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By E. J. Rapperport, M. F. Smith

A presentation of the W-Ru constitution diagram is given. Techniques utilized in the determination of phase boundary values include electron micro-probe analysis of two-phased alloys and diffusion couples, as well as normal metallographic and X-ray methods. The primary features of the diagram are: 1) a terminal solid solution of ruthenium in tungsten with a maximum solubility of 23 at. pct Ru at 2300°C; 2) a terminal solid solution of tungsten in ruthenium with a maximum solubility of 48 at. pct W at 2205°C; 3) a o phase of maximum breadth about 6 at. pct based on the composition W3Ru2 which forms peritectically from the melt at 2300°C, and which decomposes eutectoidally at 1667 °C to form a twigs ten and 0 ruthenium; 4) a eutectic at 45 at. pct Ru and 2205°C with the products being o plus ß ruthenium. THE W-Ru diagram has previously been studied only in a cursory fashion. Raub and alter' obtained a 1400°C isotherm in which they observed no intermediate phases, and on which they established the limits of solubility as 36.5 at. pct W in ruthenium and about 1.5 at. pct Ru in tungsten. In addition, Obrowski2 found a o phase forming peritectically from the melt and existing only above 1650°C. Below this temperature the phase was presumed to decompose eutectoidally. The present work finds the diagram as given in Fig. 1. I) EXPERIMENTAL PROCEDURE The materials used for alloy preparation in determining the W-Ru constitution diagram were 99.9 pct pure ruthenium powder supplied by Baker Chemical Co., and 99.9 pct pure tungsten powder from General Electric Co. Typical analyses of these elements are given in Table I. Initial alloys at 10 at. pct intervals were prepared from the metal powders by the following method. Powders sufficient for 25 g of the alloys were weighed out with an accuracy of 0.1 mg and blended mechanically. After blending, the powders were compacted, in a steel die, at approximately 30,000 psi. The compacts were sintered in an electric vacuum furnace in order to remove adsorbed gases and to achieve partial densification prior to arc-melting. Vacua of 10-4 mm Hg or less were maintained in sintering as the furnace temperature was raised to approximately 2000°C. Sintering times ranged from 10 to 20 hr. The sintered compacts were arc-melted under a protective atmosphere of purified helium. Melting was conducted on a water-cooled copper hearth, utilizing a nonconsumable tungsten electrode. In the melting process, each alloy was turned over and re-melted on opposite sides from four to six times to ensure complete melting and to eliminate gross in-homogeneities. The arc-melter used had a vacuum capability of 5 X 10-6 mm Hg, and a leak rate of about 20 -liters per hr. Chemical analysis techniques for refractory metal-platinum group metal combinations are not well-established; therefore, composition control and determination depended principally upon weight-loss observations and calculations. This consisted in weighing each alloy after sintering and after arc-melting, and calculating the maximum and minimum composition values, assuming the total weight losses to be first all tungsten, and then all ruthenium. Since composition uncertainty was directly related to weight loss, care was taken to minimize losses in handling, compacting, and melting. Prior to homogenization and equilibration the as-arc-melted alloys were analyzed in several

Jan 1, 1964

By R. L. Perrine

This paper presents results obtained by consider ation of unstable miscible displacement within a porous medium as a quasi-turbulent displacement process, that is, a process characterized by fluctuations around a simpler, mean flow behavior. The instability usually results from the miscible displacing fluid having a viscosity lower than that of the displaced fluid. Such instability is evidenced in suitable experiments by the presence of viscous fingering. A unified theoretical relationship applicable to both stable and unstable displacement is derived. Parameters in the theory are obtained by empirical means. Although the theory describes an idealized conceptual model, agreement with experiment is quite reasonable up to moderately adverse viscosity ratios, such as 17:1. INTRODUCTION Many experimental studies of miscible displacement in porous media have been conducted with prediction of reservoir displacement efficiency as the ultimate objective. Most such studies have utilized lower displacing than displaced fluid viscosity, scaled to potential reservoir fluid pairs. Theoretical approaches have been largely limited to unit viscosity ratios, however, in spite of the necessity for an understanding of the mechanism of the unstable, adverse viscosity ratio displacement process. An obvious reason is the difficulty of describing in mathematical form the viscous fingering characteristic of these conditions. Observation of experiments conducted with dyed fluids in transparent systems suggests an analogy between unstable miscible displacement and turbulent flow in a pipe. In both cases there are fluctuations around a simpler, mean flow behavior. An important difference is that flow behavior of interest in the porous medium is entirely transient, contained within a transition zone between displacing and displaced fluids. Transient behavior complicates description in that coefficients in the equations become variables rather than constants. In the study reported here, the analogy with turbulent flow has been used in treating unstable miscible displacement as a quasi-turbulent displacement process. The purpose has been to derive, even if restricted to an idealized conceptual model, a unified theoretical relationship applicable to both stable and unstable displacement. A relationship meeting these specifications up to moderately adverse viscosity ratios, such as 17:1, is presented. One fluctuation parameter in the theory and dispersion coefficients are obtained by empirical means. The idealized theory is compared with experimental results. UNSTABLE MISCIBLE DISPLACEMENT AS QUASI-TURBULENT DARCY FLOW The miscible displacement of one fluid by another within a porous medium is considered in this study. Flow conditions are such that Darcy's law is applicable. It is further assumed that, by the stability criterion proposed by perrine,1 initial flow conditions lie well within the regime of instability. Thus substantial viscous fingering is assured. We wish to show how this flow regime can be represented as quasi-turbulent. That is, the Reynolds number for the established flow conditions is below that for inertial or turbulent flow within a porous medium, and lies within the regime for which Darcy's law is valid. Yet flow behavior can be described as the combination of some relatively simple average result, and characteristic fluctuations that are superimposed on the simpler behavior. Stated another way, flow behavior includes the movement of layers of fluids with different velocities past or over one another. Such descriptions are characteristic of turbulent pipe flow. The fluctuations in the present case are a direct consequence of the local viscous fingering which accompanies the unstable displacement process. Should displacement become stable, fluctuations would die out. It is of particular importance to note that fluctuations such as these can interact in a way that contributes to material transport by the basic flow. The basic transport equations required for engineering calculations must be modified to reflect this fact.

