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By D. R. Wieland, H. T. Kennedy

The object of the work reported here was to determine the content of elemental sulfur in gaseous methane, carbon dioxide, hydrogen sulfide, and in mixtures of these gases, at pressures and temperatwes encountered in natural gas reservoirs. Sulfur content at equilibrium is reported for pure methane, carbon dioxide, hydrogen sulfide, and on three binary mixtures of each of the three pairs of gases at pressures of 1,000, 2,000, 3,000, 4,000, 5,000 and 6,000 psia and at temperatures of 150°, 200° and 250°F. In addition, the sulfur content of three ternary mixtures at the same temperatures and pressures are reported. The results indicate that the sulfur content is higher in the gases at higher temperatures and pressures. The content is highest in hydrogen sulfide, intermediate in carbon dioxide and lowest in methane. INTRODUCTION At ordinary pressures and temperatures, the concentration of a nonvolatile material, such as sulfur in a gas at equilibrium, is a function of the vapor pressure of the material and is independent of the nature of the gas. As the pressure and temperature increase, the gas assumes some of the properties of liquids, including the power to dissolve other liquids and solids, to an extent dependent on the nature of both the gas and the material dissolved. At equilibrium, the content of sulfur in the several gases considered here may thus be considered as solubilities which are fixed for a given composition of gas, temperature and pressure. The study of the solubility of elemental sulfur in gases is of interest because sulfur is sometimes present in reservoirs producing natural gas and must be present in the vapor phase. Upon reduction of pressure and temperature, the sulfur precipitates from solution in the reservoir and in the tubing and fittings. Due to the fact that the greatest pressure drop in the reservoir is around the wellbore, the volume of sulfur precipitated will be greatest in this locality and can cause a substantial reduction in the permeability of the formation in this area. As the natural gas flows up the tubing string, the pressure and temperature are further decreased, causing further sulfur precipitation. If the volume of free sulfur is large and remedial measures are not taken, complete plugging of the tubing can occur. Knowledge of the content of sulfur as a function of composition, temperature and pressure will enable the operator to determine what changes in pressure and/or temperature are necessary to keep the sulfur in solution. If the sulfur solubility is large and can be controlled, the operator may desire to produce the well at a high wellhead pressure and temperature and reclaim the sulfur at the surface. The high solubility of sulfur in hydrogen sulfide (5.6 per cent by weight at 5,000 psi and 200°F) suggests the feasibility of recovering sulfur by injecting this gas into sulfur-bearing reservoirs and expanding the produced gas to precipitate out the sulfur. The present project was designed to measure the solubility of sulfur in carbon dioxide, methane, hydrogen sulfide and mixtures of these three gases at various temperatures and pressures. These gases were the major constituents of the gas well where plugging by sulfur was encountered. A study of the published literature shows no data on the solubility of sulfur in any gas, although Hannay and Hogarth,' in 1880 reported that it was soluble in carbon disdlide above the critical temperature of carbon disulfide. EQUIPMENT AND PROCEDURE Fig. 1 shows the layout of equipment employed to bring gases to equilibrium with sulfur and to isolate the quantity of sulfur contained in a known volume of gas. Pure gases were measured in the charging bomb at known temperatures and pressures and displaced into the reservoir bomb to make up the desired mixtures. When equilibrium was achieved

By F. Forward, H. Veltman, A. Vizsolyi

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By T. D. Teimann, R. L. Stone

The rate of extraction of silica from certain Wisconsin and Minnesota taconites was investigated by autoclave digestion in sodium hydroxide solutions over the temperature range from 296° to 416°F. Rates obtained were from 7 to 254 g mol per cm2 per sec giving activation energies from 15,000 to 19.000 cal per mol. Activation energy was found to increase with increase of sodium hydroxide concentration. Digestion of different forms of quartz indicated the rate of extraction to be solely a function of surface area under similar conditions of digestion. The results of an experimental investigation on the caustic extraction of silica from certain Wisconsin and Minnesota taconites were presented in a recent publication.' It was shown that residual concentrates containing as much as 65% iron can be produced by this method. The occurrence of silica as a micro-crystalline variety of quartz with high specific surface area gave correspondingly high mean rates of extraction in solutions of sodium hydroxide. The present paper extends this previous work by presenting the results of a study of the specific rates of extraction of silica from these ores as related to temperature, sodium hydroxide concentration and variety of quartz. Calculated activation energies for the dissolution of silica are presented and some possible mechanisms are discussed. TACONITES The low-grade siliceous iron ores investigated included taconite from the Wisconsin Gogebic range and a semi-taconite2 from the Minnesota Mesabi range. These are adequately described in the former paper1 and by the U. S. Bureau of Mines. The principal iron minerals are hematite (Fe2O3) and goethite (Fe2O3 . H2O), while the gangue is essentially a microcrystalline variety of quartz. Minor amounts of other minerals are present. Typical analyses show the Wisconsin taconite to contain approximately 28% Fe and 54% SiO2 and the Minnesota semi-taconite 39% Fe and 39% SiO2. Analyses of the actual samples used are given in Table I. The taconite samples were prepared for digestion by reducing the original ore to minus 200 mesh in a Braun pulverizer. QUARTZ Three varieties of quartz were studied in the investigation: Ottawa sand, chert and chalcedony. The Ottawa sand was obtained from the Ottawa Silica Co. The chert and chalcedony came from Wards Natural Science Establishment. A minus 200 plus 400 mesh fraction of the Ottawa sand, used as a surface area standard, was repeatedly washed in hot concentrated hydrochloric acid followed by distilled water before autoclaving. The other two varieties were used directly after grinding through 200 mesh in a laboratory hammer mill. Analyses of these samples appear in Table 11. Microscopic examination of the silica samples by the oil immersion method showed that the Ottawa sand consisted of clean, uniform spheres of quartz with little deviation in size from a mean diameter of 82µ determined by a distribution count. The other two varieties consisted almost entirely of microcrystalline aggregates of quartz crystals; the aggregates ranged from 10 to 70µ. The individual crystals in the chert aggregates were estimated to be of the order of

