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By R. T. DeHoff

A theoretical development is presented which reformulates Fick's first law for diffusion in the solid state. The diffusion flux of component i in a multi-component system, Ji, is related to its local concentration, ci, and local jump frequency, ri : where a is a geometric factor and d is the jump distance. The product, ciri , is defined as the local concentration of atomic jumps for component i. The analog to Fick's second law is also derived. A solution to this equation is presented, which permits the experimental determination of the variation of atom jump frequency with composition in multicomponent systems. HISTORICALLY, the description of diffusion in the solid state has been presumed to be best approached as an application of more general diffusion laws, known as the phenomenological equations. These equations relate the flux, Ji, of the various components, expressed in atoms, grams, or volume, to the driving force involved, expressed as either a compositional or chemical potential gradient, sumption that the flux is simply proportional to the driving force is the foundation of this approach. The phenomenological equations take the form: where the concentration gradients are assumed to be the driving force, and: if the chemical potential gradient is taken as the driving force. The coefficients Dij in Eq. [1.] are the "diffusion coefficients"; the elements of the corresponding matrix in Eq. [2], the Mij, are called the "mobilities". Eqs. [I] and [2] may be considered to be definitions of these phenomenological coefficients. A formidable body of literature has been generated about these equations; this literature dates back to their original formulation for the simplest case of binary diffusion in a fluid, by Adolf Fick, in 1855.' This description has been shown to be self-consistent. However, the "constants of proportionality", the Dij or ,Mij, are not constant: they vary with composition in all but the simplest systems. Even in the case of tracer diffusion, wherein it can be shown that the diffusion coefficient is constant, the mobility, which is considered in irreversible thermodynamics to be the more physically meaningful quantity, varies with the concentration of the tracer involved.' In more complex systems, it is necessary to evaluate the entire matrix of phenomenological coefficients, as a function of composition, in order to describe diffusion locally. Further, in order to determine this matrix experimentally, it is necessary to produce diffusion couples that have different sequences of compositions; the matrix may be evaluated only at points where these "composition paths" cross.* Finally, and perhaps most

Jan 1, 1969

By A. H. Tousley

Current problems in the cement industry are discussed and suggestions for solving them by modernization are made. Cement facility modernization is discussed in considerable detail with examples illustrating before and after conditions. Itemized are the improvements realized in better working conditions, better efficiency, higher production, lower costs, and better community relations. These improvements are related to the overall profitability of the particular plant or facility.

Jan 1, 1972

By J. R. Morison, M. P. O’Brein, J. W. Johnson, S. A. Schaaf

The force exerted by unbroken surface waves on a cylindrical object, such as a pile, which extends from the bottom upward above the wave crest, is made up of two components, namely: 1. A drag force proportional to the square of the velocity which may be represented by a drag coefficient having substantially the same value as for steady flow, and 2. A virtual mass force proportional to the horizontal component of the accelerative force exerted on the mass of water displaced by the pile. These relationships follow directly from wave theory and have been confirmed by measurements in the Fluid Mechanics Laboratory of the University of California, Berkeley. The maximum force exerted by breakers or incipient breakers is impulsive in nature, reaching a value much greater than that produced by unbroken waves but enduring for only a short time interval. This impulsive force represents the ultimate development of the accelerative force and is produced by the steep wave front and large horizontal acceleration at the front of a breaker. This impulsive force greatly exceed. the drag force computed from the particle velocities of the breaker. The reader is cautioned that these preliminary results are applicable only to single piles without bracing and are likely to be modified somewhat where multiple piles are driven, one within the influence of the other or where multiple piles are connected by submerged bracing. This paper is essentially a preliminary report submitted at this time because of the current importance of wave forces in the design of offshore structures. An extended series of additional experiments is planned for the near future. Theoretical Relationships For the sake of simplicity of treatment, the theory will be developed from the equations for waves of small amplitude. The horizontal displacement of a water particle is described by the equation 2p cosh — (d + z) H L 2pt X =----------------------sin ----- . , (1) 2 2pD T sinh------ L The horizontal component of the orbital velocity is obtained by differentiation with respect to time as 2p cosh — (d + z) pH L 2pt u = ------------------- cos— .... (2) sinh- L The acceleration of the water particles at any position is obtained by again differentiating with respect to time as 2p cosh — (d + z) 9 u -2vH L 2pt -----=----------------------------sin ----- . . (3) 3 t T2 2pd T sinh------ L where H = wave height — ft L = wave length — ft d = still water depth — ft z = depth below the still water measured negatively downward — ft. T = wave period — sec t = time — sec The force exerted on a differential section, dz, in length is pD2 s u pD 1 dF= [CM (p/4) st + Cn/2 u2] dz • • (4) where D = pile diameter — ft p = water mass density — slugs/ft3 C, = coefficient of mass C,, = coefficient of drag Substituting for a s u/s t arid u2 from Eqs. (3) and (2), the force per unit length at any position z is dF p2 pD H2 &apos; / = — [- fM sin ? ± fD cos2 ? ] . . . (5) dz 2T2 fM D fD 2pt Cm = pA/H:CD = A2;? = T [+ cos2 ? for 0 < ? < p/2 cosh— (d+z) 3p L — < o < 2p Sin L -cos2 ? for p/2 <? <3p/2 The sin 9 term (inertia) i- negative for 0 < 0 < p and positive for p < ? < 2p. Values of A and A&apos; appear in Fig. 1

Jan 1, 1950

By H. F. Kendall, J. H. Ffolliott

MANY papers and reports have been devoted to the geology and ore deposits of the Ducktown district, Tennessee, especially the complete report by W. H. Emmons and F. B. Laney, published as Professional Paper 139, by the U. S. Geological Survey. The present paper discusses the work of the geological organization of the Tennessee Copper Co., which is based on the field work of the above paper and the consulting work of W. H. Emmons. The Ducktown basin lies in the southeastern corner of Tennessee and extends a short distance into Georgia and North Carolina. All productive mines are contained in an area of 15 sq. mi. in the center of this basin, which is an undulating plateau at an elevation of 1650 to 1800 ft. above sea level. It is surrounded by the relatively high mountains of the southern Appalachian region. The rocks are of early Cambrian age. Deposition of the ores probably took place during the latter part of the Paleozoic era. The ore deposits are rudely tabular to lens-shaped bodies of massive sulfide, varying from a few feet to over 200 ft. in width. In general they all strike northeast and dip southeast at angles from 45° to 70°. Locally, where affected by folding and faulting, the variations in dip may be even greater. The lodes usually are parallel at distances of from one-half to one mile measured normal to the strike. The deposits are a replacement of a fairly continuous bed or a series of disconnected limestone lenses, highly folded and somewhat faulted, which probably represent the same stratigraphic horizon.

