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By Michael P. Robinson

It has been suggested that streaming potentials are not nomlally logged because the streaming potentials known to be generated across mud filter cakes are substantially cancelled by streaming potentials generated in contiguous shale beds. Laboratory measuments of streaming poterztials acrons hand specirnens of shale have been adduced as evidence to support the suggestion. The experiments show that streanzing potential depends on the resistivity of the equilibrating solution and on pressure drop. Meizsurenlents were made perpendicular to the bedding planes of the shales. The mechanism of streaming potential generation in shale which the suggested cancellation theory iniplies has been critically examined. Conclusions reached are tested by comparing self potentials logged before and immediately after changing the resistil~ity (but not the weight) of mud in a borehole. The resultant SP change is found to equal the theoretical electrochetnical potential change, i.e., cancellation of .strearning potential is independent of mud resistivity. Since streaming po/entials generateal across mud filter cakes depend critically upon mud reistivity, shale .strearlling potential in situ must he equally sensitive. Using plausible values for the pemleahility, porosiy arzd compressibility of shale, the van Ererdingerl-Hurst approach shows that the pressure drop between horehole pressure and formation pressure in a radially honzogeneous shale is unlikely to coincide with the zone of filtrate invasion. If, perchance. this coincidence occurs with one mud a chatzge 10 a second must result in non-coincidence, i.e., a .YP logged in the second mud should show a streaming potenlial. The dilernrna may he overcome by postrrlating: (I) perrneabilities of shale7 parallel to their beddine planes greatly exceed their cross-bedding permeabilities; (2) a resistivity-sensitive mud cake of low permeability forms either on the face of, or probnhly in the lanlinations of, many shales. These postulates are examined with reference to the pres.sure and SP histories of the McClosky and Aux Vases zones in the Illinois Basin and some srcpport for them found. It is concluded that a definitive solultion to the streaming potential problem does not exist. INTRODUCTION Recently Gondouin and Scala' published a contribution to the streaming potential problem which is notable particularly for the elegance of its experimental techniques. The conclusions drawn by Gondouin and Scala from their studies amplified those previously suggested by Schehck'. In essence they suggested that the streaming potentials known to develop across mud filter cakes" are not normally observed on SP logs because they are largely cancelled by streaming potentials generated in adjacent shales. This suggestion appears so reasonable that many workers in the logging field will be prone to accept it. We incline strongly to the view that the suggestion is basically correct. Nevertheless, it is important to realize that the cancellation hypothesis in the form put forward by Gondouin and Scala does not appear to meet all the known experimental facts. It is the principal intention of this note to call attention to what appears to be a flaw in the relevancy of the experimental evidence adduced by Gondouin and Scala and to suggest an alternative hypothesis to remove it. The consequences of the new hypothesis are compared with field data which, we believe, are unique. A second but not less important purpose of this note is to emphasize that even the new hypothesis does not fully explain all field observations. Hence we conclude that further study of the streaming potential problem is required before it can be said that a definitive solution to it has been attained. The bare experimental bones of laboratory data on streaming potentials appear to be as follows. 1. A streaming potential is developed across a mud filter cake. This streaming potential is virtually independent of cake thickness but depends on the mud resistivity. The relationship is of the form, 2. A streaming potential is developed across a shale. This potential is independent of shale thickness but depends on the resistivity of the permeating solution if the shale has been first equilibrated in this solution. The relationship is of the form, The relationship in (1) was determined first by Wyllie3, confirmed by Gondouin and Scala and qualita-

By C. F. Wang

Page I. Introduction............:.............. 395 Manchuria in General ....................... 395 Pen-hsi-hu............................ 397 Pen-hsi-hu Coal & Iron Co., Ltd................... 399 I1. organization........................... 400 III. Coal Deposit........................... 402 Location..............................402 Geology............................. 403 Coal Mining...........'.................. 404 Mining Methods........................407 Mining Cost.........................408 IV. Coal Washing Plant.......................408 V. Coking Plant..........................410 VI. Iron Deposit...........................413 Magnetite Belt.......................... 413 Origin of Deposit......................... 414 Iron Mining........................... 415 VII. Concentration Plant........................ 417 VIII. Briquetting Plant.......................... 418 IX. Blast-furnace Smelting...................... 418 iNTKODtrCTION Manchuria in General Manchuria. called the "Three Eastern Provinces" in Chinese. forms the northeastern corner of China and is bordered by Siberia on the north and northeast. and by Korea on the east. It is a land famous in Chinese annals as the place of origin of the Ching dynasty. and in more recent times it has bcen an arena for diplomatic maneuvering and commercial competition between the Russians. advancing from the north. and the Japanese from the southeast. It derives its name of "three eastern provinces" from the fact that it is divided into three provinces; Hei-

Jan 1, 1918

By AIME AIME

THE second meeting of 'the Open-Hearth Committee, 'sub-division of the Iron and Steel Committee of this Institute, was held at the Hotel Cleveland, Cleveland, Ohio; on Oct. 13-15. On Oct: 12, the Open-Hearth Superintendents visited the plants of the Youngstown Sheet and Tube Co. and. the Republic Iron and Steel Co. These men were courteously entertailled by the two companies and every facility for a thorough inspection was furnished. Luncheon was severed at the plant bf the Youngstown Sheet and Tube Co. The meeting was opened Tuesday morning with addresses by J. V. W. Reynders, President of the Institute, and Herbert M. Boylston, Chairman of the Ohio Section of the Institute. E. A. Whitworth, of the Gathmann Engineering Co., presided at the meeting and L. B. Lindeinuth was secretary.