Jan 1, 1964

By T. J. Whalen, S. M. Kaufman

Surface-tension measurements for liquid Fe-C-Co and Fe-C-Ni alloys were performed by the sesszle-drop technique at 1350o and 1425°C. Cobalt was shown to he more effective than nickel in lowering the surface tension of Fe-C alloys A minimum value for surface tension of 1640 dynes per cm was found in the Fe-C-Co system at a concentration of 1.5 pet C and 12pet Co. Analysis of these measurements in terms of adsorption and desorption behavior indicated that cobalt and nickel lower surface tension in Fe-C alloys by replacing carbon at the liquid-vapor interface. Comparison of results to date for Fe-C liquid alloys has shown that most substitutional-type elements having about the same atomic diameter as iron also have relatively the same influence on surface tension when present in dilute amounts. It has been shown previously that surface-adsorption behavior in liquid Fe-C ternary alloys is related to the manner in which the ternary addition affects the activity of carbon in the bulk solution.' Certain ternary additions, such as chromium, tending to decrease carbon activity cause adsorption of carbon and chromium to the liquid-vapor interface. Additions, such as silicon, increase the carbon activity, resulting in a desorption of carbon and an adsorption of silicon. Both cases were shown to cause a decrease in surface tension due to adsorption. It is the object of this paper, as part of the writers' continuing interest in the effect of alloying additions on the surface tension of Fe-C alloys, to present and discuss surface-tension data on solutions in the ternary systems Fe-C-Co and Fe-C-Ni. Available activity measurements for these systems in the solid state indicate a strong increase in carbon activity when either nickel or cobalt is added to Fe-C alloys.2, 3 EXPERIMENTAL PROCEDURE The alloy compositions used are shown in Table I. These alloys were prepared by vacuum melting in stabilized zirconia crucibles and then vacuum casting into cold-steel molds. The nominal analyses for the alloys used in this investigation are given in Table I. Surface tensions and densities were measured by the sessile-drop method4,5 in conjunction with the tables of Bashforth and bdams.' Specimens were prepared by slicing 1/4-in. cubes from the center of the vacuum-cast ingots and grinding the edges of these cubes until their shapes approximated spheres with flat bottoms. Proper handling techniques, including an acetone rinse immediately before use, assured minimum contamination from sources extraneous to the actual melting. For each experimental run a sample was placed on a BeO plaque and positioned and leveled inside a vacuum induction heating apparatus. The sample and plaque arrangement sat inside a molybdenum tube which acted as the susceptor. Diagrams of this apparatus may be found in the literature.= After heating to temperatures just above the liquidus at pressures of the order of 10-4 to 10- 5 mm Hg, photographs of the drop profile were made using its natural thermal radiation as a light source. Some measurements were made with partial pressures (-1 cm Hg) of a mixture of H2 and He gases. The H2-He atmospheres proved to be necessary at higher nickel contents to retard excessive vaporization losses. Chemical analysis for carbon and the ternary addition was performed for each alloy sample after completion of the experimental run.

Jan 1, 1964

By Stuart S. Forbes

Changes and additions made to the Canadian Copper Refiners Ltd. electrolytic refinery between 1949 and 1955 are reviewed. The effect of high current density on current efficiency and section work is discussed. OPERATING and physical changes which have been made to the electrolytic tank house of Canadian Copper Refiners Ltd. suggest a review of present conditions. Previous papers1 a have described the general arrangement. Since then, expansion, closer anode spacing, and higher current densities have increased annual cathode capacity from 112,000 to 182,000 tons. A recent extension to the tank house, begun in the spring of 1954 and completed in August 1955, was undertaken to handle the monthly production of about 3,000 tons of anodes from Gasp6 Copper Mines. The anticipation of these additional receipts and large stocks of unrefined copper caused by the increase in custom smelting at Noranda made it necessary to increase production without immediately available additional cell capacity. Accordingly, from December 1954 through March 1955, the tank house was operated successfully at a current density of 24.0 amp per sq ft. Again, as of September 1955, one of the two tank house circuits is being operated at this high density. Although other refineries may operate at current densities higher than 24 amp per sq ft, none is doing so with anodes which contain silver and gold content as high as those being refined at Canadian Copper Refiners Ltd. General Arrangement The original building consisted of two parallel bays, each 660 ft long and 60 ft wide, with a 24 ft pump bay extending along the west side of the building. A previous expansion, completed in 1939, was to the west of the original building and consisted of two 60 ft parallel bays 240 ft long. The length of these two bays was extended in 1954 to 540 ft, adding one stripper and 12 commercial sections to No. 2 electrical circuit. Space is still available for an additional six commercial sections and one stripper section. Construction on these seven sections started in September 1955, and will be completed early in 1956. The tank house capacity will then be 206,000 tons of cathodes per year. In the two tank houses there is a total of 900 cells distributed as follows—commercial, 468; stripper, 36; total, 504 in the No. 1 tank house (No. 1 circuit): commercial, 360; stripper, 36; total, 396 in the No. 2 tank house (No. 2 circuit). Section arrangement consists of nine cells to a tier and two tiers or 18 cells to a section. Anodes, weighing 620 lb each, are cast with a Baltimore groove and are refined by the multiple system. Solution enters each cell through a bottom inlet at one end and overflows at the top of the opposite end. Rate of solution flow through the cells is controlled by valves at each section to 4.5 gpm. Electrical power to the tank house is now provided by nine 675 kw motor generator sets. Each set consists of a 135-12 v 5000 amp dc generator, driven by a 980 hp 2300 v synchronous motor. When No. 1 circuit is operated at 22,000 amp, five sets, at 4400 amp each, are connected in parallel. As the maximum allowable current on No. 2 electrical circuit has recently been set at 18,000 amp, only four sets are connected in parallel on No. 2 circuit. A tenth set, now being installed, will be reserved as a spare, for use in either circuit as required. Recent Changes In 1949, the annual capacity of the tank house was increased from 112,000 to 132,000 tons by closing the

