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By H. W. Kerr, B. Soutiere

THE possibility of using unidirectionally solidified eutectic alloys as high-strength composite materials has been investigated by several workers. Unidirectionally solidified lamellar and fibrous eutectics have been shown to have good short-time structural stability at temperatures close to the eutectic melting temperature.'-4 Several investigations of both short-time high temperature tensile properties and creep properties of eutectic alloys have been carried out,3-" with promising results. Little work has been reported, however, on the thermal stability of eutectic alloys which have been unidirectionally solidified and subsequently deformed in compression. Since processes such as rolling and grinding introduce compressive stresses, and since the properties depend on the spacing and perfection of the composite structure10,11 this aspect is of definite importance if unidirectionally solidified eutectic alloys are to be considered for commercial use. A Cd-Zn alloy made from 99.999 pct starting materials was cast into a graphite boat and zone levelled12 to obtain a completely lamellar structure at one end of the bar. Sections from this region of the bar were removed, recast into 6.5 mm I.D. Pyrex tubing, and solidified unidirectionally upwards at a rate of 2.8 cm per hr. Specimens were cut from the solidified rods, heated in air at 200°C (0.88 of the eutectic melting temperature) for various lengths of time, and examined metal-lographically. Compression specimens were also cut from the solidified rod carefully machined to a length of & in., and deformed with the compressive axis parallel to the original growth axis to produce a total longitudinal strain of 12 pct. Some of these specimens were examined metallographically; others were heated in air at 200°C for various lengths of time and then examined. Metallographic examination of the deformed specimens showed the two types of deformation previously described; slip lines13 (smoothly bent lamellae) and kinks13,14 (sharply bent lamellae). Very close to the specimen ends there were a large number of deformation bands, but at a distance of about -re- in. the deformation was very localized, as shown in Fig. 1.

Jan 1, 1970

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

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

By S. H. McFarlane, K. H. Zaininger, G. W. Cullen, C. C. Wang, G. E. Gottlieb

Heteroepitaxy of silicon on stoichiometric spinel has been studied. Both boron-doped (p-type) and arsenic-doped (n-type) single-crystal silicon films have been grown by the pyrolysis of silane on sioichiometric spinel (MgAl2O4) substrates prepared by a flux technique. The spinel crystals are free from strain and subgrains, and exhibit no thermal instability at temperatures employed for silicon deposition. The growth parameters of epitaxial silicon have been studied. Effects of substrate orientation, surface preparation, and growth conditions on the silicon Properties have been determined. The silicon-spinel composite was characterized by X-ray diffraction, electron diffraction, electron microscopy, and optical techniques. Information on epitaxial orientation relationship, defect structures and film-substrate interface has been obtained. A parallel orientation relationship was found between silicon and spinel. The silicon films exhibit no subgrain structures. However, growth pyramids, microtwins, stacking faults, and dislocations are the prevalent defects. The deformation of epitaxial silicon was measured by an X-ray technique. It was found that the epitaxial silicon is strained under compres-sive stress due to the thermal expansion difference between the film and substrate. The stress was estimated using the classical plate theory and beam equation. Electrical properties of the epitaxial silicon have been measured, including resistivity, carrier concentration, and Hall mobility. MIS and vertical through diffused junction structures have been fabricated wing silicon-spinel composite. Information on MIS characteristics, minority carrier life time, and junction properties has been obtained. THE achievement of single-crystal growth of large area silicon semiconductor films on oxide insulating substrates is of technical importance to many solid state electronic devices. The semiconductor-insulator composite structure is also of scientific interest because the heteroepitaxy is determined by the spatial relationship between the atomic arrangement in the substrate and that of the atoms in the appropriate crystallographic plane of silicon. The degree of crystalline perfection of the silicon deposits depends also on the physical condition of substrate surface. Epitaxial growth of silicon on commercial flame fusion Al-rich spinel (MgO:3.3A12O3) has been reported by several investigators.'-4 The lattice of spinel of this composition is distorted. The material cracks and exsolves the excess alumina in the lattice at temperatures (-1200°C) used in fabricating silicon devices. Stoichiometric MgA12O4 spinel exhibits neither lattice distortion nor thermal instability. Results are given on the epitaxial growth and characterization of silicon on stoichiometric spinel. EXPERIMENTAL Fabrication of Silicon-Spinel Composite Structures. The MgA12O4 spinel substrate wafers were prepared from bulk single crystals grown at about 1200°C by a flux technique5 using a PbF2 flux. The crystals are free from strain and subgrains, and exhibit a typical dislocation density of less than 50 lines per sq cm. The crystals are thermally stable without cracking and exsolution of alumina to at least 1500°C. The spinel crystals were oriented for cutting by the Laue X-ray back-reflection method.6 Substrate wafers (about 25 mil thick) of (Ill), (loo), and (110) orientations have been obtained bu cutting the X-ray oriented crystals using a standard type diamond wheel. An accuracy of better than 1/2 deg is maintained throughout the operation. The spinel substrate wafers were mechanically lapped and polished to produce the flat and smooth surface which is required for silicon epitaxy. Lapping was carried out with about 30-µ boron carbide abrasives to obtain a flat coplanar surface. The lapped surface was further polished using successively finer grades of alumina, ending with the 0.3-µ grade. After polishing the wafers generally have a flatness of ±0.4 µ per cm, as revealed by interferometry. Fig. 1 shows (111) oriented MgA12O4 spinel wafers of various shapes.

