures under ordinary diamond-growing conditions was usually observed but the role of carbide formation as an intermediate step in diamond growth needs more study. EXPERIMENTAL METHODS The melting and solidification temperatures of various nickel-graphite compositions were observed by latent-heat arrests in the sample holder illustrated in Fig. 1. The samples were composed of mixtures of carbonyl nickel powder and National Carbon Co.'s SP-1 graphite packed to densities of about 6.4 g per cu cm. They were contained within

Jan 1, 1965

By P. A. Beck, Hsun Hu

It has been known for many years that in cold drawn polycrystalline aluminum the recrystallization texture is practically identical with the deformation texture.l,2,3 V. Goeler and Sachs4 stated that in cold rolled polycrystalline aluminum, too, the deformation texture is retained upon recrystallization. This behavior was interpreted by Dehlinger9 as an indication that each recrystallized grain inherits the orientation of the matrix in which it grew. However, Burgers and Basart showed6 that in deformed aluminum single crystals the orientation of the recrystallized grains strongly deviates from that of the matrix. Barrett demonstrated8 that even in deformed polycrystalline aggregates the local orientation within each deformed grain changes on recrystallization. No explanation has as yet been offered of how the aggregate texture can be retained, while the local texture is everywhere changing. According to Burgers and Louwerse6 the orientation change on recrystallization in compressed and rolled aluminum single crystals corresponds to a rotation around [112] axes lying in the active slip planes and perpendicular to active slip directions. This orientation change was rationalized by them on the assumption that the orientation of the recrystallized grains is determined by the orientation of the available nuclei, and that these nuclei are small fragments of the deformed crystal, rotated in the deformation process. Barrett pointed out,? however, that these assumptions were by no means proven, and that the total volume of material necessary for the nuclei is so small, that it must be available in any orien- tation whatever. It is, therefore, unlikely that an "oriented nucleation" theory could satisfactorily explain the orientation changes in recrystallization of a deformed crystal. Furthermore, in contradiction to Burgers and LOU-werse's conclusions, Barrett's results for the orientation change could be best expressed in terms of rotations around. [Ill] axes. Thus agreement is lacking not only in the interpretations but apparently even in the experimental results contributed by the various investigators. The orientation relationships on coarsening* in a highly oriented polycrystalline matrix were first investigated by Burgers and Basart.5 They produced a fine grained highly oriented matrix by the recrystallization of a compressed or rolled single crystal of aluminum, and studied the orientation relationships in three successive generations of crystals: the "deformation texture" in the single crystal, the recrystallization texture, and the coarsening texture. Burgers24 showed that the preferred orientation of each successive generation was almost always widely different from that of the preceding one, but that the coarse grains often approximately reverted to the orientation of their grandparent, the deformed single crystal. This observation, and the idea that the orientation of the coarse grains is determined by that of the available "nuclei," led to the concept that the coarse grains are nucleated by the remnants of the deformation texture.12,15 On the other hand, Bowles and Boas16 found, in a carefully conducted experiment, that in recrystallized fine grained copper of cube texture coarse grains grow in orientations which can be derived from the orientation of the recrystallized matrix by rotation around a [lll].] direction: the coarsening texture here does not appear to be related in any simple manner to the original rolling texture from which the cube texture had been obtained by recrystallization. It may be assumed that in a recrystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as "nuclei" for the coarse grains, provided that the conditions are favorable for their growth. The existence of a coarsening texture may be considered as an indication that grains with certain relative orientations with respect to the preferred orientation of their neighbors can grow much faster than others. This "oriented growth" theory was briefly suggested by van Arkel, as early as 1936,13 and it was mentioned by Burgers." Recently, C. G. Dunn produced direct