Jan 1, 1957

By Richard H. Rein, John Chipman

The activity of SiO2, in the entire liquid system SiO2-CaO-Mg0-A12O3 at 1600°C is calculated from the distribution of silicon between these slags and Fe-Si-C alloys saturated with either graphite or silicon carbide, the activity coefficient of silicon in these alloys, and the requisite thermodynamic data. The activities of the other components in the ternary systems SiO2-CaO-A12O3, SiO2-MgO-CaO, SiO2-MgO -A12O3 are computed from these data by the IrON blast-furnace slags can be regarded as consisting of the four major oxide components, SO2, CaO, MgO, and A12O3 along with minor proportions of other oxides and of sulfur. The purpose of this study is to measure the activity of silica in the liquid solutions of these four oxides at iron-making Gibbs-Duhem equation with the aid of the known free energies of several of the interoxide compounds and the accepted phase diagrams. Based on these activities, new data are Presented for the free energy of formation of a number of the interoxide compounds. The free energy of mixing the liquid metasilicates of CaO and MgO shows slight positive deviations from the ideal. temperatures and to obtain activities of the other components by application of the Gibbs-Duhem equation and the properties of several interoxide compounds. Recent investigations on the activity of silica in the SiO2-CaO-A12O3 system1-3 and recogntion of a serious error in older data for the free energy of formation of SiO2 (Ref. 4) have succeeded in bringing a fair degree of concordance into the results of different investigators. In the present study, the activity of silica is obtained from the silicon-distribution experiments described in a previous paper,' the revised activity coefficient of silicon

Jan 1, 1965

By F. Forscher

Pronounced porosity, decreasing with distance from the fracture surface, is found in the necked region of tensile specimens tested at room temperature or liquid nitrogen temperature. A hydrogen solution treatment followed by a quench prevents pore formation in tests at —196°C, but has little effect on tests made at room temperature. Reduction of area values at —196°C are strikingly improved by the same treatment, but show no improvement in room temperature tests. The experimental results support the hypothesis that strain-induced porosity results with hydride initially present or, in material containing less than 50 ppm H, with hydride precipitated by strain aging. ZIRCONIUM'S advent as an engineering material in nuclear reactor construction has brought forth many investigations concerned with the properties of this metal and its alloys. Some attention has been given to the ductility of the metal.1, 2 Particularly, the effect of hydrogen on the impact strength was noted," indicating a pronounced dependence of ductility on the hydrogen content and its distribution in the metal. Micro graphic:' and X-ray diffraction studies' have shown that a precipitated hydride phase causes embrittlement in zirconium,' which implies a distinctly different mechanism from that causing hydrogen embrittlement in steels."-' In the latter case, it is assumed that atomic hydrogen diffuses to rifts, where it forms molecular hydrogen under such internal pressures that it causes the rifts to enlarge, leading to fracture. Thermo-dynamic studies of the Zr-H system8, 9 also indicate that the internal pressure of molecular hydrogen would be too low to cause any damage to the zirconium at room temperature, and the formation of a zirconium hydride (d phase) is favored." It is noteworthy that this phase has a face-centered-cubic structure and nearly 18 pet larger molar volume than close-packed-hexagonal a-zlrconlum' Other features of the ductility of zirconium are the absence of a typical cup-cone failure upon tensile testing, a pronounced strain-induced porosity in the necked region of a tensile bar, Fig 1, and the associated spongy appearance of the fracture surface A tremendous improvement in ductility at liquid nitrogen temperature can be observed following a heat treatment that retains the commonly present quan- tities (10 to 50 ppm) of hydrogen in solution. Such tests show a typical cup-cone failure and the absence of strain-induced porosity, Fig. 2. The present paper reports results of an investigation into the causes of strain-induced porosity in zirconium. Room temperature tensile fractures of mild steel, aluminum, and titanium have also been examined for strain-induced porosity. In each case porosity could be detected, but the amount was orders of magnitude less than was found in zirconium. Of the three metals, titanium showed the strongest effect. Material, Specimens, and Preparation The greater part of this investigation was done on Westinghouse crystal bar zirconium, are-melted, forged, and hot-rolled. Chemical analyses of the hot-rolled plates are given in Table I, along with those of the Foote crystal bar zirconium used in this work. The specimens were machined from the hot-rolled plate (1550°F) of 1/2 in. thickness and subsequently heat-treated according to one of the treatments shown in Table IS. All specimens were machined round, the longitudinal axis in the rolling direction, with a gage

