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By John V. Beall

If there is one thing that makes a fellow feel like the years are catching up with him, it is to go through a second cycle in which the adequacy of mineral resources is being "viewed with alarm." The first time we experienced such a flap was in 1951. At that time, the United Nations convened a meeting at Lake Success to study ways and means of averting a crisis in minerals. Presently there is some sentiment being expressed about the mineral scarcities that will occur in the decades ahead, in view of world population trends and increasing per capita consumption of metals. To be greatly concerned about the adequacy of metal supplies is to be highly pessimistic about the capabilities of technology. As in the past, shortages will be of temporary duration for as far ahead as the most ambitious prognosticators are projecting. The study of mineral economics is a fascinating and surprising subject. The law of supply and demand is but a starting point. The iron ore market for the steel industry is an example which comes to mind because of our receipt this week of the United Nations report "Survey of World Iron Ore Resources."

Jan 1, 1970

By John R. Gould

A mathematical treatment of multiple-pass floating-zone refining of semiconductors, including the evaporation of solutes from the melt at reduced pressure, is presented. Vapor pressures and evaporation rate constants for phosphorus, arsenic, and antimony in germanium have been determined from floating-zone experiments conducted at 10 mm Hg. Rate sensi-tivity of arsenic in germanium has been examined over the range of 1 to 10 in. per hr growth rate. The equilibrium value of the segregation coefficient of arsenic in germanium, as determined by an extrapolation of these data, was found to be 0.09. PFANN has treated the segregation of nonvolatile solutes in the zone-melting process, Bradshaw and Mlavsky2 considered the evaporation of solutes in a vacuum during the growth of crystals by pulling from the melt, and van den Boomgaard3 has shown that it is possible to bring a volatile impurity element homogeneously into an ingot by means of zone-melting under a constant pressure of that element. This paper is concerned with the volatilization of solutes during zone - melting in a vacuum. The mathematical analysis by Lord4 of multiple-pass zone melting is extended to include evaporation of solutes. A method is presented in which evaluations of vapor pressures, evaporation rate constants, and distribution coefficients may be derived from the variation of solute concentration in the floating-zone refining of germanium at 105 mm Hg. EXPERIMENTAL Ingots of zone refined germanium, approximately 1/4 in. in diam and 10 to 12 in. in length, were subjected to several floating-zone passes at 105 mm Hg in order to provide intrinsic material for these studies. These ingots were then seeded in a [Ill] direction and solid-doped to a constant impurity concentration of approximately 1015 atoms per cmS in a forming gas ambient (10 pct H - 90 pct A) at 1/2 atm gage. The resulting crystals were subjected to repeated floating-zone passes at 105 mm Hg and a concentration profile along the length made after termination of each pass. Concentrations were determined from four-point probe resistivity measurements, and proper precautions were taken to prevent contamination during handling. A constant zone length, crystal cross section, and growth rate were maintained during zoning. A stationary coil and moving crystal system were employed for floating-zone growth with neither the section of crystal above nor below the melt rotated.

