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By Corliss R. Kinney

Since the first atomic bomb exploded over Japan, a great deal of speculation has been published about the use of atomic energy instead of coal for the production of power. Atomic energy, in time, may displace coal for this purpose, but atomic energy will not displace coal in supplying chemical raw materials to the rapidly expanding carbon-chemicals market. Modern civilization demands large quantities of carbon compounds and the logical source of many of these is coal. Consequently, many progressive operators are considering the possibilities of the utilization of coal as a chemical raw material as never before. Furthermore, the demand for clean, smokeless, and ashless fuels will continue to increase and the only way to handle coal under those conditions is to take it apart, just as crude petroleum is taken apart. One can readily imagine where the petroleum industry would be now if it had insisted on selling customers only crude oil, perhaps emulsified with a little salt water to correspond to the moisture and mineral matter in raw coal. The time seems to be coming at an accelerated Dace when mine operators will find that competing for a highly selective fuel market by producing a larger tonnage at smaller cost will be less profitable than to increase the value of a smaller tonnage many fold by producing something more valuable to industry and civilization than raw coal. For example, about 750,000 tons of carbon black selling for $50 to $60 per ton was produced in the United States in 1945. This tonnage is insignificant compared with the total production of coal in the United States, but a very tidy tonnage, together with the coal necessary to operate the process, for any mine operator fortunate enough to obtain a method of producing a better carbon black from coal. From the point of view of tonnage, the manufacture of coke of various kinds and its by-products is at present the most important source of carbon chemicals from coal. Nearly 20 per cent of the coal mined in this country is used for this purpose. A large proportion of the coke is used for the production of iron and steel, but even in this operation a considerable part of the coke is used for a chemical purpose; that is, the reduction of the ore to metallic iron. In addition, large quantities of coke are used in manufacturing many important products that find their way into the market. Possibilities of Acetylene One of the important chemicals manufactured from coke is calcium carbide, from which many products are made. One of these is acetylene. This hydrocarbon can also be manufactured from natural gas or from waste oil-refinery gas and these industries will probably offer competition for the manufacture of acetylene. Coke-oven gas can be used for making acetylene and should receive consideration

Jan 1, 1947

By Corliss R. Kinney

Since the first atomic bomb exploded over Japan, a great deal of speculation has been published about the use of atomic energy instead of coal for the production of power. Atomic energy, in time, may displace coal for this purpose, but atomic energy will not displace coal in supplying chemical raw materials to the rapidly expanding carbon-chemicals market. Modern civilization demands large quantities of carbon compounds and the logical source of many of these is coal. Consequently, many progressive operators are considering the possibilities of the utilization of coal as a chemical raw material as never before. Furthermore, the demand for clean, smokeless, and ashless fuels will continue to increase and the only way to handle coal under those conditions is to take it apart, just as crude petroleum is taken apart. One can readily imagine where the petroleum industry would be now if it had insisted on selling customers only crude oil, perhaps emulsified with a little salt water to correspond to the moisture and mineral matter in raw coal. The time seems to be coming at an accelerated Dace when mine operators will find that competing for a highly selective fuel market by producing a larger tonnage at smaller cost will be less profitable than to increase the value of a smaller tonnage many fold by producing something more valuable to industry and civilization than raw coal. For example, about 750,000 tons of carbon black selling for $50 to $60 per ton was produced in the United States in 1945. This tonnage is insignificant compared with the total production of coal in the United States, but a very tidy tonnage, together with the coal necessary to operate the process, for any mine operator fortunate enough to obtain a method of producing a better carbon black from coal. From the point of view of tonnage, the manufacture of coke of various kinds and its by-products is at present the most important source of carbon chemicals from coal. Nearly 20 per cent of the coal mined in this country is used for this purpose. A large proportion of the coke is used for the production of iron and steel, but even in this operation a considerable part of the coke is used for a chemical purpose; that is, the reduction of the ore to metallic iron. In addition, large quantities of coke are used in manufacturing many important products that find their way into the market. Possibilities of Acetylene One of the important chemicals manufactured from coke is calcium carbide, from which many products are made. One of these is acetylene. This hydrocarbon can also be manufactured from natural gas or from waste oil-refinery gas and these industries will probably offer competition for the manufacture of acetylene. Coke-oven gas can be used for making acetylene and should receive consideration

