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By J. M. Dumore

If in a vertical, downward miscible displacement, the transition zone between the displacing and displaced fluids is neglected, a criterion for stable displacement can be obtained by considering a small hypothetical protrusion of one of the fluids into the other. This criterion leads to the definition of the well-known critical rate, uc = kg p/p. The consideration is further extended by taking into account the transition zone that develops as a result of diffusion and mixing. A generalization of the previous criterion leads to the definition of another characteristic rate, the stable rate, which in actual miscible drives will be less than the critical rate. In such drives, the entire transition zone is stable at rates less than the stable rate. At rates between the stable and critical rates, the displacement is only partly stable, i.e. part of the transition zone adjacent to the displaced fluid is in an unstable position. From that part of the transition zone viscous lingers will develop. At rates greater than the critical rate the entire displacement is unstable and viscous lingers will develop more strongly. Results of laboratory experiments are in agreement with the expected behavior based on the theoretically deduced stability of the displacement. INTRODUCTION The simplest form of miscible drive in an oil-bearing formation is the injection of a fluid that is completely miscible* with the oil under reservoir conditions. In general, such a fluid, a solvent for example, is less dense and less viscous than the oil present in the formation. If it is injected into a horizontal homogeneous layer, gravitational forces will lead to the formation of a gravity tongue of solvent in the upper part of the layer and the adverse solvent-oil viscosity ratio will cause viscous fingers to develop. If, however, the solvent is injected up-structure into ,a dipping layer, gravity has a favorable effect, because it tends to keep the less dense solvent up-structure. Tongue formation and viscous fingering are consequently reduced and it is even possible that they will be suppressed completely. Viscous fingering and gravity tonguing are the consequences of the instability of the displacement. A stable displacement cannot result in growing viscous fingers and/or growing gravity tongues. Since large amounts of oil can be bypassed if there is viscous fingering and/or gravity tonguing, the stability of a miscible drive is very important with respect to the recovery efficiency of the drive. The stability is of particular importance in miscible-slug drives, as it determines how quickly the miscible slug between the displaced and displacing fluids will be distorted and broken up, after which the drive is no longer completely miscible. Stability is thus a most important factor in determining the success of a miscible drive, and it is considered that the aspects of stability considered in this paper will make a useful contribution to existing theories. Consideration is given only to vertical downward displacements, in which no gravity tongues can develop and which are therefore simpler than downward displacements in sloping layers. THEORY CRITERION FOR STABLE DISPLACEMENT Let us consider a vertical column of a homogeneous permeable medium saturated with oil. A solvent less dense and less viscous than the oil is injected at the top of the column at a constant rate; in the column the velocities of oil and solvent are assumed to be uniform. Diffusion and mixing of oil and solvent will at first be neglected, i.e. we assume that solvent and oil are divided by a sharp interface. An additional assumption is that the interface is horizontal. Continuity of pressures exists at the interface, because no capillary forces are present between the two miscible fluids. Consequently, at the interface (Z = I)):** Ps = Po - P-where Ps is the pressure at the solvent side and

Jan 1, 1965

By J. H. Scaff, W. G. Pfann

The effects of impurities on the electrical properties of silicon are discussed in a companion paper by Messrs. Scaff, Theuerer, and Schumacher.' It was shown that an ingot of silicon which contained boron and phosphorus in certain concentrations consisted partly of p-silicon and partly of n-silicon2 and that the common boundary between these regions was the source of a photo-voltage. These features were ascribed to the segregation of boron and phosphorus during solidification of the ingot. Because of different rates of segregation the first portion of the ingot to freeze contained a molar excess of boron over phosphorus and hence was p-silicon. The last-solidified region contained a molar excess of phosphorus and was n-silicon. This paper is concerned with the microscopic examination of such ingots. The microstructures are rather unusual in certain respects and their study has helped to show how the segregation of minor elements modifies the electrical properties of silicon. The microstructures of ingots prepared from two lots of silicon, designated 1 and 2, will be described. These lots were obtained from the Electro Metallurgical Co. Both contain 99.8+ pct silicon, but they differ in impurity analysis. For each lot will be shown the microstruc-ture of a slowly cooled ingot, for which the time of solidification is 6 min., and that of a rapidly cooled ingot, for which the time of solidification is 2 min. The ingots were prepared from 45 g charges of silicon. When an alloy freezes a cored structure is generally produced because of insufficient diffusion to remove concentration differences established during freezing. As a result of coring the first portion of a crystal to freeze is usually poorer in solute than equilibrium requires, while the last material to solidify is richer. In a columnar grain, growth is principally unidirectional and coring can produce a concentration gradient along the entire grain. By carrying the picture of the coring process from a single grain to an entire ingot in which columnar grains are aligned more or less radially, one can easily see that a composition gradient could be established between the outside and center of the ingot. This, to a considerable extent, occurs during the solidification of a slowly cooled ingot of silicon. Slowly Cooled Ingot In slowly cooled ingots of both lots of silicon, columnar grains which are approximately radial in direction and longest at the top of the ingot enclose a region in which the shapes and align- ment of the grains are considerably less regular. The central region is last to solidify and contains cavities and inclusions. The sketch of Fig 1 illustrates some of these features, as well as others which will be described below. If a polished section of an ingot is etched in a mixture of 2 parts of 20 pct HF and 98 parts of HNO3 the p-n barrier becomes visible. The overall shape of the barrier in a slowly-cooled ingot is roughly oval, as may be seen in Fig 1. The proportion of n-silicon, that is, the region enclosed by the barrier, is considerably greater in ingots of lot 1 than in those of lot 2. A sample about 34 x 1/8 X 1/8 in. was cut from a slowly cooled ingot of lot 1 with its long direction extending from the top of the ingot to the porous region. Thus its upper half was psilicon, its lower half n-silicon. A longitudinal face was polished and etched in the acid mixture. The areas of interest are identified in Fig 2. A band of parallel markings extends across the sample in the columnar region. These striae are roughly parallel to the upper surface of the ingot and cross grain boundaries with only slight deviations. They are quite distinct in the n-silicon,