Jan 1, 1925

By W. M. Gray

The determination of the state of stress existing at a point in any solid body requires the determination of the six components of the stress tensor relative to a convenient set of axes. One general method of doing this in rock is to make strain or deformation measurements associated with local relief of stress in a number of boreholes penetrating a limited volume in the vicinity of the point at which the stress is to be determined. The stress is assumed to be constant throughout this volume. Leeman1 has described a number of the instruments that have been developed for making deformation or strain measurements in boreholes. Panek2 has described the application of statistical methods to the determination of the average components of ground stress from sets of measurements made in boreholes by means of deformation meters of the type developed by the U.S. Bureau of Mines. In this paper attention is given initially to the strain cell developed for use on the flattened ends of boreholes by the Council for Scientific and Industrial Research (CSIR) , South Africa. The equations required for evaluating the average components of ground stress from measurements made by means of the CSIR strain cell are derived. These equations are similar in form to those applying to measurements made by the borehole deformation meter developed by the U.S. Bureau of Mines. The results of an investigation of the properties of the equations are described. These results are important in the practical use of both the instruments mentioned above and any instrument based on similar principles.

Jan 1, 1968

By J. Lohrenz, C. R. Clark, B. G. Bray

Procedures to calculate the viscosities of in situ reservoir gases and liquids from their composition have been developed and evaluated. Given a composition expressed in methane through heptanes-plus, hydrogen sulfide, nitrogen and carbon dioxide together with the molecular weight and specific gravity of the heptanes-plus fraction, the procedures are capable of calculating the viscosity of the gas or liquid at the desired temperature and pressure. The procedure for reservoir liquids was developed using the residual viscosity concept and the theory of corresponding states, and was evaluated by comparing experimental and calculated results for 260 different reservoir oils ranging from black to highly volatile. The average absolute deviation was 16 per cent. This is the first known procedure for calculating the viscosity of reservoir liquids from their compositions as normally available, i.e., including the heptanes-plus fraction. The procedure for reservoir gases uses a sequence of previously published correlations. Evaluation of the procedure was accomplished by comparison of 300 calculated and experimental viscosities for high-pressure gar mixtures in the literature. The average absolute deviation was 4 per cent. The calculations are useful for (I) determining viscosities in compositional material balance computations and (2) predicting the viscosity decrease which occurs when gases, LPG, or carbon dioxide dissolve in reservoir oils. INTRODUCTION Methods to predict viscosities of reservoir fluids from the normally available field-measured variables have been presented. Beal,1 Standing,2 and Chew and Connally3 orrelated oil viscosities with temperature, pressure, oil gravity and gas-oil ratio. Carr, Kobayashi, and Burrows4 and Katz et al.5 have presented correlations for reservoir gas viscosities as a function of temperature, pressure and gas gravity. Lie all intensive physical properties, viscosity is completely described by the following function: Eq. 1 simply states that viscosity is a function of pressure, temperature and composition. These previous correlations1- hay be viewed as modifications of Eq. 1, wherein one assumes more simple functions may be used. The assumptions are practical, because the composition is frequently not known. Further, the assumptions are sufficiently valid so that these correlations are frequently used for reservoir engineering computations. In compositional material balance"' computations, the compositions of the reservoir gases and oils are known. The calculation of the viscosities of these fluids using this composition information is required for a true and complete compositional material balance. For reservoir gases, Carr, Kobayashi and Burrows4 have presented a suitable compositional correlation. For reservoir oils, no correlation is available, and data from reservoir fluid analyses have been used7-9 for compositional material balance calculations.* From a theoretical point of view, this is entirely invalid. The reservoir fluid analysis, whether flash, differential, or other process, does not duplicate the compositions which occur during the actual reservoir depletion process, therefore the viscosities measured during reservoir fluid analysis are not those which occur in the reservoir. From a practical point of view, the "error" of using viscosities from reservoir fluid analysis is of varying and unknown significance. One can say qualitatively that the error is greatest where compositional effects are greatest, i.e., for volatile oil and gas condensate reservoirs and pressure maintenance operations. The first requirement to obtain a quantitative estimate of the significance of the error is to develop a reliable compositional correlation for the viscmities of reservoir oils. No such correlation has been available. Consistent with this requirement, the objective of this study was to develop a procedure to predict the viscosity of reservoir fluids from their compositions. Normally, the compositions of reservoir fluids are available expressed as mole fractions of hydrogen sulfide, nitrogen, carbon dioxide and the hydrocarbons methane through the heptane-plus fraction, with the average molecular weight and specific gravity of the latter. The final correlation was to use the composition in this form. While the more challenging objective of the study was the development of a correlation for the viscosities of reservoir oils, the viscosities of reservoir gases were also studied. The end result of the study was a procedure to calculate the viscosities of reservoir gases and liquids suitable