By Avnulf Muan, P. V. Riboud

The effect of Cr2O3 on melting relations of iron oxide at oxygen pressures slightly above those prevailing in contact with metallic iron has been determined. Liquidus and solidus temperatures of wüstite are raised by the addition of Cr2O3, from 1385°C for pure iron oxide to 1420°C at the peri-ledie point where wüstite, iron chromite, liquid, and gas coexist in equilibrium under the atmospheric conditions used in the present investigation (CO2/H2 = 1). It has been shown in a previous investigation1 that the liquidus and solidus temperatures of iron oxide are drastically increased by the addition of Cr2O3 under the relatively oxidizing conditions prevailing in air. This is to be expected in view of the easy substitution of cr3+ for Fe3+ in crystalline oxide structures which are stable at high oxygen pressures, as demonstrated for instance by the completeness of the solid solution series Fe2O3-Cr2O3 at high temperatures (>1000°C). The stable phase of iron oxide at oxygen pressures approximating those prevailing when metallic iron is present is wüstite. This phase, although commonly represented by the simplified formula FeO for sake of convenience, in reality has a defect structure in which a part of the iron ions are present as Fe3+. It is to be expected that at least a limited amount of cr3 ions will substitute for Fe in this structure when Cr2O3 is added to wüstite. Depending on the ease of this substitution in comparison with that of cr3 substitution for Fe in iron oxide-Cr2O3 liquids under the same atmos- pheric conditions, the liquidus and solidus temperatures of wüstite may increase or decrease upon addition of Cr2O3. The methods of establishing these melting relations and the results obtained are presented in the following. I) EXPERIMENTAL METHOD 1) General Procedure. The quenching technique was used in this study. Oxide mixtures were heated at chosen constant temperatures in an atmosphere consisting of equal parts of CO2 and H2 until equilibrium was established among gas and condensed phases. The samples were then quenched in mercury to room temperature, and the phases present were determined by microscopic and X-ray investigation. 2) Preparation of the Mixtures. Starting mixtures were prepared by weighing and thoroughly mixing Fe2O3 and Cr2O3, or wüstite and Cr2O3. The Fe2O3 and Cr2O3 used were "Baker Analyzed" reagent grades, whereas wüstite of composition was synthesized by reducing Fe203 at 1325°C in an atmosphere consisting of equal parts of CG andHz. In order to avoid contact with crucibles, the equilibration runs were made with small pellets suspended from thin (-0.004-in.) platinum wires. Mixtures made from FOs and Cr203 were readily pelletized at a pressure of 500 atm in a 9.5-mm die, whereas mixtures made from wüstite and Cr203 when treated identically were too weak for handling. In order to obtain a stronger product, these pellets were sintered by heating for 2 min at -1200°C in the same atmosphere as was subsequently used for the equilibration runs (CG/H2 = 1:1). During the sintering, these pellets were wrapped in thin (0.0004-in.) platinum foil, which was stripped off before the equilibration runs. In order to reduce the time needed for equilibrium to be attained, preliminary equilibration of relatively large pellets of each mixture was carried out at -1200°C for 4 to 12 hr. Smaller pellets

Jan 1, 1964

By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami's reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."' A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. ' J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

By E. P. Polushkin, Henry L. Shuldener

THIS paper describes the results of microscopic examination of a series of brass pipes removed from apartment and office buildings in New York City, adjacent localities on Long Island, and Philadelphia. They were selected as typical of approximately four hundred pipe specimens obtained over a period of five years during an investigation of corrosion in hot-water installations. A part of the investigation is reported in this paper and includes a brief history of the pipes, a description of their inside surface and microstructure, and a study of the effects of corrosion, with particular reference to the structural aspects of local and selective dezincification. Although the bibliography on the corrosion of brass pipes is quite extensive, it refers almost entirely to corrosion in sea water. The authors believe that their examination of this series of pipes, which had been subjected to the corrosive action of fresh water for various lengths of time, may throw some additional light on the problem of corrosion. PIPES EXAMINED The pipes were made by different manufacturers and their sizes range from ¾ in. to 4 in. nominal inside diameter, the majority being within I to 2 in. They can be divided into two groups according to chemical composition: (I) with a copper content of 60 to 62 per cent and (2) with a copper content of 65 to 68 per cent. The first group (pipes made of Muntz metal) comprises 22 pipes and the second (pipes made of high brass) comprises 18 pipes. The pipes had been in service in various locations in the hot-water systems of the buildings involved. Some were taken from horizontal lines in the basement, some from overhead distributors and some from vertical risers. The distance, in terms of feet of pipe, of the specimens from the hot-water generator was no less than 75 ft. and often 100 to 300 ft. In the majority of cases the water-heating equipment was provided with a regulator to limit the temperature of the hot water supply. The normal range of temperature in pipe systems of this kind is 100° to 160°F. WATER SUPPLIES The average chemical composition of the water supplies carried by the pipes is shown in Table I. In evaluating the corrosiveness of a natural water, four factors are considered of prime importance: namely, hardness, alkalinity, pH and silica content. The waters listed in Table I are characterized by relatively low hardness, low alkalinity, low pH and low silica content. The waters of lower pH and higher CO2 content are more corrosive. A characteristic of all of these waters is that they do not deposit a protective mineral coating as do waters with high bicarbonate of lime content, which would be reflected