Jan 1, 1957

By C. E. Violet, R. J. Borg, E. M. Howard

The miscibility gap in the Au-Ni system has been determined by Mossbauer spectroscopy, with used as a probe. The phase boundaries were determined from the compositional dependence of both the isomer shift and Curie temperature. X-ray diffraction measurements were also used to confirm the Mossbauer results. 1 HE purpose of this research is to demonstrate the application of Mbssbauer spectroscopy to the determination of phase boundaries and to redetermine the miscibility gap by an independent and novel technique. The techniques evolved in this study are readily applicable to other polyphase systems and are generally as quick and accurate as the more conventional methods, e.g., metallography, X-ray diffraction, thermal analysis, and so forth. To be sure, not all polyphase systems will lend themselves favorably to Mijssbauer investigations, but this is a problem met in the use of conventional methods as well. The Mbssbauer spectrum responds to a different set of physical parameters, and consequently provides an entirely independent method of analysis. It is especially useful if the system has either a ferromagnetic or an antiferromagnetic transition. The Au-Ni system was selected because alloys containing more than -60 at. pct Ni become magnetically ordered at low temperatures; also the miscibility gap is quite well established (see Ref. 7 for a compilation of pertinent references, also Fig. 11, and thus provides a reliable test of this novel procedure. As Fe is the most commonly used Mijssbauer isotope, there exists a wealth of information concerning its behavior in iron-containing alloys and compounds. However, as yet there have been relatively few experiments using it as a probe to investigate nonferrous systems. By choosing a nonferrous alloy system, we are able to demonstrate that its use is not restricted to systems containing iron as one of the major constituents. Wertheim and ~ernick' have used the same method to investigate Cu-Ni, and demonstrated that one can obtain a systematic variation in the isomer shift and magnetic hyperfine field. However, we believe this to be the first time these techniques have been used to establish phase boundaries. Two hyperfine interactions were measured and used to determine the phase boundaries, viz., the magnetic hyperfine splitting and the isomer shift which in this alloy system are both strong functions of composition. Calibration curves were established based upon single-phase solid solutions obtained by quenching from temperatures well above the maximum of the miscibility gap, see Fig. 1. Solid solutions containing 25, 50, 65, 75, 85, 92, and 96 pct Ni as well as pure nickel were used in the calibration procedure. Fig. 2 shows the Curie temperature, TC, and the isomer shift, v,, as determined from the Mbssbauer spectra, and variation in lattice parameter as determined by X-ray diffraction, as functions of composition. The compositions of the two-phase systems quenched from temperatures within the miscibility gap are obtained by comparing their respective values of TC and v0 with the calibration data. I) EXPERIMENTAL Mbssbauer sources were made by fusing the component metals in a tungsten arc melter, which has a water-cooled copper hearth. Both nickel and gold were 99.999 pct pure, and the melting was done in an atmosphere of purified argon. The alloys were rolled, diced,

Jan 1, 1969

By L. Kaufman

An equation is derived relating AF a", the difference in free energy between austenite and martensite, to temperature and composition in the iron-chrmnium and iron-chromium -nickel systems. This equation is used to calculate at M,for low-carbon stainless steels. A method for utilizing the energetic equations to calculate M, in stainless steels is suggested. In addition, an explanation is given for the anomalous effect of chromium in forming a y loop concurrent with the lowering of M, in iron-base alloys. It has been demonstrated that the effect of alloying elements on the Ms temperature is strongly dependent upon the influence of the alloying element on the thermodynamic properties of the y and a phases. Notwithstanding the fact that alloying elements affect the Ms temperature by changing the lattice parameters, elastic constants, and inter-facial energies of the a and y phases, their primary role is a thermodynamic one. Thermodynamic analyses have been presented for the iron-carbon'-4 and iron-nickele systems in which equations are derived for Fa and FY, the free energies of the b.c.c. (or b.c.t.) and f.c.c. phases. These equations, which can be obtained with the aid of the equilibrium diagrams, can be used to help predict the Ms vs composition curves. This paper deals with a calculation of the thermodynamic properties necessary to compute AFffLY for iron-chromium alloys. In view of the lack of direct information concerning the activity of chromium in the a and y phases of iron, the regular solution approximationa,g was utilized to bridge the gap. After the necessary equations were derived for the iron-chromium system they were used to calculate AFff— Y for stainless steels by combining them with the previous results obtained for iron-nickel alloys. The results of these calculations offer a means of rationalizing the anomalous behavior of chromium in iron-base alloys. The latter depends on the regular solution approximation in contrast to the explanation offered by zener , which is based upon the "magnetic specific heat effect." THERMODYNAMICS OF THE IRON-CHROMIUM SYSTEM If y represents the atomic fraction of chromium in an iron-chromium alloy, then the free energy of the b.c.c. phase Fa, the f.c.c. phase FY, and the difference in free energy between the f.c.c. and b.c.c. phases of the same composition are given through [3] and Fmy represent the free energies of mixing of the a and y phases; while @era -' and uFea 4Y represent the difference in free energy between f.c.c. and b.c.c. chromium and iron respectively. The values of AEFe0ff4Y in the temperature range between 0" and 900K ( .

Jan 1, 1960

By F. von Gemmingen, E. J. Fasiska, L. Zwell

EARLIER studies of the dependence of creep on structure1 and of the dependence of creep rupture on creep behavior2 did not include detailed discussion of the phases present in the specimens under examination. It is of interest to determine the nature and amounts of such phases present since it is well known that these are dependent on composition, heat treatment and creep conditions.3 This investigation has therefore been undertaken to identify these constituents and to determine their relative amounts. This report presents the results of this investigation and describes an improved "extraction replica" technique developed in the course of the work. The composition of the Type 316 austenitic stainless steels studied in this investigation is given in Table I. The specimens were solution treated at 2000°F for 1/2 hr and water quenched. Those specimens subjected to prestrain at room temperature Methods for extracting precipitate particles from materials for electron and X-ray diffraction analysis have been described by Fisher,4 Smith and Nutting: and Booker and coworkers.6'7 Electrolytic extraction methods have been described by Andrews and Hughes.8 The first two methods have been used at this Laboratory, but have not proved satisfactory for many problems requiring X-ray diffraction analysis. It has been difficult to remove the replicas or to avoid tearing them during removal. These difficulties are overcome by backing the replica with a water-soluble plastic such as Dupont 51-05 Elvanol (polyvinyl alcohol). The backing increases the thickness of the replica so that it can be mechanically stripped from unloosened particles without folding or tearing. This procedure eliminates the stripping of wet replicas, which usually have a low tear strength. By stripping replicas after drying, it is possible to extract partially loosened particles which otherwise would remain imbedded in the metal. The modified method is as follows: after the specimen is polished, it is etched for 60 min in modified glyceregia consisting of 30 ml glycerol, 7 ml nitric acid, and 4 ml of hydrochloric acid. The sample is then washed, air dried, and coated with a 20 pct Baker and Adamson 1611 collodion (85 pct amyl acetate by volume) film. After the collodion film is dry (about 15 min), the sample is again etched in the modified glyceregia for 50 min, washed with isopropyl alcohol (to prevent dissolving the collodion) and air dried. A very thick coat of polyvinyl alcohol (about 50 pct solution "Elvanol Dupont 51-05" in water) is poured over the sample and is permitted to dry for about 24 hr. The composite film containing the precipitates is then stripped from the specimen and floated, polyvinyl alcohol side down, in water (at about 50°C) until the polyvinyl alcohol dissolves. This usually takes about 15 min. Should any of the polyvinyl alcohol remain on the replica, it does not give a crystalline diffraction pattern and therefore does not hinder identification of the precipitates. The extraction replica, floating in water, is picked up on a glass fiber and mounted in the Debye-Scherrer camera for X-ray diffraction analysis. Concentration of the etchant, and also etching time, had to be increased for several of the samples. Fig. 1 shows two extraction replicas taken from different areas of spec. M74-37; X-ray analysis showed a strong diffraction pattern of M23C6 and a medium one of u phase. A