Jan 1, 1970

By F. W. Jessen, N. Mungan

The plastic flow characteristics of clay water suspensions were first recognized by Binghaml in 1916 and further studied by Ambrose and Loomis' in 1931-1932. Many physical and chemical properties of clay suspensions are deeply influenced by particle size distribution as well as by the exchange cation. Separation of a number of fractions is particularly helpful in making a detailed study of a suspension. A limited amount of work has been conducted on the effects of particle size on specific properties of mud drilling fluids. A knowledge of particle size distribution is essential for a better understanding of fundamental properties of clay suspensions, particularly viscosity and gel strength. The purpose of this investigation was to study the effect of particle size on the viscosity and gel properties of clay suspensions and to determine any changes in mineral composition accompanying variation in size. EXPERIMENTAL PROCEDURE Numerous methods may be used to fractionate a poly-dispersed clay suspension into nearly mono-dispersed systems. Particles larger than 44 micron (325-mesh) may be obtained by wet screening. For sizes from 44 to 1 micron, the fractionation may be accomplished by sedimentation, elutriation plus microscopy,' or turbidimetry.6 When dealing with systems which contain a major portion of particles below l-mi-cron size, slit ultramicroscopy,7 centrifuge methods of Svedberg,5 eams,9 and McBain,l0 and X-ray methods" may be employed. The Sharples super centrifuge has been proved suitable for the economical separation of suspended particles of submicron range.12,13,14 Three-hundred and forty-five gal of 1 per cent by weight Aquagel suspension was mixed in a high-speed 5-gallon mud mixer and the suspension was allowed to stand in 5-gal glass bottles for 30 days to assure full hydration. All particles larger than 44 microns were removed by wet screening. Five fractions in the range of 44 to 1 micron were obtained by sedimentation. The Sharples super centrifuge method described by Hauser and Reed.13 Norton and Speil,14 Ha user and Lynn,15 and Hauser and Schachman,10 as employed to yield five fractions of submicron size. A super centrifuge operation chart prepared by Fancher, Oliphant, and Houssierre12 was used to determine operating conditions for the desired particle ranges. The clay suspension, after removal of all material above 1-micron size, was centrifuged. During rotation of the bowl, the particles were deposited on a thin plastic liner which fit closely inside the bowl. After passing 5 gal of suspension through the centrifuge, the liner was removed and the particles on the liner were scraped off, remixed and recentrifuged. This was repeated five times. Thus, Fractions H, I, K, and L were obtained. The finest fraction, M, remained in an approximately 0.4 per cent suspension. Water was evaporated under reduced pressure from this suspension to yield the finest particles. Results of the fractionation are included in Table 1. In order to achieve proper orientation and humidity conditions for X-ray diffraction analysis, the following procedure was employed. The dilute suspensions were placed on glass slides and allowed to dry at room temperature. This was repeated several times. Previous to measurement each sample first was placed in a water desiccator for half an hour and then allowed to stand for 15 minutes at room temperature. thus yielding an equilibrium condition of about 52 per cent relative humidity. The relative humidity of the room in which the X-ray diffraction was carried out was maintained at approximately 50 per cent so that there was no change in the spacings during the X-ray examination. Samples

By R. L. Pober, L. Kaufman, E. V. Clougherty

Composite structure of hafnium, zirconium, and titanium diboride with additions of metals and/or compound phases were prepared by reactive high-pressure hot pvessing and evaluated in air and in mixtures of oxygen and helium at temperatures up to 2400°K and at linear flow rates of 0.1 to 0.2 ft per sec stp. Oxidation characteristics, principally depth of conversion of diboride to dioxide, were determined by a gas analysis method and by postoxidation metallo-graphic analyses. The best oxidation resistance was observed for hafnium diboride-silicon carbide composite which exhibited a 6-mil conversion to dioxide for a 1-hv oxidation in air at 2200°K compared to a 20-mil recession for hafnium diboride with no additive. Analogous improvements in oxidation resistance were observed for the addition of silicon carbide to zirconium. EARLIER investigationof the oxidation behavior of the diborides of the transition elements of Groups IVA and VA in flowing gas mixtures have produced a ranking of these compounds according to which HfB2 is the most oxidation-resistant followed in turn by ZrB2 > TiB2 > TaBz > NbB2. Other ~tudies~-~ have examined the physical, thermal, and thermodynamic properties of these diborides to provide a sound basis for the more detailed and specialized investigations which are required to generate the information needed to assess the usefulness of such materials in high-temperature oxidizing environments. Recent oxidation studies7 have examined the effect of variations of metal and boron content on the oxidation characteristics of zirconium and hafnium diboride in flowing gas mixtures including air and helium plus oxygen. Results obtained in the latter investigation confirmed the superior oxidation resistance of HfB2 over ZrB2. Moreover, metal-rich compositions of hafnium diboride showed improved oxidation resistance over boron-rich compositions at temperatures up to 2000°K; at higher temperatures the differences are not distinguishable. In particular HfBI.7 exhibited a diboride to dioxide conversion depth of 4 mils in 1 hr at 2000°K; HfB2. 2 exhibited a conversion depth of 16 mils for the same exposure.~ Specimens for the study of metal and boron stoichiometry on the oxidation characteristics of HfB2 and ZrB2 were prepared by high-pressure hot pressing, a specialized type of fabrication which produced dense crack-free bodies of the desired compositions with no significant impurity introductions. The purpose of the present investigation was to explore the possibility of further improving the oxidation resistance of the metal-rich ZrB, and HfB2. The plan to accomplish this objective was based in the formulation of several diboride compositions containing other compounds and phases which are generally known to have good oxidation resistance in one or more types of test environment. Ideally, such additives would also enhance or at least not diminish other boride property values principally mechanical strength and those parameters related to thermal stress resistance. The additions selected for HfBz included zirconium, aluminum, and (Ta + TaB2) designed to produce ternary metal diborides, hafnium to form a discrete HfB phase, chromium to provide a metal skeletal phase, (Hf + Si) to form a discrete hafnium silicide phase, and Sic to provide a discrete second phase. Additions to ZrB2 included A1 + B designed to produce a ternary metal diboride, Zr + Si to form a discrete zirconium silicide phase, and Sic to provide a discrete second phase. All the specimens were prepared by high-pressure hot pressing which was used to advantage to fabricate billets of the variety of compositions desired and suitable for oxidation testing. The present investigation also included the evaluation of high-pressure hot-pressed TiB2and TiB2-20 vol pct Sic, conventionally hot-pressed Boride 2,' and KT silicon carbide. Boride

Jan 1, 1969

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By J. Nutting, D. H. Kirkwood