Jan 1, 1965

By R. Schuhmann

Distribution of material in the fine sizes of a comminution product generally is well represented by the empirical equation' y = 100 (x/k)a [1] in which y — cumulative percent finer, x = particle size, a -= distribution modulus, and k = size modulus. Charles3 found that the energy consumption in comminution is usefully expressed by another empirical relation, E = Ak(1-D) [2] in which E = energy input per unit volume of material, A = a constant, k = size modulus based on Eq. 1, and n = a constant; (1-n) is the slope of a plot of log E vs log k. Holmes3 has presented energy equations similar to Eq. 2. The constants a and n in Eqs. 1 and 2 have been shown to depend both on the nature of the material and on the comminuting device. Moreover, Charles showed that within experimental error a and n are a — n+1 = 0 [3] Combining Eqs. 2 and 3, E = A k-a [4] In the first sections of this article it is shown that the energy equation, Eq. 4, can be derived directly from the size distribution equation for the fine sizes, Eq. 1. The derivations are made without assuming any of the specific relationships between energy and particle size which have been common in previous literature. For comminution processes in which Eqs. 1 and 4 adequately represent the experimental data, the constant A in Eq. 4 is found to be a simple and useful inverse measure of grindability. That is, A is the energy consumption per unit volume of comminution product finer than unit size as determined from the straight line portion of the log-log plot of the size distribution. These considerations all lead to a unifying hypothesis of comminution mechanism from which both Eq. 1 and Eq. 4 can be derived. Finally, it is pointed out that this hypothesis raises serious questions as to the significance of the Rittinger hypothesis, the Kick hypothesis, and other theories in which energy numbers are systematically assigned to various size fractions of comminution products in order to calculate theoretical energy consumptions. Derivation of the Energy Equation from the Size Distribution Equation: For simplicity, consider the comminution of 100 volumes of a feed material of relatively uniform particle size. The comminution process may be considered as the summation of many individual and independent comminution events. The extent of comminution is most easily expressed as the number of comminution events, z. In the first derivation, the key assumption is that the characteristics of the comminution events in a given crushing or grinding process are substantially constant and do not vary with the progress of the comminution process. Accordingly the characteristics of an average comminution event may be defined. In one such event, a quantity of energy $E is applied to a single particle of size f and volume $v. The crushing of this particle produces fine particles with a size distribution similar to that given by Eq. 1: yw=100(x/ka)a0 [51 In this equation yo, a0, and k0 are used to characterize the product of an individual comminution event rather than the product of the comminution process as a whole. In using Eq. 5, we will not be concerned with values of x close to the feed size f and will therefore assume only that the equation is applicable to the finest sizes of the material. In 100 volumes of total product, the actual volume of product finer than x from a single comminution event, or dy, is given by The total volume of material below size x, resulting from z events, is then given by y = z(dy) =z(dv) (x/ka)a0 =" Eq. 7 reduces to Eq. 1 when we let a, = a and [8a] z =100/dv (ka/k )1 or k = ka (zdv/100)-1/a [8b] Eq. 8a shows that the distribution modulus of the comminution product is the same as for the product of an individual comminution event. Eq. 8b shows how the size modulus of the comminution product k varies with the extent of comminution as measured by the number of events, z, or as measured by the fraction of the feed actually subjected to com- minution1 zdv/100. The energy input to 100 volumes of total feed, or 100E, is the sum of the energy inputs for all the comminution events: 100E =z (dE) [9]

Jan 1, 1961

By Carl Floe

A NUMBER of proposals have been made for the hydrometallurgical recovery of copper from flotation concentrates, but as yet no process has been developed that has demonstrated an ability to compete with the present smelting methods under ordinary conditions. The treat-ment of copper concentrates by hydrometallurgical methods is in general similar to that used in the present electrolytic zinc process and involves roasting, leaching with H2S04 solution, separation of solutions, control of impurities and electrodeposition. While many of these steps are simpler and more readily carried out for copper than for zinc, a number of inherent difficulties have prevented the general adoption of the process. To compete with smelting, the following problems must still be con-fronted, although many solutions for their have been proposed: (1) con-duction of the roast in such a way that leaching will give an extraction of copper comparable to that obtained by smelting; (2) regulation of the ferric iron content of the solutions during electrolysis; (3) disposal of the excess acid regenerated from the sulphates formed in roasting; (4) eco-nomical recovery of the precious metals from the leach residues. The roasting problem is largely one of preventing the formation of copper ferrites, CuO.Fe2O, and Cu20.Fe2O3, which are quite insoluble in dilute sulphuric acid. These ferrites are apparently formed' to a small extent even at low temperatures and above 650° C. their formation is rapid1. While it is possible to carry out laboratory roasts in such a way that less than 5 per cent of the total copper is present in the insoluble ferrite form, a closer temperature control is required than can readily be obtained in industrial furnaces. The flash" roasting effects and consequent high temperatures that occur as the calcine falls from hearth to hearth in the ordinary multiple-hearth roaster are probably largely responsible for the inevitable formation of some ferrites. The result is that in a commercial plant the extraction of copper would not average more than 90 per cent in a single 10 per cent H2SO4 leach. This is

Jan 1, 1937

By Paul A. Farrar, Sanford Adler

The Tz-Zr system was reinvestigated using both metallographic and X-ray diffraction techniques. It mas found that titanium and zirconium are soluble in all proportions in both the a and 0 phases. The minimum in the transformation was found at 50 at. pct and 535°C. THE Ti-Zr system has previously been the subject of several investigations.1-6 A study by Hayes et al.5 using magnesium-reduced titanium and zirconium melted in graphite crucibles indicated that the system was a continuous series of solid solutions in both a and 0 phases with a minimum at approximately 545°C and 65 pct* Zr. These conclusions were substantiated by the work of Duwez4 as well as by the limited data of Craighead et al.,3 Fast,2 and deBoer.1 However, a more recent investigation of the titanium-rich region by Ence and Margolin6 indicated that the solubility of zirconium in a, titanium at 500°C is approximately 22 pct with the a + 0 field extending to approximately 47 pct Zr. Therefore in order to resolve this discrepancy the following investigation was initiated. EXPERIMENTAL PROCEDURES The alloys used in this investigation were prepared as 20- to 30-g buttons by nonconsumable electrode melting in a helium atmosphere. The starting materials were Bureau of Mines titanium BHN 71 and Foot Mineral iodide crystal bar zirconium. The titanium was premelted before the alloys were prepared to avoid excessive weight losses in the final melting. The compositions of the alloys prepared were as follows: Ti-12.0, 22.2, 29.0, 39.6, 50.0, 58.0, 72.4, 83.5. and 90.8 pct Zr. Prior to heat treatment the alloys were cold-worked 10 to 20 pct, stopping at the first signs of cracking. Specimens for heat treatment were wrapped in molybdenum sheet and annealed in argon-filled quartz capsules for the following times and temperatures: 750°C-40 days, 675°C-61 days, 600°C—109 days, 575°C-112 days, 550°C-112 days, 525°C—127 days, and 450°C —153 days. Quenching was accomplished by breaking the capsules in an iced-brine solution. The standard techniques used for polishing the specimens involved belt grinding, grinding on emery paper, polishing electrolytically, and etching with Remington "A" etch7 or "R" etch 8 Debye-Scherrer X-ray powder photograms were obtained for a number of samples using a 114.6-mm camera and CuK, radiation. Exposure times were from 19 to 23 hr. The powder samples were obtained by filing to 270 mesh size. After filing the samples were wrapped in molybdenum foil capsuled in quartz and reannealed at the temperature of original heat treatments; following the heat treatment the samples were quenched into iced brine without breaking the capsules. RESULTS AND CONCLUSIONS On the basis of the microstructural examinations of the heat-treated samples and of the X-ray diffraction data, the Ti-Zr system shown in Fig. 1 was constructed. The data indicate that a, and 0 titanium form a complete series of solid solutions with a, and ß zirconium. The minimum was found to occur at 65 pct (50 at. pct) Zr and 535°C, in excellent agreement with the earlier investigations,1-5 see Fig. 2. Typical microstructures are shown in Figs. 3 to 7. Figs. 3, 4, and 5 show the 22.2, 39.6, and 50.0 pct Zr alloys after heat treatment at 675°C for 61 days with the 22.2 pct Zr showing equiaxed a, and the 39.6 pct Zr alloy a + transformed ß, while the 50 pct Zr alloy shows only transformed B. Figs. 6 and 7 show the 29.0 and 39.6 pct Zr alloys after heat treatment for 109 days at 600°C. The 29 pct Zr alloy has an equiaxed a structure while the 39.6 pct alloy has a partially recrystallized a+ß structure. X-ray diffraction data obtained from the 50 pct Zr alloys after heat treatment at 525° and 450°C as well as from the as-cold-rolled material showed only those lineos which couid be indexed a: a titanium, good agreement with the previously published values. 2,4,5,9 Chemical analysis* of the 50 pct Zr alloy