Jan 1, 1962

By G. P. Marino

The "conductivity ", Kr, of a spherical void in a linear temperature gradient due to radiation is calculated by integration of the general expression for diffuse radiation between two gray surfaces of arbitrary orientation. The spherical geometry allows an exact evaluation of the phenomenon without resorting to up-proximate expressions for the radiant heat flux. The resulting expression for Kr is three quarters of the approximate value obtained by Loeb. IN the determination of the thermal conductivity of porous materials such as sintered UO2 and ThO2 fuel pellets, the magnitude of the thermal conductivity in the pores due to radiative heat transfer across the pore, Kr, may be important in assessing the total conductivity of the pellets. Loeb' has calculated Kr for various pore geometries by approximating the net flux of heat between two surfaces of temperature difference AT as 4eT~AT and obtained: K,=4yoet3odp [1] where a is the Stefan-Boltzmann constant, E is the emissivity of the radiating surface, To is the average absolute temperature of the region across which radiation occurs, dp is the largest dimension of the gap in the direction of heat flow, and y is a geometric factor. That is: y = 1 for laminar pores and cylindrical pores with axes parallel to the heat flow direction, y = 2/3 for spherical pores, y = /4 for cylindrical pores with axes perpendicular to heat flow direction. It was the purpose of this work to obtain an exact expression for K, in spherical pores by integration of the general expression for the net heat transfer between two incremental areas on the surface of a spherical pore. This procedure yields a value of Kr 3/4 of that obtained by Loeb. I) CALCULATION OF Kr Fig. 1 illustrates the general geometry which defines the problem. The total emissive power for a gray body is given by: E = EoT4 [2] where E is the radiated energy per unit area of the radiation surface per unit time, T is the absolute temperature, o is the Stefan-Boltzmann constant (o = 5.67 X lo- '' watt per sq cm-"K1), and E is the emissivity of the surface. Although Eq. [2] gives the exact expression for the total emissive power of any gray body, all practical problems involve the net exchange of thermal radiation between a body and surrounding bodies. The two major considerations in the solution of such problems are a) shape and relative position of the surfaces and b) the emissivities of the surfaces. In this work it shall be assumed that all incremental areas on a pore have the same emissivity and, further, that little or no reflection occurs (i.e., the radiation hitting a surface is either absorbed or transmitted). Thus, the solution of the stated problem requires only that consideration a be satisfied. Consider two incremental surface areas dA 1 and dA2 of the same material in a general orientation to one another. Let dAl be at temperature TI and dAz be at T2. Fig. 2 illustrates the geometrical parameters involved. That is, 71, is the normal of dA, n2 the normal of dA2, r the line connecting the centers of each area, 81 the angle between nl and r, and Q2 the angle between 7,2 and r. Using Eq. [2] and the Lambert cosine law of diffuse radiation it is easily shown that:293 WdAf- dA, = ecr T*------^fpi------" dAidA2 [ 3a 1 and

Jan 1, 1970

By M. E. Wadsworth, R. L. Pearson

THE dissolution of UO, in carbonate solutions can occur only il the tetravalent uranium is oxidized to the hexavalent state. The carbonate system is of particular interest because it provides a means whereby the oxidized uranium may be dissolved by forming the complex ion UO,(CO3)3-1. In the presence of oxygen the over-all reaction may be written UO+1/2O,4CO3T+2HCO2UO,(CO4)11+H2O [1] UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. The mineral ulrichite is the natural counterpart of the synthetic UO, used. The kinetics of the leaching of UO, should be similar for any of the uraninite type minerals. A pressurized system was used not with the hope it could be extended to commercial systems as a primary purpose but simply to provide the means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The importance of such pres-