Jan 1, 1933

By Paul M. Tyler

MARKETWISE the year 1935 was rather a good one for most of the rare and minor metals; as a class they climbed out of the depression much faster than the common metals. The diamond market, too, was better than it had been for years, attributable only in part to investment buying, as there was a genuine pick-up in consumer demand. Wars and rumors of war tended to speed up purchases of certain metals, but consumption for peaceful purposes was the principal factor. Significant was the important role played by new industrial uses. New discoveries during the year were disappointingly few, considering the broad extent of this research frontier. Scientific developments were far from being at a stand-still, of course, but the dominant note was the cashing in on research consummated in former years. With even a moderate upturn in general business a surprising number of laboratory ideas donned overalls and found jobs in industry.

Jan 1, 1936

By C. J. Bauer

WHEN the pipe lines from the Middle East to the Mediterranean are completed, the Middle East supplies will relieve the strain on Western Hemisphere petroleum resources, part of which are now shipped for Eastern Hemisphere use. A sketch of the world petroleum situation as it appears today and in the immediate future will help in understanding the future place of Middle East oil supplies. Anticipated 1951 world demand is slightly under four billion barrels. To meet this requirement, crude output and refinery runs throughout the world (including Russia) must be increased about two million barrels per day above the average of 1947. This increment, together with pipe lines, tankers, and other facilities, will require in excess of ten billion dollars of new capital in the next four years. We are, therefore, looking forward to the greatest expansion program in the history of the industry.

Jan 1, 1948

By R. M. Goldhoff, H. J. Beattie

The high-temperature properties of a 1 Cr-Mo-V forging steel are described. A series of controlled heat treatments was designed to delineate the effects of austenitizing and tempering treatments, temile strength, and grain size on such properties. Studies indicate that the mechanical properties and their varlations under creep can be described by the initial metallurgical structures and their changes droPirzg exposure, particulavly the carbide reactions. Such structures are described and correlated with the mechanical properties. FOR many years the large steam turbine industry has relied on the 1 Cr-Mo-V type forging steel for critical applications. Because of its adequate heat resistance and relative economy, it is currently in use in the temperature range up to about 1050" to 1075°F. Attempts to understand the large property variations attainable in this steel involve the structural modifications due to the wide latitude in its heat treatment. The heat treatment essentially involves a two-step process which includes solution-ing of carbides in the austenite range followed by a suitable tempering treatment below the critical to adjust the level of properties. The latter step is referred to as "secondary hardening" and is basically an ordinary aging reaction involving carbides. In the commercial heat treatment of large components of such steel, homogenizing and stress-relief anneals may be included and have some importance in determining subsequent properties. Several studies of the engineering properties of this steel as a function of transformation micro-structure have been reported.1 3 However, in this steel the carbide reactions, which are a function of composition and heat treatment, appear to be the property-controlling factor rather than the micro-structure defined as a transformation product. Thus, the tempering resistance of this type of alloy steel is mainly a function of the size and distribution of alloy carbides.4 However, it is also necessary to consider the stability of the microstructure and the effect of dynamic carbide reactions on subsequent properties. It is the purpose of this paper to show the interdependence of properties and corresponding structures, particularly carbide reactions, developed for a limited set of controlled heat-treatment conditions applied to 1 Cr-Mo-V steel. MATERIALS AND PROCEDURE The material for this work came from a large production forging whose chemical composition is shown in Table I. The property data accumulated on this steel as a function of heat treatment were room-temperature tensile and smooth- and notch-bar creep rupture at 1050°F (notch geometry: shank diameter = 0.357 in., depth = 50 pct, radius = 0.005 in.). To achieve controlled structural variations the temperature and time of both austenitizing and tempering were varied in a manner to produce a series of eight steels each at one of two grain sizes and one of two hardness levels in proper combination for valid comparisons. This will be clear upon examination of Table I. Structural studies involved the use of optical and electron microscopy as well as X-ray and selected-area electron diffraction. To reveal the nature of carbide precipitations, electrolytic extraction techniques were used with subsequent analysis of the residue by X-ray diffraction. Weight losses of the steel specimens during electrolysis were measured and successive chemical fractionations of the residues were applied and checked by X-ray examination. The details of fine structural distributions, morphologies, and crystallography of the precipitates as well as dislocation distributions were investigated by examining in the electron microscope three common types of preparation. a) Relief Replicas. Mechanically polished sections were etched in 2 pct nital, replicated with a nitrocellulose film, which was shadowed by chromium vapor deposited at a glancing angle of 20 deg. b) Extraction Replicas. A thin film of carbon was vapor-deposited on the polished and etched surface. The carbon films were then etched off and gathered on electron-microscope supporting grids. The carbides left imbedded in the carbon replica in their original distribution were then examined crystallo-graphically by selected-area electron diffraction. c) Thin Films. Specimens were mechanically ground and polished down to a thickness of 0.001 to 0.003 in. Final thinning was done electrolytically in a "chrome-acetic" electrolyte. When holes began to appear in the foil, the voltage was interrupted and applied in several 1-sec bursts. Sections of the foil between holes were thin enough to pass a 100-kv electron beam that carries an image.