Jan 1, 1947

By T. R. Graham, J. R. Long

This report is concerned with part of a series of investigations carried on by the Federal Bureau of Mines on alloys, particularly nonferrous alloys, made with electrolytic manganese. A broad general program instituted after commercial quantities of electrolytic manganese became available was necessary in order to compare the effects of electrolytic manganese with those of the ordinary commercial grades. Representative analyses of these two materials show the commercial manganese metal to contain up to 2 per cent iron, a maximum of I per cent silicon and 0.06 per cent carbon, while the electrolytic manganese rarely exceeds 0.01 iron, 0.02 sulphur, with no silicon or aluminum. In the literature, the emphasis has been largely on high-strength casting alloys containing up to 5 per cent manganese, and few data are available on wrought manganese alloys. These factors, coupled with the strategic position of copper and zinc, have given impetus to the Bureau's War Research Program for the development of alloys containing nonstrategic manganese for the purpose of supplementing or providing alternates for the more strategic metals. The alloy reported here was studied, along with several other ferrous and nonferrous alloys, as possible cartridge-case material, and was chosen after a review of the properties of the ternary alloys of copper-manganese-zinc. Preliminary Work In a cursory survey of this system, alloys ranging from 60 to 95 per cent copper, o to 50 per cent manganese, and 5 to 40 per cent zinc were investigated. The alloys containing 60 per cent copper were found to fall into the two-phase alpha plus beta region of the system, and since those containing 70 per cent would not permit a saving, only alloys containing 65 per cent copper were considered. The tensile properties of these 65 per cent alloys are plotted in Fig. I as a function of manganese content for annealed material and for four conditions of cold-work In the annealed condition the increases in strength and decreases in elongation are minor up to 15 per cent manganese; beyond this, the changes become more significant. In the cold-worked condition, the first 5 to 10 per cent of manganese appears to have the greatest strengthening effect, the rate of increase dropping off as the manganese increases beyond this amount. These effects are more pronounced with moderate than with severe cold reduction. It is also interesting to note that while the elongation of annealed material drops regularly with increasing manganese, the elongation in the cold-worked state is relatively little affected by increasing manganese content, particu-

Jan 1, 1944

By J. R. Long, T. R. Graham

This report is concerned with part of a series of investigations carried on by the Federal Bureau of Mines on alloys, particularly nonferrous alloys, made with electrolytic manganese. A broad general program instituted after commercial quantities of electrolytic manganese became available was necessary in order to compare the effects of electrolytic manganese with those of the ordinary commercial grades. Representative analyses of these two materials show the commercial manganese metal to contain up to 2 per cent iron, a maximum of I per cent silicon and 0.06 per cent carbon, while the electrolytic manganese rarely exceeds 0.01 iron, 0.02 sulphur, with no silicon or aluminum. In the literature, the emphasis has been largely on high-strength casting alloys containing up to 5 per cent manganese, and few data are available on wrought manganese alloys. These factors, coupled with the strategic position of copper and zinc, have given impetus to the Bureau's War Research Program for the development of alloys containing nonstrategic manganese for the purpose of supplementing or providing alternates for the more strategic metals. The alloy reported here was studied, along with several other ferrous and nonferrous alloys, as possible cartridge-case material, and was chosen after a review of the properties of the ternary alloys of copper-manganese-zinc. Preliminary Work In a cursory survey of this system, alloys ranging from 60 to 95 per cent copper, o to 50 per cent manganese, and 5 to 40 per cent zinc were investigated. The alloys containing 60 per cent copper were found to fall into the two-phase alpha plus beta region of the system, and since those containing 70 per cent would not permit a saving, only alloys containing 65 per cent copper were considered. The tensile properties of these 65 per cent alloys are plotted in Fig. I as a function of manganese content for annealed material and for four conditions of cold-work In the annealed condition the increases in strength and decreases in elongation are minor up to 15 per cent manganese; beyond this, the changes become more significant. In the cold-worked condition, the first 5 to 10 per cent of manganese appears to have the greatest strengthening effect, the rate of increase dropping off as the manganese increases beyond this amount. These effects are more pronounced with moderate than with severe cold reduction. It is also interesting to note that while the elongation of annealed material drops regularly with increasing manganese, the elongation in the cold-worked state is relatively little affected by increasing manganese content, particu-

Jan 1, 1944

By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:' C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:' C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By Che, C. W. Spencer, C. A. Steidel, Yu Li

Grain boundary grooving as it occurs in a 5.5-deg simple-tilt nickel bicrystal immersed in a saturated Ni-S liquid has been studied. A 1/3 (t= time) dependence for the depth of the groove indicates that the rate -controlling meckanism for groove developvnent is volume diffusion in the liquid. The activation energy for the diffusive process is estimated at 15 kcal per mole. Using an extended form of W. W. Mullins&apos; analysis for grooving reactions, a computer is employed to fit the appropriate diffusion equation by a numerical method. From the analysis a possible method of measuring L.S. the solid-liquid interfacial tension is demonstrated. WHEN a polycrystalline solid is heated in equilibrium with a saturated fluid phase, grooves will form at the intersections of the grain boundaries and surface. The equilibrium root angle of these grooves is determined by the balance between the grain boundary and solid-fluid interfacial tensions. The grooves deepen and widen with time due to a difference in chemical potential between the flat interface and the curved interface of the groove. In this investigation solid-liquid interaction at a grain boundary is studied, with the object to determine the mechanism of grain boundary grooving in the presence of a saturated liquid. Extension of Mullin analysis then permits the estimation of the solid-liquid interfacial tension. Herring has demonstrated by dimensional analysis that the quasi-steady state change of the dimensions of a small particle during sintering is proportional flow, evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, respectively, if geometric similarity of consecutive configurations of the particles holds. Mullins has extended this analysis to grain boundary grooving. In the case of shallow grooves he solves the diffusion equations for evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, and obtains the same time dependence for any linear dimension of a groove as Herring found for the change in dimension of small particles. In Mullins&apos; analysis2&apos;3 grain boundary grooving of a bicrystal by volume diffusion in the presence of a saturated fluid phase was considered. Several assumptions were made prior to the analysis: 1) the solid-fluid interfacial tension is independent of crystallographic orientation; 2) the Gibbs-Thompson equation relating curvature and chemical potential is applicable at the solid-fluid interface; 3) the relaxation time of the diffusion field is small compared with the time for appreciable changes in the curvature of the groove, so that the diffusion is divergence-less; and 4) the groove has a small slope relative to the initial flat interface. Usually this last condition is fulfilled only for solid-gas systems. The solution of the diffusion equation under the above conditions produces a t1/3 dependence for any linear dimension of the groove in the case where volume diffusion is rate-controlling. The t1/3 dependence is valid because geometric similarity of the grooves exists for all time. EXPERIMENT In the experiment a 5.5-deg nickel bicrystal of <100> simple-tilt orientation was used.4 Grooving was studied in the presence of a saturated Ni-S liquid alloy as a function of time at 750°, 800°, 850°, and 900°C. A low-angle bicrystal was chosen for study to insure that 2L.S. > .b., where l.s.