Jan 1, 1962

By T. W. Watson, D. R. Flynn

Measurements have been made of the thermal conductivity and electrical resistivity of two specimens of 0.005-cm (2-mil) Be-Cufoil over the temperature range -140° to +200°C. The thermal cmductivity of Be-Cu Alloy 125 was found to be significantly higher than that of Alloy 25, which had a higher impurity content. The thermal conductivity and electrical resistivity values obtained were in concordance with the Smith and Palmer relation for copper alloys which states that ? = 0.0239 (T/p) + 0.075 where A is thermal conductivity (W cm-' deg-'), p is electrical resistivity (microhm-cm), and T is absolute temperature (OK) , indicating that the Smith and Palmer relation can be used to predict the thermal conductivity of this type of Be-Cu alloy over the temperature range -140" to + 200°C to within an accuracy suitable for most engineering applications. THE National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, Md., requested the National Bureau of Standards to measure the thermal conductivity of 0.005-cm Be-Cu foil which was to be used to fabricate antennae for use in Radio Astronomy Explorer space craft. It was felt that measurements had to be made on the actual antenna material, rather than on a thick bar of similar material, since the cold-working and age-hardening properties of the alloy would make it very difficult, if not impossible, to place a thick bar in the same metallurgical state as the 0.005-cm material. As discussed in Section 111 of this paper, the thermal conductivity of many copper alloys can be computed rather accurately from electrical resistivity data using an empirical relation developed by Smith and palmer' and further confirmed by owell.' However, there has been very little work done on correlating thermal and electrical conductivities on Be-Cu alloys. We were reluctant to assume the validity of the Smith-Palmer relation on Be-Cu alloys because of the very large mass difference between beryllium and copper. As will be seen, however, our experimental results indicate that the Smith-Palmer relation is valid for the two alloys on which we made measurements. I) DESCRIPTION OF SAMPLES Samples of Be-Cu Alloy 25 and Be-Cu Alloy 125 were furnished to NBS in the form of rolled strip material, 0.005 cm thick by 5.08 cm wide. The Be-Cu Alloy 25 was purchased by NBS in the form of a continuous length of flat strip. The Be-Cu Alloy 125 was furnished to NBS by Goddard Space Flight Center in the form of two lengths of strip that had been formed into "tubing" of about 1.2 cm diam, with one side of the strip overlapping (but not connected to) the other side by about 90 deg. This "tubing" had been opened up to be flat and then rolled onto spools of about 3 cm diam. When unrolled, the strip would spring back into tubular form. Samples of both of the Be-Cu alloys were chemically analyzed by the NBS Analytical Chemistry Division. The beryllium content was determined quantitatively by the phosphate-gravimetric method to be 1.83 wt pct for Alloy 25 and 1.80 wt pct for Alloy 125. The two alloys were also examined by a general qualitative spectrochemical method for metallic elements. The Alloy 25 specimen contained between 0.1 and 1.0 wt pct Al, Co, Fe, and Si and between 0.01 and 0.1 pct Ni. The Alloy 125 specimen contained between 0.1 and 1.0 pct Co and between 0.01 and 0.1 pct Al, Fe, and Si. Other metallic elements present were in amounts less than 0.01 pct. The NBS Engineering Metallurgy Section measured the tensile strength, elongation, and Knoop hardness of both the Be-Cu Alloy 25 and the Be-Cu Alloy 125. These are given in Table I. The NBS Engineering Metallurgy Section also prepared photomicrographs of the two alloys; these are shown in Figs. 1 and 2.

Jan 1, 1969

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 H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe's formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade's exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By L. J. M. Smits

A theoretical equation is developed describing membrane potentials of shaly sands as a function of the cation-exchange capacity per unit pore volume of the rock and saturating water salinity. This equation is based on the same simple physical model as that employed earlier7 describing the electrical conductivity of shaly sands. Experiments conducted with NaCl solutions showed that the equation is obeyed, except in the case of saturated salt solutions where minor deviations were observed. A possible explanation is given for this discrepancy. As the clay content and the porosity of shales may vary appreciably, shale membrane potentials also vary. It was found that membrane potentials of shales can be calculated accurately with the aid of the same theory. Consequently, changes in membrane potentials can be accounted for by simple measurement of cation-exchange capacities per unit pore volume of both shales and shaly sands. Charts are given to facilitate interpretation of the electrochemical part of the SP in terms of cation-exchange capacities and the salinities of mud filtrate and formation water. INTRODUCTION A spontaneous potential (SP) log is a record of the way in which the electrical potential of a sonde varies as it passes down a borehole. Such variations frequently reflect rock texture, e.g., permeable beds intercalated in an impermeable series often are indicated by a sharp change in potential. Nowadays it is recognized that SP logs may be interpreted in terms of formation-water salinity and formation shaliness. The four sources of the SP are illustrated in Fig. 1. El and E4 represent streaming potentials generated by the flow of mud filtrate through mud cake opposite permeable formations and through shale, respectively. An extensive review of the literature on the evaluation of these streaming potentials is given by Lynchl and will not be discussed here. The remaining part of the SP generally is called the electrochemical potential, which is divided into two parts: a membrane potential across the shale (E3, Fig. 1) and a membrane potential in the permeable sand at the diffusion boundary between formation water and mud filtrate (E2, Fig. 1). It was found by wyllie2 that the membrane potential across the shale, E3, is the most important contribution to the electrochemical potential, the shale acting as a semi permeable membrane. When the sand is clean it does not influence the diffusion process, so E2 equals the value of the so-called liquid-liquid junction potential observed when the two solutions diffuse freely into each other. When the sand contains clay, however, this interferes with the diffusion process and affects the diffusion potential generated. The greater the proportion of clay, the stronger this effect will be. Wyllie,3 Doll4 and Poupon et al.5 took this effect into account theoretically, starting from a physical