Jan 1, 1950

By S. S. Marsden, S. H. Raza

An experimental study of the flow of line-textured. aqueous foams through Pyrex tubes is described. The foams range in quality F (ratio of gas volume to total volume) from 0.70 to 0.96 and behave like pseudoplastic fluids. At lower flow rates they exhibit laminar flow ad have apparent viscosities which increase with quality, and which cover a range of 15 cp to 255 poise for tubes of 0.25- to 1.50-mm radius rj. At higher flow rates a plug-like type of flow is developed, the extent of which increases with both T and ri. When the same foams flow through either open or packed Pyrex tubes, remarkably high streaming potentials ?E are often generated. These can easily reach 50v if nonionic foaming agents are used, but are at least an order of magnitude less for ionic foaming agents. A linear relationship between ?E and the pressure differential ?p is observed; this usually extrapolates to positive values of ?p at ?E of zero. The slope of the line increases with both F and ri. An equation was derived to describe the streaming potential of non- Newtonian fluids in circular tubes and was used to correlate experimental results. The calculated < potentials are of the right order of magnitude. INTRODUCTION Foams are both unusual and inniguing in their physical properties, and have been the subject of many scientific studies. However, present knowledge of foams is still fragmentary, specific and often contradictory. Apparent viscosity of foam is the physical property of greatest interest to both rheo1ogists and engineers. sibreel reported that the apparent viscosity decreased with increasing shear rate in a manner similar to some non-Newtonian fluids. Penny and Blackman2 reported that fire-fighting foams had both a limiting shear stress and a tensile yield stress. There is little doubt that some foams at least behave like non-Newtonian fluids, and have apparent viscosities considerably higher than those of either constituent phase. The high apparent viscosity of foam with its concomittant effect on mobility ratio and sweep efficiency no doubt prompted several attempts by research groups to use foam as a displacing agent in porous media. Based on recent experience, most of these groups probably succeeded in completely blocking fluid flow in the porous media and then abandoned their efforts. Two groups apparently found the successful combination of experimental parameters at about the same time.3,7 Others have recently added to our knowledge of foam flow in porous media and its use as a displacing agent.8-13 An experimental problem encountered by Fried3 was a transient blockage of foam flow in porous media when distilled water was used to prepare the foam-producing solution. Fried surmised that this was due to an electrokinetic effect and he eliminated it by using electrolytes in preparing foaming solutions. He also measured the streaming potential of a number of foams in capillary tubes which he found to be appreciably higher than those obtained when the constituent liquid flowed under comparable conditions. This paper presents results of a more comprehensive study of the streaming potential generated by aqueous foam flowing in both open and packed Pyrex tubes. It also adds to knowledge of the rheology of these foams as deduced from their flow behavior in open tubes. APPARATUS AND PROCEDURE A diagram of the apparatus used is shown in Fig. 1. Details of its construction, testing and use are described elsewhere.14 Careful selection of materials, extreme cleanliness and rather elaborate electrical insulation and shielding were necessary to obtain reproducible results (±5 percent). Both streaming potential and streaming current were measured with an electrometer. The design of the foam generator developed for this work is novel (Fig. 2). It will produce uniform fine-textured foams at pressures sufficiently

By T. E. Seidel, A. U. MacRae

The dependence of the electrical and crystalline properties of silicon containing ion implanted boron atoms have been studied as a function of the incident dose, substrate temperature, and annealing tempera-ture. Hall effect studies show that the compensation due to defects is negligible after annealing at and above 500°C for a dose of 1013 ions per sq cm. Steps occur in the isochronal annealing curve for the sheet resistance at 300°C and 800°C and the mechanisms responsible for these steps are discussed. The range of the ions at 150 kev is 3500 * 5001. Electron diffraction studies on samples implanted with 150 ker ions show the existence of damaged (polycrystalline) silicon closer to the surface than the range of the ions. Etching and subsequent annealing of etched and unetched specimens suggest that the poly crystalline silicon is closer to the surface than the bulk of the distribution of ions. THE purpose of this study is to investigate some electrical and crystalline properties of ion implanted boron in silicon. Sheet resistance, Hall measurement, depth distribution by chemical staining, thermal probe and electron diffraction have been used to study the properties of samples implanted in a random direction with ions having energy up to 150 kev. The boron-silicon system has been the subject of considerable study&apos;-7 due to its possible application in the fabrication of electronic devices. The implanted ions produce considerable crystalline damage to the substrate crystal before they lose most of their primary energy and come to rest. Fortunately, most, if not all, of this damage can be removed by subsequent annealing or by holding the substrate at an elevated temperature during the implantation process. Sheet resistivity measurements of the p-type layers produced by boron implantation into room-temperature silicon, reveal that the annealing occurs in a two-step process: the first occurring at -300°C and the second at -800°C.&apos; Electron-microscope and low-angle electron diffraction studies of this damaged material indicate that the bombarding ions produce an amorphous silicon region about the trajectory of each ion.&apos; At high doses, these damaged regions overlap and an amorphous surface layer results. Furthermore, the 800°C annealing step, appears to be associated with the elimination of this gross damage. The depth distribution of the as-implanted and also the annealed samples have been studied by an angle lap and staining technique as well as by Hall measurements.3-7 We find the experimentally determined ranges of the boron are less than those calculated by the Lindhard-Scharff-Schiott theorys (hereafter referred to as the LSS theory). Our results are in essential agreement with pre- vious results. In addition, we have made Hall measurements on samples bombarded with a low dose (2 x 1013 ions per sq cm) to minimize impurity banding effects, and find that deep ionized levels influence the carrier concentration and room-temperature hole mobility until the sample is annealed at temperatures above 500°C. Above this temperature, the data corresponds to that obtained when silicon is doped with boron by conventional techniques. We have also made a depth distribution determination of the crystalline damage due to the implanted boron by using glancing angle electron diffraction techniques. It was found that the gross damage depth distribution of heavily implanted samples is closer to the surface than the depth distribution of the electrically active boron. By removing this gross damage, without affecting the distribution of the implanted boron, we have determined that the 800°C annealing stage is not exclusively due to the improvement in the crystalline perfection of the amorphous material but also appears to be associated with the annealing of some point defects. These results and their relation to previous results are discussed in the following sections. IMPLANTATIONS Boron ions were implanted into silicon samples using an accelerator capable of operating from 10 to 150