Jan 1, 1959

By Shozo Saito, P. A. Beck

Mettrllographic and X-ray diffraction study of Cb-Co alloys in the Composition range of 7 to 33 nt. pct Cb, after annealing at 1175 °', showed that near 25 al. pct Cb on MgNi,-lype hexagonal Laves Phaseexists in a narrow composition range, and that an MgCl- type cubic Laves Phase occurs between approximately 27 and 32.6 ut. pd Cb. Lattice parameter and density measures indicated that, in both phases. the deviations from proper Loves sloichimetry result from the substitution of cobalt atoms for some 0f the columbium atoms. Tlle same phases occurant 1000'C, together with an additional phase of unknown structure, which appears between the hexagonal Laves phase and the cobalt-bose terminal solid solutions KOSTER and Schmid' identified a phase corresponding to the composition VCo,, and more recently the crystal structure of this phase has been determined.' In the Ta-Co system Korchynsky and Fountain recently found two intermediate phases at the composition Taco,, one of them metastable. In contrast to the V-Co and the Ta-Co systems, in the Cb-Co system no intermediate phase has been found4 at the composition CbCo,. The present investigation was undertaken in order to reexamine the question of the existence of such a phase. EXPERIMENTAL PROCEDURE Twelve alloys were prepared by arc-melting in a water-cooled copper crucible under helium atmosphere. Electrolytic cobalt and 99.9 pct pure colum-bium powder have been used as starting materials. It was found that melting losses can be reduced by compressing the colunlbium powder in the form of thin pellets before melting. For the alloys used the melting losses were not higher than 1 pct. The intended compositions of all alloys and the chemical analyses of three of them are given in Table I. Specimens from all alloys were annealed in evac- uated fused silica tubes at 1175°C for 3 days and quenched in cold water. A second set of specimens of most alloys was annealed at 1000°C for 7 days and then quenched in cold water. The annealed and quenched specimens were examined metallographically, using the following etchant: 60 pct glycerine +20 pct H,NO, + 10 pct HF + 10 pct water. Powder specimens for X-ray diffraction were prepared by crushing annealed solid specimens in a mortar. Alloys containing 27.3, 28, 29.7, and 32.6 at. pct Cb annealed at either 1175" or 1000°C were very brittle and it was found unnecessary to reanneal the powders. However, alloys containing 24.8 at. pct Cb, or less, especially those annealed at 1000°C, were much less brittle and re-annealing was required to remove the strains present in the crushed powders. In each case reannealing was done at the same temperature at which the corresponding solid specimens were annealed and it, too, was followed by quenching in cold water. In many instances X-ray diffraction patterns were also taken of the polished and etched solid specimens and compared with the corresponding X-ray diffraction patterns obtained with powders. The X-ray diffraction patterns were taken with an asymmetrical focusing camera, using CrK radiation. For precision lattice parameter measurements some X-ray diffraction patterns were taken with a symmetrical focusing camera, again using CrK radiation. EXPERIMENTAL RESULTS A microscopic examination of the alloys annealed at 1175°C revealed that the alloy containing 25.5 at. pct Cb was composed of a single phase, but that the 24.8 at. pct Cb alloy did contain a small amount of a second phase, identified by means of X-ray diffraction as having a fcc structure, undoubtedly the terminal solid solution based on cobalt. Apart from the few very weak lines corresponding to this minor phase, the X-ray diffraction patterns of these alloys could be well interpreted in terms of a MgNi,-type hexagonal Laves phase structure. The indexing of the X-ray diffraction pattern, Table 11, yas based on the lattice parameter values a, = 4.740A and c,

Jan 1, 1961

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young's modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young's modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman' noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig' observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity' or the paramagnetic susceptibility.' Likewise, no one has noted a change in crystal symmetry. In the present investigation Young's modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,' and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.' The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder' the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young's Modulus: For measurement of Young's modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young's modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young's modulus at 25°C, Fig. la, is 28.2~10" dynes per cm' (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;' the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure' which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies' have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969

By J. Orkiszewski

A method i.s presented which can accurately predict, with a precision of about 10 percent, two-phase pressure drops in flowing and gas-lift production wells over a wide range of well conditions. The method is an extension of the work done by Grifith and Wallis and was found to be superior to five other published methods. The precision of the method was verified when its predicted values were compared against 148 measured pressure drops. The unique features of this method over most others are that liquid holdup is derived from observed physical phenomena, the pressure gradient is related to the geometrical distribution of the liquid and gas phase (flow regimes), and the method provides a good analogy of what happens inside the pipe. It takes less than a second to obtain a prediction on the IBM 7044 computer. INTRODUCTION The problem of accurately predicting pressure drops in flowing or gas-lift wells has given rise to many specialized solutions for limited conditions, but not to any generally accepted one for broad conditions. The reason for these many solutions is that the two-phase flow is complex and difficult to analyze even for the limited conditions studied. Under some conditions, the gas moves at a much higher velocity than the liquid. As a result, the down-hole flowing density of the gas-liquid mixture is greater than the corresponding density, corrected for down-hole temperature and pressure, that would be calculated from the produced gas-liquid ratio. Also, the liquid's velocity along the pipe wall can vary appreciably over a short distance and result in a variable friction loss. Under other conditions, the liquid is almost completely entrained in the gas and has very little effect on the wall friction loss. The difference in velocity and the geometry of the two phases strongly influence pressure drop. These factors provide the basis for categorizing two-phase flow. The generally accepted categories (flow regimes) of two-phase flow are bubble, slug, (slug-annular) transition and annular-mist They are ideally depicted in Fig. 1 and briefly described as follows. RUBBLE FLOW (FIG. 1A) The pipe is almost completely filled with the liquid and the free-gas phase is small. The gas is present as small bubbles, randomly distributed, whose diameters also vary randomly. The bubbles move at different velocities depending upon their respective diameters. The liquid moves up the pipe at a fairly uniform velocity and, except for its density, the gas phase has little effect on the pressure gradient. SLUG FLOW (FIG. 1R) In this regime, the gas phase is more pronounced. Although the liquid phase is still continuous, the gas bubbler coalesce and form stable bubbles of approximately the rame size and shape which are nearly the diameter of the pipe. They are separated by slugs of liquid. The bubble velocity is greater than that of the liquid and can be predicted in relation to the velocity of the liquid slug." There is a film of liquid around the gas bubble. The liquid velocity is not constant—whereas the liquid slug always moves upward (in the direction of bulk flow); the liquid in the film may move upward but possibly at a lower velocity, or it may move downward. These varying liquid velocities will result not only in varying wall friction losses, but also in a "liquid holdup" which will influence flowing density. At higher flow velocities, liquid can even be entrained in the gas bubbles. Both the gas and liquid phases have significant effects on the pressure gradient. TRANSITION FLOW (FIG. 1C) The change from a continuous liquid phase to a continuous gas phase occurs in this region. The liquid slug between the bubbles virtually disappears, and a significant amount of liquid becomes entrained in the gas phase. Although the effects of the liquid are significant, the gas phase is more predominant.