Jan 1, 1950

By G. Derge, Ling Yang, John Henderson

Self-diffusion coefficients of aluminum have been measured by the capillary reservoir technique in liquids of the CaO-SiO2-Al2O3 system containirg equimolar portions of CaO and SiO2, in the temperature range 1400o to 1520oC. For the melt containing 6.0 mole pct Al2O3 the results can be expressed by the equation D = [(4.3 * 0.3) x 104] exp [(-85,000 * 17,500)/RT]cm~sec-'; for the melt containing 12.5 mole pct Al2O3, by the equation D = (5.4 i 0.2) exp [(-60,000 * 10,00O)/RT] cm2sec-: A concept of the constitution of these melts has been developed which proposes that the ratios O/(Si +Al) and Al2 O3/CaO determine the dominant species present. In recent years considerable work has been done on the system CaO-SiO2-A12O3 with a view to elucidating the structure of liquids of this system. Conductivity,' electromotive force, 3 density,4 and activity5 measurements have all contributed to an understanding of the problem, but as yet there is no entirely satisfactory theory that can account for all the observed experimental results. In principle, measurements of self-diffusion coefficients should give further information which is not obtainable in other ways. Self-diffusion coefficients for calcium, silicon,6 and oxygen7 have been measured. The present investigation extends the series of self-diffusion coefficient measurements to include aluminum and develops a concept of constitution for liquids of this system which is compatible with all the observed experimental results. EXPERIMENTAL The technique used in the measurement of the self-diffusion coefficient of aluminum was the capillary-reservoir method,8 A126 being incorporated in the melt contained in the capillary and inactive aluminum in the reservoir melt. This method was chosen because it minimizes convection currents' in the diffusion zone. It has the further advantage that the boundary conditions are such that a slight modifica- tion of Anderson and saddington's8 solution of Fick's Law yields an equation which requires measurements only of the length and the initial and final average specific activities of the solidified melt within the capillary. where t is the diffusion time, Co is the average specific activity of the melt contained in the capillary at t = O, C is the average specific activity of the melt contained in the capillary at t = t, 1is the length of the capillary, and D is the self-diffusion coefficient. The equation is of somewhat different form than those previously applied to high temperature diffusion studies because the specific activity of the melt in the reservoir was negligible both before and after diffusion. The diffusion apparatus is shown schematically in Fig. 1. It consisted of a silicon carbide resistance furnace containing the inactive melt in a graphite crucible, internal dimensions 7/8 by 4 in., enclosed in a 1 1/4- by 1 1/2- by 30-in. McDanel tube. A 3/8-in. McDanel thermocouple sheath to which graphite radiation shields and a graphite protection tube were affixed, was used to hold the capillaries. By moving this sheath through a rubber seal at the top of the McDanel tube the capillaries could be lowered into or raised out of the melt. Temperature was measured with a Pt-Pt 13 pct Rh thermocouple which was calibrated periodically against a standard couple. The furnace temperature was controlled to ± 5°C through the thermocouple immersed in the melt. Temperature variation over the depth of the melt was less than ± 3°C. The inactive melts were prepared from pure native quartz, assaying better than 99.9 pct SiO2, A.R. grade A12O3 and A.R. grade CaCO,. The same quartz and CaCO3 were used in preparing the active melts, the