Jan 1, 1964

By R. W. Snyder, H. J. Ramey

This paper presents the results of applying the Buckley-Leverett&apos; displacement theory to petroleum reservoirs consisting of a finite number of layers. The layers are assumed to communicate only in the wellbores, and the reservoir may be represented as a linear system. Most previous investigations of this nature were limited by assumptions and by inconsistent calculation techniques. This study improves on previous work by applying the Buckley-Lev-erett displacement theory to a noncommunicating layered system where permeability, porosity, initial saturation, residual saturation and relative permeability vary from layer to layer in a logical and consistent manner. Gravity and capillary-pressure effects are neglected. A modification of the Higgins-Leighton calculation method was used in this study. Waterflood predictions were made with all properties varying, and then with only permeability varying using several inability ratios. These results were compared with the Stiles and Dykstra-Parsons predictions. It is shown that the latter methods generally give poor values for the breakthrough recovery and pessimistic predictions for the performance after breakthrough. Similar results were obtained for a gas-displacement case. lNTRODUCTION Field experience with immiscible displacement usually shows constant producing conditions until breakthrough of the displacing fluid. Then oil production continues at increasing displacing-to-displaced fluid ratios until the economic limit is reached. Three different ideal mechanisms are known that will produce this behavior: (1) relative permeability effects as described by Buckley-Leverett frontal advance theory,&apos; (2) vertical stratification as considered by Stiles,2 Dykstra and Parsons5 and others and (3) different path lengths involved in areal (two-dimensional) flow between wells as described by Dyes et al.4 Without question, a combination of these factors modified by formation heterogeneity and other known and unknown factors actually does control the behavior of real systems. This paper presents results of an investigation of certain factors that should affect performance but which have received little attention to date. In 1944, Law5 demonstrated that porosity and perme- ability are often found to have normal and logarithmic-normal distributions, respectively. throughout cored intervals in natural formations. This led to the concept of the noncommunicating, multilayered reservoir model for immiscible displacement. This model assumes that the reservoir is composed of a number of layers that communicate only at the wellbores. Each layer is individually homogeneous, but may be different from every other layer. Stiles&apos; presented one of the earliest applications of this model to waterflood performance. In addition, Stiles assumed that the initial saturations and relative permeabilities were the same for each layer, porosity was the same. displacement was piston-like, fluids were incompressible and injection into each layer was proportional to that layer&apos;s permeability capacity (permeability-thickness product). The last assumption would be true if the mobility ratio for the displacement were unity.21 Dykstra and Parsons" used the same model as Stiles, but rigorously included mobility ratios other than unity for piston-like displacement. Dykstra and Parsons used their general result to produce charts for log-normal permeability distributions between layers. Similarly, Muskat6 Pub1ished analytical solutions for linear and exponential permeability distributions. In 1959, Roberts&apos; described a scheme for calculating water-drive performance for the noncommunicating, layered reservoir model which considered two-phase flow in the displaced region. Roberts used the same model and assumed that the injection rate into a layer was proportional to that layer&apos;s permeability capacity, but that flood front locations could be evaluated from the Dykstra-Parsons results. These assumptions are inconsistent, and a material balance cannot be maintained except for a mobility ratio of unity. At the same time, Kufus and Lynch8 coupled Buckley-Leverett displacement theory with the layered model to provide an improvement of the Dykstra-Parsons method that was consistent. In 1960, Higgins and Leighton9 resented a numerical method for calculating waterflood performance also considering two-phase flow in the displaced region. The result was used to investigate variation in absolute permeability and oil viscosity. An excellent, detailed history of using the noncomrnunicating, layered reservoir model was presented by Nielsen.&apos;" The preceding techniques (and many related ones) were similar in that differences in initial saturations, residual saturations and relative permeabilities from layer to layer were neglected. It is well known that the irreducible water saturation is an important function of absolute permeability. Calhoun11 showed that the irreducible water saturation