Jan 1, 1944

By John Garcia

IN some districts of the bituminous coal field the problem of construct-ing bulkheads to seal off water under pressure is becoming increasingly important. Recently this matter has been brought very much to the front by the loss of a large Illinois mine due to failure of a bulkhead that separated it from several old, flooded mines. As this great misfortune has provoked much inquiry about proper bulkhead design, it-is felt that a description, of the successful and extensive water-sealing practice at three mines that have different natural conditions will be of considerable interest to those connected with properties having a present or future water problem and to engineers that may have to design safe bulkheads of economical construction. These three mines are the Saxton and Dresser, near Terre Haute, Ind., and the Hegeler, near Danville, Ill. All three have water conditions that make it necessary to regularly seal off all worked-out sections of the mine, and there are considerably over a hundred bulkheads in each. As far as the writers know, these three mines are the only ones in the bitu-minous coal fields of the United States with anything like so large number of water seals and experience, although a number of other mines are known to have a few bulkheads. More detail will be included herein on the Saxton mine than on the others, as the writers are more familiar with it.

Jan 1, 1937

By A. B. Parsons

DOWN in Washington an army of individuals constituting the government of a so-called "'democratic" nation is trying to manage the conduct, in its rnultifold phases, of the greatest war in history for the country that is potentially, at least, the strongest in the world and on which, consequently, the major responsibility rests. The enterprise is one of unprecedented magnitude and complexity. That individuals and groups have made and are making serious blunders, both as to the establishment and execution of policy, is to be expected.

Jan 1, 1942

By T. E. Leontis

ONLY a limited amount of information has been published on the effect of thorium as an alloying ingredient in magnesium. McDonald13'2 showed that the addition of thorium in amounts up to 3 pct increases significantly both the ductility and the strength of rolled magnesium sheet. A recent publication by Sauerwald" indicates that thorium contributes strength and creep resistance at elevated temperatures to magnesium in both the cast and wrought states. The observations of Sauerwald are confirmed in this paper, which presents the results of a systematic study of the effects of compositional variation on the tensile properties, creep resistance, conductivity, density, and metallography of Mg-Th alloys containing up to 50 pct Th both in the sand-cast and in the extruded states. The effect of the addition of cerium to Mg-Th alloys is also reported. Experimental Methods The alloys studied in this investigation were pre.pared in small laboratory melts according to the melting practice described by Nelson4 as the crucible method. Electrolytic magnesium was used as the starting material to which the thorium* was introduced in metallic form. It was observed that the behavior of thorium in molten magnesium with respect to reaction with protective fluxes is similar to that of rare-earth metals. In order to obtain the highest possible alloying efficiency, it is necessary to use non-MgC1, fluxes and to apply all the precautions described by Marande6 for melting, alloying, and casting magnesium-rare-earth alloys. .Under these conditions it is possible to obtain an alloying efficiency in the range of 85 to 95 pct. The Mg-Th-Ce alloys were made with cerium of the highest purity available, not with the commercial product "misch-metal" which contains approximately 50 pct Ce. The total rare-earth content of this material was 97.1 pct, of which 0.3 pct was rare-earth metals other than cerium; the major impurities comprising the balance were iron and magnesium. The thorium and cerium contents of each alloy were determined chemically. Test bars 6% in. long with a 2% in. long reduced section of % in. diam were cast in sand molds using a four-baf pattern. In most cases, a 3 in. diam extrusion billet 10 in. long was cast in a steel mold from the same melt used for making the sand-cast test bars. For the higher thorium alloys, it was necessary to remelt the foundry scrap from the test bars in order to make the extrusion billets. The billets were scalped to a diameter of 2 15/16 in. and the ends faced to a length of 9% in. as limited by the size of the extrusion container. The alloys were extruded into % in. diam rod on a 500-ton direct-extrusion press. The details of the extrusion process are as follows: Billet preheat 925°F (2 to 16 hr) Container temperature 900 °F Die temperature 900°F Extrusion speed 10 ft per min Reduction ratio 36:1 Percent reduction 97.3 Alloys containing up to 10.2 pct Th were preheated at 925°F for 2 hr; all alloys with higher thorium contents were preheated for 16 hr. In order to establish the effect of extrusion temperature, billets of

Jan 1, 1953

Jan 1, 1885

By Arthur A. Center

WAR demand- motivated developments in the zinc industry during 1942. Stocks of Prime Western were built up and High-Grade remained tight. The Prince The Prime Western stocks are expected to be cut down and the demand for High-Grade more easily filled as the Depue reflux plant of the New Jersery Zinc Co. increases - production. Subistition of steel for brass in artillery shell cases will have a considerable effect on the zinc situation of the country one estimate of the saving in zinc in 1943 by this substitution being a little under 100,000 ton, of metal. The metal saved will, of course be High-Grade. If the substitution occurs, the present tight situation in High-Grade may be entirely relieved as new production comes on the market and zinc may find itself approaching a situation as comfortable as that of lead provided the supply of zinc-hearing raw materials is sufficient to keep all reduction plants tip to capacity production. The premium price of the per pound of zinc over set quotas which went into effect early in 1942, helped to bring about the new lead-slag-fuming plant and other new sources of raw materials.