By A. O. P. Casbarian

An analytical method is developed to determine the variation of the ultimate lateral resistance of a plate in a cohesionless soil with depth. This analysis is based on a modification of Rankine's classical earth pressure theory and the theory of plasticity as applied to soils. The ultimate resistance is defined as the product of the effective stress at the midpoint of the plate, the area of the plate and a dimensionless variable termed the ultimate resistance factor. This variable has been plotted us the depth ratio: i.e., the ratio of of the depth of embedment us the height of the plate. The resistance of a plate may then be calculated using the values af the ultimate resistance factor from the chart provided or the equation may be programmed for use in an analysis of anchor systems in cohesionless soils. It is emphasized that the analysis is semitheoretical. The theory has been compared with experimental results reported in the literature and results indicate general agreement. Actual field tests are necessary to further verify this theory. INTRODUCTION With the exploration for oil offshore in waters all over the world, it is of importance to determine the behavior of the various soils in relation to their ultimate resistance to deformation. Examples of such problems are the holding capacity of anchors and the lateral resistance of piles. Very little information is available in the published literature on the design and performance of anchors, in either cohesive or cohesionless soils. The analysis developed in this report is the first step in obtaining a solution for the determination of anchor holding capacity in a cohesionless material. DISCUSSION The theory used in the analysis is based on the ultimate strength of the soil and is the maximum resistance developed by the plate against further movement. In such a state the elastic deformations are disregarded in comparison with the plastic deformations. Hence, the plate can be considered as completely rigid. The theory of plasticity determines the three unknown stresses at any point by means of two equilibrium conditions for a small earth element in combination with the failure condition. However, the exact solutions can only be carried out in a few simple cases such as, for example, when the rupture or failure lines are straight (Rankine theory) or with spiral and straight rupture lines (Prandtl theory).l Kiitter 2 derived a single equation expressing the variation of the stress in any given rupture line. To utilize this equation, it is necessary to know the stress in the rupture line at a certain point. Unfortunately, this is difficult to obtain unless the rupture line intersects the free surface at a certain angle or when the earth is cohesion-less and unloaded. A method to overcome this is to consider only the boundary conditions at both ends of a rupture line without investigating the equilibrium of the earth above the rupture line. This assumes that the rupture lines meet the surface at statically correct angles, so that boundary stresses may be determined. As Kiitter's equation furnished a relation between these stresses, the unit earth pressure may be calculated at the point where the rupture line meets the wall. Another way in which Kotter's equation may be applied is in investigating the equilibrium of a soil mass above a rupture line. This method assumes that the failure or rupture line is known and that the boundary stresses in the rupture line at the ground surface can be determined. In this case it is possible to determine the earth pressure from the equations of equilibrium.

Jan 1, 1967

By G. C. Rauch, T. H. Courtney, J. Wulff

The superconducting behavior of Nb-Ti alloys containing 40 and higher wt pct of Nb and variable oxygen content was studied as a function of thermomechanical processing. Critical current density (Jc) us applied transverse magnetic field (H) data were obtained for 0.010 in. diam wires at 4.2° Kin steady fields up to 120 kOe. The precipitate responsible for increase in Jc in each of the alloys studied was related to niobium and oxygen content. In alloys containing 40 to 60 wt pct Nb with less than about 1600 ppm of oxygen, w precipitation in the range 350° to 450°C appears to be responsible for the maximum value of Jc observed. In alloys of higher oxygen content (-2500 ppm), the oxygen-enriched a phase which precipitates in the temperature range 450° to 550°C is a more effective fluxoid pinner. Maximum Jc in low oxygen (350 ppm) 80 wt pct Nb alloys was achieved by 600°C aging heat treatments. Measurements of resistive critical field also reflect the changes in composition accompanying precipitation in these alloys. It is well known that the superconducting critical current density, Jc, of solid solution superconducting alloys can be increased by precipitation heat treatments.1-4 The precipitate, to serve as an effective superconzlucting fluxoid pinner and increase Jc, must be of proper size and spacing.' Its electronic properties must also be different from those of the matrix.6 As in age-hardenable systems, optimum temperature and time of aging are dictated by the composition and history of the particular solid-solution alloy under consideration. The alloy diagram of Ti-Nb7-9 shown in Fig. 1 is typical of ß-stabilized Ti alloys. Precipitation to achieve high Jc in Ti-Nb and Ti-Ta alloys is usually carried out in what is believed to be a two-phase a + ß region.1,2,4,10 Previous work on Ti-Nb4,11 and on other ß-stabilized systems such as Ti-V, Ti-Mo,12-14 has shown, however, that the first precipitate to appear is not necessarily (Y. Under specific conditions the meta-stable w phase is precipitated instead. A further complication arises in such alloys from the strong influence of contained oxygen on the phase stability and on the kinetics of precipitation.15,16 The superconducting critical current density of Nb-Ti alloy containing less than 36 wt pct Nb has been studied by Vetrano and Boom1 and Kramer and Rhodes.4 The most effective aging temperature was found to be about 425°C; fluxoid pinning was attributed to the precipita- tion of a by Vetrano and Boom and of w by Kramer and Rhodes. Although the latter workers used recrystal-lized material and the former cold-worked, studies carried out in our laboratory lead us to believe that the type of precipitate responsible for increased Jc is unaffected by prior cold-work.17 That other types of precipitates may also be effective, especially in higher oxygen-containing alloys, has been demonstrated by Reuter, et al.2 in this laboratory with the aid of electron microscopy. Reuter et al. found that at an aging temperature of 600°C, fee-TiO is precipitated, resulting in high values of Jc. Even higher values of Jc were observed after heat treatment at 500°C, but the precipitate could not be indexed as fee-TiO. Whether the precipitate was oxygen-rich w or a could not be clearly distinguished. The work nevertheless indicates that appreciable amounts of oxygen alter the nature of the phases precipitated at different temperatures, at least in alloys containing more than 36 wt pct Nb. Since such compositions are more readily worked into suitable wire than lesser niobium content alloys, it was decided to study the response to aging of the alloy compositions reported in the present paper with the hope of clarifying the effect of composition on the precipitation processes responsible for high values of Jc. I. EXPERIMENTAL Nb-Ti alloys containing 40, 50, 60, and 80 wt pct Nb were prepared by are-melting 35 g ingots of iodide crystal bar titanium and electron-beam melted niobium.