By J. A. Musselman, P. F. Gnirk

A study was made of indexed penetrations by a single dull bit tooth under statically applied loads into rock subjected to confining pressures from atmospheric to 5,000 p.si and atmospheric pore pressure. Experimental results obtained with a 45" wedge tooth over the above range of pressures are presented for two limestones and a sandstone, a variely of indexing distances and two degrees of tooth dullness. The optimum distance between successive bit-tooth penetrations required for maximum rock damage and chip formation decreases substantially with increa.sing confining pressure above the brittle-to-ductile transition pressure of a particular rock. However, the distance remains approximately constant for a variation in confining pressure below the transition pressure. At a given confining pressure, the bit-tooth force required lor chip formation is constant for indexing distances greater than optimum, but generally decreases linearly with decreasing indexing distance for distances less than optimum. The chip-formation force data obtained at confining pressures for which the chip-generation mechanism is macroscopic-ally of a pseudoplastic nature compare favorably with previous theoretical results for indexed dull hit-tooth penetrntion into an idealized, rigid, perfectly plastic rock. INTRODUCTION To study the cutting action of a roller-cone bit, the interaction of a penetrating bit tooth with craters formed in a rock surfacc by the passage of previous bit teeth must be considered. Current knowledge of the basic mechanics of bit tooth-rock intcract:on under simulated borehole environmental conditions has been extensively reviewed.&apos;,&apos; Particularly of current interest are the effects of bit-tooth shape, distance between successive penetrations and differential pressure at the rock surface on the extent of the interaction. Pertinent to this paper are results of an experimental investigationb f the interaction between successive penetrations by sharp, wedge-shaped bit teeth. It was demonstrated that both bit-tooth angle and differential pressure influence the extent of rock damage between successive bit-tooth penetrations. Specifically, the optimum or minimum distance between successive penetrations required for maximum interact&apos;on or chip generation tends to decrease with decreasing bit-tooth angle and increasing differential pressure. In addition, at differential pressures on the order of 2,000 psi for four va- rieties of limestones and sandstones, the macroscopic mechanism of chip formation exhibits a transition from brittle to ductile. In this paper, experimental consideration is given to successive or indexed penetrat ons by wedge-shaped bit teeth. Since pore pressure in a rock sample is maintained at atmospheric pressure, the differential pressure at the fluid-rock interface is equal to the confining pressure. The degrees of bit-tooth dullness include teeth with flat and round apexes (Fig. 1). Of primary concern in this paper are the bit-tooth forces required for chip formation, the macroscopic mechanism of chip formation and the minimum distance between successive penetrations, i.e., optimum indexing distance required for maximum rock damage, as functions of differential pressure. Of further interest is a comparison of actual bit-tooth chip formation forces at elevated differential pressures with calculated forces from previous theoretical results4 for indexed dull bit tooth penetration into a rigid-plastic rock. EXPERIMENTAL APPARATUS AND PROCEDURE The experimental apparatus consists of a pressure vessel equipped with a piston through the side of the vessel (Fig. 2). A single bit tooth inserted in the lower end of the piston is forced at a desired rate into the rock when the ram pressure chamber is pressurized. Electrical instrumentation incorporated into the apparatus yields a graphical plot of force on the piston as a function of bit-tooth penetration or displacement into the rock. Since the piston and ram assembly are in force equilibrium for a constant confining pressure in the main vessel, the fluid volume in the vessel remains constant during bit-tooth penetration. Hence, the force resisting penetration of the tooth is independent of the force exerted on either end of the as-

By S. R. B. Cooke, S. W. Clark

Adsorption of calcium and magnesium by quartz was determined over a wide pH range using flame photometry for solution analysis. A parallelism was noted between calcium adsorption at alkaline pH and flotation of activated quartz by means of various fatty acid collectors. Abstraction of calcium from 100 ppm solutions increased above pH 10.5 until all of the calcium was removed at pH values between 12 and 12.5. Calcium was desorbed from the quartz over the pH range 12.5 to 13.0 and returned to the solution. Precipitation of magnesium hydroxide prevented measurement of magnesium adsorption above a pH of 9.9. A calcium adsorption isotherm determined at pH 9 matched measurements of barium adsorption by other investigators over the range where adsorption corresponded to the equation of a Freundlich adsorption isotherm. In accordance with the Gouy-Chapman theory for adsorption in the diffuse layer, adsorption of the divalent cations under these conditions was four times the adsorption of monovalent sodium. Activation of quartz by multivalent metal cations in flotation using anionic collectors has been studied by many investigators. The occurrence of activator cations in the water of flotation mills makes depression of silaceous gangue very difficult. Alternatively, in some flotation systems it is practical to cause activation of quartz so that it is floated from the desirable mineral values. The present study was initiated to investigate the activation of quartz by measuring adsorption of calcium and magnesium ions as a function of solution pH. Early empirical tests showed that quartz would be activated to flotation using anionic collectors if any of a number of divalent or trivalent metallic cations were present in the pulp.1*2 Subsequent studies by Clemmer,3 Cooke and Digre,4 Cooke,5 Schuhmann and Prakash,6 and Cooke, Iwasaki, and Choi,7-8 showed that flotation depended strongly upon the alkalinity of the flotation pulp, the concentration of the activating cations, and the chain length and structure of the organic collectors used. The concept of the electrical double layer has been applied to the case of the quartz-aqueous solution interface by Gaudin and Fuerstenau,9-10 and by de Bruyn 11 to explain the activation of quartz by multivalent metal cations. Studies of the surface of quartz by Gaudin and Fuerstenau9,10,12 and by Li " using the streaming potential technique contributed much information on the electro kinetic condition of the surface of quartz in the presence of various organic and inorganic ions. Measurement of adsorption of ac-