Jan 1, 1965

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.&apos; At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir&apos;s work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.&apos; Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By P. S. Kotval, O. H. Nestor

Stacking fault energy measurements of nickel-base alloys have been mainly confined to binary and ternary systems. In this paper, the stacking fault energy has been measured by the rolling texture method in a series of ten alloys which comprise successive additions of Cr, Mo, Fe, and C to pure nickel, eventually resulting in an alloy of the composition of Hastelloy alloy X. The alloys studied here are single-phase, solid solutions with the exception of two alloys in which some undissolved particles of "primary" carbide have been retained. It is found that successive additions of chromium, molybdenum, and iron all lower the stacking fault energy, with iron having only a minor effect. The stacking fault energy is found to increase when carbon is added in solid solution. The results from the rolling texture measurements are correlated with thin foil observations of dislocation substructures in these alloys. In a recent paper&apos; it was pointed out that the dislocation substructure of various superalloy matrices could be classified into three broad categories based on &apos;high&apos;, &apos;medium&apos;, and &apos;low&apos; stacking fault energy. It has also been demonstrated2 that the dislocation substructure in each of these categories has a well defined role in the nucleation of strengthening precipitates which is different from the role played by the dislocation substructure in other categories. Thus, it becomes desirable to understand the influence of various solute elements on the stacking fault energy and hence on the dislocation substructure of the matrix, before any further development of superalloys by mi-crostructural predesign can be undertaken. Recently, Beeston and France have studied the influence of increasing solute additions on the stacking fault energy of a series of binary nickel-base alloys relevant to the Nimonic series using the rolling texture method, and have then estimated the effect of a given alloy addition in five commercial Nimonic alloys. However, comparison with stacking fault energy data from other investigations&apos;&apos;5 suggests that the influence of a given solute element in a nickel-base binary system is not necessarily the same in a ternary or more complex superalloy system. Accordingly, the present work was undertaken to study the effect of successive addition of solute elements to pure nickel, the final composition being the nominal composition of Hastelloy X. The rolling texture method of stacking fault energy measurement was used since it can be used for the whole range of stacking fault energy values and does not have the disadvantage of, say, the Node method which is only applicable to low values of stacking fault energy. In addition, the rolling texture method provides a means of determining the stacking fault energy which is statistically more significant than that provided by other methods. EXPERIMENTAL TECHNIQUES Button heats of alloys of the compositions shown in Table I were prepared. Each button was remelted not less than four times. After a slight deformation (approximately 5 pct) all alloys were homogenized at 2200°F except alloys, H . I, and J. Alloys H and I were solution heat treated at 2150°F and alloy J at 2282OF. The buttons were cold worked by rolling, using "end-to-end" passes and intermediate anneals at the homogenization temperatures mentioned above. After each annealing treatment the samples were rapidly water quenched to avoid any precipitation. In alloys F and I, however, a few particles of "primary" carbides were retained even after the homogenization treatments at the temperatures mentioned above. Part of the solution heat treated material was cold worked to 0.04-in.-thick sheet and the penultimate reduction was -50 pct of deformation as recommended by Dillamore et al. All annealing was carried out in vacuo within sealed quartz capsules. Some of the material from each alloy was rolled down further to 0.004 in. strip for thin foil transmission electron microscopy specimens. Specimens of this strip were annealed at the homogenization temperature for 1 hr and then strained 7 pct by rolling at room temperature. Thin foils were prepared from the strip specimens by the &apos;window" technique using an Ethanol-Perchloric acid electrolyte at 32°F and a voltage of 22 v. Stainless steel cathodes were employed. All transmission electron microscopy was performed in a JEM-7 electron microscope using an accelerating voltage of 100 kv. Specimens from the 0.04 in. sheet which had been rolled -60 pct in the final pass were electropolished to remove the surface layers to a depth of approximately 0.002 in. Rolling texture pole figures for all the alloys were determined using a Schulz ring and nickel filtered CuKa radiation at 50 kv and 20 ma. The texture parameter Io/(lo + I,,) (where Io is the

Jan 1, 1970

By K. G. Davis

Dilute alloys of silver and of thallium in tin have been solidijzed unidirectionally under controlled conditions, to study the segregation associated with a cellular interface under conditions where both thermal and solute convection are present. Autoradiography and radioactive tracer counting techniques were combined with electron-probe microanalysis to study both macro- and microsegregation. It was found that, for concentrations giving only small amounts of constitutional supercooling, cell formation had little effect on the macroscopic distribution of solute along the specimen. At higher concentrations the effective distribution coefficient was higher than that expected for a smooth interface. Node spacing was independent of initial solute content at lower concentrations, becoming greater as keff increased. Silver content at the segregation nodes of silver in tin alloys was independent of initial concentration and considerably in excess of the eutectic composition. SINCE the investigation of cell formation at advancing solid-liquid interfaces by Rutter and Chalmers,&apos; a large volume of work has been dedicated to the determination of solidification conditions under which a planar interface will break down into cellular form. Early experiments were explained satisfactorily by the concept of constitutional supercooling,2 but, due to poor measurement of temperature gradients in the liquid, lack of accurate data on liquid diffusion and equilibrium distribution coefficients, and uncertainty about the effects of thermal and solute convection, these experiments cannot be used as proof for the theory. More recent work, however, has shown that under conditions where convection is eliminated or can be ignored good correlation is observed.3,4 Investigations into segregation at cell caps5 and at cell nodes6-&apos;&apos; have been made, but no measurements appear to have been done on the overall, macroscopic segregation down a unidirectionally solidified rod of material which has solidified with a cellular substructure. This has practical importance in casting, where regions of material with cellular substructure are often encountered, and also in zone refining where the thermal conditions necessary for a planar interface are unattainable. Further, as will be shown, the macroscopic segregation can give information on the following question. Granted that a cellular solid-liquid interface develops from a planar one when the conditions for constitutional supercooling are exceeded, how much supercooling is present after the cells have formed? EXPERIMENTAL PROCEDURE AND RESULTS Specimen Preparation. Specimens 25 cm long with a square cross section 0.6 by 0.6 cm were grown in graphite boats by solidification from one end. Alloy compositions are given in Table I. Two specimens of each composition were grown. The tin was 5-9 grade and the silver and thallium both 4-9 grade. Ag110 and Tl204 were used as tracers. Each composition had the same quantity of tracer so that auto radiographs of specimens containing different concentrations of the same element could be easily compared. Thermocouples inserted through the lid of the boat into a dummy specimen showed that, over the first 10 cm of growth, thermal conditions were quite steady, with a rate of interface advance of 5.8 cm per hr and a temperature gradient in the melt ahead of the interface of 3.0°C per cm. The specimens were seeded from tin crystals of a common orientation to eliminate orientation effects. Dilution of the specimen by seed material was minimized by the provision of a narrow neck between specimen and seed crystal. Macrosegregation. After growth, the specimens were sectioned with a spark cutter. The rods of silver alloy were cut into 1-cm lengths and analyzed for Ag110 using a y -ray counter with fixed geometry. The specimens containing thallium were cut into 2-cm lengths and analyzed for T1 204 by taking 13 counts from each end of the cut lengths through an aperture in lead sheet approximately 0.4 cm square. The results are summarized in Figs. 1 and 2. To find the effective distribution coefficient for the silver in tin alloys under smooth interface conditions, the region of substructure at the bottom surface of one of the 10 ppm specimens, see Fig. 3, was removed by spark machining before counting. Autoradiography. For both alloy systems the samples were polished on sections taken alternately parallel and perpendicular to the growth direction, and autoradiographed by placing the polished surfaces in contact with Kodak "Process Ortho" film. Figs. 3 and 4 show the structures revealed. The alloy containing 10 ppm Ag showed substructure only after a few centimeters of growth, and then substructure was limited to a narrow layer at the base. The "speckled" substructure reported previously in this system4 is here clearly seen to be an intermediate stage between planar and cellular interface conditions. The other samples show a remarkable similarity considering