Jan 1, 1943

McCulloch, Leon.-Experiments with Sherardizing. Discussed by Fred. L. Wolf, Willis M. Peirce, Jesse L. Jones, O. W. Storey, David R. Kellogg, William H. Finkeldey, L. H. Marshall 2 Bassett, W. H. and Davis, C. H.-Spectrum Analysis in an Industrial Laboratory. Discussed by C. S. Brainin, C. H. Davis, W. H. Bassett, George K. Burgess, George K. Elliott, Leonard Waldo, Keivin Burns 8 Roast, Harold J. and Pascoe, Charles F.-Arsenical Bearing Metals. Discussed by Jesse L. Jones, William A. Cowan,. William K. Frank, William M. Corse, Harold J. Roast 10 Bain, Edgar C.-Crystal Structure of Solid Solutions. Discussed by Ancel St. John, Edgar C. Bain, Paul D. Merica 14 Peirce, Willis M.-Studies on the Constitution of Binary Zinc-base Alloys. Discussed by George K. Burgess, Willis M. Peirce, D. H. Ingall, J. L. Haughton, K. E. Bingham 16 Webster, William R.-Application in Rolling of Effects of Carbon, Phosphorus and Manganese on Mechanical Properties of Steel. Discussed by George B. Waterhouse, J. O. Liebig, Ralph H. Sweetser, H. T. Morris, F. D. Carney, W. P. Barba, John H. Nelson, George K. Burgess 19 Barba, W. P. and Howe, Henry M.-Acid Open-hearth Process for Manufacture of Gun Steels and Fine Steels. Discussed by W. J. Priestley, Haakon Styri, C. T. Patterson, Harry Brearley, W. P. Barba, George F. Comstock, Alexander L. Feild 24 Kellogg, David R.-Electrolytic Deposition of Iron for Building up Worn or Undersized Parts. Discussed by Jesse L. Jones, William Blum, C. R. Hayward, George K. Burgess, C. P. Perin, David R. Kellogg 33 McQuaid, H. W. and Elm, E. W.-Effect of Quality of Steel on Case-carburizing Results. Discussed by H. J. French and L. Jordan, W. J. Priestley, M. H. Schmid, A. E. White, H. J. Stagg and S. C. Spalding, Henry S. Rawdon, J. S. Vanick 35 Phillips, Arthur and Davenport, E. S.-Malleableizing of White Cast Iron. Discussed by Samuel Epstein, H. A. Schwartz, A. E. White, R. S. Archer.... 58 Priestley, William J.-Effect of Sulfur and Oxides in Ordnance Steel. Discussed by Harry T. Morris, William J. Priestley, C. P. Perin, James H. Gray, W. P. Barba, Haakon Styri, Frank D. Carney, W. L. Harbrecht, George F. Comstock, E. J. Janitzky 67

Jan 5, 1922

By Michael S. Koleda

Less than two years ago, the, Congress, with broad bipartisan support, passed the Energy Security Act of 1980. A decade marked by ten- fold increases in world oil prices and two major interruptions in oil flows from the Middle East had ended. An all-out national commitment to transform America's vast tar sands, oil shale and coal resources into conventional fuels had begun. The national synfuels effort was to be public-private cooperation at a scale unmatched in peace time. Private industry would own and operate the synthetic fuels facilities. Government would reduce market uncertainties to acceptable levels. The potential government commitment was substantial. Up to $88 billion would be available through the Synthetic Fuels Corporation, principally in the form of contingent financing. Billions more would be spent through Department of Energy programs. Additional incentives for alternate energy development were contained in the Energy Tax Act of 1978. The Energy Security Act clearly specified national synthetic fuels production objectives: 500,000 barrels per day by 1987 -- 2 million barrels per day by 1992. Finally, said Congress, Uncle Sam was going to do something about rapidly rising oil prices, uncertainties of energy supply, and the resulting disruption to the U. S. economy. Simply put, the purpose of the Energy Security Act of 1980 was to provide government guarantees sufficient to get synthetic fuels projects off the private sector drawing boards and into commercial production. Because of their huge cost, technological uncertainty, and lengthy pay-out period, these projects were always second place to projects of smaller size, known technology and more rapid pay-out. The Energy Security Act was the legal expression of public policy to bring the free-market synfuels timetable into line with the faster paced political timetable in the interest of national energy security.