Jan 1, 1967

By A. Phillips, D. H. Killpatrick, V. Kerlins

The tensile failure of two dispersion-strengthened Ni-20 Cr alloys was studied and compared to the fracture of a similar alloy with no dispersoid. The fracture characteristics were studied using electron fruc-tography and transmission electron microscopy. In all three cases, the mode of failure was found to be microvoid coalescence. The failure in the dispersion-strengthened alloys was found to have initiated at the particles. The size of the dimples in the fracto-graphs was found to be related to the spacing of the particles, but not to the total elongation before failure. The elongation before failure was found to be related only to the amount of dispersed phase. These results are compared to those predicted by a theoretical model of ductile failure. THE continually increasing strength requirements for creep-resistant materials capable of long life at service temperatures above 1600"F (875"C) have developed considerable interest in dispersion-strengthened nickel-base alloys. The high yield strength of these alloys results from the presence of a dispersion of fine particles of thoria which act to impede the normal motion of dislocations. Many theories have been presented to explain the role of the dispersion in the strengthening of these alloys. A good review of these theories is presented by Ansell.' The ultimate strength of such alloys is not only related to mechanisms raising the yield strength, but also to the amount of work-hardening which occurs. This work-hardening is determined by the work-hardening rate and the amount of plastic strain before failure. Since fracture limits the amount of plastic strain, a study was undertaken to gain a better understanding of the fracture mechanisms in these alloys. Electron fractography and transmission electron microscopy were used to study the fracture characteristics in two dispersion-strengthened alloys and one similar alloy containing no dispersoid. These results are related to the tensile properties of the dispersion-strengthened alloys at room temperature and at 2000°F (1095°C). The results are also related to a theory for ductile fracture. 1) PROCEDURE Standard tensile specimens were made from 0.020-in. (0.051-cm) sheets of three different Ni-Cr alloys. The alloys had nominal compositions of Ni-20Cr, Ni-20Cr-2Th0,, and Ni-2OCr-4Th0,. All alloys were supplied in an annealed condition. The specimens were fractured in tension at room temperature to determine the effect of the dispersed thoria on the fracture appearance. The tensile properties were determined from the average of a minimum of three ten- sile specimens for each condition tested. The fracture surface of all of the alloys was examined by electron microscopy using standard two-stage plastic-carbon replica techniques. Thin foils of the dispersion-strengthened alloys were used to investigate the size and spacings of the dispersion particles, and to investigate sections of the 2 pct thoria alloy taken from areas of the specimen adjacent to the fracture surface. The thin foils were mechanically ground to 0.010 in. (0.025 cm) and then chemically polished to approximately 0.001 in. (0.003 cm) in a solution of 29 g of ferric chloride and 10 ml hydrochloric acid in a liter of water. The polishing solution was maintained at 150"F (65°C) during the thinning operation. The final thinning of the foil was done electrolytically using a solution of 700 ml ethanol, 100 ml 2-butoxy eth-anol, 120 ml distilled water, and 78 ml perchloric acid (70 pct). The potential was maintained at 15 v and the bath temperature at -20°~ (-29°C) during the thinning operation. The final thickness of the foil was approximately l000A as determined from the width of twins boundaries observed in many of the foils. 2) RESULTS AND DISCUSSION The electron fractographs of the fracture surfaces of the alloys are shown in Figs. 1, 2, and 3. The normal interpretation of this type of fractographz is that, as a result of the difference between elastic and plastic properties of the matrix and the particles or other inhomogeneities in the alloy, microvoids are formed

Jan 1, 1969

By Edward Keller

Although the subject matter contained in this paper is presented under a new title, its writing was induced by the work of S. Skowronski and K. W. McComas.' A discussion of the latter is here combined with the presentation of new and independent data. The' physical constants quoted by the authors of that paper, such as melting and boiling points, as also the chemical reactions of the substances involved, are so well established that the numerous confirmatory experiments and their application to metallurgical conditions leave little or no room for criticisms. On the contrary, they will greatly aid to dispel any lingering skepticism as to possible considerable losses of copper accruing when the metal is melted in the presence of its own and, probably, other chlorides and when no provision is made for the recovery of volatile products. Exception may be taken, to some degree, to that part of the work under the caption Melting Drillings of Copper Mixed with Sodium Chloride. These experiments should have been extended in order to make the implied reactions clear and the results convincing. The latter are stated to be, "that when sodium chloride is present above certain minimum quantity relative to copper some of it is found to volatilize in the melt while another part reacts with the metallic copper to produce the volatile cuprous chloride, and that when smaller quantities of sodium chloride are present the reaction is complete and all chlorine is found to have volatilized as cuprous chloride." Metallic copper and sodium chloride are mentioned as the sole reagents in this chemical process, acting, according to the authors, in a neutral atmosphere of carbon dioxide. The chemist, quite naturally, wi11 inquire into the formula according to which that reaction takes place and will find that it presents itself as follows: 2Cu + 2NaCl = 2Na + Cu2Cl2 It would appear that the truth of this formula will be challenged and a more rational explanation of the reaction sought. Apparently, carbon dioxide is neutral relative to metallic copper in its molten state; whether it remains neutral in the presence of sodium chloride is quite another