Jan 1, 1969

By Harry V. Welch

Early in the development of the art of metallurgy, it was noted that a distinct difference existed in the character, collection possibility and health hazard of the "smoke" from lead furnaces and those from copper plants. Zinc-plant fumes, although not so detrimental to health, were closely allied in nature to those of the lead works. In Cottrell plants, there are sufficiently distinct differences in operation and amount of construction between those for lead and copper to justify their consideration under separate headings; therefore, while the application of the process at copper-reduction works was covered by the writer some two years ago in the Transactions1,† this discussion will confine itself more distinctly to "fume" collection. General information on the process has been presented in numerous articles and by many authors: Cottre112, Schmidt3, Bradley4, Anderson6, Labbe6, Shiga7, Rathbun8. "Fume" may be defined as material, metal or nonmetal, elemental or compound, evolved as a vapor from a furnacing or chemical reaction and condensing, chilling or reacting within the gas stream to yield a solid form, and in this definition liquid particles are solids in a sense as distinguished from gases or vapors. Such condensed particles are of minute form, on the order of "smoke," and, for example, on the order of a few hundredths of 1 micron (1 micron = 1/25,000 in.) to perhaps 3 microns, with agglomerates, in relatively small proportions of many particles. Metallurgically typical fume products are lead compounds, oxides, carbonates and sulphates; elemental zinc, more commonly encountered as a fume particle of zinc metal with a surrounding "skin" of zinc oxide; arsenic, both metal and oxide and some of its more complex salts such as added sulphates as found in flue dusts; antimony, more particularly its oxide forms; and elemental sulphur, sometimes a troublesome product, in Dwight-Lloyd sintering-plant fumes. These products, particularly the elemental or lower oxide forms, have relatively appreciable vapor pressures at the existing operating temperatures as reported by Welch and Duschak9, Ingold10, Johnstonll, Millar12,13.

Jan 1, 1937

By George Rice

THE subject of dust explosions in coal mines first appears in the Transactions of this Institute following the first great mine disaster that happened in bituminous mines of the United States. This was the Pocahontas explosion, which occurred Mar. 13, 1884, causing the loss of 112 men. The operating company wisely asked the technical assistance of the Institute, requesting that a committee be appointed to investigate and report. This committee consisted of Messrs. Bramwell, Buck, and Williams, who, after careful study, reached the conclusion that the explosion was due "either to dust alone or to dust quickened by an admixture of fire-clamp too slight for detection by ordinary means." This is perhaps the first time in this country that coal dust was considered to be the chief agency in a mine explosion.. The report is given in the Transactions, vol. xiii, p. 237 (1885). It is particularly worthy of note that the committee called attention to "the necessity of full-sized tests and systematic experiments. " In the same volume of the Transactions, there is a most interesting paper reviewing the literature relating to coal dust, by E. S. Hutchinson, entitled Notes on Coal-Dust in Colliery Explosions. Mr. Hutchinson gives a historical account of observations on the part played by coal dust in mine explosions, beginning with Messrs. Lyell and Faraday&apos;s report on the Haswell colliery explosion in 1844, in which it is said "much coal gas had been made from this dust in the very air itself in the mine by the flame of the firedamp, which raised and swept it along, and much of the carbon of the dust remained unburned only from want of air." The subject lay dormant until 1875 when William Galloway began some coal-dust experiments in a small gallery at a mine in South Wales of which he was manager. At that time he considered the presence of firedamp necessary for continued propagation of a dust explosion; but in 1884, the year of the Pocahontas disaster, he stated that no earlier author-than himself had credited coal dust with being a principal factor in mine explosions, relegating firedamp to a secondary place.

Jan 10, 1914

By Nicholas J. Grant, Raymond E. Cairns

A high-purity chromium, made by solid-state extrusion, and a series of molten, extruded, dilute alloys containing carbon, oxygen, nitrogen, and sulfur were studied to establish the effects of composition, cooling rate, grain size, strain rate, and prior strain on the transition temperature for brittle THE transition from ductile to brittle fracture with decreasing temperature remains of extreme interest especially among the refractory metals, such as tungsten, molybdenum, and chromium, which have relatively high transition temperatures. Fracture, yield stress, and hardness. Tension tests at a strain rate of 0.015 per min were generally utilized. Results are interpreted in terms of the quantity of each element retained in solid solution. Of these elements, chromium has been studied the least, but deserves additional attention because of its superior oxidation resistance for high-temperature use. In the past, impurity elements which have received attention are carbon, nitrogen, oxygen, and sulfur;&apos;-&apos; of these, nitrogen has usually been considered to be the most detrimental. Unfortunately, because of different levels of both specific and total impurity content, and because of the many different test and evaluation techniques used, a clear, definitive picture of brittle fracture in chromium has not been forthcoming. However, many

Jan 1, 1964

By Stephen E. Merritt, T. Carl Shelton

Surveying and mapping are used to locate and visually portray objects, lines, or areas in relation to a reference point or line. The actual making of the measurements to locate the objects and points falls under surveying while mapping is concerned with putting the survey information into a graphical form. Generally, the type or class of proposed survey depends on the precision required. Some surveys may need only approximate measurements which can be obtained by simply pacing or by using an ordinary measuring tape; others may require much accuracy, thus calling for the use of an engineer&apos;s transit or theodolite along with a graduated steel tape for horizontal measurements, or a level and a graduated rod for measuring vertical distances. Mapping is likewise dependent on accuracy requirements. For example, a general layout showing the relative position of surface facilities may not call for a large scale of dimension or great precision whereas for detailed work, a large scale plus care in plotting points and drawing lines and curves are important factors. SURVEYING METHODS There are many kinds or types of surveying methods. Some examples include: land surveying for determining boundaries of land areas ; route surveying for locating roads, highways, right-of-ways, and haulways; city surveying for laying out lots, streets, and alleys ; and mining surveying for projecting mine openings and locating mining operations. There are other types of surveying than those named, but in general, the type of method to be used will depend on the purpose for which the survey is to be made.