Jan 1, 1982

By A. H. Geisler, F. Keller

Although the subject of precipitation from solid solution appears to be one of the more profitable fields in metallurgy for study with the electron Microscope, few comprehensive studies have yet been made. Occasionally electron micrographs have been published that illustrated alleged precipitation in various alloys, but frequently the apparent size, shape and distribution of the particles do not fully agree with those expected from theory or from observations of the Precipitate when the particles have grown to a size resolvable with the light microscope. The presence of a Widmanstatten pattern for submicroscopic precipitate particles has been demonstrated for only a few aged a1loys.l The initial problem has been the development of suitable techniques for applying the transmission-type instrument to a field that has been inherently associated with reflection-type microscopes. The various techniques have been the subjects of numerous publications, and instead of describing them individually here it will sufficc to say that the oxide film method has proved to be the most satisfactory method yet found for studying the microstructure of aluminum alloys with the electron microscope. This method has the definite characteristic advantage that the actual surface layer of the specimen is examined and not a plastic or silica replica. Doubtless suitable methods for forming and removing the oxide film could be developed for alloys of other metals. The purpose of this report is to point out the characteristics of the oxide film method that have been observed during the studies of numerous aged aluminum alloys and to present the results of these studies. Preparation OF Specimens The oxide film method for preparing specimens of aluminum alloys for examination in the electron microscope has been described in detail previously,¹,² Briefly, the procedure consists of preparing the metallographic specimen, forming the film by anodic oxidation and removing the film from the prepared surface of the oxidized specimen, The specimen is polished accordillg to the usual procedure for microscopic examination.³ he specimen may then be etched to remove flowed metal but etching to attack the alloy constituents or to leave them in relief as in the replica processes is not necessary. Electrolytic polishing is not generally recommended, Deep-etched specimens are used frequently, however, since they provide information that is not revealed by polished specimens and frequently present the same information more clearly than do the polished specimens, The surface preparation of specimens to be deep-etched is not important, since specimens that have been subjected to the first wet PoliShing operation are generally used, but frequently the as-rolled surface is Suitable. These specimens are then etched using a suitable macroetching reagent.

Jan 1, 1947

By F. Keller, A. H. Geisler

Although the subject of precipitation from solid solution appears to be one of the more profitable fields in metallurgy for study with the electron Microscope, few comprehensive studies have yet been made. Occasionally electron micrographs have been published that illustrated alleged precipitation in various alloys, but frequently the apparent size, shape and distribution of the particles do not fully agree with those expected from theory or from observations of the Precipitate when the particles have grown to a size resolvable with the light microscope. The presence of a Widmanstatten pattern for submicroscopic precipitate particles has been demonstrated for only a few aged a1loys.l The initial problem has been the development of suitable techniques for applying the transmission-type instrument to a field that has been inherently associated with reflection-type microscopes. The various techniques have been the subjects of numerous publications, and instead of describing them individually here it will sufficc to say that the oxide film method has proved to be the most satisfactory method yet found for studying the microstructure of aluminum alloys with the electron microscope. This method has the definite characteristic advantage that the actual surface layer of the specimen is examined and not a plastic or silica replica. Doubtless suitable methods for forming and removing the oxide film could be developed for alloys of other metals. The purpose of this report is to point out the characteristics of the oxide film method that have been observed during the studies of numerous aged aluminum alloys and to present the results of these studies. Preparation OF Specimens The oxide film method for preparing specimens of aluminum alloys for examination in the electron microscope has been described in detail previously,¹,² Briefly, the procedure consists of preparing the metallographic specimen, forming the film by anodic oxidation and removing the film from the prepared surface of the oxidized specimen, The specimen is polished accordillg to the usual procedure for microscopic examination.³ he specimen may then be etched to remove flowed metal but etching to attack the alloy constituents or to leave them in relief as in the replica processes is not necessary. Electrolytic polishing is not generally recommended, Deep-etched specimens are used frequently, however, since they provide information that is not revealed by polished specimens and frequently present the same information more clearly than do the polished specimens, The surface preparation of specimens to be deep-etched is not important, since specimens that have been subjected to the first wet PoliShing operation are generally used, but frequently the as-rolled surface is Suitable. These specimens are then etched using a suitable macroetching reagent.