Jan 1, 1970

By J. C. Melrose

The contact angle is one of the boundary conditions for the differential equation specilying the configuration of fluid-fluid interfaces. Hence, applying knowledge concerning the wettability of a solid surface to problems of fluid distribution in porous solids, it is important to consider the complexity of the geometrical shapes of the individual, interconnected pores. As an approach to this problem, the ideal soil model introduced by soil physicists is discussed in detail. This model predicts that the pore structure of typical porous solids will lead to hysteresis effects in capillary pressure, even if a zero value of the contact angle is maintained. The model is generalized to situations in which the contact angle takes on values between zero and 40 degrees. For the imbibition branch of the capillary- pressure function, the model predicts a considerable departme ftom the usually assumed cos 0 relationship. In fact, according to the model, it is possible that a displaced wetting phase will not be able to reimbibe, even when the contact angle does not exhibit hysteresis. INTRODUCTION The subject of capillarity in porous media has long been of interest in many branches of engineering and applied science. The earlier investigators were those concerned with the physics of soils. 1-5 More recently, petroleum engineers and others dealing with the problems of petroleum production from reservoir rock have given much attention to the subject.6-10 Also, important additions to the literature of capillarity have been contributed from the field of chemical engineering.11-12 These attest to the wide range of industrial applications in which capillary phenomena play a role. The present paper is concerned with the role which wettability plays in capillary action in porous media. As is well known, capillary-rise (or capillary pressure) phenomena have frequently been interpreted with the aid of a model employing the concept of a cylindrical capillary tube. This approach has enjoyed a certain degree of success in correlating experimental results.13 The generalization of this model, however, to situations which involve varying wettability, has not been established and, in fact, is likely to be unsuccessful. In this paper another approach to this problem will be discussed. A considerable literature relating to this approach exists in the field of soil science, where it is referred to as the ideal soil model. Certain features of this model have also been discussed by Purcel114 in relation to variable wettability. The application of this model, however, to studying the role of wettability in capillary phenomena has not previously been attempted in detail. In the present paper, additional features of the model are introduced. These features are critical in determining the quantitative behavior of the model. GENERAL FEATURES OF CAPILLARY HYDROSTATICS BASIC PRINCIPLES When the interstices of a typical porous solid are occupied by two or more immiscible fluid phases, the fluids are microscopically commingled. Hence, fluid-fluid interfaces are found within a certain fraction of the pore openings. The fundamental equation of capillarity specifies the configuration of these fluid-fluid interfaces. This is known as the Laplace equation, when derived from mechanics, and as the Gibbs-Kelvin equation when derived thermodynamically.15 Given two fluid phases, a and ß, in hydrostatic equilibrium, the Laplace equation states that the respective fluid pressures in regions close to the interface are related by Here oaß is the surface or interfacial tension and rl and r2 are the principal radii of curvature of the surface or interface. The pressure difference, Pa-Pß, is the capillary pressure, PC. As Buff15 has shown, Eq. 1 states the condition for hydrostatic equilibrium within the two-phase confluent region, which is referred to as the interface. It thus can

Jan 1, 1966

By W. B. Gogarty

The reported decreases in water mobility do not seem unusual in view of non-Newtonian fluid properties. Shear stress vs shear rate diagrams have been reported for other solutions of water-soluble polymers. Some of these polymers are similar to the type mentioned by the author. Generally, the shear stress-shear rate is a non-linear function for these solutions. Data for plotting apparent viscosity vs shear rate can be obtained from this function. Apparent viscosity is defined as the ratio of shear stress to shear rate at a given shear rate. When plotted, the apparent viscosity decreases with increasing shear rate. This behavior is typical of a pseudoplastic fluid. For some water-soluble polymer solutions, the apparent viscosity decreases more than 50 times while the shear rate increases 1,000 times. Thus, viscosity of a pseudoplastic fluid only has meaning at a specified shear rate. Results of Fig. 1 could be explained in these terms. Viscosities measured in the Ostwald viscometer represent values at a given shear rate. Some average shear rate is affecting the polymer solutions while flowing through the core. This average value fixes the apparent viscosity as long as the flow rate remains constant. Viscosities measured by the two methods will be equal if shear rates are the same. The results indicate that shear rate in the core is lower (higher apparent viscosity) than in the viscometer. In the paper by Johnson, Bossler and Naumann, the relative permeability is independent of viscosity ratio. Thus, the relative permeability with respect to water flow at residual oil should be independent of the flowing phase viscosity. Polymer solutions will appear as Newtonian fluids The discussion emphasizes the nature of the "resistance factor effect" as discussed in the paper. Repeated anomalies arising in hundreds of experiments led us to the conclusion that non-Newtonian flow is not the only factor. Several of the key anomalies are as follows: 1. Measured viscosities over a range of shear rates from <1 sec-&apos; to 1,000 sec-&apos; do not account for but a minor fraction of the R observed in cores when compared in similar shear-rate ranges. 2. The slope of R vs flow rates in cores is always different from that expected from viscometer shear-rate measurements as shown in Fig. 2. in a core, the level of viscosity being fixed at a given flow rate. With these conditions, the definition of resistance factor R by Eq. 2 is simplified to Since , is constant with rate, R becomes a measure of the apparent viscosity in a core at a given flow rate. Variation in flow rate could easily account for the changes of R shown in Fig. 5. Also, this points to the fallacy of assuming R to be a unique parameter. The constant resistance factors at different flooding velocities appear to be in disagreement with the above discussion. The author furnishes Fig. 2 to support his arguments. As shown, the resistance factors remained substantially constant in the two cores over a considerable range of flooding velocities. However, in the 73-md core, the factor increases at lower rates. This behavior agrees with known characteristics of some pseudoplastic material. These materials act both as Newtonian and as non-Newtonian fluids in different regions of shear rate. Some exhibit first Newtonian, then non-Newtonian, finally, Newtonian character. Others are first non-Newtonian and then Newtonian. This latter type would explain the results with the 73-md core. The Fann-instrument results are not significant since shear rates in the core may be much different than with the viscometer. The higher resistance factor at high rates in the 150-md core is more difficult to explain. The greater resistance at increased flow rates could be attributed to what might be termed temporary bridging. As envisioned, changes in polymer configuration occur at the higher energy associated with the increased flow rate. These changes could cause less effective passage of polymer through the core. Correspondingly, increases in pressure drop will occur. These will be interpreted as higher resistance factors. 3. Most polymer solutions are non-Newtonian and many are more shear-rate sensitive than the polymers in question, yet only a very few polymers demonstrate useful R values. Gogarty&apos;s assumption that viscosities in cores and vis-cometers will be the same if measured at the same shear rate is only valid if non-Newtonian rheology is the only parameter. The experimental evidence does not validate this assumption. The anomalies observed in the equilibrium displacement experiment shown in Fig. 5 are not explained on the basis of varying flow rates since the rates were held constant. M