Jan 1, 1969

By N. A. Gokcen, John Chipman

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

Jan 1, 1953

By J. O. Brittain, E. P. Lautenschlager, D. A. Kiewit

Compression tests were run in the temperature range of 700° to 900°C ox 0&apos; phase NiAl intermetal-lic alloys of several grain sizes. At these temperatures the minimum strengths were observed at the stoichiometric composition. While significant increases in strength occurved in both the low-nickel (vacancy) and high-nickel (substitutional) regions, the highest strengths were found in the high-nickel region. During deformation serrated flow was sometimes observed in the low-nickel alloys. After deformation transgranular cvacking and deformation striations were observed in all compositions tested. AS part of a general investigation of the properties of NiAl inter metallic compounds, a preliminary study of the role of point defects upon plasticity was made by high-temperature compression tests on ß&apos; NiAl specimens of several grain sizes and compositions. ß&apos; NiAl is an intermetallic compound having a CsCl structure and a rather wide range of composition from A1-45 at. pct to 60 at. pct Ni.1 According to Bradley and Taylor2 and to cooper,&apos; it possesses a defect lattice in which departures from stoichiometry in the direction of decreased nickel content lead to the presence of vacant nickel sites (although Cooper&apos;s work indicates that a small amount of substitution also occurs) whereas departures on the high-nickel side lead to substitution of nickel on aluminum sites. NiAl forms congru-ently from the melt at approximately 1650°C,1 and thus has a higher melting point than either of its component elements. Up to this time, although this and other high-melting intermetallic compounds have been suggested for elevated-temperature usage,4 only the hardness4 and a few tensile-strength measurements5 have been reported for NiAl at high temperatures. In the present investigation the effects of composition upon the compressive-strength properties in a range of 700° to 900°C have been measured for NiAl of several grain sizes. EXPERIMENTAL PROCEDURES The alloys were made as described elsewhere6 from an A1-46.8 at. pct Ni master alloy furnished by the International Nickel Co. with additions of high-purity nickel and aluminum. The charges were vacuum-induction-melted in A12O3 crucibles with small amounts of helium added to the atmosphere to suppress vaporization. They were cooled slowly from the melting temperature to achieve uniform grain size. In order to refine the as-grown grain size a special rolling technique was developed. Alloys were packed into 0.10-in. wall-type 302 stainless-steel tubes which were partially filled with magnesium oxide to prevent bonding between the alloy and the steel jacket. The ends of the tubes were closed by hot forging, and the packets were then hot-rolled. The alloys with greater than 50 at. pct Ni were rolled at 1100°C, but it was found necessary to increase the temperature to 1350° C before alloys with less than 50 at. pct Ni would roll without cracking. With these temperatures, reductions as high as 48 pct were achieved in a single pass. The rolled alloys will hereafter be referred to as "fine grained" whereas the as-grown material will be designated "coarse-grained&apos;&apos;. The compression specimens were made by cutting square cross-sectional pieces, approximately 3/16 by 3/16 by 1/2 in., with a water-cooled diamond cut-off wheel from the as-grown or the rolled alloys. Specimens were ground to their final dimensions by polishing through 3/0 grit silicon carbide papers. The final shape was a rectangular parallelepiped of square cross section having a height-to-width ratio of 3:1. Compression testing was carried out in a compression rig of our own design mounted on an In-stron Floor Model. The specimen chamber could be heated to 1000°C and was controlled within ±2°C. The compression rig was enclosed within a bell jar and was maintained at a 50 µ of mercury vacuum throughout the duration of the test. The test cham -ber was heated from room to test temperature within 15 min. Specimens were then held at the test temperature 30 min prior to testing. Previous experiments indicated that no grain growth would occur within this time. An Instron Variable Crosshead speed unit was used to adjust for small variations in specimen lengths in order to have a constant initial strain rate, €, for all specimens of a group. For the fine-grained specimens the strain rate was changed rapidly at constant temperature by a factor of 10 with the speed lever on the Instron. For a given € the compression data was analyzed in terms of true plastic strain (E) and true compressive stress (0).