Jan 1, 1947

By G. W. Healy, L. F. Sander

was investigated by reacting thin discs of calcium oxide with gas mixtures of CO2, CO, and Son. Its value was 19,300 * 300 cal independent of temperature in this range. No solid solubility of sulfur in calcium oxide was detected within the limits of the experimental method and it is estimated to be below 0.025 pct by weight. The importance of lime in desulfurization is well-established but complete information on the pure phase equilibrium: CaO + 1/2 s2 = CaS + +02 [11 is not yet available. The goal of this work was to evaluate solid solubility of CaS in CaO and to determine the free-energy change associated with Reaction [I] at temperatures of 1400" to 1650°C. The equilibrium constant for Reaction [1] can be written: It is convenient to rewrite Eq. [2] in the form: where A = {Ps /PqJ1'2 has been referred to' as the "sulfurizing power' of a gas mixture. In this work, thin discs of CaO were suspended in a vertical tube furnace and exposed to CO + CO2 + SOz gas mixtures having known values of A. The samples were then analyzed for sulfur. As expected, X-ray diffraction confirmed that CaS was the only sulfur-bearing phase formed at the relatively low oxygen pressures used. EXPERIMENTAL PROCEDURE Reagent-grade CaCO3 was pressed in a 3/8-in.-diam pill die and prefired in air to produce CaO discs weighing between 0.004 and 0.01 g. Several discs were used to provide a suitable weight for chemical analysis while maintaining a large surface area to react with gas mixtures. These were placed in a platinum mesh basket and suspended in the gas stream in the hot zone of a vertical tube furnace. Desired gas mixtures were prepared from cp grade CO and CO2 and anhydrous grade SO2. The method of soap bubble displacement was used to calibrate capillary flow meters. While this gave excellent results with CO and Con, some problems with bubble insta- bility and soap film "drag" arose with the use of SO2 at low flow rates. Hence, frequent sampling and analysis of gas mixtures was carried out to insure proper control of the ingoing SOZ. The furnace used for gas:solid equilibration was a vertical mullite tube externally wound with 60 pct Pt-40 pct Rh wire having a diameter of 0.028 in. An inner tube of $ in. ID served as the reaction chamber having Pyrex ground joints sealed to the mullite to provide gas-tight connections at top and bottom. A Pt-Pt 10 pct Rh thermocouple was inserted into a protection tube adjacent to the sample basket to measure sample temperature during a run. Constant-temperature control to 2C was observed at any desired set point within the range of this investigation. This was accomplished by a control thermocouple imbedded in the furnace windings which served to actuate an electronic controller wired for high-low operation. The sulfur analyses of the solid samples were carried out using a stoichiometric combustion technique based on the method of Fincham and Richardson. Some analyses were done using a modified evolution method3 but these were used primarily to check the results of the combustion method. The results were in good agreement but the combustion technique of-ferred an advantage in economy of time and material. CALCULATION OF GAS EQUILIBRIA Heating a given mixture of CO + CO + SO2 to high temperatures gives rise to a large number of product species. The details of calculating the partial pressures of these products of interaction and dissociation can be found in several references4,5 and need not be repeated here. The thermodynamic data selected for the major species in the gas mixtures are shown in Table I. Equilibrium constants from these reactions were combined with oxygen, carbon, and sulfur balances and a computer program written to facilitate the calculations. Some early difficulties in reproducing experimental results were finally traced to the effect of atmospheric pressure changes. No reference to consideration of this question had been found in the

Jan 1, 1969

By Robert K. Waits

The resistivity, temperature coefficient of resistance, stability at 200°C, and structure of annealed Si-Cr films have been studied as a function of film cowposition. Colorimetric analyses of the films indicated 20 to 60 wt pct Cr over the resistivity range of 1 to 10-4 ohm-cm. Resistors were delinealed by photolithographic etching, contacted with aluminum, and mounted in TO-5 packages. The average temperature coefjicient of resistance, a, between 50" and 150°C is related empirically to the film resistivity, p, by a (ppm per °C) = -2900 - 1140 log p (ohm-cm). Near a resistivity of 3.5 x 10-3 ohm-ctn (30 at. pct Cr) , the temperature coefficient changes from positive to negative. The temperature at which the resistance maximum occurs increases with decreasing resistivity. The conduction mechanism between —196" and +360 C appears to have two components—an activated conduction dominating a1 lord chromium content and higher temperatures and a linearly temperature-dependent conduction dominating at high chromium content and low temperatures. Electron diffraction patterns showed the films to consist of Cr3Si and amorphous silicon. Resistors thicker than 150A typically drifted less than 0.6 pct after 5000 hr stor-age at 200°C. Resistors as thin as approxinzately 80°A that had a silicon overlayer showed similar stability. Such films had sheet resistivities of 10 kilohm per square and temperature coefficients near —600 ppm per "c. THIN-FILM resistors having sheet resistivities greater than 1 kilohm per square are required in many integrated circuit applications. A process for producing such resistors should be compatible with present circuit fabrication and packaging, including exposure to maximum temperatures of 300° to 570°C during contact alloying, die-attach, and ceramic package sealing. In addition, the resistors should have a low temperature coefficient of resistance and change less than 1 pct during storage at temperatures up to 200°C for 1000 hr or longer. Reports of work beginning in 1949 at Battelle Memorial Institute indicated that, among other materials, the silicides of chromium, Cr-Co, molybdenum, tantalum, and tungsten were worthy of further study as high-stability resistive films. Later work on Si-Cr films vacuum-deposited by flash evaporation from a tungsten boat1 led to the conclusion that Si-Cr had "excellent properties for development into high- stability ... resistive elements". More recently, Si-Cr films have been vacuum-deposited from a tantalum boat,2 from a BeO-coated tantalum boat,3 by flash evaporation from an electron-beam-heated tungsten Source,4 and by triode sputtering.5 This paper describes a study of Si-Cr films vacuum-deposited by electron-beam heating of Si-Cr alloys. Resistivity, temperature coefficient of resistance, stability at 200°C, and structure were studied as a function of film composition. EXPERIMENTAL PROCEDURE Film Deposition. Si-Cr sources were prepared by vacuum-melting pressed pellets of mixtures of powdered chromium (99.9 pct, -100 mesh, Lunex Co., Pleasant Valley, Iowa) and silicon (99.99 pct, -325 mesh, United Mineral and Chemical Co., New York). A permanent-magnet focused electron-beam gun having a water-cooled copper crucible was used to heat the pellet until complete melting occurred. The mixture was then kept molten for an additional 5 min. The alloy thus formed was used as the source material for Si-Cr film depositions using the same electron-beam gun. Pieces of semiconductor-grade silicon ingots were used as sources for silicon depositions. The films were deposited within a standard vacuum evaporator having an 18-in.-diam Pyrex bell jar, a liquid-nitrogen-cooled trap, and a Consolidated Vacuum Corp. 6-in. diffusion pump containing Dow Corning DC-705 pump fluid. The substrates were thermally oxidized* silicon wafers 2 to 2.5 cm in diam. The