Jan 1, 1969

By J. A. Hren, G. Thomas

A high-temperature stage has been used to study precipitation and dissolution in thin foils of Al-20pct Ag alloy directly in the electron microscope. The results show that the aging characteristics are similar to those observed for bulk materials, and in addition, direct evidence is presented for clustering at the solid solution temperature. The limit of solubility of G. P. zones is-350°C. The heterogeneous precipitation, the growth and dissolution of ?&apos;have been studied in detail. Growth of ?&apos; parallel to the basal planes, occurs by continuous motion of inter -facial partial dislocations. Growth stops at intersecting particles due to formation of sessile a/6 <110> interfacial dislocations. Growth normal to the habit plane occurs by the spontaneous nucleation of partial dislocations on alternate (111) planes and the thickening rate is --10-3= times the lengthening rate. The precipitates dissolve in layers and the final product is a whole a/2 <110> dislocation . The nucleation -growth -dissolution processes are thus completely reversible. Kinetic data obtained from the dissolution rates of ?&apos;particles enable the diffusion coefficient to be determined and the activation energy is found to be 37.5(±4) kcal mol-1, which is that expected for dzffusion of silver in aluminum. The velocity of the interfacial dislocations is thus dependent solely on the rate of diffusion of silver atoms. RECENTLY it was demonstrated that a high-temperature stage could be effectively used in the electron microscope to follow directly the processes of precipitation and dissolution in thin foils of A1-4 pct Cu alloy.&apos; These experiments also provided kinetic data which enabled the diffusion coefficient to be estimated. This new development of electron metallography opens up many fruitful areas of research and it was decided to investigate the aging behavior in thin foils of A1-20 pct Ag alloy, particularly the mechanism of heterogeneous precipitation (i.e., precipitation on lattice defects). This system was chosen because the aging characteristics of bulk specimens are now well known,2"7 and because we wished to obtain more details of the role played by partial dislocations and stacking faults in the nucleation growth and dissolution of the hcp ?&apos; phase. This is of interest for the general case of fcc-- hcp transformations. Part of the A1-Ag phase diagram is shown in Fig. 1. The use of a high-temperature stage also enables a study to be made of the clustering process (formation of G. P. zones) and to determine the structure of the solid solution prior to the usual quenching and aging procedures. It is also possible to obtain kinetic data from measurements of the rates of dissolution of precipitate particles. Unlike the results of previous experiments on A1-4 pct CU 1 where much of the initial precipitation occurred on the foil surfaces, the results on the A1-20 pct A1 alloy were identical to those reported for bulk specimens6,7 and no surface precipitation was ever observed. Thus, it was possible to follow the aging sequence: G.P. zones — ?&apos; — ? directly in the thin foils. This paper is concerned with the formation and dissolution of zones and the ?&apos; phase, and no attempt has been made so far to follow the mode of discontinuous precipitation of ?. I) EXPERIMENTAL DETAILS The high-purity A1-20 pct Ag alloy was prepared by the Aluminum Co. of America in the form of 0.001-in.-thick sheets. These were cold rolled with intermediate anneals to a thickness of 0.0004 in.,

Jan 1, 1963

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE mechanism by which the super-saturated solid solution of 20 per cent silver in aluminum decomposes has been reported in two previous publications. 1,2 The analysis of streaks in Laue photograms showed that thin platelike particles (the so-called Guinier-Preston aggregates) form upon {111} matrix planes in the early state of decomposition.1 The size of these particles is larger, the higher the temperature at which they form in accordance with nucleation theory;3 at all temperatures they increase in size with aging.2 When they have grown thick enough to afford three-dimensional diffraction, powder X-ray photograms show that the structure is not that of the equilibrium precipitate y but that of a transition lattice ?&apos;. Since this is also platelike in shape and also lies upon the {111} matrix planes with the {110} direction in the matrix parallel to the {11.0} direction in ?&apos;, it seems likely that the original platelet particles are merely ?&apos; in an early stage of formation, and thus finely dispersed. The atomic spacing and pattern on the {00.0} plane in ?&apos; are identical with those on the {111} matrix plane to which it lies parallel, and since comparable directions in the two planes are parallel, the lattices are thus coherent at the interface; an analogous coherence has been found in aluminum-copper alloys.3 The structures ?&apos; and y are both close-packed hexagonal and are oriented alike; they differ only in interatomic distances. Consequently, ? &apos; is regarded as y strained from its ordinary dimensions by the lattice coherency between it and the matrix.2 The lattice movements that transform the matrix to the equilibrium precipitate appear to be very simple.2 The mechanism of precipitation in this system is simpler and is more precisely known than that in any other system,2,4 hence the system should be a profitable one for the difficult task of correlating property changes with structural alterations. The present report provides additional studies on powder X-ray diffraction from alloys of 10 per cent, 20 per cent and 30 per cent Ag, and presents the correlation of crystallographic changes with changes in microstructure, Brinell hardness and electrical resistivity of the three alloys. PREPARATION OF SAMPLES AND EXPERIMENTAL PROCEDURE The preparation of the 20.2 per cent Ag alloy has been described.2 Alloys containing 9.9 and 29.7 per cent Ag were prepared from 99.97 per cent Al and 99.99+ per cent Ag using a similar procedure. Rolled

Jan 1, 1943