Jan 1, 1965

By R. J. Reynik

A semiempirial small flunctation theory of diff- sion in liquids is presented, which employs a fluctuation energy assumed quadratic for a small atomic or molecular displacement and Einstein&apos;s random-iralh model. The resulting diffusion equation is given by In these equations. D is the diffusivity, is the average liquid shite coordination number (at interatomic distance d. cm. T is the absolute temperature, xu. em, is (the diffusive displacement. K, is the quadratic fluctuation energy force constant, and rg, cm, are the radii oj diffusing atoms A and B, respectively. The quantities Xn and K are calculated from the computer-filled values of the slope and intercept. respectively. The radius of self-diffusing atom or radii and of diffusing atoms A and B are eta United and compared with values reported in the literature.. The predicted linear variation of diffusivity with. It tempera lure htm been observed in approximately thirty-iire metallic liquid systems, and in over seventy-fiee other liquid systems, including the organic .alcohols, liquified inert gases, and the molten salts, ALTHOUGH the average density within a macroscopic volume element of liquid is constant for fixed total number of atoms. pressure. and temperature, there exist microscopic: density fluctuations within the respective volume element. As such the microscopic volume available to an atom and its Z first nearest neighbors at any instant of time fluctuates above and below the average volume available to these atoms. If one assumes that liquid state atoms vibrate as in a solid. and further postulates that the mean position of any atom in the liquid state is not stationary. but shifts during every .vibration a distance 0 5 j 5 xo. then every atom in the liquid state continuously undergoes diffusive displacements which vary in the range 0 5 j 5 ro. Mathematically. for a binary liquid system consisting of atcrms A and B. the maximum diffusive displacement. .YO, is defined by the equation: where d is the average liquid state interatomic distance at specified liquid state coordination number Z. and v~ \ and vg are the effective radii of diffusing atoms A and B: respectively. For self-diffusion. r^ equals rg , and Eq. [I.] reduces to: It is interesting to note that Eq. [l] or [2] can be used to compute the radii of the diffusing atoms, provided one had an experimental evaluation of xo. As such. the computed radii could be compared with metallic or crystallographic ionic radii to ascerlain the electronic character of the diffusing atoms. Thus it is proposed that in the liquid state the n~otion of an atom relative to its original equilibrium position of oscillation represents the thermal vibration of any atom and its Z first nearest neighbors. while the small and variable displacements. 0 5 1 5 xc,. of the centers of oscillation represent the complex diffusive motions of the atoms at constant temperature and pressure. This is consistent with data obtained from slow neutron scattering by liquids1 &apos; and resembles an itinerant oscillator model of the liquid state.&apos;" It is further postulated that the atomic displacements characterizing the liquid state diffusion process are essentially a random-walk process. As such. it nlay be described by Einstein&apos;s equation:&apos; where D is the diffusivity. sq cm sec-&apos;. j2 is the mean square value of the diffusive displacement. and i> is the frequency of density fluctuations giving rise to diffusion. FORMULATION OF DIFFUSION EQUATION The effective spherical volume occupied by an atom, as a consequence of a microscopic density fluctuation which enlarges the volume available to any atom, exceeds its average liquid state atomic volume by an amount: where AV is the enlarged spherical volume, v is the radius of the diffusing atom. and j is the elementary displacement distance from the original center of oscillation of the vibrating atom to a new center of oscillation position. For small atomic displacements. where c is a constant whose value depends upon the assumed geometry of the enlarged volume. For a spherical increase in volume, c equals 4nr2. Following the treatment of Furthl&apos; and ~walin." assuming the enlarged volu~nes AL7 for the diffusing atoms are distributed in a continuunl. the probability of finding a fluctuation in the size range 0 5 j 5 xo defined by Where c includes the geometric constant cl and Eij) is the fluctuation energy causing the volume change. But the proposed model assumes all the Z first nearest-neighbor atoms are centers of oscillation. and hence the probability that any of these atoms is adjacent to a fluctuation of magnitude 05j5xo is unity. Thus:

Jan 1, 1970

By D. Mills, G. B. Craig

ZIRCONIUM has been float-zone-refined in an electron-beam furnace and the redistribution of oxygen, iron, and tungsten has been measured. The iodide zirconium used in the present experiments initially contained both oxygen and iron in the range 100 to 200 ppm by weight, and tungsten in amounts less than 10 ppm. Float-zone refining of zirconium, using induction heating, has previously been attempted by Kneip and Betterton1 and Langeron.2 Kneip and Betterton were primarily interested in the removal of iron and nickel. They achieved some purification, with respect to both these elements, in material given up to six passes at 150 mm per hr under an argon atmosphere. Langeron reported purification for a large number of elements after four completed passes in a static vacuum system operating at pressures less than 10-6 mm of Hg and with rates of zone travel between 30 and 40 mm per hr. He did not report oxygen concentrations, but stated that there was inverse segregation of this element. westlake5 has also used a minimum of four zone passes to remove iron from zirconium. No rates or conditions were given. Belk6 has shown that tungsten contamination can occur during electron-beam melting. He reported an increase from 0.01 to 0.05 pct by weight tungsten in molybdenum after four complete zone passes. The vacuum system for the electron-beam unit used in the present investigation consisted of a single-stage rotary pump backing a liquid-air-trapped oil-diffusion pump. A pressure of less than 10-8 mm of Hg was obtained with Dow-Corning 705 fluid in the diffusion pump. In order to avoid contamination of the zirconium by evaporation from the tungsten filament, a special focusing cage4 was employed. Three rates of zone travel, 114, 38, and 4 mm per hr, were investigated, with the liquid zone moving from the bottom to the top of the bar. The bars used were 3 mm diam and the total melted length was 130 mm. Oxygen was analyzed by neutron-activation analysis using a neutron flux of 10&apos; neutrons per sq cm per sec to form the isotope N16 by the 016 (n,p) N16 reaction. The standard deviation is quoted for each oxygen determination. The iron and tungsten analyses were performed spectrographically, and the precision is estimated to be ±6 pct. Analyses for tungsten were all below the detectable limit of 10 ppm, confirming the protection given by the focusing cage. No significant redistribution of oxygen was found at the two higher rates of zone travel. The redistribution of oxygen and iron obtained after five passes at a rate of zone travel of 4 mm per hr (1.1 x 10-4 cm per sec) is recorded in Tables I and 11. Burris, Stockman, and Dillon3 have estimated the distribution of solutes during multipass zone refining. Using their curves for an effective distribution coefficient of Keff = 1.5 and 2 for oxygen and Keff = 0.3 for iron, the expected concentrations were estimated for the present material. These are shown in Tables I and 11, along with the experimentally measured values. The calculated concentrations are based on a molten-zone length of 10 pct of the total melted length, whereas in the present experiments the molten zone was approximately 5 pct of the total melted length. The effect of zone length on solute redistribution is most pronounced after a large number of zone passes. Comparison with Pfann&apos;s published data8 for solute redistribution for various Keff&apos;s and zone lengths indicates only small differences at low numbers of completed zone passes. It is evident that the expected distribution has not been realized in the case of iron. Scrapings of material deposited on the inner surfaces of the electron-focusing cage were found to be magnetic. It is, therefore, concluded that redistribution of iron is masked by evaporation. Deposition of iron inside the focusing cage was observed at all rates of zone travel. The results of the investigation may be summarized as follows: 1) Segregation of oxygen is typical for a solute with a distribution coefficient, Keff > 1. 2) No redistribution of oxygen takes place at high rates of zone travel. 3) The distribution coefficient for oxygen lies between 1.5 and 2.0. 4) Purification with respect to iron occurs mainly by evaporation. 5) The focusing cage is effective in preventing tungsten contamination.