Jan 1, 1969

By P. Pietrokowsky

lntermediate phases in the binary metal alloy systems Ti-Zn, Ti-Hg, Zr-Zn, Zr-Cd, and Zr-Hg have been investigated by X-ray powder diffraction methods. Gamma-TiBHg and Zr3Hg have a beta tungsten structure; TiHg and ZrHg are analogous to ordered AuCu (L l0 type); delta-TixHg and ZrHg, are isomorphous with ordered AuCu,, (L l2 type); ZrZnz is face-centered cubic (C 15 type); TiZna crystallizes in a C 14 type structure; and Zrll-, occurs in cubic and tetragonal modifications in which a random distribution of atoms exists. Additional information for the intermediate phase TiZn, is presented. THE physical metallurgy of titanium and zir-conium when alloyed with elements in subgroup 11-B of the periodic table has received comparatively little attention in the literature. Laves and Wallbaum' reported the existence of several intermediate phases in the system Ti-Zn. They identified TiZn as a CsCl (B 2) structure and described TiZn, as an ordered Cu,Au (L 1, type) crystal structure. Gebhardt' investigated very limited zinc-rich regions in the systems Ti-Zn and Zr-Zn. Phase relationships in these partial constitution diagrams were deduced from the results of thermal analysis and metallography, X-ray results being inconclusive. The first zinc-rich intermediate phase in either system was not identified. More recently, Anderson, Boyle, and Ramsey" have had occasion to refer to a partial Ti-Zn phase diagram (unpublished data) covering the region 0 to 10 atomic pct Ti, wherein two intermediate phases corresponding approximately to TiZn,, and TiZn,, were indicated. The metals used in this investigation and typical analyses as determined by the suppliers are given in Table I. The iodide-process zirconium which was used was not hafnium free. Experimental Methods Alloy Preparation: The relative ease with which titanium and zirconium combine with other elements places extensive restrictions on the methods by which alloying can be achieved. The direct current electric arc melting procedure was found to be unsatisfactory for preparing these binary alloys and for this reason solid state diffusion methods were utilized. The iodide process titanium and zirconium rods were filed by hand. Fines were subjected to a magnetic separation and classified as to size as either finer than 200 mesh or coarser than 200 but finer than 80 mesh. Powder mixtures of various binary combinations of titanium and zirconium with zinc and cadmium were compacted in a 12 mm diameter die and then placed in Vycor or quartz vials which were evacuated and sealed. The mercury alloys were prepared in a similar manner; the proper weight of liquid mercury being placed in a vial with minus 200 mesh titanium or zirconium. These ampoules were then heat treated at various temperatures and times depending on the characteristics of the particular alloy system. Upon completion of the heat treatment the ampoules were cooled rapidly and the specimens weighed. The loss in weight varied from 1 to 3 pct (except as noted in the text) and for this reason the calculated compositions were accepted as a fair measure of the actual alloy compositions. X-Ray Dif raction Techniques: Powder diffraction experiments were conducted at room temperature with a 143.2 mm Debye-Scherrer X-ray camera in which the film was placed in the Straumanis arrangement. When copper radiation was used, a nickel filter was employed, and for the cobalt target a filter of iron oxide was used. In both cases, the /i? filter was placed between the X-ray target and the powder specimen which was mounted on a glass fiber. The lack of information based on optical metallography placed reliance on the results obtained from the X-ray experiments for determination of

Jan 1, 1955

THE purpose of this chapter is to present a general outline of the basic open-hearth process for the benefit of students, practicing open-hearth operators, and metallurgists who wish to review the subject. The discussion is limited to a description of the sequence and purpose of the operations, illustrated by data and examples. Subsequent chapters deal with more detailed and fundamental studies of the subject. The function of the basic open-hearth furnace is to convert various types of ferrous material into finished steel of given com- position and quality. In comparison with other steelmaking methods, the basic open-hearth process is one of the most versa- tile, both from the standpoint of the raw materials that can be used and the types of steel that can be produced. The process can be considered as a sequence involving melting, refining, and deoxidation. With some types of liquid-metal charges, the melting stage is not present, but refining and deoxidation in varying degrees are fundamental features of the process. GENERAL DISCUSSION OF BASIC OPEN-HEARTH PROCESS The first consideration in open-hearth practice is the type of charge on which the operation is based. This consists of three components-fluxing, oxidizing, and metallic materials. Fluxes. In the basic process the fluxing material is primarily lime, added in the form of either limestone (CaC03) or burnt lime (CaO) . This is supplemented by magnesia (MgO) and lime from the furnace bottom and banks. The function of these fluxes is to form a slag with the silica (SiO2) , manganese oxide (MnO), iron oxides (FeO and Fe203), and phosphorus oxide (P205) that are produced by the oxidation of varying amounts of the silicon, manganese, iron, and phosphorus in the charge during melting and refining. The slag, composed of the basic fluxes and the neutral and acid oxides, floats on top of the steel bath when the charge is melted. The composition of this slag depends on the amount of each slag-forming element present in the charge and on the extent of oxidation of these elements during the course