Jan 1, 1962

By L. Adler

Any design of a mine roof in bedded deposits which ignores differential deflections at the supports can quickly lead to dangerous overstressing. As illustrated by the typical case presented on page 1029, if one support deflects only 0.1 in. more than its neighbor, stresses 50 pct higher than anticipated will result. Previous studies1-3 have assumed that the mine roof acts like a beam clamped at both ends, with no deflection or slope' at the supports (Fig. 1). Essentially this assumes:5* ?A = ?, = ?b and dA = dB = 0. However, a host of conditions can cause differential sag or deflection at one support, and even an apparently trivial deviation can have major consequences in the beam: variations in spacing, size, and material of supports; local settlement due to floor heaving or lower mine openings; non-uniformity in wedging or bolt tensioning.8 In one particular instance concrete pillars, poured in place, shrank away from the roof upon setting.' When understood and controlled, differential sag becomes a definite advantage, permitting the transfer of loads from one support to another. Where one support is a bolt or prop and the other a pillar or rib, the load on the former can be reduced while the load on the pillar or rib is increased. This means two things: 1) savings can be effected by using smaller artificial supports such as props and bolts and 2) loads can be increased in the rib to induce eventual failure for longwall caving. In this last respect, another factor underlying coal bumps becomes understandable. The design of a mine roof by beam theory assumes that when a bedded formation is homogeneous, iso-tropic, and elastic, it will act like a uniformly loaded beam, fixed or clamped at both ends,6 s in Fig. 1.'" These are important assumptions. The uniform load is the weight of the beam itself or its body load. For a beam of unit width, this load becomes per foot: w = yhb. w = uniform load y = specific weight, lb per ft3 h = depth or thickness of beam, ft b = width of beam, ft Since b = 1, w - yh [ 1 ] A beam fixed at both supports is statically indeterminate to the second degree, that is, two equations in addition to those for static equilibrium are required to determine the reactions at the supports. These equations result from the geometry. From statistics: ^F,= 0;RA + RB — wL = 0 [2] wU S,M0 = 0 ; MB H------------MA — RBL = 0 [3] it Using superposition in which the left support is kept intact and the right one resolved into an active force and moment, we obtain from Fig. 2:" ?b = ?m + ? b2 + ?B3 = 0 dB = dB1 + dB2 + dB3 / wU Ma RBL \ V d°=(-r+-2—r)-zr [5] Where: Subscripts refer to position on axis of beam R = force, lb M = moment, ft-lb w = uniformly distributed load, lb per ft L = span, ft 0 = slope, radians d = deflection, ft E = Young's Modulus, lb per ft" 1 = Moment of inertia about the neutral axis, ft4 Solving Eqs. 2 through 5 for the four unknown reactions, we obtain: 2 L3 Fig. 3 is obtained by plotting MA and M, vs d, and then plotting RA and R, vs d, and adjusting their scales to coincide with MA and M, vs d,. It should be noted in Eqs. 6 and 7 that as dB increases, MA increases the same amount that Mn decreases. Eqs. 8 and 9 show a similar relationship between RA and R,. Proof that MA is the maximum absolute moment occurring in the beam is as follows: where M, = moment at x wx-When where M,., = maximum positive moment Eqs. 6 and 8 into above: For small dn: MA> M,,,

Jan 1, 1960

HenRy Clay FRick, a pioneer in modern coke and steel industry and, in more recent years, one of the outstanding financiers of America, died on Dec. 2, 1919, at his home on Fifth Avenue, New York. Although he had been ill since election day, when he had an attack of indigestion which developed into ptomaine poisoning, his death was a surprise to all. He is survived by his widow, Adelaide Howard Childs Frick; a son, Childs Frick, one unmarried daughter, Helen C. Frick, and four grandchildren. A quiet funeral service was conducted at the Frick home on Wednesday afternoon by the Rev. Dr. Leighton Parks, pastor of St. Bartholomew's Episcopal Church. This was attended by members and very intimate friends of the family, Trustees of the Metropolitan Museum of Art, Officers of the Links Club, and Directors of the United States Steel Corpn. Henry Clay Frick was born Dec. 19, 1849, in West Overland, Westmoreland Co., Pa. His father, John W. Frick, was a farmer of Swiss ancestG, and his mother, Elizabeth Overholt Frick, a member of an old Mennonite family. Until he was sixteen, he spent his time at school, on his father's farm, and in his grandfather's distillery, where he kept books. He attended Otterbein University, in Ohio, for a year. Frick, learning that coke was an essential of the already rapidly developing steel business, early invested every cent he could get in coking-coal lands. With the help of an associate of his grandfather, he formed the corporation of Frick & Co., coke dealers, and acquired fifty-one ovens in the Connellsville region and 300 acres of soft-coal lands. During the panic of '73, with the help of Judge Thomas Mellon, a Pittsburgh 'banker, he bought out his partners and while coke was selling at 90 cents a ton enlarged his purchases of suitable lands. Later, the price of coke increased until it was selling at $5 a ton. Before he was 30 years old, Frick was rated a millionaire. Association with CaRnegie In 1878, he sold an interest in the business Do E. M. Ferguson of New York, and later a share to Mr. Ferguson's brother. Four years later the business was reorganized into the H. C. Frick Coke Co. with vast coal lands, great banks of ovens, and a capitalization of $2,000,000. Then began his association with Andrew Carnegie. He exchanged a part of his coke interest for shares in Carnegie Brothers of Pittsburgh,