Jan 1, 1965

By J. Chipman, M. N. Dastur

The importance of dissolved oxygen as a principal reagent in the refining of liquid steel and the necessity for its removal in the finishing of many grades have stimulated numerous studies of its chemical behavior in the steel bath. From the thermodynaniic viewpoint the essential data are those which determine the free energy of oxygen in solution as a function of temperature and composition of the molten metal. A number of experimental studies have been reported in recent years from which the free energy of oxygen in iron-oxygen melts can be obtained with a fair degree of accuracy for temperatures not too far from the melting point. Certain discrepancies remain, however, which imply considerable uncertainty at higher temperatures; also several sources of error were recognized in the earlier studies. It has been the object of the experimental work reported in this paper to reexamine these sources of uncertainty and to redetermine the equilibrium condition in the reaction of hydrogen with oxygen dissolved in liquid iron. The reaction and its equilibrium constant are: H2 (g) + Q = H2O (g); K1 _ PH2O / [1] Ph2 X % O Here the underlined symbol Q designates oxygen dissolved in liquid iron. The activity of this dissolved oxygen is known to be directly proportional to its concentrationl,2 and is taken as equal to its weight percent. The closely related reaction of dissolved oxygen with carbon monoxide has also been investigated:3,4,5 co (g) +O = CO?(g); K _ Pco2___ [2] K2= pco X % O [2] The two reactions are related through the wat,er-gas equilibriuni: H2 (g) + CO2 (g) = CO (g) + H2O (g); K2 = PCO X PH2O [3] PH2 X PCO2 and with the aid of the accurately known equilibrium constant of this reaction, it has been shown5 that the experimental data on reactions [1] and 121 are in fairly good, though not exact, agreement. Experimental Method Great care was taken to avoid the principal sources of error of previous studies, namely, gaseous thermal diffusion and temperature measurement. The apparatus was designed to provide controlled preheating of the inlet gases and to permit the addition of an inert gas (argon) in controlled amounts, two measures found to be essential for elimination of thermal diffusion. A known mixture of water vapor and hydrogen was obtained by saturating purified hydrogen with water vapor at controlled temperature. This mixture, with the addition of purified argon, was passed over the surface of a small melt (approximately 70 g) of electrolytic iron in a closed induction furnace. After sufficient time at constant temperature for attainment of equilibrium the melt was cooled and analyzed for oxygen. GAS SYSTEM A schematic diagram of the apparatus is shown in Fig 1. Commercial hydrogen is led through the safety trap T and the flowmeter F. The catalytic chamber C, held at 450°C, was used to convert any oxygen into water-vapor. A by-pass B with stopcocks was provided so that the hydrogen could be introduced directly from the tank to the furnace when desired. From the catalytic chamber the gas passed through a water bath W, kept at the desired temperature by an auxiliary heating unit, so that the gas was burdened with approximately the proper amount of water vapor before it was introdvced into the saturator S. All connections beyond the catalytic chamber were of all-glass construction. Those connections beyond the water bath were heated to above 80°C to prevent the condensation of water vapor. After the saturator, purified argon was led into the steam-hydrogen line at J, and finally the ternary mixture was introduced into the furnace. THE SATURATOR The saturator unit comprised three glass chambers, as shown in Fig 1, the first two chambers packed with glass beads and partially filed with water and the third empty. Each tower had a glass tube with a stopper attached for the purpose of adjusting the amount of water in it. The unit was immersed in a large oil bath, which was automatically controlled with the help of a thermostat relay to constant temperature, ± 0.05ºC, using thermometers which had been calibrated against a standard platinum resistance thermometer. The performance of the saturator over the range of experimental conditions was checked by weighing the water absorbed from a measured volume of hydrogen; the observed ratio was always within 0.5 pct of theoretical.

Jan 1, 1950

By E. T. Turkdogan, Klaus Schwerdtfeger

OelSEN and Maetz1 detected some 20 years ago the existence of a miscibility gap in iron oxide-CaO-P2O5 slags melted in iron crucibles at about 1400°C. Because of the importance of this system for the dephos-phorization of steel in the basic Bessemer process, equilibria between liquid iron and selected iron oxide-CaO-P2Q slags have been measured since by numerous investigators.2-5 When in equilibrium with metallic iron, the iron oxide of the slag is present mainly as FeO. In connection with oxygen-blowing steelmaking processes, it is useful to know the phase relations in the slag system at higher oxygen pressure, when major parts of the iron oxide are present as Fe2O3. This problem was investigated by Turkdogan and Bills7 by equilibrating the oxide mixtures contained in platinum crucibles with CO2-CO mixtures at 1550°C. It was found that increasing the Fe2O3 content decreases the composition range of the miscibility gap strongly so that the miscibility gap has almost disappeared at pco2/pco = 75. This result was refuted by the careful work of Olette et a1.,&apos;&apos;&apos; who equilibrated their slags with controlled Ha-H2-Ar gas mixtures. Their equilibrium measurements, at 1600°C and at oxygen pressures of 5 x 10"* and 10"5 atm, showed that the oxidation state of the iron has almost no influence on the formation of the miscibility gap. The present experiments were undertaken to check the previous results of Turkdogan and Bills. The experiments were performed at 1625°C in the strongly oxidizing atmosphere of air (PO2 = 0.20 atm) for which no experimental data are available. About 10 g of slag were melted in platinum crucibles and held at constant temperature for 1 hr. After equilibration, the crucible was rapidly pulled out of the furnace and cooled in air. The platinum crucible was removed from the sample. The two slag layers were carefully separated with a small diamond disc, and the surface of the top layer, which may have changed its oxidation state during cooling, was removed. The slags were crushed and analyzed chemically for CaO, P2O5, Fe2+, and Fetotal. The starting mixtures were prepared by sintering the desired amounts of reagent-grade 2CaO . P2O5 - H2O, CaCO3, and Fe2O3. Sintering and subsequent crushing were done three times to ensure homogenization. Molybdenum wire resistance heating was used. The furnace was provided with a recrystallized alumina reaction tube which was left open to air at the top. The temperature was controlled electronically. The reported temperature was measured with a Pt/Pt-10 pct Rh thermocouple and is estimated to be accurate within +5°C. The composition of the equilibrated melts is given in Table I. For the graphical illustration of these quaternary slags the type of projection suggested by Trömel and Fritze10 was used. In this representation, Fig. 1, the composition point of a mixture within the tetrahedron Fe2O3-CaO-P2O5-FeO is projected into the Fe2O3-CaO-P2O5, triangle (triangle I) so that the direction of projection is parallel to the side FeO-Fe2O3, and into the triangle Fe2O3-P2O,-Fe0 (triangle 11) so that the direction of projection is parallel to the side CaO-P2O5, of the tetrahedron. The projected point has the coordinates wt pct CaO, wt pct P205, and wt pct (FeO + Fe2O3) in triangle I and wt pct FeO, wt pct Fe2O3, and wt pct (CaO + PzO5) in triangle 11. Both triangles are turned into the same plane around the Fe203-P20, side of the tetrahedron. An illustration of the projection of a quaternary point in the present system is shown in Fig. 1. The advantage of this type of projection is that all four components for an equilibrium curve can be read directly from the diagram. The present results are shown graphically in Fig. 2. The curves depicting the miscibility gap are dashed in parts where no experimental points were obtained. The composition range covered by the miscibility gap