Jan 1, 1964

By P. E. Baker

An experimental study of heat flow in steam flooding was carried out with steam displacing water in a plane-radial fluid-flow model. Temperature distributions in the model reservoir, overburden, and substratum were measured at frequent intervals during flooding by means of a fixed array of thermocouples. Heat losses to overburden and substratum and the division of heat between the steam and hot-water zones in the reservoir were calculated from the temperature data by performing numerical integrations over the appropriate volumes. Temperature profiles and heat distribution results are presented. Some results were (1) the fraction of injected heat that is lost to overburden and substratum, when expressed as a function of time, did not depend on injection rate; (2) a significant portion of the injected heat was contained in the hot-water zone ahead of and underlying the steam front in the reservoir. The division of heat between the steam and hot-water zones did depend on injection rate; and (3) considerable gravity override was observed. The experimental results are compared with those of several published theoretical studies of heat transfer in hot-fluid injection; approximate agreement on heat losses is found with some of the most idealized theories. A valid comparison cannot be made in regard to steam us hot-water zone; basic interpretation of the hot-water zone, in terms of a vertical steam front, is clouded by gravity override in the experiments. INTRODUCTION The experimental study reported here primarily concerns two problems of heat transfer in steam flooding that have economic and engineering importance. These are (1) the fraction of injected heat lost to the overburden and substratum, and (2) the division of the remaining heat between a zone containing steam and a zone of hot water at lower-than-boiling temperature. The volume of the steamed region, which has a direct effect on oil recovery, can be calculated readily from these results. Several valuable theoretical studies have been published on this problem, but no experimental tests of the theories have previously appeared. Tests were needed because the effects of the necessary simplifications in the theories could not be determined otherwise. The basic, untested theoretical problem is the effect of "decoupling" heat and mass transfer, and the resulting inability to include the effects of heat transfer and condensation on fluid flow. The theoretical problem solved so far has been a heat transfer problem in which fluid is present as a heat carrier and flows in a stipulated manner, either linear or plane-radial. The simplifications that have sometimes been made in regard to thermal conductivity by, for example, Marx and Langenheim,l Lauwerier2 and Thomas3 apparently do not have an important effect on heat loss calculations, although the results of the different methods disagree to a certain extent, as shown by Spillette4 and by Ramey.5 A recent paper by the author6 compared the results of experiments in hot-water flooding with several theoretical results and showed a rather poor agreement. It will be seen that the experimental heat loss results for steam flooding, however, show acceptable agreement. These comparisons are discussed in a later section. EXPERIMENTAL APPARATUS AND PROCEDURE The system studied was one in which a sand pack, initially water saturated and at a uniform temperature, was flooded with steam at a constant rate and temperature. The temperature distribution in the "reservoir" and adjacent "strata" was measured with an array of thermocouples, and heat losses were determined from these measurements. The sand pack contained no oil because the only concern of the experiments was heat flow, and it was important to have the flow pattern as simple

Jan 1, 1970

By B. L. Landrum, P. B. Crawford

The rise of a new laboratory model for studying tran-sient fluid flow problems, is described. The theory of he model is based on the analogy between the equa-ions which describe the flow of compressible fluids in porous media and the conduction of heal m solids. The "thermal model" is used to study the Iransient Pressure distributions during fluid displacement in five Standard well patterns. The studies indicate quantita-ively how die pressures change with lane at any poit in the reservoir. It was found that, in general, the equipressure contours are more radial about the wells early in the program than after steady-state conditions are established. In addition two studies of fractured five-spot patterns are presented to illustrate the opplicability of the model for a wide range of reservoir conditions. INTRODUCTION In reviewing the oil recovery techniques involving fluid displacement it was found that a very considerable quantity, if not all of the fluid within the pattern, mav be displaced (during a time-dependent or transient period rather than the usually applied steady-state conditions. Since the oil is displaced during a transient period, it was believed desirable to study the nature of the transients for several of the commonly used fluid displacement patterns. A literature review indicated fairly complete studies of the streamlines and isopotentials for steady-state: yet few data were available on the transient displacement process. Several simulated steady-state multiwell displacement programs were carefully mapped by Foster and Lodge on an electrical conducting sheet as early as 1875, hut the more recent work of Muskat provides the best source for steady-state phenomena having direct petroleum production applications. In order to study the transient phenomena a new lab-oratory model was developed which is based on the similarity of the equations that describe the flow of fluids and the conduction of heal. The equations describing heat flow were developed early in the nineteenth century. Regorous solutions tor most transient problems are in gcneral complex and usually limited to fairly restricted houndary conditions.2 the thermal model may be used to obtain approximate solutions for many transient problems without some of the restrictions required for analytical solution. The application of the analogy between heat conduc-. tion in solids. electrical flow and fluid flow, in a porous media has long been recognised. Techniques originally developed for the solution of heat conduction prol?lems have in many instances proved useful in ohtaining solutions to fluid flow prohlcms. Ir is not surpri5ing then that a heat conduction or thermal model might bf usefull in sludying transient fluid flow. As an example ol the problems suitable for the study with the thermal model, transient pressure distributions during fluid displacement programs are studied for the five-spot, line-drive, staggered line-diibe. seven-spot 211 two fractured patterns. A model was constructed of an iron plate of geometry similar to the reservoir patterns under study. The principle of mirror images as suggested by Bryan was employed in shaping the model. A temperature differential was obtained by soldering two sections of copper tubing to the plate at points analogous to the well location in the field. Hot and cold water was passed through the tubing. The temperature distribution, analogous to the pressure distribution in the field. was obtained a a function of time from thermocouplcs distributed over the plate.