Jan 1, 1967

By A. Steiner, K. L. Komarek

Activities of aluminum in solid Ni-A1 alloys have been determined between 20 and 60 at. pet Al and 1200" and 1400°K by an isopiestic method in which nickel specimens, heated in a temperature gradient, are equilibrated with aluminum vabor in a closed all-alumina system. The activity of aluminum shows a strong negative deviation from Raoult&apos;s law at low concentrations but increases by three orders of magnitude within the ß(NiAl) phase. The partial molar enthalpy and entropy of mixing are negative. Using Wagner and Schottky&apos;s theory of ordered compounds, a degree of disorder of 4 x 10 -4 for NiAl and 1.25 X 10-2 for FeAl has been calculated THE Ni-A1 system has been studied by a great number of investigators, and the results, as far as the phase diagram is concerned, have been compiled by Hansen.1 The phase boundaries from 0 to 50 at. pet Ni are well-established. At higher nickel contents the boundaries are still in dispute and an additional phase, A12Ni3, has been reported.&apos; The phase diagram is dominated by a very stable high-melting compound, NiA1, with a relatively wide range of homogeneity. Heats of formation of solid alloys have been determined calorimetrically by Oelsen and Middel3 from 20 to 95 at. pet Ni and by Kubaschewski4 from 25 to 80 at. pet Ni. According to the most recent compilation5 no other thermodynamic investigations have been reported for the Ni-A1 system. Due to the corrosive nature and the low vapor pressure of aluminum, a method has been employed for determining activities of aluminum which was previously developed for the Fe-A1 system.= Nickel specimens, heated in a closed evacuated alumina system in a temperature gradient, were equilibrated with aluminum vapor from a source within the system kept at constant temperature. After complete equilibration the specimens were analyzed and activities calculated from the known vapor pressure of aluminum. APPARATUS AND EXPERIMENTAL PROCEDURE Materials. The nickel specimens were made from wafers of electrolytic nickel (International Nickel Corp.) of 99.99 pet purity which were rolled to a 0.001-in.-thick foil by Driver-Harris Co. and to a 0.005-in.-thick sheet in our laboratory. The aluminum (Aluminum Corp. of America) had a purity of 99.99+ pct. The alumina tubes and crucibles were made of impervious recrystallized alumina with an alumina content of 99.7 pet (Triangle RR, Mor-ganite Inc.). Experimental Procedure. Annular specimens were punched from the sheet, the punching burrs removed, and the specimens degreased in carbon tetrachloride and acetone and weighed on a micro-balance to within an accuracy of ±0.01 mg. The specimens were positioned with alumina spacers along an alumina tube, and the positions measured. Aluminum metal was machined into cylindrical shape, and placed into an alumina crucible. The tube with the specimens was then inserted into a hole drilled into the aluminum metal. An alumina tube with its closed end at the top was slipped over the specimens so that its lower end fitted snugly into the alumina crucible. The assembled reaction tube was inserted into a mullite tube with a water-cooled brass head which had an opening for a quartz thermocouple protection tube and a metal-to-glass connection to a conventional vacuum system. A Pt-Pt 10 pet Rh thermocouple could be raised and lowered in the quartz tube which was placed along the outside of the alumina reaction tube. The mullite tube was heated by two separately controlled resistance-tube furnaces so that in the experimental temperature range an over-all temperature gradient of approximately 150o to 250°C could be imposed on the reaction tube. The position of the mullite tube was adjusted so that the surface of the aluminum metal was always at the temperature minimum. The reaction tube was thoroughly evacuated before and during slowly heating the assembly up to the melting point of aluminum. A pressure of less than 2 µ (Hg) was maintained during an experiment. Once the aluminum had melted, it isolated the contents of the alumina tube from the surroundings. Several times during an experiment the temperature gradient was carefully measured. An experiment lasted from 3 to 6 weeks and it was terminated by air cooling the evacuated mullite tube. For further details of the experimental procedure the paper on the Fe-A1 system6 should be consulted.

Jan 1, 1964

By D. L. Kelley

High-viscosity water injection has been proposed for use in reservoirs containing high-viscosity crude oils. Previous publications have largely ignored the possible effects of the connate water on the proposed process. This paper describes experimental work which indicates that the connate water will be forced ahead of the injected water to form a bank of low-viscosity water. This decreases the oil recovery which would be expected if such a bank were not formed. These effects are shown for a range of fluid mobilities and connate-water saturations for a five-spot injection system. In general, oil recoveries using viscous water are significantly greater than for untreated water even though they are less than would be expected if no connate water bank were formed. INTRODUCTION The effect of mobility ratio on the oil recovery of wa-terfloods has been known for many years. Muskat first pointed out that the fluid mobilities (k/µ) in the oil and water regions would affect the performance of the water-flood, and he estimated the general effect of these variables.&apos; Since this early work, studies of the effect of mobility ratio on secondary recovery have been reported where mathematical,&apos; potentiometric3 and scaled flow models&apos; were used. These studies have shown that a reduction in the mobility ratio between the oil and the displacing fluid would cause additional oil recovery when water-flooding reservoirs containing viscous crude oils. Studies reported by Pye- nd Sandiford 8 have indicated that chemicals to increase injection water viscosity are now available and can be used to reduce the over-all mobility ratio of a waterflood. Where mobility ratios are controlled by the injection of viscous fluids, the connate water of the reservoir can play an important part in the displacement of the reservoir oil. The purpose of this study was to determine the effect of the connate-water saturation in waterfloods where viscous waters are used for injection. DISPLACEMENT OF THE CONNATE WATER Russell, Morgan and Muskat7 were the first to recognize the mobility of connate waters in waterflooding. They conducted waterfloods on oil-saturated cores containing 20 and 35 per cent irreducible water saturations, and found that from 80 to 90 per cent of the "irreducible" water was produced after only one pore volume of water was injected. However, their experiments were conducted at rates of flow significantly higher than those ordinarily occurring in waterfloods. Also, the cores were only from 4.0 to 8.5 cm long. Brown 4 studied a 100-cm linear sand pack which had been prepared to contain connate water and oil. He used 140- and 1.8-cp oils with injection water of essentially the same viscosity as the connate water. He found that all of the connate water was displaced by the injection water in both cases. However, the injection volumes required for complete displacement of the connate water were considerably higher in the case of the more viscous oil. To verify the results of the foregoing experiment, a 10-ft-long linear model was constructed by packing 250-300 mesh sand in a 1/2-in. diameter nylon tube. The model was evacuated, saturated with a brine of 1-cp viscosity, and flooded with a 41-cp mineral oil to the irreducible water saturation of 10.9 per cent. The model was then waterflooded by the injection of a water solution which had an apparent viscosity of 42.6 cp. The solution consisted of 0.5 per cent methylcellulose in distilled water. The viscosities of the oil and connate water were measured with an Ostwald viscosimeter. The viscosity of the polymer solution was calculated by Darcy&apos;s law using pressures measured during actual flow conditions. The ratio of the mobility in the oil region to the mobility in the inject ion-water region was approximately 0.32. The mobility ratio of the oil region to the connate-water bank was approximately 14. The mobility ratio between the connate-water bank and the injection water region was 0.024. Approximately 84.5 per cent of the recoverable oil was produced before water breakthrough. Immediately following breakthrough, oil and connate water were produced at an increasing water-oil ratio until the viscous injection water broke through. At viscous-water breakthrough, 96 per cent of the original connate water had been produced. After breakthrough of the viscous water, there was no additional production of connate water or oil. The near-