Jan 1, 1968

By A. K. Csazar, L. W. Holm

This paper describes our investigation of a post-water-flood, oil recovery process which consists of injecting a slug of propane followed by water. Also described are the results obtained by applying a modification of the process in which gas was injected ahead of the water. Under the conditions of the latter experiments, misci-bility was not achieved between the propane and gas. Preliminary experiments or) uniform, watered-out sandstone cores showed that an oil bank could be formed and produced by applying this recovery process. However, since reservoirs are not uniform in structure, the process also was applied to porous media containing irregular porosity and to stratified sand systems. As a supplenzerrt to the experinlental work, a mathernatical procedure was developed for calculating the performance of the recovery process in a bounded, layered, porous system with crossflow between layers. As a specific example, the method was applied to predict the perforrnance of the recovery process in a 6-ft long, two-layer, stratified, unconsolidated sand model for comparison with experinlental data. The calculations were programed for the ZBM 704 computer. The equations and calcula-tional procedure presented can be extended to systems containing any number of randomly distributed permeability variations or any number of parallel layers. INTRODUCTION The problem of recovering the oil that remains in a reservoir which has been waterflooded is receiving considerable attention now as an increasing number of water floods reach an economic limit. A large number of the waterflood projects are in shallow reservoirs which are at pressures below 1,000 psi. It has been demonstrated in the laboratory that post-waterflood oil can be recover-ered by miscible displacement, but the LPG-gas, miscible flood and the enriched gas drive cannot be applied effectively at pressures below 1,000 psi. Only a few reports have appeared in the literature2-4 on low pressure, partially miscible recovery methods. However, it is possible to use LPG in a partially miscible displacement process in a reservoir where pressures of 200 to 1,000 psi can be achieved. Under these Pressures and at normal reservoir temperatures, propane is miscible with the oil; but, of course, gas or water used to drive the propane slug would not be miscible with the propane. Because of the lack of complete miscibility, it has generally been concluded that excessive amounts of propane would be required to recover oil and that such a recovery method would not be economical; however, we have found that under conditions present in certain reservoirs, an imrniscible recovery process can be applied effectively. The oil saturation in reservoirs at the economic limit of waterflood projects is usually in the range of 20 to 35 per cent of the pore space." A certain portion of this oil is left trapped by water in various size pores of the rock, but a good part of this so-called "residual" oil can be present in the less permeable lenses or layers of the reservoir rock which were by-passed to some degree by the water. The oil in these permeability traps can be produced only if favorable pressure gradients are formed in the reservoirs between adjacent zones of high and low permeabilities. A low viscosity liquid, miscible with the oil in place, which is driven by water through a stratified or heterogeneous porous system can aid in the development of these favorable pressure gradients. The oil that is released thereby from the permeability traps can be recovered by the subsequent water flood. Studies were made to determine how much oil could be recovered from homogeneous and stratified cores and models, which had been water flooded, by injecting a slug of propane and driving it with water. The effect of injecting a slug of gas ahead of the water was also determined. Most of the work described herein was done with the propane-water combination; unless otherwise specified, no gas was injected. The principal objectives of the investigation were to determine (1) if an oil bank could be formed and (2) what ratio of oil recovered to propane injected would be obtained. A further objective was to develop a method for calculating fluid-flow performance in stratified systems which would account for fluid transfer between zones in hydrodynamic communication but of different permeabilities. THEORETICAL ANALYSIS In a theoretical study of the recovery process, analytical expressions were derived to calculate the pressure distribution, the fluid flux in longitudinal (parallel to layers) and transversal (across the layers) directions, and the fluid distribution at any point in the system. The equations were developed for a two-layer porous system in which it was assumed that the fluids in the system were incompressible and that capillary and gravity effects were

By T. I. Moore, L. A. Painter

THE electrolytic zinc plant of the American Zinc Co. of Illinois was described by Davidson&apos; in 1944. Since then, improvements as well as expansion of the plant facilities have been made. In order to increase the production of high grade zinc which was needed for war purposes, an expansion program designed to double the slab zinc capacity was started in 1942 and completed in March 1943. This expansion was propagated by a contract between the American Zinc Co. of Ill. and the Defense Plant Corp. The contract included the facilities of the Fairmont City, Ill., property of the American Zinc Co., where a suspension-type roaster with contact acid plant, cadmium distillation furnace, Waelz oxide and densifying plant, and horizontal retort furnaces were installed. The expanded Monsanto, Ill., plant and the additional facilities of&apos; the Fairmont plant were designed to integrate the metallurgical treatment of zinc concentrates for the production of special high grade zinc at Monsanto with the production of acid, cadmium, high grade zinc from furnace skimmings and the Waelz treatment of leach residue at Fairmont. In general, the original flowsheet was not changed, except for the addition of the filtering, drying and reclaiming of leach residue, and the treatment of purification cake for the recovery of copper, cadmium sponge, and zinc. Fig. 1 is a flow diagram of present operations. The original plant facilities, desi-gned for 50 tons daily production of slab zinc, had some units which were more than adequate. Therefore, in expanding the facilities to 100 tons per day, it was not necessary to double all operating components. Table I gives the comparison of the changes made in the unit operating components for the original facilities, 1941, the 1943 expansion, and the 1951 facilities. During the past 11 years a number of improvenients have been made resulting in: 1—an increase in slab production, 2—higher recoveries on the calcine treated, 3—better quality of slab zinc produced, 4—higher current efficiencies, and 5—less man hours Table I. Changes in Operating Facilities Operating Unit 1941 1943 1951 Calcine unloading (pneumatic), 10 tons per hr 12 calcine unloading track hpr. and elev., 60 tons per hr 1 Calcine storage, tons 1,000 2,000 2,000 Leach tanks, 35 vol. tons. No. 3 5 6 slurry mixing 6x6 ft stainless tank, No. 1 Ball mill. 4.5 rt x 16 in. conical. No. 1 CLassifier duplex, No. 1 1 Thickeners. 50 it diam. No. 2 9 2 Filter thickeners, sq ft &apos;-- Moore filters, sq ft 5.760 11,520 Drum filters, 10 ft diam x 16 ft, No. 3 3 Rotary arlers, No. 1 2 1st stage Cu-As purificatlon tank. 90 vol. tons, No. 3 Solution heaters, No. 3 Filter press, 30x30 bronze, No. 4 Zinc dust purification tanks, 45 vol tons. No. 3 5 4 Filter press, 36x36 bronze, No. 3 5 3 Cadmium recovery plant: Process tank. No. 5 2 Cake roaster, 20 ft diam x 4 hearth. No. 1 Filter press, 24x24, No. 4 1 Sponge wash box, 4x6 ft, No. 1 Evaporative cooling unit (vacuum), No. 1 Purified storage tank, vol. tons 400 400 400 Cell acid storage, vol. tons 400 400 400 Electrolytic cells, No. 180 372 372 Cell room ventilation, cu ft per min 35,000 125,000 125,000 Cell cooling water. gal per min 1,500 2,300 2,300 Deep well 16 in. x 95 ft, 1500 gal per min, No. 2 3 3 Melting and casting furnace, 130 ton. No. I Furnace fume scrubber unit, No. 1 Dross drums, No. 2 Dross roaster, 8 ft diam x 8 hearth, No. 1 Electrolysis power conversion, kw 6,250 23,750 23,750 Power transformers, 13,800/440, kva 1,000 1,500 2,000 Steam boilers fire tube, 15 psi, lb per hr 12,000 18,000 18,000 Steam boilers water tube. 125 psi, Ib per hr 30,000 Air compressor, 2 stage. 300 cu ft per min. 100 psi, No. 1 2 Air compressor, 1 stage, 300 cu ft per min, 20 psi, No. 1 Vacuum pumps, 18x7, 720 cu ft per day, No. - - . Vacuum pumps, 24x11, 1.633 cu ft per day, No. 3 3 Building area, sq ft 60,854 113,568 115,000 per ton of metal produced. In the summer of 1944, the "reverse" leaching process was placed in operation and since it has been described,&apos; no further description will be given. Other facilities and changes which have contributed to the process improvements were the scrubbing of fume from the melting and