The oxidation of lead sulfide in air between 200° and 350°C has been investigated by electron diffraction from thick sulfide films and from galena surfnces. It has been demonstrated that sulfate is the stable reaction product up to 570°C. Sulfate is HAGIHARA has investigated' single crystals of galena roasted in air by the reflection electron-diffraction technique, which owing to the very limited penetration of the beam into the crystal gives information of the nature of the surface only. He has shown that up to 280°C the first oxidation product is lead sulfate, followed by lead mono-oxysulfate (PbO . PbS04). At longer times and higher temperatures more complex patterns appeared which could not be analyzed. All of these patterns were of streaks or spots arising from crystals oriented on the galena surface, and it is probable that these crystals are lead compounds whose structures have not been determined, such as the other oxysulfates (2Pb0 • PbS04 and 4Pb0 . PbS04) or a number of oxides. Certain lead sulfide films, formed chemically, give ring patterns in transmission electron diffraction2 because they are polycrystalline, and should also give ring patterns of the products after oxidation. It was thought that a diffraction study would reveal the sequence of phases produced in the reactions at different temperatures, since X-ray powder patterns are available for many lead compounds. PREPARATION OF FILMS The films were prepared by passing H2S over a saturated solution of lead nitrate in water. Once a silvery film had formed on the solution surface, no further thickening was apparent. The films were transferred by a gauze to a bath of distilled water for washing and pieces of film were caught on small discs on which they were dried. The discs were formed initially on galena up to temperatures of 300°C, followed by oxide and oxysulfates in turn at longer times. The appearance of- these phases is believed to result from an inadequate rate of supply of sulfur to the top surface 01. the crystal. standard Siemens mounts, made of platinum alloy, and had seven 20-p apertures drilled through them. The parts of the film which had dried onto the disc surface were light blue in color, which is the interference color of a film about 600A in thickness. A strong pattern of lead sulfide was obtained in transmission electron diffraction through the apertures but slight broadening indicated a crystallite size of around 200A. Tilting a sulfide film in the beam produced arcing of the rings, increasing the intensities of the (Ill), (3111, and (222) rings and reducing (200) and (220). This arises from preferred orientation in the film, a [loo] direction of the crystallites being normal to the plane of the film. These specimens were oxidized in an oven maintained at the required temperature. The reported times include that taken to heat the film to the reaction temperature. STABLE PHASES FORMED IN OXIDATION The conditions in which various oxidation products of lead sulfide are stable have been considered by the authors in a previous paper.3 It was shown that in a normal atmosphere, taken as containing lo-' atm of SOs, lead sulfate would be stable up lo about 570°C. This was confirmed by oxidizing thin films of sulfide for several days, and the analysis of the transmission-diffraction pattern is given in Table 1. The fit with the patt$rn from X-rays is good, except for the missing 3.62A ring. Some disagreement in intensities of reflections given by X-rays and electrons is to be expected. Up to 570°C a spotty pattern of sulfate was still obtained, indicating grain growth, but above this temperature the film disintegrated. Probably this is associated with the decomposition to PbO . PbS04. It needs to be emphasized that the atmosphere

Jan 1, 1965

By J. M. W. Mackenzie

The interactions between oil drops and mineral surfaces have been examined for the cetyltrimethylammonium bromide (CTAB)-quartz and sodium dodecyl sulfate (SDS)-hematite systems. The results have been interpreted using a electrical double layer interaction model, a "sweeping-penetration" model based on steric interactions and a free energy of adhesion model. The adsorption of long-chain ions at the mineral interface was also studied and found to follow a Fuerstenau-Modi model of combined Coulombic and chain-chain interaction forces. The basis of the emulsion flotation process and the feature which makes it differ from conventional flotation is: encounter, followed by adhesion, between oil drops and mineral particles which are suspended in an aqueous environment. The manner in which the adhesion between these two phases contributes to the flotation process may be through the formation of min-eral-oil drop-mineral linkages, mineral-oil drop-air bubble linkages, or a combination of both. Possible flotation mechanisms derived from these adhesion processes are shown schematically in Fig. 2 while Fig. 1 shows an example of the first mechanism for quartz particles which have been floated using a cetyltrimethyl-ammonium bromide (CTAB)-Nujol emulsion as collector. In Fig. 2 the three phases, mineral, oil, and air, for convenience have been shown as having approximately equal size. This would not always be the case in an actual emulsion flotation operation. For the flotation of sand-sized particles of approximately 0.5 mm diam, the mineral particles would be at least ten times the size of the largest emulsion drops present in the system, while in the flotation of —10u slime particles, the mineral phase may be of the same order of size as the oil phase. The air bubbles in a flotation cell are normally about 1 to 2 mm in diam and therefore, in general, would be larger than the oil drops. Although the relative size of the three phases does not alter the basic adhesion processes between oil drops, mineral particles, and air bubbles, which depend on the physical and chemical properties of the interfaces involved rather than on the extent of these interfaces, it does alter the degree of deformation of the oil drops and air bubbles which will occur on adhesion. For mechanisms 1 and 2 to take place, the oil-water and mineral-water interfaces must be partially replaced by a mineral-oil interface while in mechanism 2 there is the additional requirement that the oil-water and air-water interfaces must be replaced by an oil-air interface. In view of the importance of the oil drop-mineral particle encounter and subsequent adhesion stages to both of the emulsion flotation mechanisms discussed, a study has been made of some physicochemical factors which control these processes for Nujol-cetytri-methylammonium bromide (CTAB)-quartz and Nujol-sodium dodecyl sulfate (SDS) -hematite systems. Experimental Electrokinetic Measurements.—The zeta potential of mineral particles was measured using a streaming potential technique similar to that described by Fuerste-nau.1 The streaming potential was measured using a multirange electrometer while the plug conductivity was measured using a 50 cycle sec1 bridge. Measurements were made on 28 x 65 mesh particles. Contact Angle Measurements.—A captive bubble technique was used to measure the contact angles for air bubbles and oil drops. The angles were measured on fracture faces of unmounted minerals which proved easier to clean than polished mounted specimens and should more closely represent a flotation system. Reagents: These have been described in a previous publication.0 Minerals: Rock crystal quartz from the New England district, N.S.W., was used for contact angle and streaming potential measurements. The quartz was hand