Jan 1, 1920

NEW MEMBERS. The following list comprises the names of those persons who became members during the month of November, 1913: Members. AGNEW, JOHN L., Gent Supt Copper Cliff, Ont., Canada. BAILEY, FRANK C, Mine Mgr 2003 IV. Snito Ave., Spokane, Wash. BATEMAN, ALAN M., Min. Geol.,Care L. C. Graton, Geological Museum, Cambridge,Mass. BERRYHILL, JAMES G.,Atty.-at-law and Mining Investor, Equitable Bldg., Des Moines, Ia. CARTLIDGE, OSCAR, Mgr. State Mine Rescue Station, 452 W. South Grand Ave.. Springfield. Ill.

Jan 12, 1913

By Will B. Jamison

It is a fact that the most serious safety problems encountered in US underground coal mines are related to roof-bolting operations. It is also true that roof bolting is usually the operation which limits coal production from a mine section. There has been a recent focus on activity involving roof bolting research, development, and new ideas as people concerned about mine worker safety and productivity realize that significant progress can be made in these areas, even with equipment presently available.

Jan 7, 1977

By J. H. Jackson, P. D. Frost, C. H. Lorig, L. W. Eastwood, A. C. Loonam

R. S. BUSK*—I wish first to congratulate the authors of this paper both for the work done and the presentation of that work. We have also been working on this type of alloy development, but any technical contribution I might have is better reserved for a separate paper which is planned in the near future. However, I would like to insert a word of caution. The alloys described in this paper are still very much in the laboratory stage. There still remains the quite vexing problem of property stability at slightly elevated temperatures which must be solved before the properties quoted can be effectively utilized. These alloys are extremely interesting and I am confident that the problems can be solved. However, the present existence of those problems must not be overlooked. I have one question with regard to the work-hardening test. If the work harden-ability of magnesium is compared to aluminum using a more standard test such as the Meyer Analysis the magnesium is found to work harden the more rapidly. Is the test developed for this work truly a work-hardening test or a measure of something else ? J. H. JACKSON (authors' reply)—I am sure we appreciate the comments of Mr. Busk and we are pleased that the Dow Chemical Co. has also undertaken work in this field. It is a big field. We, of course, are continuing our research for the Navy Bureau of Aeronautics, since, as clearly shown in the paper, the alloys are not completely developed. With regard to Mr. Busk's comments on the relative work-hardenability of aluminum and magnesium, the comparison we cited in the paper was intended merely to show that the results obtained by our method of testing were independent of the yield strength of the materials. We believe that this test method afforded a rough indication of the work-hardenability of the magnesium-lithium base alloys. It is not known whether this method affords greater or less accuracy than the Meyer Process, which is based upon a hardness-test impression. It is quite possible, since work-hardenability is a function of metal purity, that our results, obtained for commercial aluminum and magnesium, would be different if high-purity metals had been used. A. C. LOONAM—Lithium has some very interesting effects on magnesium. The paper showed that even small percentages increased ductility. These small amounts changed the axial ratio of the hexagonal magnesium from 1.624 in the pure metal to 1.606 in the saturated alpha solution, a value close to that of titanium, which has a ratio of 1.601. You will recall an article in the January, 1949, issue of the Journal of Metals where it was stated that titanium can be cold-rolled over 90 pct without any significant edge cracking. At 4.9 or 5 pct lithium, a change begins in crystal structure—from a hexagonal close packed to body centered cubic. There are two phases over a short range of lithium content, but at 10 pct the structure becomes completely cubic. The melting points of alloys in this range of lithium content are relatively high. Alloys even up to the six ratio have melting points above 500°C; this represents a relatively small reduction in melting point from pure magnesium itself. The magnesium-lithium system has a number of very interesting characteristics. This is only a very small part of the story. J. H. JACKSON—I would like to remind you that Mr. Loonam is one of the authors of this paper, and the fact is that this work is based on many of his ideas. I am sure we appreciate his additional comments in this discussion. R. LEITER*—I am interested in Fig 19 in which Mr. Jackson compares