Jan 1, 1953

By N. A. Gokcen, John Chipman

SILICON is the most commonly used deoxidizer and an important alloying element in steelmak-ing; hence a detailed study of this element in liquid iron containing oxygen is of considerable interest. The equilibrium between silicon and oxygen in liquid iron has been studied by a number of investigators but generally with inconclusive or incomplete results. The variation of the activity coefficients of silicon and oxygen with composition is entirely unknown. Published investigations deal with the reaction of dissolved oxygen with silicon in liquid iron and the results are expressed in terms of a deoxidation product. For consistency and convenience in comparison of the published information, the deoxidation product as referred to the following reaction is expressed in terms of the percentage by weight of silicon and oxygen in the melt in equilibrium with solid silica: SiO (s) = Si + 2 O; K&apos;l = [% Si] [% 012 [I] Theoretical attempts to calculate the deoxidation constant for silicon in liquid iron from the free energies of various reactions yielded results which were invariably lower than the experimental values. Thus, the deoxidation "constants" calculated by McCance,1,2 Feild,3 Schenck, and Chipman were of the order of 10, which is below the experimental values by a factor of more than 10. Experiments of Herty and coworkers" in the laboratory and steel plant resulted in an average deoxidation constant of 0.82x10 &apos; at about 1600°C. The technique employed in their investigation was crude and the reported temperature was quite uncertain. The concentration of silicon was obtained by subtracting silicon in the inclusions from the total. Since at least some of the inclusions resulting from chilling must represent a fraction of the silicon in solution at high temperatures, such a subtraction is not justifiable. Results of Schenck4 for K&apos;1 from acid open-hearth plant data yielded a value of 2.8x10-5, which was later revised as 1.24x10 at 1600°C. Similarly Schenck and Bruggemann7 obtained 1.76x10-5 at 1600OC. The discrepancies and errors involved in the acid open-hearth plant data as compared with the results of more reliable laboratory techniques were attributed by these authors to the lack of equilibrium and the impurities in liquid metal and slag, and are sufficiently discussed elsewhere." Korber and Oelsen" investigated the relation between dissolved oxygen and silicon in liquid iron covered with silica-saturated slags containing varying concentrations of MnO and FeO. The deoxidation products obtained by their method scatter considerably, and their chosen average values of 1.34x10, 3.6x10-5, and 10.6x10-5 1550°, 1600°, and 1650°C, respectively, represent the best experimental results which were available until quite recently. Darken&apos;s10 plant data from a steel bath agree approximately with their data at 1575° to 1625°C. Zapffe and Sims" investigated the reaction of H2O and H2 with liquid iron containing less than 1 pct Si and obtained deoxidation products varying by a factor of more than 20. Inadequate gas-metal contact and lack of stirring in the metal bath should require a longer period of time than the 1 to 5.5 hr which they allowed for the attainment of equilibrium. Furthermore, their oxygen analyses were incomplete and irregular and confined to a few unsatisfactory preliminary samples. Their results did indeed indicate that the activity coefficient of oxygen is decreased by the presence of silicon, although they made no such simple statement. They chose to attempt to account for their anomalous data by the unlikely hypothesis that SiO is dissolved in the melt. Hilty and Crafts" investigated the reaction of liquid iron with acid slags under an atmosphere of argon, making careful determinations of silicon and oxygen contents at several temperatures. Despite erroneous interpretation of the data at very low silicon concentrations, their data represent the most dependable information on this equilibrium that has been published. In the range 0.1 to 1.0 pct Si, their data yield the following values for the deoxidation product: 1.6x10-5, 3.0x10- &apos;, and 5.3x10 at 1550°, 1600°, and 1650°C, respectively. The purpose of the work described herein was to study the equilibrium represented by eq 1 as well as the following reactions, all in the presence of solid silica: SiO2 (s) + 2H2 (g) = Si + 2H2O (g);

Jan 1, 1953

By F. N. Rhines

Sintering may be defined as the process by which powders bond themselves into coherent bodies, usually, although not necessarily, under the influence of pressure and elevated temperature. For the sake of clarity and simplicity, the present survey will exclude from consideration the sintering of mixed or alloyed powders, with attendant complications, but at the risk of overlooking information of general applicability. Sintering in the presence of a liquid phase is thus automatically eliminated. The sintering of alloys involves much additional subject matter and deserves separate consideration. Since the literature of the subject is extensive and widely scattered, it will not be feasible to consider the contributions individually. Instead, the subject matter will be classified according to experimental observations and theory, and will be presented in summary form. It should be noted that the appended list of references does not constitute a complete bibliography; it includes only those works quoted below. More extensive bibliographies are included in several of the references; see particularly references 7, 9, 28, 34, 38, 50, 52, 54, a "Bibliography on Powder Metallurgy" published by the Library of Congress and a pamphlet published by the Metals Disintegrating Co. entitled "The Field of Powder Metallurgy and Bibliography." 11. Summary of Experimental Observations The following classified list is composed of general statements of established fact derived from the experimental results reported in the published literature. A few contested observations are included, because of their potential importance; these are labeled as such. Any satisfactory and complete theory must be capable of explaining all of the uncontested facts. Obviously, some important facts may be missing from this list and these may hold the key to the correct explanation of the sintering process, but the possible lack of such material should not deter attempts to understand the subject on the basis of what is available here. A, The Initial Bond at Room Temperature a. To a limited extent uncompressed powders and massive metals adhere at room temperature. Clean tin powder forms a weak "cake" on standing at room temperature, the strength increasing with time. Clean gold surfaces adhere on light con-tact, as do those of many other substances, including nickel.27 b. Upon compression the strength of the bond- is increased progres-ivelv. There is a limit of pressure

Jan 1, 1946

By F. N. Rhines

Sintering may be defined as the process by which powders bond themselves into coherent bodies, usually, although not necessarily, under the influence of pressure and elevated temperature. For the sake of clarity and simplicity, the present survey will exclude from consideration the sintering of mixed or alloyed powders, with attendant complications, but at the risk of overlooking information of general applicability. Sintering in the presence of a liquid phase is thus automatically eliminated. The sintering of alloys involves much additional subject matter and deserves separate consideration. Since the literature of the subject is extensive and widely scattered, it will not be feasible to consider the contributions individually. Instead, the subject matter will be classified according to experimental observations and theory, and will be presented in summary form. It should be noted that the appended list of references does not constitute a complete bibliography; it includes only those works quoted below. More extensive bibliographies are included in several of the references; see particularly references 7, 9, 28, 34, 38, 50, 52, 54, a "Bibliography on Powder Metallurgy" published by the Library of Congress and a pamphlet published by the Metals Disintegrating Co. entitled "The Field of Powder Metallurgy and Bibliography." 11. Summary of Experimental Observations The following classified list is composed of general statements of established fact derived from the experimental results reported in the published literature. A few contested observations are included, because of their potential importance; these are labeled as such. Any satisfactory and complete theory must be capable of explaining all of the uncontested facts. Obviously, some important facts may be missing from this list and these may hold the key to the correct explanation of the sintering process, but the possible lack of such material should not deter attempts to understand the subject on the basis of what is available here. A, The Initial Bond at Room Temperature a. To a limited extent uncompressed powders and massive metals adhere at room temperature. Clean tin powder forms a weak "cake" on standing at room temperature, the strength increasing with time. Clean gold surfaces adhere on light con-tact, as do those of many other substances, including nickel.27 b. Upon compression the strength of the bond- is increased progres-ivelv. There is a limit of pressure