Jan 1, 1971

By Keith R. Bock, Norman Parlee, Albert M. Barloga

Coils of pure iron and iron-carbon alloy wire (0.05 to 0.80 pct C) and sufficient sulfur to saturate the solid phase were equilibrated in evacuated or argon filled tubes. After rapid cooling, and removal of the outside nonmetallic layer, the wires were analyzed for carbon and sulfur and the data used to construct an Fe-S binary and isotherms of the Fe-C-S ternary in the range 1149° to 1427°C. THE solid solubility of sulfur in steel is of interest in connection with such phenomena as hot shortness, burning, and so forth. "Burning," the more or less permanent damage that some steels suffer when heated for forging or rolling, has been shown to be related closely to the behavior of sulfur and less closely to carbon and oxygen.' Attempts to interpret burning phenomena in steels fail because of lack of data on the Fe-C-S and the more complex systems in this family. Rosenqvist and Dunicz 2 and Turkdogan, Ignatowicz, and pearson3 have largely elucidated the Fe-S diagram in the region of interest but no information on the Fe-C-S diagram in this region appears to be available in the literature. This paper deals with the elucidation of the Fe-C-S diagram in these interesting ranges. The method employed is different from those used by previous workers2'3 on the Fe-S system. EXPERIMENTAL METHOD Pure iron wires (Ferrovac E) or iron carbon alloy wires of 1 mm in diam were cleaned with acid and acetone, coiled, and placed in silica tubes (7 mm OD and 5 mm ID) previously closed at one end. Enough sulfur was added to assure saturation of the solid iron phase. The filled tubes were either simply evacuated and sealed, or filled with argon at a reduced pressure and sealed. The argon was required at the higher temperatures to prevent collapse of the tubes. The filled and sealed tubes were placed in the middle uniform temperature zone of a Globar tube furnace and equilibrated at temperatures ranging from 2100°F (1149°C) to 2720°F (1493°C). After equilibration the tubes were removed from the furnace and quenched in air or water, the form of quenching being found to have no effect on the results. The tubes were broken open and the coils were placed in a 1 : 1 HC1 solution to remove the sulfide-rich layer. The coils were then cut into small pieces and analyzed for sulfur and carbon. In the early stages of the investigation different equilibration times ranging up to 17 hr were tried and the cores of the wires were analyzed to test for saturation. One hour appeared to be sufficient to reach maximum sulfur content at 1454°C and 2 hr sufficient at 1149°C. The practice adopted was to use at least 3 hr at the higher temperatures and at least 5 hr at the lower temperatures. The iron-carbon alloy wires used were made by carburizing pure iron wire with carbon monoxide gas in a one inch diameter ceramic tube at about 1204°C. Differing carbon contents were obtained by allowing fairly large coils to react with the gas for varying lengths of time at a flow rate of 800 cc per min. The reacting times ranged from 15 min to 4 hr depending upon the amount of carbon desired. The furnaces used were controlled by means of Leeds and Northrup Speedomax Type H instruments with D.A.T. Control attachment. Thermocouples were calibrated against the melting points of gold and copper. The temperatures recorded appear to be accurate within i2.7OC. Starting with run No. 85 and continuing with the

Jan 1, 1962

By C. G. Dunn

This note describes a method for revealing micro-structures in tantalum through an {hkl} effect which was found during a study involving amorphous and crystalline tantalum oxides. Three steps are involved. First, an amorphous film of Ta2O5 is formed anodically1 on the surfaces of the tantalum. The amount needed depents on the thickness of the substrate tantalum; 1600Å of oxide, however, is generally satisfactory in the 1/2 -mil (12 µ) to 3-mil thickness range. The film at this point is uniform in color. Second, the anodized specimen is heated to 800°C in. vacuo during a period of a few minutes and held at temperature for 5 min. During such a treatment some oxygen leaves the oxide through dissolution into the substrate tantalum (e.g., at 10-8 Torr oxide films thinner than about 800 completely disappear on 5-mil strip). Considerable crystallization of the amorphous oxide also occurs adjacent to the metal/oxide interface but not throughout the oxide thickness. The thickness of oxide needed as a residue is not too critical; values between 500 and 1000Å (optical estimate') may be most useful. (The presence of a residual oxide layer after the heat treatment usually is not apparent; in fact, in most instances the surfaces have a metallic appearance. This can be the case also for thicker residual films needed in the detection of a crystalline oxide phase by surface X-ray diffraction—e.g., if the initial oxide film is 3000Å thick, enough crystalline oxide is formed for X-ray detection.) The third step eliminates the metallic appearance at the surface and reveals (or produces) a varied colored film of tantalum oxide. Two methods can be used and both will be illustrated. If the specimen is dipped in 48 pct HF for a few seconds, the tantalum is found to be covered with a multicolored oxide. Moreover the colors correlate with the grain structure of the substrate tantalum through an orientation dependence of the type illustrated in Fig. 1, where results of an orientation analysis by the Laue X-ray method have been plotted. Other film conditions would have provided a different set of colors for the same orientations. Any such correlation, however, provides a basis for a qualitative assessment of the distribution of orientations in a large sample. The cold-rolled structure of tantalum foil produced by a recrystallization anneal and a cold-rolling reduction of 95 pct is not easily obtained by usual metal-lographic methods.' The structure, however, is easily revealed by the present technique, Fig. 2. The alternative third step is to reanodize the specimen. The optical nature of the final anodic film depends on the presence of the crystalline oxide phase; color variations indicate optical thickness variations in the film. As the reanodization voltage is increased from zero, straw and light brown colors appear (as usual), followed now by variations in color from grain to grain depending on {hkl} orientation. Suitable end points, which are determined by voltage and time, are easily established. Fig. 3, for example, shows the grain structure developed in 5-mil tantalum strip during a 30-min re-crystallization and grap-growth anneal at 1800°C. An anodic film of 1600Å thickness was added prior to the special 800°C anneal. Reanodization was done at constant current density (near 0.2 ma per sq cm) in an aqueous solution of H3PO4 (0.01 pct) and was terminated after the initial brown colors were replaced by a deep blue at approximately 30 v. Although good grain contrast can be obtained with bright field illumination, even greater contrast for black and white micrographs may be obtained with polarized light, as in Fig. 3.