Jan 1, 1973

By B. G. Matson, M. A. Whitfield, G. R. Dysart

This paper describes the development of u computer program to calculate changes that occur in the length of tubular goods due to temperature and pressure changes during stimulation operations. Due to the numerous variables involved and the uncertainty of all static and dynamic conditions that could exist, it becomes a staggering task for individuals charged with completions to perform the necessary mathematical calculations. The computer program permits advance calculations for several sets of conditions. INTRODUCTION In the Delaware basin of West Texas alone, 50 wells were contracted or drilled to 15,000 ft or deeper in 1965. Deep well activity is continuing in this and other areas on an expanding scale. Many of these deep wells require extensive stimulation for successful commercial production, and during these operations, pressures and temperatures are encountered that have a pronounced effect on the length of tubular goods. This length change during a large-volume, high-pressure stimulation treatment utilizing fluids considerably cooler than bottom-hole temperature can be of such a magnitude that permanent damage to casing and tubing will result unless mechanical design, pressures and fluid temperatures are evaluated and controlled. These pressure and temperature effects can be calculated. However, the process lends itself well to computer solutions because of the mathematical nature of the problem and the calculating hours involved in arriving at an answer. The engineering-hour demand becomes more severe as tapered strings are involved. On initial treatments on a given well, surface pressure and injection rate conditions are unknown, and offset well conditions have not proven to be a reliable method for making predictions. For these reasons, it has become rather standard procedure for operators to compensate for these uncertainties by placing unnecessary pressure and fluid temperature restrictions on stimulation design. On a number of occasions treating fluids have been preheated to as much as 160F as a means of compensating for thermal contmction resulting from pumping cool fluids. The maintenance of packer seals has been treated by Lubinski, Althouse and Logan&apos;,&apos; and the problem of therma1 effects on pipe has been explored by Ramey." These works were expanded and the results made applicable to everyday oilfield terminology before submitting them to computer programming. The pressure and temperature effects on tubing movement previously mentioned occur simultaneously as fluid moves through the pipe. The pressure changes, for purposes of explanation, are categorized here as to the various effects these pressures have on a tubing string. These divisions are (1) the piston-like results of forces acting on horizontal surfaces exposed to pressure, (2) swelling or ballooning of the tubing along its entire length due to the forces of pressure acting against the tubing walls, (3) the elongation of tubing due to frictional drag and (4) corkscrewing of the pipe due to internal pressure. Thermal changes are also of great importance, as their results may be more significant than any of the pressure effects. Steel is an excellent conductor of heat and the earth is a relatively poor conductor. It has been calculated that pipe temperatures at depths of more than 20,000 ft approach within as little as 25" the temperfature of the surface fluid after pumping for 2 hours, or a drop in temperature in some treatments of more than 220F. The equations presented in this paper were developed for computer programming and simplicity of input information; therefore, numerical constants such as Young&apos;s modulus for steel (28 X 10\ si), the coefficient of thermal expansion of steel (6.9 X 10."IF) and Poisson&apos;s ratio for steel (0.3) are included with unit conversion factors. The moment of inertia of tubing cross-sectional area with respect to its diameter was changed to a constant times (D&apos; — d&apos;) where D is outer diameter and d is inner diameter. Units in the equations are length in feet, diameter in inches, density in pounds per gallon, pressure in psi, rate in barrels per minute and time in hours. PISTON-LIKE REACTIONS A change in tubing internal dimensions and the exposure of other horizontal surfaces to different pressures on the inside and outside of the tubing result in a reaction much like a piston under pressure. Such is the case when the internal diameter changes in a combination string of pipe, when seals of a slick joint assembly are subject to pressure and in the end effects of a tubing string. The change in tubing length due to the piston effects of a slick joint packer is affected by the various diameters involved, the tubing pressure Ap,, the casing pressure ,Ap,, length of pipe L, densities of fluid in the tubing before and during pump-

By Ernest A. Kaarsberg

This paper presents the results of studies of the elasticity of some isotropic and anisotropic rock samples based on longitudinal- and shear-wave pulse velocity measurements. Experimental evidence from velocity measurements on isotropic steel samples is also presented to show, within error limits, that any two of the elastic constants required to completely describe the elasticity of an isotropic solid can be obtained from any two of the following four velocity measurements: longitudinal "rod,&apos; "plate," extended medium (infinite medium equivalent), or shear wave. Measurements of three of these velocities in an approximately isotropic basaltic rock sample are used to illustrate this application to this type of rock. For the anisotropic study, a suite of Colorado oil shale samples is used. These rocks exhibited transverse isotropy. The five elastic constants required to completely specify this type of anisotropy are obtained from longitudinal- and shear-wave pulse velocity measurements made in directions parallel, perpen-dicular, and at 45° to the bedding plane. Density, velocity, and elastic modulus relationships among these shales are also given. Duvall 1 has described a method for determining the elastic constants of isotropic and, in two cases, anisotropic rock samples. This method is based on ultrasonic pulse techniques and on resonance-frequency measurements of rock samples in the shape of rods (diamond drill cores). Rock samples, however, are not always available in rod form. When this is the case, other methods can be used to study their