Jan 1, 1969

By S. J. Harrison

One of the operations of the J. L. Shiely Co. is quarrying in a hard granite gneiss with intrusions of gabbro or trap. During the winter of 1948-1949 the quarry ramp was lowered about 30 ft and during the 1949 season practically all drilling was done from the quarry floor, developing a face from 72 to 83 ft for the entire quarry area. The performance and cost table shows our record for 1948 and 1949.

Jan 9, 1950

By Robert H. Palmer

Sacuranao Field.—Bacuranao field is about 12 miles east of Havana, along the contact between Cretaceous sediments and a serpentine intrusion. The zone lies within an extensive anticlinorium. The field had no developments during the year 1939. The production of 9½ bbl. per day is distilled and the gasoline and kerosene are extracted. The asphalt residue. is sold for road construction. The gas is compressed and

Jan 1, 1940

By Robert H. Palmer

Sacuranao Field.—Bacuranao field is about 12 miles east of Havana, along the contact between Cretaceous sediments and a serpentine intrusion. The zone lies within an extensive anticlinorium. The field had no developments during the year 1939. The production of 9½ bbl. per day is distilled and the gasoline and kerosene are extracted. The asphalt residue. is sold for road construction. The gas is compressed and

Jan 1, 1940

By John Chipman, Daniel Dutilloy

The equilibrium of gaseolis H2O-H2 mixtures with liquid iron-phosphorus alloys in the range 0 to 3 pct P is used to establish the increuse of the activity coefficient of oxygen, in the presence of phosphorus. Two different sampling techniques are used. THE importance of oxygen as a refining agent in steelmaking operations makes it desirable to improve our understanding of its behavior. Phosphorus which is always present in the ores has adverse effects on steel properties and its removal is necessary. The present study was undertaken to evaluate the interaction of oxygen and phosphorus in molten iron. Bookey, Richardson, and welch1 have studied the phosphorus-oxygen equilibria in liquid iron in the presence of lime. They used a mixture of hydrogen and water vapor to control the oxygen potential and worked with crucibles made of tetracalcium phosphate and lime. At low phosphorus concentration, i.e., at high oxygen, they observed a marked deviation in their results. They tentatively ascribed this to a large negative effect of oxygen on the activity of phosphorus. This was then included by chipman2 in his review of interactions in liquid iron. Pearson and Turkdogan 3 have later reported an interaction parameter They equilibrated a mixture of hydrogen and water vapor with an iron-phosphorus alloy contained in an alumina crucible and sampled the melt by suction in a silica tube. The solubility of oxygen in iron-phosphorus alloys has been studied by Levenets and Samarin.4 They reported an interaction parameter

Jan 1, 1961

By D. Gupta, S. Weinig

This investigation comprises the study of dislocation-oxygen interactions in a! titanium and its effect on the ductile to brittle transition in titanium. Internal friction techniques using a low-frequency lorsion pendulum were used to study the oxygen atom interactions with dislocations in "superpurity" titanium. A calculation of the interaction energy between an oxygen atom and a dislocation, based on the "breakaway" strain resulted in a value of 0.015 ev as compared to theoretical values of 0.022 and 0.035 ev for edge and screw dislocations, respectively. Both the saturation of the room temperature decrement and the transition from ductile to brittle behavior occurred at 1.5 at. pct 0. It was proposed that the embrittlement was due to oxygen atoms immobilizing the dislocations. It was possible to increase the ductility of the Ti-0 binary alloys by decreasing the oxygen pinning. The increase in uniform elongation was 30 pct for an increase in the preanneal temperature of 300°C. ThE room-temperature ductility of a titanium is significantly affected by interstitial solutes. Although oxygen has a solid solubility of 15.5 pct by weight, the room-temperature ductility extends only to 0.6 pct.' The ductility precipitously falls at this concentration and the fracture characteristics change from ductile to brittle.2 The small effective bulk composition of solute required to destroy the room-temperature ductility of the titanium must be indicative of an in-homogeneous distribution of solute atoms. Internal friction techniques were used in this investigation to