Jan 1, 1967

By R. F. Mehl, G. T. Horne

Diffusion coefficients and mobilities were determined as functions of concentration in the a phase of the Cu-Zn system. Use was mode of incremental diffusion couples to determine the Kirkendall effect at various concentrations. Darken's analysis was used to calculate the individual diffusion coefficients and mobilities from these data. The general diffusion coefficient is a single-valued function of the concentration in this system to within the limits of accuracy of the experimental methods used. The form of the various functions (diffusion coefficients and mobilities) of concentration is the same in every case: it is essentially the same as the usual D vs c curve. AS Darken' has pointed out, the knowledge that the movements of different atoms diffusing in the same lattice need not proceed at the same rate is old. Ionic lattices are the classical examples; application of the generalization to lattices with metallic bonding was much more slowly accepted. It remained for Kirkendall'' to show clearly that metallic diffusion need not be symmetrical with respect to both species. Several investigators" have confirmed the initial observation of a "Kirkendall effect:" marker movement accompanying diffusion. They have extended it to other systems and conditions. The theoretical interpretations have been many; ne of the first and simplest of these is that of Darken"' which is essentially mechanism independent. Darken has shown that the Kirkendall experiment permlts a calculation of the individual diffusion coefficients and, coupled with activity data, offers a means of measuring the mobilities of the separateatoms in a binary diffusion process. There is no published information on the effects of concentration and temperature on the individual diffusion coefficients or on the mobility values in binary solid solution; this paper provides such information for zinc and copper in a brass. For purposes of clarity, the overall D value obtained, for example, from the Boltzmann-Matano solution to Fick's law, will be designated as the "general diffusion coefficient;" and the diffusion co- efficients for the separate diffusing species will be designated as the "individual diffusion coefficients." Experimental Procedure The authors have accepted Darken's analysis and have measured mobilities on this basis. The findings of da Silva and Mehl are accepted: that the Matano interface, defined as the origin of coordinates for the Boltzmann-Matano solution to Fick's law, coincides with the original weld interface; that the "shift" of a marker is the distance between the Matano interface and the marker; that the observed porosity is too small sensibly to affect this result; and that the shift is a linear function of the Matano area, the area defined as the absolute magnitude of the area on either side of the Matano interface. Alloys: The a-phase of the Cu-Zn system was chosen for investigation. The measurements were made on incremental couples for two separate reasons: l—it has been questioned whether D, the general diffusion coefficient, is a single-valued function of concentration (a comparison of the D-values for couples with small concentration range, e.g., 10 vs 20 pct Zn, against those from a wide concentration range, e.g., 0 vs 30 pct Zn, will answer that question); and 2—on the Darken analysis, the mobility can be determined only at the concentration at which the marker is observed to lie (this is but one concentration in a single couple) but choosing a series of incremental couples in the range between 0 and 30 pct Zn provides mobility values at several concentrations, thus giving mobility as a function of concentration. Four alloys were chosen; nominally, pure copper, copper with 10 pct Zn, copper with 20 pct Zn, and copper with 30 pct Zn. This allowed six different types of diffusion couples to be prepared, promising mobility determinations at six different concentrations, but having a minimum range of 10 pct Zn. The copper was an especially prepared pure copper supplied through the courtesy of the Ameri-

Jan 1, 1956

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

A series of laboratory experiments was conducted in which oil was displaced from a porous medium by water-driven slugs of alcohols or similar solvents. The solvents used were soluble to some degree in both oil and water and covered the range of solubilities from complete solubility in oil to complete solubility in water. Displacement experiments were conducted on 2-and 3%-in. in diameter consolidated cores and 1-and 2-in. in diameter unconsolidated sand packs. The cores and sand packs ranged in length from 1 to 30 ft, and they were saturated with brine and crude or refined oils. The solvents used included ethyl alcohol, isopropyl alcohol (IPA), tertiary butyl alcohol (TBAI, secondary butyl alcohol (SBA), n-amyl alcohol (NAA), methyl ethyl ketone, acetone and others. It was found that all of the oil present in a porous medium could be miscibly displaced by injecting a slug of mutual solvent and driving it with water. The oil-recovery efficiency was dependent upon (1) the relative solubilities of the solvent in oil and water, and (2) the distance traversed by the flood. For complete oil recovery from cores, a smaller amount of a preferentially oil-soluble solvent was required, compared to the amount of preferentially water-soluble solvent needed. The size of the solvent slug required varied inversely with the linear flooding-path length raised to the 0.65 power. Water-driven dual solvent combinations (an oil-soluble solvent slug followed by a water-soluble solvent slug) were found to effect complete oil recovery with less total solvent than any single solvent used. In these dual-solvent displacement experiments, the slug size required varied inversely with length raised to the 0.55 power. Based upon the experimental results, a theory was developed to describe the displacement of oil and water by mutual solvents, and equations are presented to predict the production history in a linear system. These equations take into account the properties of the solvents and the porous medium. INTRODUCTION Oil-recovery processes which utilize displacing fluids that are miscible with the reservoir fluids have been studied extensively in recent years. Because of the poor contact efficiency and high pressure requirements of the LPG-gas displacement process there has been considerable interest in the alcohol-water process, and a number of studies have been made on the recovery of oil through the use of solvents which are mutually soluble in oil and water. An investigation by Sievert, Dew and Conleyl indicated that the use of mutual solvents would be limited because the presence of water in a porous medium would cause a phase break in the leading edge of the displacing solvent. Their study also showed that, in consolidated cores containing. only oil, the displacement of oil by a water-driven mutual-solvent slug of tertiary butyl alcohol (TBA) was affected by the viscosity ratios of the fluids involved. Gatlin and slobod3 concluded that an isopropyl alcohol (IPA) slug acts as a miscible piston, completely displacing both oil and water until the alcohol content of the mixing zone falls below the concentration necessary to maintain miscibility. Their study was conducted on uniform unconsolidated sand packs. They concluded further that IPA could be used effectively to recover oil from a watered-out sand. In a paper by Taber, Gamath and Reed4 relating an investigation on sandstone cores, it was stated that the displacement of oil by mutual solvents, particularly IPA, was not a miscible displacement and that no improvement in efficiency could be expected with increase in flooding-path length. However, their analytical analysis of the displacement mechanism using TBA is, in fact, one which indicates that the displacement is controlled by miscible mixing. They suggested that the lack of improvement in efficiency with flooding - path