Jan 1, 1967

By A. E. Bibb, J. R. Fascia

Single-crystal wafers of zirconium have been exposed to 680°F neutral water. The single crystals were of known orientation and weight-gain data as a function of crystal orientation were obtained. These data show that all the crystal faces studied obeyed a cubic rate law out to the time of transition whereupon the crystals corroded at an approximately linear rate. The time to transition varied from 114 days for (1074) crystals to about 325 days for the (2130) faces. The epitaxial relationship be-tween metal and monoclinic oxide was found to be (0001) H (111) and [1120] 11 [101]. A black tight adherent oxide layer was formed on the crystals in the pretransition range. This black oxide was found to be monocrystalline. The white corrosion product produced after transition was found to be polycrys-talline but highly oriented. X-ray line-broadening studies found that the black oxide was a highly strained structure whereas the white oxide was relatively strain-free. These results indicate a strain-induced re crystallization or fragmentation accompanies the change from protective black oxide to nonprotective white oxide. ZIRCONIUM alloys have been used quite extensively in high-temperature aqueous environments. Alloy additions can be made to commercial sponge zirconium which enhance the corrosion resistance of the zirconium in both water and steam media, which raise the tolerance limit for certain impurities detrimental to corrosion resistance, and which reduce the amount of free hydrogen pickup during corrosion. The development of the corrosion-resistant zirconium alloys has been a long and tedious job involving trial and error methods. This technique has been necessary because of a lack of fundamental data and hence understanding of the corrosion mechanisms. The objective of the work described herein was to provide some fundamental data with respect to the aqueous corrosion of zirconium crystals as a function of the orientation of the exposed surfaces. Hg. The zirconium chunk was then cooled to below the transformation temperature (862°C) and reheated to 1200°C for 8 hr. The ultimate size of the zirconium grains increased with the number of cycles. Rapid or even furnace cooling through the transformation temperature produces a considerable amount of substructure which was intolerable in corrosion experiments as it would be in the study of any crystallographically dependent property. It was found that a high-temperature a-phase anneal for approximately 4 days reduced the substructure below the limits detectable by visual or X-ray means. Crystals so produced were carefully cut from the massive zirconium chunk and oriented by standard back-reflection Laue techniques. The crystals were then mounted in a goniometer head and, by using the three degrees of freedom available, slices on the order of 0.015 to 0.020 in. were cut parallel to any desired crystal plane. These slices were then carefully polished on both sides to produce smooth flat faces, pickled to remove about 0.002 in. per face, annealed for 1/2 hr at &apos;750°C in a vacuum of approximately 10"5 mm Hg, flash pickled, and checked for orientation. The pickling solution was 45-45-10 vol pct HN0,-H20-HF and continuous agitation was provided to eliminate pitting of the slices. Any slice that was not within 2 deg of the desired orientation was discarded, and any evidence of substructure as indicated by the Laue spots was also grounds for discarding the sample. Thin slices were used for the corrosion tests because weight gain per area data could be obtained with only a minimum area exposed to the corrosive media that was not of the desired orientation. The thin single-crystal slices were of irregular shape and as a result the areas were determined by placing a crystal inside an inscribed square of known area, enlarging a picture of this assembly about X5, and tracing both the enlarged square and crystal with a planimeter. The zirconium used to produce these single crystals was crystal-bar grade, a typical analysis of which is given in Table I. An oxygen analysis on prepared crystals gave a concentration of 205 ppm. The hydrogen concentrations are believed to be less than 15 ppm due to the dynamic vacuum anneal given each crystal. Typical nitrogen values for zirconium treated in this manner are about 10 to 20 ppm. RESULTS AND DISCUSSION Single-crystal wafers have been exposed to de-oxygenated, deionized water in static autoclaves.