Jan 1, 1960

By Robert D. Pehlke, Kazuhisa Okajima

ThE prediction of the activity coefficient for a solute in a multicomponent liquid metallic solution based on measurements in the related binary systems has been the object of study for some time, particularly in iron-base alloys.1,2 Very few measurements, however, have been made on nonferrous systems; furthermore, measurements made for the specific purpose of testing various prediction equations are almost nonexistent. The measurements here described of the activity coefficient of cadmium in liquid lead alloys were directed toward this goal. One of the most direct means by which the activity coefficient can be calculated has been based on the independent influences of each solute. When solute metals i,j, k, and so forth are present, the activity coefficient, y, of one of these (i for example) may be expressed as a product of factors which represent the effects of each of the other components:

Jan 1, 1964

By S. R. Goodman, Hsun Hu

A detailed study of texture developmenf in poly crystalline copper atzd 70-30 brass has been completed. Textural changes as a function of deformation are shoum by pole jigmres and by intensity measurements oF- various rejlectiotzs from the rolling plane and the rolling direction. These examinations were accompanied by measurements of stacking fault frequency, hardness changes, and microstructure. Some of the results were briefly presented earlier. Additional results reported here are consistent with the idea that deformation faulting or slip by partial dislocations is of primary importance in the formation of deformation textures in fcc metals. lo examine the idea that deformation faulting is of primary importance in determining whether the texture is the copper type or the brass type an extensive study of the development of polycrystalline textures in copper and 70-30 brass was initiated. Besides the determination of complete pole figures, the intensities of the various reflections from both the rolling plane and the plane perpendicular to the rolling direction, the peak shifts due to deformation stacking faults, and the hardness of the rolled specimens were examined at various reductions from 10 to 99 or 99.5 pct. Mi-crostructures were examined by transmission electron microscopy. Some of the results were briefly presented in an earlier publication.' Since then, additional information has been obtained. This is given in the present paper. EXPERIMENTAL PROCEDURE Material and Specimen Preparation. The material used was a commercial electrolytic copper bar 1i in. wide and 2 in. thick and a 70-30 brass bar la in. wide and 1i in. thick. Chemical analysis indicated a purity of 99.97 pct for the copper, with 0.025 pct 0 as the major impurity. The 70-30 brass was of higher purity with 0.0016 pct 0 as the major impurity. Extreme care was taken in the preparation of the starting material to insure uniformly fine grains with a nearly random initial texture. The two bars were first cold-forged and then annealed to eliminate any original texture. The grains were then refined by several cold rolling (approx 30 pct reduction) and annealing treatments. The + -hr anneals were carried out in a salt bath at 390" to 440°C for copper and at 490°C for brass. The resulting penultimate grain size was 0.06 mm for copper and 0.03 mm for brass, and both showed very little preferred orientation. The number of prior cold rolling and annealing cycles was such that the final thickness after various final reductions of 10 to 95 (for brass) or 99 (for copper) pct was the same (0.020 in.). These annealed strips were rolled in two directions by reversing end for end between passes according to the following schedule: 0.006 in. per pass to 0.100 in., 0.003 in. per pass to 0.050 in., 0.002 in. per pass to 0.025 in., 0.001 in. per pass to 0.020 in. Texture Determination. The development of rolling textures was studied by examining complete pole figures determined from the (111) reflection. Specimens thinned from one face of the strip to half thickness (0.010 in.) were used to obtain the central portion of the pole figures, while specimens thinned from both faces to 0.003 in. were used to obtain the peripheral portion. The reflection and transmission techniques have been described previously. In addition to X-rav pole figures, texture development was also studied b; examining the intensity variation of the (Ill), (200), (2201, (311), (331), (420), and (442) reflections from the rolling plane and from the plane normal to the rolling direction, as a function of deformation. The same specimens used for the central portion of the pole figures were used for the intensity measurements of the various reflections from the rolling plane. For intensity measurements from the plane normal to the rolling direction, composite specimens were prepared by mounting sections cut parallel to the transverse direction of the strip. An epoxy resin was used to bond these sections together, and the entire composite was then mounted in a cold-setting resin to facilitate subsequent polishing and etching to remove distorted metal at the cut. The intensities were expressed in units of the integrated intensities measured from an annealed copper specimen having almost no preferred orientation. Stacking Fault Frequency Determination. Following the analysis of Warren: the stacking fault frequency, a, was determined from the change in the peak separation (A%) of two neighboring reflections of a deformed specimen, as compared with the normal peak separations of a fully annealed specimen. To obtain sufficient intensities for the second-order reflections, (222) and (400), composite specimens were prepared from parallel sections cut from the strip at 30 deg to the rolling direction for copper and 25 deg for the brass.* From texture data, these sections are known to contain a large population of both (111) and (200) planes. Since residual stresses can also cause X-ray line shifts (the direction of line shifts depends upon the sign of the stress), the use of composite specimens consisting of sectioned planes should help compensate for these effects as the residual stresses change sign from the surface to the central section of a rolled strip. Since the amount of peak shift is almost un-measurable in brass rolled 15 pct and in copper rolled