Jan 1, 1969

By T. K. Perkins, O. C. Johnston

Because of the influence of dispersion on miscible-displacement processes, diffusion and dispersion phenomena in parous rocks are of current interest in the oil industry. This paper reviews and summarizes a great deal of pertinent information from the literature. Porous media (both unconsolidated packs and consolidated rocks) can be visualized as a network of flow chambers, having random size and flow conductivity, connected together by openings of smaller size. In such a porous medium, the apparent diffusion coefficient D is less than the molecular diffusion coefficient Do, as measured in the absence of a porous medium. For packs of unconsolidated granular material the ratio D/D, is about 0.6 to 0.7. For all porous rocks, both cemented and unconsolidated, the ratio of diffusion coefficients can also be represented as D/Do = 1/FF where F is the for- mation electrical resistivity&apos; factor and 4 is the porosity. If fluids are flowing through the porous medium, dispersion may be greater than that due to diffusion alone. At moderate flow rates the porous medium will create a slightly asymmetrical mix zone (trailing edge stretched out), with the longitudinal dispersion coefficient approximately proportional to the first power of average fluid velocity (if composition is nearly equalized in pore spaces by diffusion). If the velocity in interstices is large enough, there will be insufficient time for diffusion to equalize concentration within pore spaces. In this region, longitudinal dispersion increases more rapidly than fluid velocity. At low velocities in interstices, transverse dispersion is characterized by a region in which transverse diffusion dominates. If the fluid velocity gets high enough, there will be a transition into a region where there is stream splitting with mass transfer but with insufficient residence time to completely damp-out concentration variations within pore spaces. There are several variables that must be con- trolled to get consistent longitudinal and transverse dispersion results, viz., (1) edge effect in packed tubes, (2) particle size distribution, (3) particle shape, (4) packing or permeability heterogeneities, (5) viscosity ratios, (6) gravity forces, (7) amount of turbulence, and (8) effect of an immobile phase. INTRODUCTION Diffusion and dispersion in porous rocks are of current interest to the oil industry. This interest arises because of the influence of dispersion on miscible-displacement processes. In a recovery process utilizing a zone of miscible fluid, there is the possibility of losing miscibility by dissipating the miscible fluid or by channeling or "fingering" through the miscible zone. Diffusion and dispersion are two of the mechanisms that may lead to mixing and dissipation of the slug. On the other hand, dispersion may tend to damp-out viscous fingers which may be channeling through the miscible slug. 58 Hence, dispersion may be detrimental or beneficial (if it prevents fingering through the miscible zone). Therefore, it is doubly important that we understand these processes. In this paper we review, summarize and interpret a great deal of information from the literature. In particular, we will briefly discuss molecular diffusion in miscible fluids. Then we will discuss what differences to expect for diffusion in a porous rock. If there is movement of the fluid through the rock, then there may be an additional mixing or "dispersion". Furthermore, the dispersion longitudinally (in the direction of gross fluid movement) and transverse to the direction of fluid movement will not be equal. We will discuss both types of dispersion as well as several variables which can affect dispersion (viscosity differences, density differences, turbulence, heterogeneity of media, etc.). This group of variables has sometimes led to difficulty when comparing literature data. DIFFUSION OF MISCIBLE FLUIDS If two miscible fluids are in contact, with an initially sharp interface, they will slowly diffuse into one another. As time passes, the sharp interface between the two fluids will become a diffuse

By Charles Prasky

ABOUT five years ago the Bureau of Mines began a study, at Minneapolis, of the various methods for beneficiating the low-grade manganese deposits of the Cuyuna range. Several samples of green carbonate slate from the Cuyuna range, containing about 7 pct Mn and about 28 pct Fe, were obtained for this study. The component minerals in the carbonate slate formation were so intimately associated that mineral dressing methods were not suitable for concentrating manganese to a ferrograde product. Although upgrading of manganese and iron minerals has been effected by flotation methods, it appears that manganese cannot be separated from iron except by chemical means. Because the flotation studies at Minneapolis were carried out simultaneously with the hydrometallurgical studies, only crude slate was available for process testing. An important economic consideration in selecting any one of the several chemical methods proposed for recovering ferrograde manganese is the availability of the chemical reagent. Fortunately, large tonnages of sulfur are available on the Cuyuna range in low-grade pyrite and pyrrhotite deposits that are readily concentrated by flotation to a suitable feed for a sulfide roasting furnace as indicated by a Bureau of Mines investigation in 195 0-1951.1 The roasted residue from the sulfide concentrates is a potential source of marketable iron oxide. Therefore, if these sulfide deposits were employed in recovering manganese, utilization of two heretofore unused mineral deposits would be accomplished. Laboratory investigations of several proposed leaching processes were made as a preliminary step in the investigation of hydrometallurgical methods for the treatment of Cuyuna carbonate slate using sulfur as a chemical reagent. From results obtained in the laboratory tests, these leaching processes did not appear entirely suitable for treating Cuyuna carbonate slate. The method developed at the North Central Experiment Station and selected for a more intensive pilot-plant investigation has been termed the differential high-temperature sulfatizing process. Essentially, this sulfatizing process consists of the following steps, described in the order in which the small-scale pilot-plant investigations were made. The first and perhaps most significant step in the process consists of a sulfate roast. Carbonate slate is roasted in an atmosphere of sulfur dioxide gas and air. The overall chemical reaction for converting manganese carbonate to a sulfate at a high temperature in a sulfur dioxide atmosphere follows MnCO8 + SO2 + 1/2 0, = MnSO4 + CO2 (H077°O = —64,180 cal per g mol) .&apos; The need for concentrated sulfuric acid is avoided. Fine grinding is not essential. Removal of carbon dioxide from the slate during roasting produces a more porous structure and permits easier permeation by the sulfatizing gas mixture. The temperature limits for this conversion of manganese have been established as 600" and 850°C. Iron sulfate is unstable and is not formed at these temperatures; phosphorus is not converted to a water-soluble form; and polythionates are not formed. The second step in the process consists simply of a water leach of the sulfatized product. Manganese sulfate in the sulfatized product is dissolved in water. Iron, phosphorus, and calcium remain in the leach residue as water-insoluble products. The third and final step consists of the recovery of ferrograde manganese oxide from manganese sulfate leach solution. Water is evaporated from the leach solution, and impure monohydrate crystals of manganese sulfate are recovered. The moist crystals are formed into pellets or extrusions and thermally decomposed to produce a ferrograde manganese