Jan 1, 1946

By J. M. Lovejoy

Various estimates have been made as 60 the percentage of oil left in a field after the wells have become so small that it is no longer practical to produce them. Engineers have given the matter much study and can substantiate their figures by data taken from fields from the Appalachians to California. The average oil sand has a porosity of about 20 per cent., which gives a capacity per acre-foot of approximately 1500 bbl. The sand thickness in Oklahoma pools averages 20 ft. With 20 per cent, porosity and a 20-ft. sand thickness, the capacity per acre is 30,000 bbl., yet these pools will seldom yield more than 5000 bbl. to the acre. These figures gupport the theory that at least 50 per cent. of the oil remains in a sand after all known methods to recover it have been used. Certainly we can never recover all the oil, unless in years to come oil becomes so rare and yet so necessary that the price will justify sinking shafts into the abandoned fields and regular mining methods of drifting and stoping. However, with improved methods of production and conservation of the natural agencies of expulsion, we should be able to increase recovery. It is with this in mind that this paper, relating to the effect of back pressure on wells, is presented. Except in the fields where production is caused by hydrostatic pressure, the chief agency for getting oil out of the sand into the hole is the gas that occurs with the oil. After the pressure has declined, probably gravity also is a factor, but not an important one. With a given amount of oil in a sand and a given amount of gas occurring with the oil, the ratio of gas volume per barrel of oil is the key to the ultimate recovery from that sand. Our efforts should be along lines that will lower this ratio and make the gas, the agency given us by nature, do its work better and yield more of the oil, of which it is a part. T. E. Swigart,&apos; of the U. S. Bureau of Mines, has published an extract of the paper he is preparing under the title "The Effect of Back Pressures. on Wells." The experiments described were made on two

Jan 1, 1924

By R. E. Ogilvie, H. C. Gatos, R. E. Hanneman

The effect of high pressure on the stability of the (any phase transformation in the Fe-V system was studied by experimental and theoretical methods. The maximum solubility limit of the y loop of the atmospheric phase diagram was found to increase by a factor of five at 40 kbars pres-sure. The solubility limits of (Y and y phases are calculated on an approximate thermodynamic basis at pressures of 20, 40, and 50 kbars as a function THE high-pressure behavior of the a =^ y transformation in iron and iron-base alloys has been the subject of considerable interest recently. For those binary or higher-order alloy systems possessing a closed y loop, the effect of pressure is to extend the region of solubility of the more dense y phase. Although quite accurate calculations have been made of the a y temperature-pressure diagram of pure iron,&apos; only very approximate thermodynamic calculations or experimental measurements have been made of the pressure dependence of a ^ y equilibria in binary systems exhibiting a y loop.2"4 of temperature and are found in excellent agreement with experimental results. The experimental high-pressure phase diagrams were determined using binary diffusion couples diffused under simultaneous conditions of high pressure and temperature and analyzed with an electron microbeam probe. Approximate calculations of the stabilizing effect of high pressure on the o phase are qualitatively confirmed by experimental results. These previous calculations have primarily dealt with the slopes of the allotropic a (Y= y phase boundary at terminal solubility. The lack of detailed understanding or accurate experimental results of the pressure dependence of the two-phase a ^ y field has been due, in part, to the types of experimental methods previously employed. The primary purposes of the current paper are twofold: 1) to develop and make use of thermodynamic expressions with the aid of supplementary data, to approximately calculate the pressure dependence of the entire y loop and the two-phase ((Y + y) width in the Fe-V system; and 2) to accurately determine the corresponding experimental high-pressure phase diagrams. The current paper describes the powerful method used which enables the simultaneously measurement of phase equilibria and diffusion under high pressure and temperature. A second paper, part 11, will deal with the effect of high pressure on binary diffusion in the Fe-V system.

Jan 1, 1965

By F. N. Rhines

I. An Outline of the Theory of the Sintering of Pure Metal Powders SINTERING may be defined as the process by which powders bond themselves into coherent bodies, usually, although not necessarily, under the influence of pressure and elevated temperature. For the sake of clarity and simplicity, the present survey will exclude from consideration the sintering of mixed or alloyed powders, with attendant complications, but at the risk of overlooking information of general applicability. Sintering in the presence of a liquid phase is thus automatically eliminated. The sintering of alloys involves much additional subject matter and deserves separate consideration. Since the literature of the subject is extensive and widely scattered, it will not be feasible to consider the contributions individually. Instead, the subject matter will be classified according to experimental observations and theory, and will be presented in summary form. It should be noted that the appended list of references does not constitute a complete bibliography; it includes only those works quoted below. More extensive bibliographies are included in several of the references; see particularly references 7, q, 28, 34, 38, 50, 52, 54 a "Bibliography on Powder Metallurgy" published by the Library of Congress and a pamphlet published by the Metals Disintegrating Co. entitled "The Field of Powder Metallurgy and Bibliography." II. Summary of Experimental Observations The following classified list is composed of general statements of established fact derived from the experimental results reported in the published literature. A few contested observations are included, because of their potential importance; these are labeled as such. Any satisfactory and complete theory must be capable of explaining all of the uncontested facts. Obviously, some important facts may be missing from this list and these may hold the key to the correct explanation of the sintering process, but the possible lack of such material should not deter attempts to understand the subject on the basis of what is available here. A. The Initial Bond at Room Temperature a. To a limited extent uncompressed powders and massive metals adhere at room temperature.28 Clean tin powder forms a weak "cake" on standing at room temperature, the strength increasing with time. Clean gold surfaces adhere on light contact,"&apos; as do those of many other substances, including nickel." b. Upon compression the strength of the bond is increased progressively.28 There is a limit of pressure