Jan 1, 1921

By W. B. Clark

IN OPERATING the Alpha mine of the Consolidated Coppermines Corp., Kimberly, Nev., it was necessary to pump out approximately 1200 gallons of waiter per minute to prevent the mine being flooded. There were three levels in the mine at which water accumulated and from which it was pumped, the 1200, 1400 and the 1800- ft. levels. At each, the pumping equipment was installed in duplicate so that if for any reason one unit was out of commission the other would be available to prevent flooding. The two centrifugal pumps at the 1200-ft. level were 600 hp. each; at the 1400-ft. level, 100 hp. each; and at the 1800-ft. level, 300 hp. each.

Jan 1, 1933

By Ursula E. Wolff

The precipitation of carbides from an alloy containing 33 pct Ni, 21 pct Cr, balance iron, was investigated electron microscopically by means of extraction replicas and thinned metal foils. Annealing temperatures ranged from 565°to 870°C and up to several thousand hours. M23C6 precipitated in pain boundaries, incoherent and coherent twin boundaries in that sequence. The orientation relationship between carbides and austenite matrix was determined and correlated with the morphology of the carbides and with the type of boundary in which precipitation occurred. In large-angle grain boundaries, as well as in coherent twin boundaries, the carbides had the same orientation as one of the adjacent pains. These carbides formed sheets of individual flakes with shapes related to the orientation of the boundary. In incoherent twin boundaries carbides precipitated in ribbons composed of pavallel rods. An unidentified subcarbide was found to precede precipitation of M23C6 in these boundaries. The M 23 C6 rods had a kind of fiber texture with (110) parallel to the long dimension of the rods and ribbon, and with orientations of both of the adjacent twin-related austenite crystals Predominant in the texture of the carbide. A hard sphere crystal model has been used to discuss orientation and morphology of the carbides in terms of free volume and vacancies available in the boundaries. A number of papers have dealt with the morphology of chromium carbide (M23 C6) precipitated in austenitic stainless steels.1"7 In all these investigations, the carbides were examined in the electron microscope by means of extraction replicas. With this technique, the carbides retain the spatial distribution they had in the bulk sample. However, since the matrix is dissolved in the process, the particles can turn in an unpredictable way; and the orientation relationship between matrix and carbides cannot be established. In this paper the results of studies on extraction replicas and on thinned metal foils are reported. These studies were undertaken to determine the matrix-to-car bide orientation relationship, and to correlate the orientation of the carbides with their morphology. PROCEDURE The material used was an austenitic alloy with 33 pct Ni, 21 pct Cr, balance iron, containing approximately 0.05 pct C. Coupons of 1.25-mm sheet were first solution-annealed at 1050°C for 15 min and air-cooled. Then, to precipitate the carbides, samples were isothermally annealed in the range from 565" to 870°C for times up to several thousand hours. All further specimen-preparation procedures were carried out after the final anneal. Carbon extraction replicas from polished and etched surfaces were made with 10 pct bromine in methyl alcohol.' Thin foils were prepared from punched-out 3-mm-diam disksg which fit into the electron-microscope holder. The disks were prethinned by grinding to approximately 0.5 mm thickness, and then electro-polished in a polytetrafluoroethylene holder1' with a solution containing 5 pct perchloric acid in acetic acid to which 10 g per 1 Cro3 and 5 g per 1 nickel chloride were added (etchant modified from that of Briers et al."). This solution dissolves neither the carbides nor the austenite around the carbides preferentially. By using extraction replicas, electron micrographs and selected-area electron-diffraction patterns were taken from the same carbide arrays. By using thin foils, electron micrographs were made from a grain boundary area containing carbides. Electron-diffraction patterns were then taken from the same area and from each of the adjacent grains separately. In this manner, the orientation of each grain could be determined without interference by the carbide pattern. A peculiarity of extraction replicas should be pointed out. After the matrix is etched away, the carbide arrays float freely in the etching and washing solutions, and are held in place only at the anchoring points in the carbon replica. When the replica is picked up with a screen the carbide arrays tend to flip to one side. Thus, while the surface features are preserved, the original arrangement of the carbides may severely and unpredictably be disturbed whenever the specimen contains large amounts of interconnected carbides. Nevertheless, it is possible to correlate the different morphologies of the carbides with the type of boundary in which they have precipitated. RESULTS 1) Extraction Replicas. Fig. 1 shows that the grain boundaries usually are curved, multicornered surfaces of random orientation. The coherent twin boundaries (which are (111) planes) cut a grain into parallel slices. Incoherent twin boundaries occur at the ends and on the steps of twins and are often narrow, parallel-sided strips which are much longer than they are wide. Different morphologies can clearly be distinguished for the M23Ce carbides precipitated in each of these types of boundaries, and agree well with those observed by kinzel.2 The kinetics of this precipitation has been investigated." The first carbides precipitate in junctions of three grain boundaries and fan out from there into the adjoining boundary surfaces, Fig. 2(a). These carbides are oriented randomly, Fig. 2(b), and become coarser and thicker as annealing time increases. The large-angle grain boundaries are next to fill