Jan 1, 1958

By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult&apos;s law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and&apos; oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1&apos;2 The PbO-SiO2 melts are ionic conductors.&apos; During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By W. O. Philbrook, R. S. Kaplan

Rates of oxidation were studied for levitation-melted samples of Fe-C, Fe-Si, Fe-C-Si, Fe-C-P, Fe-C-Mn, and Fe-C-S alloys oxidized by mixtures of either 5 or 10 pct O2, in helium at several temperatures in the range 1850o to 2050°C. The concentrations of the oxidized elements decreased linearly with time. Mass transport in the gas phase was found to be the rate-controlling step. Ilowever, a mulliple -film model was necessary to account for the flux of iron and manganese vapor counter to the oxygen flow. THE advent of the basic oxygen and spray-refining processes of steelmaking has generated considerable interest in the kinetics of reactions between oxygen-bearing gases and liquid iron alloys. The object of this research was the determination of the role of mass transport in the gas and metal phases and of surface chemical reactions in the overall oxidation process. Of the reactions for elimination of elements dissolved in liquid iron, the oxidation of carbon has been investigated most extensively. Studies by Fuji and Ura,1 Fuji,&apos; and Gunji et a1.,3 done with pilot-scale basic oxygen furnaces, indicated that mass transport of gaseous oxygen was rate controlling when the metal carbon content was greater than 0.15 to 0.30 pct. When the carbon content was less than this critical amount, diffusion of carbon dissolved in the iron was thought to be rate limiting. L. A. Baker et a1.4,5 levitated samples of iron-carbon alloys and oxidized them in CO-CO2, CO-C02-He, and O2-He atmospheres at 1660°C. These investigators found that the metal carbon concentration decreased linearly with time and their samples exploded when the carbon content fell below about 0.8 pct. They concluded that the rate-limiting step was the transfer of oxidant to the gas-metal interface. A model based on this rate-limiting step predicted decarburization rates within a factor of two of those experimentally observed. The explosion of the samples was attributed to a shift in rate-controlling step from gas-phase mass transport to transport of carbon dissolved in the metal. L. A. Baker and R. G. ward6 and R. Baker7 used freely falling droplets to investigate oxidation kinetics. In both papers, the authors speculated that flame fronts may have been partially responsible for the lack of better agreement between experiment and theory. Swisher and Turkdogan8 oxidized liquid iron having an initial carbon content of 0.97 pct with CO-CO2 and CO-C02-Ar mixtures at 1580°C. They concluded that a surface reaction was the rate controlling step. Iron-silicon alloys have been oxidized by R. Baker7 and Filipov and Martynov.9 R. Baker 7 also studied iron-carbon-silicon alloys falling as liquid droplets through oxygen. He found that the rate of both carbon and silicon oxidation varied inversely with the drop radius. When the initial silicon concentration was greater than 6 pct, the samples cooled during their fall. Manganese oxidation has been studied by R. Baker,7 and by Filipov and Martynov.9 ward10 investigated the loss of manganese from liquid iron under vacuum. He found that mass transport of manganese vapor was rate limiting in argon atmospheres of 0.02 torr to 700 torr pressure. Iron-sulfur alloys were desulfurized with H2-He and H2-Ar mixtures by Peters et al.11 A model based on the transport of H2S from the gas-metal interface into the bulk gas gave fair agreement between the predictions of the model and the experimental results. EXPERIMENTAL TECHNIQUE Essentially, the technique consisted of using helium-oxygen gas mixtures to oxidize levitated samples of liquid binary and ternary iron-base alloys. The fused silica reaction tube is shown in Fig. 1. The coil design is similar to that of L. A. Baker et al.4&apos;5 A Tef-lon-sheathed, ferritic stainless steel lifter (B) and an alumina pedestal (C) were used to support the sample in the coil prior to levitation and for the recovery of the sample. Samples were inserted into

Jan 1, 1970