By H. A. Wriedt

Zinc-vapor pressures in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C were measured by an isopiestic method. Thermody-na?nic properties of zinc in these solutions were derived directly and those of iron with a Gibbs-Duhem integration. Zirzc and iron exhibit large, positive, and moderately temperature-sensitive deviations from ideality. Excess enthalpies and Gibbs energies are positive in the ranges studied. It has been establzshed in relating published phase equilibria to the Gibbs energies of forming solid solutions that positive departures from ideality also exist in the fcc solutions. Tlze stability, as defined by Darken, of the bcc solutions is small but positive at 703.5"C. Its decrease with decreasing temperature indicates that a miscibility gap may exist in the stable or metastable bcc solutions at lower temperatures. The changes of thertnodynanlic properties relatable to changes in magnetic state are minor compared to other changes due to alloying. The accuracy with which the relation between lattice parameter and composition of the bcc solutions is known has been improved. Zinc increases the lattice parameter of a iron by O.ZOZA per unit atom action zinc to at least NZn = 0.25. TO our knowledge, only Ciganl has previously investigated thermodynamic properties of the bcc solutions of the Fe-Zn system. He measured zinc-vapor pressures in the temperature range from about 320" to 360°C by an effusion technique. We have measured the vapor pressures of zinc in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C by an isopiestic technique. This investigation and the pursuant thermodynamic computations are part of a program for studying several properties of these solid solutions. In the appendix we report a remeasurement of the relation at room temperature between the lattice parameter and zinc content. Related work not reported herein embraces measuring the diffusivity2 of zinc in ferrite at 700" to 900°C and the Curie point temperature3 as functions of composition. EXPERIMENTAL METHOD AND APPARATUS Purified iron at a series of constant temperatures was saturated with zinc at a series of constant zinc-vapor pressures, the range of conditions being so limited that the equilibrated solid solutions were ferri-tic. The equilibration was conducted in long capsules, Fig. 1, that had been evacuated, gettered with titanium, and sealed. The purified iron, part of a vacuum-melted ingot of electrolytic-iron stock (Glidden Co. 1044-grade), had the impurity contents listed in Table I. It was used in the form of millings about 0.001 in. thick. A zinc of 99.999 pct purity (United Mineral and Chemical Corp.) and later one of 99.9999 pct purity (Cominco Products, Inc.) were used, with no observed difference in results. Sufficient zinc was placed in the capsule (separate from the iron and kept at a different temperature) to supply the vapor phase and the iron alloy, while leaving a pool of pure liquid zinc throughout the run. The imposed temperature of the residual zinc pool fixed the vapor pressure of zinc throughout the capsule; condensation was avoided at other locations by making this the lowest temperature in the capsule. Two common complications of nonisothermal systems were, we believe, effectively absent from ours: first, molecular species other than monatomic have no appreciable concentration in zinc vapor at 700" to 900~~: second, the development of zinc-pressure differentials in the capsules was suppressed by use of relatively large-diameter tubing and the absence of diluents in the zinc vapor other than desorbed impurities. The specimens and zinc pool were located at two isothermal zones (each ranging within 1°C over several inches) of a wire-wound, 37-in.-long vertical-tube furnace. The required temperature distribution was achieved by external adjustment of the currents in three electrically isolated windings. The temperatures of the isothermal zones were controlled independently by ther-

Jan 1, 1968

By J. B. Wagstaff, R. A. Buchanan, J. F. Elliott

High speed photography through blast-furnace tuyeres showed coke particles moving rapidly. Model studies showed a raceway was formed and gave quantitative results which were correlated with actual blast furnaces. Another study showed the similarity between hanging and the flooding of a packed column. This was explored by models. THE combustion zone before the tuyere in an iron blast furnace is a vital region because here are generated: 1—most of the gases on which the furnace depends to carry out its basic operation of reducing iron ore to the metallic state, and 2—the major fraction of the heat required in the nearby regions of the furnace for the various reduction reactions, the fusion of the slag, and the melting of the iron. Since the greater part of the coke is consumed in this region, the descent of the burden must be greatly affected by the characteristics of the tuyere zone. This region then would seem to be a profitable field for study. Fortunately, a view into this important zone is available to the operator through the tuyere peep sight. Here he sees relatively dark pieces of coke "dancing" in the blast. What he sees is of considerable help in interpreting the behavior of the furnace at a given time but the very rapidly moving particles and the intense radiation obscures what is happening very deep in the zone. This investigation was initiated in the hope that a better understanding of the combustion region could be obtained by using a high speed camera with a maximum speed of 3000 frames per sec. It seemed the best practical method of "slowing down" this characteristically violent action within the highly luminous field. Model studies and tuyere probing also have been used to aid in explaining the observed phenomena. Above the combustion zone, but below the fusion zone, there is probably a region in which the coke is comparatively stationary. Here are zones in which the gases must flow up through the granular bed counter to descending liquid slag and metal. There is no easy way to observe this zone in a blast furnace, but model studies have been of some help in explaining the nature of the zone and the laws governing the flow of the fluids involved. The whole problem is difficult and involved and any approach to a complete solution may require long investigation. This preliminary report has been written, therefore, because it is believed that appreciable progress has already been made that would be of interest to others. Tuyere Studies, Chemistry and Kinetics It is well known from the early work of Kinney and coworkers1,2 that combustion of carbon before the tuyeres appears to occur in two zones: Zone A: C + O, = CO2; AH77°F. = — 14,108 Btu per lb of carbon [I] Zone B: CO2 + C = 2CO; H77°F = + 6,183 Btu per lb of carbon [2] Zone A (Fig. 1) is close to the tip of the tuyere and zone B is somewhat farther back; there being a transition region in which both reactions occur. It is interesting to estimate the rate at which coke is burned before a tuyere with a wind rate of 90,000 cfm in a modern furnace having 18 tuyeres. Approximately 0.55 lb of carbon is consumed by eq 1 per tuyere per sec. A like amount disappears by eq 2 for a total consumption of 1.11 Ib per sec per tuyere. Assuming the coke is 85 pct C and has a bulk density of 30 lb per cu ft, this figure can be converted to a total of 1.30 lb of coke with a bulk volume of 0.043 cu ft disappearing per sec per tuyere. At the temperatures prevailing in the combustion zone (according to Kozlovich,³ he maximum is about 3400°F), the rate at which carbon is con-

Jan 1, 1953

By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".' The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley's publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1' for ?H°, and the entropy function.