Jan 1, 1969

By J. W. Eckerd, P. S. Lewis, N. H. Coates

USBM designed, constructed, and operated an 18-in.-diam fluidized-bed combustor for highly caking coals to evaluate the method for possible application to power generation. In initial tests, combustion was carried on successfully, with carbon losses as low as 0.8%+ Coal ash was not satisfactory as a bed material, but mullite proved to be acceptable. Overall heat-transfer coeffients from the bed (-20 t 50 mesh mullite) to a water-cooled tube were about 75 Btuper hr-sq ft. Fluidized-bed combustion is being investigated by the U. S. Bureau of Mines (USBM) as a potentially cheaper method of firing power plant boilers. Lower combustion temperatures in fluidized beds—only 1400" to 1800°F-—should reduce fireside deposition and corrosion and nitrogen oxides production. Fluidized-bed combustion also offers possible advantages in the use of additives to control SO, emissions and amenability to processing of high-ash, high-moisture coals without special preparation. This paper describes development of a fluidized-bed combustor and the results of preliminary tests. Equipment and Procedure Fig. 1 shows the 8-ft-high combustor. A cone-shaped plate perforated by I/8-in.-diam holes supports the fuel bed and admits the fluidizing air; water passing through the 3/4-in. pipe extracts heat from the combustion bed. Fig. 2 is a flow diagram of the system. Coal is fed pneumatically to the base of the fuel bed. Combustion products are passed through two centrifugal separators to remove most of the entrained solids, then to a water

Jan 1, 1971

By T. W. Guy

DuRing recent years, tremendous strides have been made in the economical use of coal. This has resulted in, and to some extent has been a result of, making the fuel specifications more and more rigid. For this reason, all producers have found it necessary to improve their preparation materially, both as to sizing and the elimination of impurities, either by more effective preparation underground or at the tipple and cleaning plant, or both. This cause and its effect in all producing fields seem likely to continue for several years at least. The splendid inherent qualities of the Pocahontas and New River coals are known all over the world, but their good reputation is only partly due to inherent qualities, and to natural conditions which generally favor loading coal comparatively free from impurities; it is due in large measure to the care and skill used, either with or without the aid of mechanical devices, to ship products consistently low in ash. The first coal from the West Virginia smokeless fields was mined and shipped near Quinnimont, on New River, in 1871, while the first shipments from the Pocahontas field were in 1883. The development of both fields progressed rapidly. At first activities followed the main lines of the Chesapeake & Ohio and Norfolk & Western railroads, and were extended later as branch lines were built from these roads. The Virginian R. R., about 1907, opened up the Winding Gulf territory, which has since become a large producer of smokeless coals from the Pocahontas and the New River measures. Early Cleaning Methods In the early days, the tipples were simple wooden structures, with bar screens for separating the fines from the lump coal. All cleaning was done by the miners at the face, or by pickers in the railroad cars. Gates were provided in the chutes by which the flow of coal could be stopped when necessary while the pickers raked the surface of the coal in the car and picked out the impurities. A large percentage of the fine coal or slack was used for making coke at the mines in beehive ovens. The