Jan 1, 1967

By James Boyd

Scientists and engineers must concern themselves not only with technical problems, but with the socio-economic difficulties of our scciety. The author states that raw materials are basic to the economic process and that mineral raw materials occur naturally in nearly limitless quantities. He feels that the economic pocess will provide sufficient raw materials for man's needs, and discusses in some detail the world economic environment. As our society grows in complexity, it becomes more urgently incumbent upon scientists and engineers to bring their experiences to bear on the solution, not only of technical problems, but also on socio-economic difficulties. It is to this field that I have directed a large part of my energies. RAW MATERIALS BASIC TO THE ECONOMIC PROCESS There are certain premises, frequently overlooked, which bear emphasis. As economics concerns the production, distribution, and consumption of goods, so our whole society is based on raw materials. Without the basic extractive industries of agriculture and mining, there would be no economic problems with which to deal. This principle has been expressed as "All productivity is based on three factors: 1) natural resources, whose form, place, and condition are changed by the expenditure of 2) human energy (both muscular and mental), with the aid of 3) tools.77* It seems strange that such an obvious statement needs to be made. It is forgotten by all of us, however, at one time or another when we get involved in the complicated theories of economics dealing with the financial and fiscal policies of the various governments, in the financing of enterprises, in marketing, and in labor relations. Unless decisions in all of these fields are made with this, and the rest of the "Ten Pillars of Economic Wisdom," consciously in mind, the resultant policies are doomed to eventual failure, whether these are policies of individuals, companies, or governments. The economic process is basic to society. But economics and the social aspects of humanity are inevitably intertwined. If human needs are not provided for within the basic economic structure, conflicts arise to disrupt the most carefully laid social plans. Similarly, it is the failure of society to cope with basic economic prerequisites that leads to discord within the body politic and thus to eventual economic disaster. We who are engaged in the various aspects of the mineral industry, therefore, have a large part to play in society's future development. MINERAL RAW MATERIALS OCCUR NATURALLY IN NEARLY LIMITLESS QUANTITIES Throughout my career in and out of government, I have formed my decisions on two principles: 1) Fundamentally, all mineral raw materials exist within the earth's crust in quantities greatly exceeding man's needs; 2) Any problems of supply of these materials are primarily economic in nature. With respect to my first assumption, analyses by geochemists enable them to estimate the quantities in which each of the known elements exist in the earth's crust. One of the most cautious and famous suggests that the average copper content of the lithosphere to a depth of ten miles is about 55 ppm. If this is valid, then the lithosphere contains about 1.4 quadrillion (1.4 x 10 ") tons of copper metal — an unimaginable quantity. This is 8,500,000-fold that which has been consumed by man in his existence. To illustrate further, consider that the deepest copper mine in history went to about 9000 ft below the surface; the present copper mines of the world now average less than 1500 ft in depth. We can assume that in most continental land areas of the world it is technically feasible to mine to a depth of at least one mile. The land areas of the world to an average depth of one mile, then, contain 343 billion tons (343 x 10') of copper metal, or 2000 times that which has been extracted to date. I don't believe man will ever expend his energies to extract copper from rocks which contain only a few parts per million, but he knows that each element

Jan 1, 1968

By J. W. Spretnak, V. Kandarpa

Stress -induced ordering of carbon atoms is studied in a series of Fe-Mn-C alloys. A prominent peak is found in the vicinity of 280°C at frequencies of the order of 1.0 cps, with an associated activation energy of 37 kcal per mole. The height of the peak is linearly rekzted to the concentration of carbon in solution. The distortion of octahedral holes by manganese atoms appears to be predominant over carbon-carbon pair interactions. RELAXATION by stress-induced ordering of point defects is expected whenever the introduction of these point defects produces distortions which have a lower symmetry than that of the lattice. Under zero stress, the isolated point defects occupy the crystallographic-ally equivalent positions in the lattice, as these represent states of equal energy. However, if the defect sites are asymmetric, application of an uniaxial stress will split the energy states, and a redistribution of the defects among various states will take place. This is the case of the internal friction peak called the Snoek peak,1 resulting from isolated interstitials in bcc metals. The interstitial sites in this case have tetragonal symmetry. In the case of fcc and hcp lattices, such an effect is not expected from isolated point defects because of the symmetrical nature of the interstitial sites. However, internal friction peaks arising from interstitial diffusion have been reported both in hcp2,3 and fcc4-8 lattices. These peaks are often explained on the basis of stress-induced ordering of interstitial solutes, caused by the deviation of interstitial sites from their cubic symmetry through the presence of nearby defects. In the case of fcc lattices, evidence for interactions of both the substitutional-interstitial4,6,13 and interstitial-interstitial types5'798'14 have been presented by various investigators. The purpose of the present investigation was to study the internal friction peak attributed to the diffusion of interstitial carbon atoms in high purity austenitic manganese steels and to account for the peak in the light of the existing models. MATERIALS The Fe-Mn-C alloys used in the present investigation were made in two different ways, designated as Type I and Type 11. Type I alloys were made from high purity Fe-Mn alloys obtained in the form of 0.04- in.-diam wires from Materials Research Corporation, Orangeburg, N.Y. These alloys were carburized to different levels using gas mixtures of H2 and CH4 at 1000°C. Type I1 alloys were made in this laboratory starting with zone refined iron, spectrographically pure manganese, and spectrographically pure carbon. They were melted in an argon arc melting furnace and drawn into 0.04-in.-diam wires. All the wires were annealed at about 900°C for 3 hr prior to the internal friction experiments. After the measurements of internal friction, the phases in the samples were identified by X-ray diffraction and the carbon determined by the combustion method. EXPERIMENTAL PROCEDURE In the present work, a classical Ke-type pendulum was used. The details of the equipment were described previously by D. T. Peters.9 Dry helium at 40 torr was used in all the experiments. The internal friction, measured as the logarithmic decrement of the torsion amplitude of vibration was determined as a function of temperature, from ambient to about 500°C. The background internal friction was assumed to have the form of the exponential of the inverse temperature and was subtracted from the raw data. The height of the peak was measured at the position of the maximum in the plot of the internal friction versus temperature. The activation energies of the peaks were measured by the peak shift method. The internal friction values for an alloy were obtained as a function of temperature at different frequencies of vibration. The position of the peak changes with frequency, the higher the frequency the higher the peak temperature. The activation energy of the process associated with the peak is obtained using the formula