Jan 1, 1952

By R. L. Jones, H. Conrad

The effects of gain size on the room-temperature tensile properties of commercial(A- 70)-purity and iodide-purity titanium were investigated by concurrent tensile testing and thin-foil electron transmission studies. The mechanical tests showed that the effect of grain size on the yield, flow, and fracture stresses could be expressed by relations of the Hall-Petch type. The magnitude of the grain size effect on the yield stress was larger for commercial-purity than for high-purity titanium, but in both materials it was intermediate between that typically observed for fcc and for bcc metals. The effect of strain on the gain size sensitivity of the flow stress was found to reflect the grain size dependence of strain hardening. The electron transmission study indicated that the tensile behavior could be accounted for in terms of the dislocation densities and distributions formed during deformation. It was concluded that the effect of grain size on strength could be attributed to a relationship between grain size and the dislocation densities generated in initiating and sustaining plastic flow, the difference in stress levels being due to strain hardening. The relationships between recrystallized grain size, uniaxial tensile properties, and dislocation substructure have not been explored in any detail for a titanium. With titanium and its alloys finding increasing applications in aerospace systems, such information has become essential. The research described in this paper had two objectives: first, to document the effect of grain size on the yield, flow, and fracture stresses of unalloyed a titanium by the tensile testing of recrystalliied specimens at room temperature; second, to attempt an interpretation of the mechanical test behavior in terms of the dislocation structures formed on deformation, as observed by transmission electron microscopy of thin foils prepared from deformed tensile specimens. The observations reported here are restricted to room-temperature deformation; the effect of temperature on the yield and flow stresses of a titanium and the athermal nature of the contribution of grain size to the flow stress have been discussed elsewhere.1"3 EXPERIMENTAL DETAILS Two purity grades of unalloyed titanium have been investigated: Crucible Steel A-70, a typical commer- cial-purity product, and a high-purity iodide grade supplied by the Foote Mineral Co. Chemical analyses for interstitial impurity contents are given in Table I, together with values for the total interstitial atom fractions in terms of oxygen equivalents, which were calculated by the method outlined previously.4 ,5 According to the manufacturer's nominal analysis, the A-70 grade also contains about 3700 ppm of Fe. The A-70 grade was supplied as 1/4-in.-diam centerless-ground rod. The iodide grade was supplied as crystal bar which was consolidated to approximately 1/4-in.-diam rod by a single, rapid, molten zone pass, using electron beam heating. The 1/4-in. rods were cold-swaged to 0.078-in.-diam wires and 2-in. lengths were recrystallized in a vacuum of -5 x 10-5 torr, giving grain sizes in the range 0.8 to 30 . The thermal treatments and resulting grain sizes are summarized in Table 11. Since there was in no case any obvious sign of a bimodal dis tribution of grain sizes, the grain size values quoted in Table I1 are those obtained from mean linear intercept measurements involving >I00 grains. For the two coarse grain sizes the measurements were made using conventional optical techniques. It was noted during these determinations that the etchants used (10 pct HF; 30 pct HN03; 60 pct H20 and 2 pct HF; 2 pct H202; 96 pct H20 were both tried) etched grain boundaries very nonuniformly and optical polarization effects had to be employed to reveal boundaries which might otherwise have been missed. It was found that this problem became more acute with the finer grain sizes as the usefulness of polarization diminished.

Jan 1, 1970

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull's suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin's observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin's studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several ' strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r' phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

By Michael A. Gustafson, Fernando B. Sotelino

INTRODUCTION The degree of success of any new project will ultimately depend on two factors: (i) the underlying economic strength of the project; and (ii) how successfully the parties involved can coordinate their interests to establish a financing structure which indeed capitalizes on the project's inherent economic attractiveness. A project's underlying economic attractiveness is determined by its inherent comparative advantage in accessing the factors of production, combining these factors of production to create a product and marketing this product. Initially, the decision regarding whether to go ahead with the project - the go/no go decision - has to be based on its total ability to generate cash flow returns to project participants to compensate them for resources committed and risks undertaken. The extent to which project sponsors will actually benefit from the project's inherent economic attractiveness is fundamentally dependent on their ability to establish the long-term financing arrangement which best meets the objectives and constraints of each project participant and sources the most advantageous funding. The decision regarding the financing of the project, the "how-to-go" decision, is then an attempt to find the capital structure, consistent with market terms and conditions and sound financial management policies which will best: (i) match planned outflows with cash inflows; and (ii) maximize the return for project sponsors. This article makes use of a case study to illustrate the analytical process involved in dealing with the go/no go and the how-to-go decisions on a project. Though most commonly applied to project finance situations, the guideline described herein is equally applicable to other financing situations, such as leveraged buyouts and debt restructurings, where timely repayment of debt depends largely on the future cash flows to be generated by the entity being financed. Our case study is of a hypothetical expansion of an existing copper mining operation in Latin America. The company, Latin American Copper (LAC) currently has 147 million metric tons of proven sulphide ore reserves. The existing mine complex consists of an open pit mining operation and a conventional flotation plant with a processing capacity of 20,000 metric tons of ore per day. LAC sells copper concentrates primarily to Japanese custom smelters. The mine has been in operation for 5 years, fine copper production last year was 108,240 metric tons, and LAC currently has assets of $175 million and net worth of $135 million. Due to a recent increase in proven reserves, LAC is considering doubling the treatment capacity of its flotation plant to 40,000 tons per day, and expanding its mining capacity to meet the additional concentrator capacity (the "Project"). Project capital expenditures and incremental working capital have been estimated at approximately $210 million. The construction period is expected to cover one year, including a three-month start-up phase. The Project is to be funded by a combination of equity, senior debt, including both supplier credits and/or commercial bank term loans, and subordinated debt. LAC's shareholders are willing to commit a maximum of $50 million to the Project. A government development agency, which is also a minority shareholder, might be willing to lend approximately $40 million to LAC in the form of subordinated notes, depending on the ability of the Project to generate foreign exchange reserves. Commercial banks cannot be expected to offer loans with maturities longer than ten years. The Project is expected to increase the value of the firm because: (i) It will solidify the Company's position as a low-cost copper producer by taking advantage of economies of scale. As a result of the expansion, cash production costs are expected to decrease 7.0[c]/lb. and all-in costs 11.0[c]/lb; (ii) The potential earnings stream from the sulphide ore reserves will be realized