Jan 1, 1932

By P. Duwez, L. Zwell

L. S. BUSCH—We have had presented two methods of measuring these variations in powder compacts. E. OROWAN—Tn connection with the rolling mill research work carried out at. the Cavendish Laboratory, Cambridge, with the help of the British Iron and Steel Research Association. Dr. E. A. W. Hoff, Mr. J. Los, and myself, have determined coefficients of friction at ex- treme pressures for a number of liquid and solid lubricants, both by direct measurement, and by calculation from measured values of the roll force. The most efficient lubricants at these high pressures (for the small amounts of sliding that, occur in rolling) were camphor and. in particular, borneol (Borneo-camphor). Perhaps such lubricants could be used with advantage in the kind of work described by Dr. Wulff. L. S. BUSCH—1 think Dr. Wulff has in the past mentioned experiments which have been performed in the extrusion and rolling of metals and which led to conclusions which can be applied to the compacting of metal powder. A. SQUIRE*—There have been some recent developments in the field of high pressure lubricants which indicate that boron nitride might be a very desirable material to employ as a die lubricant. At the present time its cost is prohibitive, but as the need arises for the material it will undoubtedly come down in price. The present price is $200. a pound. It is my understanding that one of the reasons for vacuum pressing both in ceramics and metal powders, is to prevent

Jan 1, 1950

By W. Mont Ferry

It is impossible to speak in exact terms of the effect that selective flotation has had, is having, and may have on the State of Utah. Its results enter into the economic structure of the state in so many ways and its ramifications are so widespread, that every line of industry is affectcd. Some effects can be definitely determined; others can be reasonably approximated; but the effect as a whole can not be set out in exact figures. Utah is essentially a mining state; mining is its basic industry and always will be. Agriculture, equally a basic industry, and of course, equally vital, can be practiced on only 6 per cent. of the 85,000 square miles of its area. It follows, therefore, that the economic future of this state depends upon a development of its natural resources. About 6 or 7 years ago, the mining industry in Utah was at a low ebb. This condition was caused partly by postwar conditions and other temporary causes, but prevailed also, which was most important, because the direet-smelting ores of the state were being rapidly exhausted and the cost of treatment of complex ores was almost prohibitive. Furthermore, the wet concentration of low-grade ores was unsatisfactory and did not result in producing a good smelting product. On visualizing this situation, one of the large smelting companies in the valley had the courage, ability and faith to develop and expand the principles involved in selective flotation of complex ores. This example has been followrd by other smelting and reduction companirs and the result has changed the entire aspect of the mining industry in Utah. The utilization of the zinc in the low-grade, lead-zinc-silvrr ores was the principal prob1t.m to be solvcd. The average yearly production from the State of Utah for the 10 years beginning 1914 and ending 1923, was something less than 10,000 tons of zinc corlcentrates. This period includes the world war, when abnormal priccs stimulated production. In 1924, selective flotation began to be practiced on a considerable scale, replacing concentration by gravity and bulk flotation which had been used generally until this time. Production and Value of Zinc Concentrates The production of zinc concentrates during 1924 was approximately 24,000 tons, or twice the average yearly production of the previous 10

Jan 1, 1928

By A. R. Powell

Four, general methods have been used in the study of the decomposition of coal. The first has been directed toward the processes of coal formation, the second has been by means of microscopic studies, the third from the data of destructive distillation, and the fourth has made use of various solvents. Applying these methods to the sulfur of coal, it has been found that the organic sulfur of plant and animal life enters into the formation of coal and remains in organic combination in the final product. The inorganic sulfur is almost entirely combined as iron pyrites and marcasite. The infiltration of hydrogen-sulfide waters is doubtless a large factor in these combinations. Sulfates are found in very small quantities except where free oxygen has entered the coal strata. The mechanical mixing of detritus with the early coal material is another source of sulfur. In this case the sulfur is distributed in microscopic particles throughout the mass. In destructive distillation, a part off the sulfur comes off as hydrogen sulfide and various thiophen compounds, but this furnishes little information as to the nature of the sulfur compounds in the coal itself. The use of solvents has given valuable data concerning the sulfur compounds in coal. Fremy1 and later E. Guignet2 noted the action of alkaline solutions on coal after treatment with nitric acid and Anderson and Roberts3 showed' the presence of large quantities of organic' sulfur in the extract so obtained. In a study of the phenol extract of coal, Parr and Hadley4 found organic sulfur in the soluble organic material. These investigations proved the presence of organic sulfur in coal in addition to the inorganic forms, such as iron pyrites and sulfates. T. M. Drown5