Jan 1, 1970

By T. B. Massalski, H. W. King

An hcp phase may be induced by cold working the ß&apos; phase of the Ag-Zn system. This phase reverts to ß&apos; on subsequent aging. No phase change occurs on cold working the o phase, but ß&apos; is formed when the deformed alloy is subsequently aged at room temperature. It is concluded that for alloys near 50 at pct Zn the ordered bcc ß&apos; phase is the equilibrium structure at room temperature. WhEN the disordered bcc ß phase of the Ag-Zn system is cooled to temperatures below 258o to 274oC, it transforms to a complex hexagonal phase <o.1,2 The nature of the o ß=o transformation has been the subject of some discussion,2&apos;3 and the structure of o has been described in detail.&apos; The latter phase appears to be stable on aging at room temperature but decomposes following cold work. When alloys containing approximately 50 at. pct Zn are rapidly quenched from the 0 phase field, the ß ? o transformation may be suppressed; but the ß phase undergoes an ordering reaction (ß ? ß&apos;). The ß&apos; structure may also be obtained as a result of cold working and aging at room temperature.4 Kitchingman, Hall, and Buckley4 have suggested that the decomposition of (o following cold work proceeds in two stages, (o ? ß followed by ß ? ß&apos;, but did not confirm this by experiment. When the ordered &apos; phases in the systems Cu-Zn5 and Ag-Cd6 are cold worked, they become unstable and transform to a close-packed hexagonal phase (( ) indicating that when order is destroyed in a ß&apos; structure the close-packed hexagonal phase may in many cases be more stable. It thus became of interest to study more closely the effect of cold work and annealing on the stability of both the ß&apos; and o phases in a Ag-50 at. pct Zn alloy. Predetermined weights of spectroscopically-pure Ag and Zn, supplied by Johnson and Matthey, were melted and cast under 1/2 atm of He in transparent vycor tubing. The ingot was homogenized for 1 week at 630°C and quenched into iced brine. Since mechanical polishing was found to induce a phase change, sections were first polished at room temperature, sealed in tubes under 1/2 atm of He, reannealed for several days at 630o or 200°C and then quenched into iced brine. Sections of the alloy thus prepared were found to be homogeneous when examined under the microscope. The sample quenched from 630°C (ß -phase region) was pink in color, whereas the sample quenched from 200°C (o-phase region) was silver. The latter sample showed the characteristic hexagonal anisotropy when examined under polarized light. Filings of the alloy were examined at room temperature, after various heat treatments, using an RCA-Siemens Crystalloflex IV diffractometer with filtered CuKa radiation. The X-ray reflections from flat powder specimens quenched from 630o and 200°C and sieved through 230 mesh were recorded graphically at a scanning speed of 1/2 deg per min. The resultant patterns are shown in Figs. 1(a) and 1(b) and may be identified as those of the 8&apos; and <02 structures respectively. The lattice parameter of the ß&apos; phase was determined as 3.1566Å.* This value compares very well withthatto be expected for a 50 at. pct Zn alloy from the data of Owen and Edmunds? and indicates that no loss of Zn occurred during casting. In order to study the effect of cold work upon the ß&apos; and o phases, filings made at room temperature and sieved through 230 mesh were mounted immediately in the diffractometer-i.e., without a strain-relief anneal. Changes in structure on subsequent aging were followed by scanning repeatedly over the regions of the low index reflections of the ß&apos; and o structures-i.e. , 28 from 35 to 44 deg. Immediately after filing the 8&apos; specimen, additional diffraction peaks were observed in the low-index region of the pattern, as shown in Fig. 1(c). These additional peaks do not coincide with those of the o structure, Fig. l(b), but may be indexed as the (10.0), (00.2), and (10.1) reflections of an hcp phase (<) with nearly ideal axial ratio. However, this hexagonal phase appears to be very unstable since within a very short time at room temperature it reverts back to the ordered ß&apos; phase, the reversion being complete within seven hours. The 5 ? ß&apos; reversion reaction is, therefore, very similar to those already reported in Cu-Zn5 and Ag-Cd6 7&apos;alloys. The action of filing caused the deformed surface of the originally pink ingot to become silver in color, indi-cating that the ( phase possesses similar reflecting properties to the o phase. Hence, the subsequent

Jan 1, 1962

By Henry M. Howe

The natural effect of large ingot-size should be to increase segregation. I have previously pointed1 to the excessive segregation in many large ingots as tending to confirm this, but I have shown that in case of ingots less than 16 in. square this expected effect of ingot-size is liable to masked by that of Note.—The "maximum enrichment" of each ingot, i.e., the excess of the richest spot over the average of the whole ingot, is first calculated in percentage of that average. The average of the maximum enrichment of the several ingots of a given group is the abscissa in Fig. 1. The number beside each spot tells the number of cases which that spot represents. FIG. 1.—Influence of Ingot-Size on Maximum EnrichNent in Steel Ingots. other variables. Under these conditions we should expect that, if large ingot-size really does tend to increase segregation, this effect would be shown by taking the average of large numbers of cases, so that the effects of these other variables might off-set and cancel each other.