Jan 1, 1946

By N. A. Gokcen, S. Fujishiro

THE pressures of Mn(g) in equilibrium with Mn7C3 and graphite have been measured by McCabe and Hudson&apos; and Butler, McCabe, and paxton2 by means of graphite, zirconia, and Ta-Mo Knudsen cells. The details of corrections in their measurements were somewhat different from those of the authors;3&apos;4 hence, further independent results at higher temperatures seemed to be warranted. The stoichiom-etry of Mn7C3 in equilibrium with graphite and its stability up to the vicinity of 1373 °K have been satisfactorily established by Kuo and persson5 (See also Hansen and Anderko).&apos; The method of investigation has been described elsewhere in detail.3&apos;4 The carbide was prepared in the manner described by McCabe and Hudson. In order to avoid possible reactions with refractory oxides, only graphite cells were used for the effusion experiments. The authors&apos; results are the runs M-1, M-2 and M-3 listed in Table I, together with those of McCabe and co-workers. The heat capacity, c;, of Mn7C3 is not known; therefore McCable et al. plotted their data as log P vs 1/T and the results were only expressed first&apos; as, and later2 as logP=- -14220+6.06 without further thermodynamic calculations. However, it is possible to estimate closely the necessary heat capacity as follows: When H; - &98 of CrC, or MnO, is plotted vs x, corresponding to various compounds, with temperature as the parameter, it is seen that the relationship is represented by a line of very small curvature. This relationship is also followed by other compounds which do not exhibit solid state phase transformations. In view of the fact that chromium and manganese have the atomic numbers of 24 and 25 respectively, it is reasonable to assume that H; - H;ae vs x for MnC, follows the same type of lines as those for CrC, for which adequate data are available.7 Similar correlations appear to be valid for oxides of two neighboring metals for which reliable data are available. The procedure is thus to move the lines for CrC, vertically (parallel to the axis of HT - H298) until they coincide with the points for MnC1/3, the only carbide of manganese whose H; - HO298 has been

Jan 1, 1963

By L. L. Newman

PUBLIC UTILITY GAS PRODUCTION IN 1802, William Murdock first used retort coal gas to light his house and the Boulton and Watt plant where he was employed. For the next three quarters of a century coal served as the principal raw material for the manufacture of city gas for general distribution. Coal continued to hold its predominant position for another half century after Prof. Thaddeus C. Lowe developed the first practical method of enriching water gas with cracked-oil vapors in an integrated operation. This position, however, was no longer maintained through the medium of direct carbonization of coal in retorts but as a result of using anthracite or coke as the generator fuel in carburretted water-gas machines. The early water-gas machines were extremely crude and the consumption of both oil and generator fuel was very high. However, the cost of installation was considerably lower than for any coal-gas system having the equivalent gas-making capacity, the labor involved was small, and the water-gas machine could be started up and shut down quickly. It thus proved very useful as standby equipment and in taking peak loads from the coal-gas plants. The flexibility of the water-gas machine, furthermore, made it possible to change the candlepower of the gas readily to suit the required conditions. Later, when calorific value replaced candlepower as the standard of gas quality, the water-gas machine was found to be equally flexible in keeping the city gas under complete and convenient control. No basic improvements were made in the Lowe carburetted water-gas process until 1898, when means were added to provide for regular reversals of the flow of steam through the fuel bed. By judicious proportioning of the quantities of up-run and down-run steam, it became possible for the operator to control the hardness and position of the clinker to a degree that previously had been unattainable. Also in 1898, the first by-product coke plant in America to supply city gas was built at Everett, Massachusetts. Later many other by-product plants, of greatly improved design and capacity, were built, but not primarily for city-gas production, chiefly because of the relatively high investment cost per unit of gas made. Cheaper plant construction has been the subject of serious study, and some progress is expected, but other factors, such as plant life,

Jan 1, 1953

INSTITUTE MEDALS AND PRIZES ASIDE from the John Fritz Medal, in which the Institute participates through its representation on the John Fritz Medal Board, the Institute itself has five major awards to make annually for excellence in technical papers, as follows The Robert W Hunt Medal, The Hadfield Prize, The J E Johnson Jr , Award, The Lewisohn Platinum Prize to senior members, and the President&apos;s Prize to junior members ROBERT W HUNT MEDAL The partners of Robert W Hunt established a fund which was presented to the Institute at a fitting ceremony on May 27, 1920, to establish an annual medal and a sum of money to be awarded under the following rules, 1 The award shall consist of two prizes, first of a gold medal, second of a sum of money, a certificate to accompany each prize The money prize shall not be awarded to a member over 40 years of age, but under unusual circumstances, both prizes may be allotted to one person provided that he is not over 40 years of age In general it will be understood that the Committee shall award the money prize to, the younger men, rather than the medal 2 The awards shall be made not oftener than once a year to that person or persons contributing to the Institute the best original paper or papers on iron and steel The scope of the term "iron and steel" shall be determined by the sub-committee consider¬ing the awards In general, papers dealing with the practical side of the subject have preference over those dealing with the theoretical side in recognition of the fact that Captain Hunt&apos;s main contributions to the industry have been in the improve¬ment of production and quality of material 3 A sub-committee of three to five, including the Chairman of the Iron and Steel Committee, shall be appointed by the Iron and Steel Committee annually to adjudge the award subject to approval 4 The awarding committee shall submit its report to the Iron and Steel Committee at its October Meeting, and the award be certified to the Secretary of the Institute in time to permit the presentation to be made at the Annual Meeting of the Institute 5 The recipient of the award shall be designated "The Hunt Medallist "

Jan 1, 1923

Without doubt Arizona was the scene of the first use of coal in North America, that by the Hopi Indians as early as the 10th century in burning their pottery and in heating their houses and kivas (ceremonial rooms). As has already been said this is the only use of coal by Indians of which we have any knowledge, but it has been well established through investigations conducted by the Peabody Museum of Archaeology and Ethnology of Harvard University. The apparatus for burning was crude, but they did have fireplaces and chimneys which would draw. The evidences of coal use were found in the Jeddito Valley, in Navajo County, during the excavation of the pueblo of Awatovi, only a short distance from the Keams Canon School. "Many fire pits and primitive stone stoves containing coal ash have been found in the houses, and in most of the kivas built between 1300 and 1600, two firepits have been found, one containing wood ash exclusively and the other coal ash."&apos; The expedition of 1939 found that coal was used much earlier than this, as stated above. It is probable that these Indians were using coal regularly before it came into general use in England and northern Europe. Apparently the use of coal was largely stopped about the time the Spaniards came to that country. The ruins are located on the southern edge of the Black Mesa and the coal seams outcrop on the mesa edge below the ruins. "The coal occurs principally in one large seam which varies from a foot and a half to six feet in thickness."1 This coal is sub-bituminous and burns well, leaving a large percentage of white ash. Another seam is found about 40 ft. above this large seam; it is from six inches to a foot thick and burns to a red ash. Both of these seams were used and coal from the larger seam was used at other houses in the valley. The pottery was usually burned close to the coal seams, and the coal was used to obtain a uniform and satisfactory color. In the Jeddito Valley, the mining was done by stripping, and the methods used are described as follows by J. 0. Brew and John T. Hack, the investigators.

Jan 1, 1942