Jan 1, 1950

By Willard Ide Pierce

THE native methods of mining and milling gold-ores in Korea may not present any specially new features, but are chiefly interesting as primitive practices, still followed at the present day. In mining where the rock is hard, wood is piled up near the face of the tunnel or drift and then set on fire. The fire bums for twenty-four hours, after which, three or four days are given for the rocks to cool, before the miners go in and extract the loosened material. The only tools in use are a hammer, a steel gad about five inches long, and a flat spoon-shaped basket. The pay-streak or chute is closely followed, and in places the workings are very small and intricate. Rock not yielding more than $6 per ton is not extracted. The manner of opening a mine is to begin on the outcrop, where the rock pays, sink a shaft or run a tunnel on the vein, and follow the pay-streak and more easily worked ore. When this is exhausted, or the influx of water interferes, the opening is abandoned and operations are begun again at a new spot on the outcrop. The place usually selected is as high up on the mountain as possible, and in no instance is advantage taken of the topography by running a cross-tunnel to tap the vein. The ore is brought in baskets to the surface, and there placed in sacks, holding about 150 1bs. each, and taken to be crushed. The rock is first crushed between two stones, as shown in Fig. 1. The upper stone is oval and rounded on the bottom, so that it can be readily rocked on the under stone. Two pieces of wood, used for handles, are placed, one on each side, in grooves in the upper stone, and held in position by means of straw rope. The lower stone is not smooth on top, but exhibits three elevations running lengthwise, with shallow depressions between them. The middle elevation acts as a fulcrum on which the upper stone may be rocked. From two to ten men, according to the weight and size of the stone used, are employed in rocking. With four men, from 300 to 350 lbs. of rock can be crushed per day, the stone making 50 complete oscillations per minute. The men squat on each side of the stone and move it to and fro by means of the wooden handles. The ore is fed, in pieces up to the size of an egg or even larger, by one of the men. During the crushing one man on each side, as the stone rocks from