Jan 1, 1985

By F. W. Jessen, R. W. Durie

The development in the laboratory of mall salt cavities illustrated that the rate at which salt dissolved was affected by the rate at which fresh water was injected into the cavity. Experiments carried out with small salt cores indicated, however, that the rate of salt removal with forced convection was not significantly different from that with natural convection, provided the flow was in the laminar range. The rate of salt removal was apparently controlled by the water salinity, which was indirectly determined by the rate at which fresh water was injected. With turbulent flow at the salt surface, the rate of salt removal could be increased several-fold with the same salinity in the cavity. A quantitative evaluation of the rate of salt removal under natural convection was attempted by using techniques developed for the analogous heat convection system. The values of the rate of salt removal obtained experimentally were considerably greater than the calculated values due to surface irregularities. To determine the effect of these irregularities, the rate of salt removal was found for a smooth surface by experimentally determining the rate of salt removal as an irregular surface developed and then extrapolating this trend back to initial time. Excellent agreement between the experimental and calculated values then were obtained. INTRODUCTION Underground cavities leached from massive salt formations have been used extensively for many years for storing LPG products. The development techniques for storing methane gases in the liquid state at a low temperature leads to speculation that underground salt cavities of controlled geometry may be quite important in this field. In any case, the increasing number of salt cavities used for storage indicates an impending need for a better knowledge of the washing process to efficiently develop maximum storage volumes within specified regions. It is the purpose of this paper to discuss some aspects of -the mechanism of the dissolution of salt in the formation of cavities of controlled geometry. Although no attempt is made to resolve the problems that may be associated with the storage of methane in the liquid state in salt formations, the fact that salt cavities can be formed at reasonable cost would appear to justify investigation in this direction. Further, underground cavities have the advantage of allowing storage at higher pressures (and hence higher temperatures) than surface installations. Although the thermal conductivity of salt is somewhat higher than frozen earths, 0.017 cal/(sec) (cm)(c) for salt at 32F vs 0.005 cal/(sec) (cm) () for ice at this temperature, this disadvantage is offset by the higher storage temperature in underground cavities. For example, at atmospheric pressure, the temperature of liquid methane would be —258F. In a storage cavity at 2,000 ft, the pressure would be approximately 1,000 psia, which would allow a storage temperature of -9OF. The formation temperature would be roughly 110F at this depth, hence the total temperature differential would be 200F. Under surface storage conditions the corresponding temperature difference would be some 333 F (75 F + 258 F). The results of this difference can be compared more readily by substituting the appropriate values of thermal conductivity, temperature difference, heat capacity and density into the solution of the diffusion equation for the unsteady linear conduction of heat. For the underground salt storage, the heat flux is 15cal/(sec) (sq cm), where t is the time in seconds from the initiation of the cooling. For the surface system, and using the thermal properties of ice at the average temperature, the corresponding figure is 21cal/(sec) (sq cm). Hence, the heat losses through ice under surface conditions would be some 30 per cent higher than the underground salt storage. This ratio would vary, considerablv. Of course, for other conditions, but it indicates that an advantage over surface facilities may be obtained by storage in underground salt cavities.

Jan 1, 1965

T.P. 1958 D. H. DAVIS.*-Mr. Carris has ably pre¬sented the problems of coal preparation, particularly those brought about as the result of increased mechanical loading. Many mines are now crushing the run-of¬-mine raw coal through 12 or 15 in. immediately after it is dumped from the mine car and before it is handled by conveyors. At certain mines the removal of large slate mechanically has been solved by the installation of scalping screens consisting of bars or rails set at spacing of 12 to 15 in. on the top deck of the main raw-coal sizing screen. At the plants where these are in use, the plus 12 or I5-in. raw material contains 60 per cent or more free rock or slate, so that it is easier to pick coal than to pick rock. After the screening at 12 or 15 in. is accomplished, the oversize material is diverted to one side of the shaker, where a picker allows the refuse to pass off the shaker into a chute and guides the coal back onto the shaker. After the large rock has been removed, it is then advisable to reduce the size of rock by crushing before putting it onto a conveyor. A great saving in picking labor has been made by the use of such scalping screens, which in addition has maintained the plant capacity when handling a dirtier feed. The great increase in percentage of coal under 1/4 or 3/8 in., coupled with a greatly increased percentage of free impurities in this size, is the most serious problem that has been brought about by mechaniced loading. Many plants that formerly prepared good quality 1/4-in. to o or 3/8-in. to 0 slack by air¬cleaning are faced with installing facilities for wet-cleaning mechanical and heat-drying and water clarification. The change to wet prepa¬ration of fines usually affects the marketing problems for many coal companies. There will also be problems involving wastage of fine solids and stream pollution. Much work will be necessary for improvements in present practice. Pneumatic and electrostatic methods for cleaning fine coal should receive consider¬able attention in an attempt to avoid wet¬cleaning of fines. The preparation supervisor and the plant personnel should not be satisfied merely to run the cleaning-plant machinery and assume that the job will be done for them. Coal is a heterogeneous substance and in many instances is constantly changing. This is more true when full-seam methods are in use. Only persons trained to observe closely and make the necessary changes in plant operation will be able to solve the many problems that will be imposed on the preparation plants. The plants will require skillful and observant operating men. With full-seam mining methods, seams of roof coal will often be mined. Under the former mining systems these strata were not mined and frequently they contain a high per¬centage of bony and banded partings. The mining of this coal will greatly alter the washability and specific gravity characteristics of the feed to the plant. Often the percentage of 1.40 to 1.60 sp. gr. increased from 3.5 to 7.5 per cent, or nearly a 1.0 per cent increase in the ash content of the 1.60 sp. gr. float coal. Thus the cleaning problem is much more difficult, and it is unlikely the same ash content of cleaned coal can be produced as before without a decrease in recovery or the produc¬tion of a "middlings" product. Mr. Carris had this in mind when he said "The quality of the

Jan 1, 1946