Jan 1, 1910

By C. R. Van Hise

PART I.-GENERAL PRINCIPLES. [ ]

Jan 1, 1902

By William L. Boyd, Eugene L. McCarthy, Laurance S. Reid

Proper control of the moisture content of natural gas is essential to reliable operation of gas transmission and distribution facilities serving northern markets. The moisture content of natural gas is usually determined by dew point measurement at the existing pressure. For any gas of constant moistrire content. the dew Point varies with the pressure. A correlation of the data of several investigators is prezented in graphical form by the authors. These data were correlated by the authors and F. M. Townsend, C. C. Tsao. M. I). Rogers. Jr.. and J. A. Porter. graduate students in chemi(.a1 engineering at the University of Oklahoma. Of articular interest are the hitherto unpublished low temperature data observed by Wickliffe Skinner. Jr., which are included in this correlation. PRESENTATION OF DATA The problem of interpreting water dew points, or saturation temperatures. of natural gas in terms of specific moisture con-tent has increased in importance during the past decade bec.arl.;e of extensive development.; in the transmission and petro-chemical phases of the natural gas industry. Virtually all gas transported to northern and eastern markets must be dehydrated to a low water vapor content to prevent hydrate formation in transmission and distribution lines and resultant interruption.; in gas deliveries. Complete dehydration is required in certain phases of tile petro-chemical industry involving low-temperature operations. It is a well-known fact that the water vapor content of pure hydrocarbon vapors and their mixtures at superatmospheric pressures cannot be predicted with accuracy by assuming validity of the ideal gas laws." Earlier interest in the general problem was concentrated on the water vapor content of pure hydrocarhons and hydrocarbon mixtures in the pressure and temperature ranges common to gas and oil producing reservoirs in order to obtain fundamental data for the improvement of production techniques and the furtherance of reservoir studies. Excellent data are published for pressures ranging from atmospheric to 10,000 psig and for temperatures ranging from 100° to 460° F4,9,10,11 and are found to be in close agreement. However, experimental data at high pressures and temperatures below 100°F are comparatively limited in scope. Experimental data in the lower temperature range have been reported by Laulhere and Briscoe.8 Deaton, et al,2,3 Hammerscllmidt,5,6 and wade," In general, the pressures employed in these investigations ranged from atmospheric to 1.000 psig while temperatures ranged from 32° to 120°F; i.e., the usual conditions encountered in gas transmission line operations, Additional data were reported by Russell, et al,12 at pressures as high as 2.000 psig and covering a rather narrow atmospheric temperature range. In 1947, Hammerschmidt published a correlation of all available data,&apos; in which the water vapor content of gases at saturation. under high pressure and low temperature. was predicted by extrapolation. In 1948, Wickliffe Skinner. Jr.. presented data on the moisture content of a low nitrogen content gas at low temperature and at pressures ranging upward to 1.500 psia.1-3 Comparison of Skinner&apos;s experimental data with the extrapolated data of Hammerscllmidt revealed an appreciable variation in the lower temperature range. emphasizing the need for a new correlation which would rely on Skinner&apos;s data at lower temperatures. Careful scrutiny of available data suggested that presence of an appreciable quantity of nitrogen in a gas mixture may affect its saturated moisture content so that data obtained from gases with more than three per cent nitrogen were not used in this correlation. CORRELATION OF DATA Data employed in this correlation are presented in Table I. The data of Dodson and Standing.4 McKetta and Katz,9 and Olds, Sage and Lacey10 were compared and found to be in close agreement so that the data of Olds. et al, re-plotted in a more convenient form by the Humble Oil and Refining Co.,&apos; were used for temperatures of 100°F and above. Skinner&apos;s data were used for temperatures below 40°F. Between these intermediate temperature limits, the data of Hammerschmidt.7 Wade" and extrapolated data of Olds. et al.1 were tabulated

Jan 1, 1950

By E. A. Anderson

THE copper-zinc phase equilibrium diagram has been the sub-ject of many investigations. Until recently, however, the boundary of the terminal solid solution of copper in zinc (eta) has not been thoroughly investigated. This paper reports determinations of the solid solubility of copper in zinc at temperatures from 100° to 400° C., the course of the liquidus and solidus for the eta solid solution and determinations of the peritectic temperature and peritectic point for the reaction between epsilon and the melt to form eta. The liquidus of the eta phase was determined by thermal analysis and the solidus by the microscopical examination of specimens quenched from temperatures above and below the solidus. The temperature of the peritectic horizontal was obtained by thermal analysis and the com-position at the peritectic point was determined by extrapolation of the solid solubility boundary of the eta phase to the peritectic horizontal. The solid solubility boundary of the eta solid solution was investigated very carefully. Particular care was used to achieve equilibrium in the alloys at each temperature selected. The X-ray, electrical con-ductivity and microscopical methods were used in determining the solid solubility limits. The X-ray method measures the changes in the solvent lattice with increasing solute content and in this manner locates the composition of the alloy at which no further change in the solvent lattice takes place, the limit of solid solubility. The method of electrical conductivity measures the conductivity of the alloys of a graded series of compositions, whereby the solubility limit is indicated by a discontinuity in the conductivity-

Jan 1, 1934

By M. C. Fuerstenau, R. B. Bhappu

The response of beryl to sulfonate flotation was examined. The dependence of flotation recovery on sulfonate concentration, pH, and the absence or presence of various ions is also demonstrated. The response of quartz and feldspar to sulfonate flotation at various values of pH is given to. show the conditions necessary for selective separation. Finally, beryl was successfully concentrated from a natural ore using a technique devised from experimental observations on systems of pure minerals. With the possible exception of quartz, the flotation characteristics of silicate minerals are rather poorly understood. This is due in part to the com- plexity of the mineral systems themselves and in part to an insufficient amount of flotation data. The complexity of the systems arises from the wide range of chemical composition that the silicate minerals can assume. This is reflected in the variability of such physical properties as hardness and cleavage. Although the chemical composition of silicate minerals can vary considerably, a general grouping can be accomplished conveniently on the basis of the assemblage of SiO4 tetrahedra in all the silicates. That is, it has been shown that six basic groups can be obtained, depending on the arrangement of oxygen sharing between adjacent silicon atoms (or substituted aluminum). When all four oxygen atoms are shared, a framework structure such as quartz or feldspar is obtained. When three oxygens are shared, infinite sheets are obtained as in the micas and clays. When two oxygen atoms of the tetrahedra are shared, infinite chains are obtained, such as those in

Jan 1, 1963