Jan 9, 1919

J. W. Tomlison—It seems probable that the author's conclusion, that the conductivity of the slags decreases with increasing content of FeO, is erroneous due to the method of plotting the data. Thus, the results of other workers2,3,13,15 show that the conductivity of molten oxide slags increase with increasing temperature, indicating that the trend of the curve shown by the authors is due to the fact that the data for the slags containing relatively small amounts of FeO are at higher temperatures than those for the slags containing relatively large amounts of this oxide. In this connection the work of Wejnarth2 may be mentioned in which in an investigation of a series of iron silicate slags, the conductivity was found to increase with increasing content of FeO; the fact that the author's slags contained TiO2 probably does not affect the issue since it has been shown15,16 that, at least as far as conductivity is concerned, this oxide behaves essentially the same as silica and that mixtures of the oxide with silica have a very low conductivity of the order of 10-4 mhos at 1750°C. In connection with the experimental technique it may be noted that bubbles of carbon monoxide would probably be produced at the surface of the graphite electrodes in contact with the melts thus rendering the accuracy of the measurements somewhat open to question. J. L. Wyatt (author's reply)—Dr. Tomlinson makes reference to works by Martin and Derge, which indicate that slag systems containing no TiO2 are characterized by an increase in conductivity with an increase in temperature. Further, I have cited his examples, which indicate a drastic increase with small temperature change. The results of Dr. Derge's work have no bearing whatsoever on the results of this paper, since the slags under study here contained up to 70 pct TiO2 One cannot generalize on slag systems as a whole on the basis of any one family, for there are definite compounds of ionic nature formed in each system, and the ionic mobilization of these is something that cannot be determined without actual experimentation. Dr. Tomlinson makes reference to an unpublished work which, he claims, shows that titanium dioxide behaves the same as silica in regard to conductivity. Since I have not had 'an opportunity to see the paper I cannot make any comments, but unless the same slag system was studied there can be no specific comparison of results. If the decrease in conductivity of the slag was due entirely to temperature phenomena, as Dr. Tomlinson indicates, then one is without an explanation of the values shown in the paper for slags containing from 10 to 20 pct FeO. I cannot agree that the deviation in findings was appreciably related to temperature change; further, I believe this point was completely covered in the paper. References 13 Endell and Hellbrügge: Glasstech. Ber. (1942) 20, 277. 14 Bockris, Kitchener, Ignatowicz and Tomlinson: Faraday Society. Discussion (1948) 4, 265. 15 Tomlinson: Thesis, London 1949. 10 Bockris, Kitchener, Ignatowicz, and Tomlinson: Unpublished work.

Jan 1, 1951

By F. Weinberg

WHEN impure Zn (< 99.99 pct)&apos;&apos;Z or Zn-Cd alloys3 are progressively solidified, a cell or "corrugation" substructure4 is produced in the solid, with a high impurity or solute concentration along the cell walls. When these materials are polished and suitably etched, etch pits are often observed along the cell walls. For the Zn-Cd alloys these etch pits have been associated with decorated dislocations, present in the corrugation boundaries to accommodate the lattice strain. In the course of an investigation of Zn-2 pct Au alloy, molten metal of this alloy was poured into cold water and the resultant solid pieces were sectioned, polished and etched with a Cr0 ethant. An extremely regular cell pattern was observed on the etched surface, similar in general to the corrugation structure previously reported for impure zinc and Zn-Cd alloys. At higher magnification, regularly spaced pits were observed along the cell boundaries. An example of the regular cell pattern at the center of a specimen is shown in the center and lower portions of Fig. 1; the top of the figure shows the pattern near the specimen surface. Typical etch pits in the cell walls are shown in Fig. 2. It was surprising that a cell pattern as regular as that shown in the center of Fig. 1 was produced at the very rapid solidification rates used (estimated as > 1 cm per sec). In addition, the distribution coefficient for the Zn-Au system is greater than 1. Accordingly, the center of the cells should be rich in solute and should etch

Jan 1, 1963