Jan 1, 1890

While coal was undoubtedly seen by the Spanish explorers in Texas, no mention can be found of it in any of their available published records; it was likely noticed by the first Americans, and coal along the Rio Grande River was reported in 1834.1 The next record is that of brown coal in Bastrop County in 1837 by James Nicholson and Judge Pinckney Hill? Dr. Riddell saw brown coal along the Trinity River in 1839 and described it as follows: "In the banks of the Trinity, associated with the iron ore, and overlying the brown coal, whole trees and fragments of trees, piled sometimes one upon another, present themselves completely transformed into stone. In some logs a diversified metamorphosis is observable; one portion of the vegetable structure having been replaced with silex, another with brown oxide of iron, and a third is bitumenized or converted into coal. "In concern with Dr. F. B. Page, I took considerable pains in the exploration of the Trinity brown coal formation., As no excavations for working have yet been made, the best places for inspecting the formation are where the Trinity cuts its way through the highlands, or where its banks present themselves in bold high bluffs, as at New Cincinnati, and near the site of the projected town of Osceola. The coal lies in horizontal strata, dipping one foot in thirty to the northwest. The main stratum at the latter place, just above Bedias creek; is represented by the concurrent statement of W. C. Brookfield, surveyor, Mr. James S. Hunter, of Huntsville, Texas, Dr. Page, and some other persons whom I consulted, as between six and seven feet in thickness, the lower portion being between three and four feet above low water mark. Unfortunately, during my sojourn there, the river was unusually high and turbid for the season of year; I could not consequently verify the same by personal observation and measurements. The most considerable coal beds which I had opportunity fully to inspect, were in the Trinity bluffs, southwest side, at New Cincinnati, six miles lower down, and just below the mouth of Salt creek, near six miles above. The workable stratum of brown coal in each of these localities is about five feet thick, and situated some fifteen feet or so above low water mark. In quality it is said to be precisely similar to the coal in the seven feet bed."2 . Moore in 1840 mentioned coal in the vicinity of Great Salt Lake, through which the Brazos flows; lignite in Bastrop County; lignite in the banks of the Colorado River a few miles above Lagrange in Fayette County; a deposit of excellent coal in the bed of the Sabine River, 30 miles above the

Jan 1, 1942

By H. Conrad Meyer

The wizardry of nucleonics has added new and greater dimensions to the almost inseparable "twins"-zirconium and hafnium. So close is their relationship that neither element is found free of the other in any presently known mineral. Although zirconium in the form of its oxide was discovered in 1789 by Klaproth, the metal in an impure, nonductile form was not isolated until 1824 by Berzelius. About 100 years later -1925-van Arkel and deBoer developed and patented a technique for the deposition in vacuo of crystalline, coherent, highly ductile metal of extreme purity on an electrically heated filament through the dissociation of gaseous zirconium tetraiodide. Within the past five years both zirconium and hafnium have been dramatized by the press and in popular science magazines. This has led to the false assumption that practically all of the world consumption of zirconium ores is used in the production of the metals. Recent statistics on the subject show that not over 15 pct of the zirconium ore consumed in 1958 went to ferrosilicon zirconium and zirconium metal. The rest was consumed in refractories, foundry sand and facings and ceramics. The importance of zirconium as a component in compact, relatively lightweight nuclear energy units, such as those now used in the submarine Nautilus,6 is well established. A rival of zirconium metal as a casing for atomic fuels is a newly developed ceramic body. It is claimed to be cheaper than zirconium-to withstand higher temperatures-and to be more resistant to corrosion. Whether such ceramic casings have the required low thermal neutron absorption cross section, high strength and easy formability of zirconium is yet to be demonstrated. Hafnium, because of its low order of abundance and its close chemical relationship to zirconium, was not definitely recognized as a new element until around 1923, despite prior claims. A study of the X-ray spectra of zirconium led to its identification. The circumstances leading to the discovery of hafnium were much less fortuitous than those surrounding zirconium. The more precise tools of arc and X-ray spectrometry lent themselves admirably to the search for elements to fill certain gaps in the periodic table. [ ] Pure, ductile hafnium-a metal similar in appearance to stainless steel-has a specific gravity of 13.3 (zirconium 6.52) and a melting point of 2,200°C. In other respects it closely resembles zirconium except in one important respect which gives it a preeminent position in nuclear energy development, namely, a high thermal-neutron absorption cross section. This explains the necessity of hafnium-free zirconium in atomic piles. The ability of hafnium to capture thermal neutrons makes it an excellent "moderator" of "governor" when used as control rods in nuclear reactors (Table 1).

Jan 1, 1960

By S. J. Salat, E. E. Burton

The new Inspiration copper smelter, which introduced unique technological innovations to the copper industry, required a plant material handling system to match. The system has been designed to convey such diverse bulk materials as copper concentrates, copper precipitates, lime, limestone, silica, flue dust, and revert materials. The moisture content in the materials varies from bone dry to a maximum of 25%. Since the summer of I974 when the smelter went into operation, the material handling system ha provided satisfactory and dependable services.

Jan 1, 1981

The Free World's largest uranium reserves are in the United States. Almost 97% of the U.S. uranium reserves occur in irregular shaped sandstone formations, widely disseminated in coarse clastic sediments that are mostly of Jurassic or Tertiary age. Without doubt, the most important deposits are located in the sandstone formations of the Ambrosia Lake district of New Mexico, near the sun-scorched town of Grantswhose proud alias, as given by the city fathers, is "The Uranium Capital of the World."

Jan 8, 1974

By R. Walker, R. J. Anslow

Today at Tampa we see the end results of a team effort: A vital link in an intermodal transportation system, the link that enables the unit-train concept to be employed with full effectiveness and the link that improves the economics of water transportation systems. Two new phosphate transfer complexes with a multi- million ton annual capacity are in operation in Tampa, Fla. Revolutionary in concept, these companion installations represent a total investment in the Tampa Bay area of $18.5 million.

Jan 1, 1970

By B. E. Cornish

Most technical and statistical data published on pyrophyllite relating to production figures, uses, markets and sales, have in the past traditionally linked the mineral with talc and soapstone. This is due to several common superficial physical properties resulting in substitute uses and applications. However, these minerals are not similar in chemical composition and do not generally occur in a similar geological environment. Pyrophyllite now stands on its own in the marketplace-particularly in ceramic applications-due to the combination of excellent heat shock and creep resistance properties of the mineral. The increase in pyrophyllite use in the field of ceramics indicates the continuing realization of these marked unique properties. Several new fields of ceramic applications, previously the preserve of high-alumina materials, have been developed on the intrinsic properties of pyrophyllite. Pyrophyllite is an aluminum silicate with the molecular formula of AI2O34SiO2H2O. It would be more appropriate to group pyrophyllite with such materials as kyanite, diaspore, andalusite, and certain high-alumina clays in relation to its general applications (Stuckey, 1928). These materials all have good beat shock resistance properties at high temperatures and are widely used for the manufacture of refractories. For those reasons they are interchangeable in some applications. Pyrophyllite also has many uses in nonceramic applications, the most important to date being as a substitute for talc in fillers. The major pyrophyllite mining operations are located in the US, Japan, Korea, Canada, and Australia, where the mineral is widely used as a raw material for general ceramic, mineral filler, and dilutant applications. Commercial Applications Pyrophyllite was first used in the last century for lining stoves and fireplaces, and also in the carving and polishing of ornamental objects. The rise in industrial demand for new products and applications resulted in the introduction of pyrophyllite as an alternative, mainly for talc and soapstone. Industrial filler applications followed for paint, paper, cosmetics, rubber, pesticides, crayons and pencils, and bleaching soap. The first use of pyrophyllite in ceramic applications was prior to World War II, in the manufacture of ceramic cladding tiles in the US. This was followed by the production of kiln furniture refractories and whiteware when pyrophyllite was offered by suppliers in North Carolina as an alternative to some local clays. The largest tonnages of pyrophyllite used today are in refractory linings in steel ladles in Japan, as seen in Table 1. The consumption of pyrophyllite in Japan is second only to clay and chamotte among refractory raw materials used. Recently this technology has been adopted in Australia. Japanese and Australian practice has resulted in appreciable technical and economic benefits, particularly when pyrophyllite is used in combination with zircon. The potential growth for this application is substantial if US and European steelmakers follow. Investigation and research into the properties of pyrophyllite determined the following main advantages of pyrophyllite-based ceramics: high corrosion resistance for molten iron, steel, and slags; good heat shock resistance; good indices of deformation under load and hot creep resistance (refractories); and increase in mechanical strength of whiteware products promoted by a better distribution of mullite in finished products (also obtained at lower firing temperatures than normally required in production of triaxial ceramics). White cement

Jan 1, 1983