Jan 1, 1964

By R. D. Daniels, T. W. Wood

The tensile properties of columbium and Cb-H alloys containing up to 455 ppm H were studied as a function of temperature and strain rate. Hydrogen, introduced into columbium at elevated temperatures, using a thermal -equilibrium technique, embrittled columbium most severely at about —77°C. This elnbrittle ment occurred even at hydrogen concentrations of an order of 20 ppm. At higher temperatures, the hydrogen tolerance of columbium increased in relation to the increased solubility of hydrogen in tile metal. Below this temperature hydrogen tolerance, as determined by ductility and fracture stress, increased slightly. Strain rate had little effect on the tensile results for cross-head speeds over the range 0.002 to 2.0 in. per min. Strain aging during the tensile test appears to explain the ductility mininmum at —77°C. The apparent increase in hydrogen tolerance at lower temperatures is attributed to the low mobility of hyhogen. Experiments were performed in which samples were prestrained in tension at room temperature and tested to failure at —196°C. Results suggest that hydrogetz segregation to preformed crack nuclei can cause subsequent embrittlement even at temperatures where hydrogen mobility is too low to cause embrittlement in a normal tensile test. COLUMBIUM is an example of the class of bcc metals with ductile-brittle transition temperatures sensitive to the presence of interstitial atom contaminants. Hydrogen is one of these embrittling contaminants. The embrittling effect of hydrogen is less potent, perhaps, in columbium than in some of the other bcc refractory metals, but it is still a problem of both theoretical and practical interest. Unlike hydrogen in iron and steels, hydrogen in columbium is exothermically rather than endo-thermically occluded. The embrittlement process in exothermic systems has not been studied as extensively as that in endothermic systems, especially at hydrogen concentrations below the limit of solubility. The purpose of this investigation was to evaluate the embrittlement process in initially pure columbium as a function of hydrogen content, temperature, and strain rate. The Cb-H phase diagram, according to Albrecht et al.,1 is shown in Fig. 1. Columbium reacts exothermically with hydrogen producing a solid solution at concentrations of less than about 250 ppm (parts per million by weight) H at room temperature. At concentrations above the highly temperature-dependent solvus a second phase is formed. Like many similar hydrogen-metal systems,2 his system exhibits a miscibility gap with respect to hydrogen solution. Albrecht found the critical temperature of the miscibility gap to be about 140°C, the critical concentration to be 0.23 atom fraction hydrogen, and the critical pressure to be 0.01 mm Hg. Above 140°C there is a solid solution of increasing lattice constant extending across the phase diagram. Hydrogen concentrations of particular interest in this investigation were those below the limit of solubility in columbium. At hydrogen concentrations above the limit of solubility, columbium will contain the hydrogen-rich second phase and will be brittle under most testing conditions because the hydride generally precipitates as platelets with coincident matrix lattice strains.1&apos;3 At hydrogen concentrations below the limit of solubility, the tensile behavior of columbium is expected to be more sensitive to the interrelationships between hydrogen concentration and mobility and the testing variables such as temperature and strain rate. Literature references to the hydrogen embrittlement of metals, especially ferrous alloys and titanium alloys, are too voluminous to mention. It is only recently, however, that detailed studies of the hydrogen embrittlement of columbium have been undertaken. Wilcox et a1.4 studied the strain rate and temperature dependences of the low-temperature deformation behavior of fine-grained are-melted columbium (1 ppm H) and the effect of hydrogen content (1,9, and 30 ppm H) on the mechanical behavior of columbium at a series of temperatures for a single strain rate. A strain-aging peak was ob-served at about -50°C which was attributed to the presence of hydrogen in the metal. Eustice and carlson5 studied the effect of hydrogen on the ductility of V-Cb alloys at a series of temperatures over the range -196° to 25°C. Pure columbium was embrittled by 20 ppm H which produced a ductility transition at approximately -70°C. Ingram et al.6 studied the effect of oxygen and hydrogen on the tensile properties of columbium and tantalum. A minimum in the notched-to-unnotched tensile ratio of hydrogenated columbium was obtained at about -75°C, but because of the relatively large hydrogen content employed (200 and 390 ppm) the ductility

Jan 1, 1965

By A. Muan

Liquidus data are presented for mixtures in the ternary system FeO-Fe2O3-SiO2 in equilibrium with a gas phase with O2 pressures ranging from 10-10.9 to 1 atm. Data obtained are combined with previously published data to construct lines of equal 02 pressures and lines of equal CO2/H2 mixing ratios along the liquidus surface. Courses of crystallization of selected mixtures under conditions of constant total composition, constant O2 pressures, and constant CO2/H2 mixing ratios are discussed. PHASE equilibrium studies of silicate systems where iron is one component are complicated by the fact that iron readily occurs in three different states of oxidation: Fe3+, Fe2+, and Fe0. Success or failure in work with iron silicate systems is to a large extent dependent on control of the oxidation state of iron and all investigations therefore must be carried out under carefully controlled atmospheric conditions. Silicate systems containing only strongly electropositive metals (like Na+, Ca2+, Mg", etc.) can, for simplicity, be treated as condensed systems, that is, the gas phase can be neglected and the phase relationships discussed in terms of the phase rule written in the well known simplified form P + F = C + 1. In the case of iron silicate systems, however, the composition of the condensed phases varies with the gas composition, and a complete picture of phase relationships can be obtained only by varying the gas composition over a wide range. In order to understand the phase relationships in the more complicated multicomponent silicate systems with iron oxide as one of the constituents, a knowledge of the ternary system FeO-Fe2O3-SiO2 is essential, since it constitutes a bounding portion of all such systems. It was with this in mind that the present study was undertaken. Previous Work A considerable amount of work has been done on various aspects of the chemistry and metallurgy of systems containing silica and iron oxides. The two bounding binary systems FeO-Fe2O3 and FeO-SiO2" The first attempt to obtain information on phase relationships of iron oxide-SiO, mixtures at different 0, pressures was made by Greig.&apos; Darken" determined the melting points of iron oxide on solid silica under various atmospheric conditions. Darken did not determine experimentally the composition of the melts at liquidus temperatures but discussed very ably the principles involved in applying the phase rule to the system. In a recent study Schuhmann, Powell, and Michal8 determined experimentally the liquidus surface of a portion of the ternary system and combined the new information with data in the literature to construct a phase diagram. Their method was briefly as follows: Homogeneous mixtures with various contents of SiO2, FeO, and Fe2O3 were made up by melting together stock mixtures in various proportions. Samples of the homogeneous mixtures, the compositions of which were determined by chemical analysis, were then heated in platinum crucibles in an inert atmosphere until equilibrium among the condensed phases was achieved. The samples were quenched to room temperature and the phases present determined by microscopic examination. Assuming that no change in composition takes place during the equilibration run in inert atmosphere, the liquidus surface can be determined, but no information is obtained regarding the partial pressures of 0, of the gas phase in equilibrium with the condensed phases. The author&apos;s method, to be described in the next section, permitted the location of points at the liquidus surface as well as a calculation of the corresponding partial pressures of O2. Experimental Method General Procedure: The standard quenching technique was adapted for a study under controlled variable atmospheric conditions. Premelted mixtures of silica and iron oxides in platinum envelopes were held at constant temperature under chosen atmospheric conditions until equilibrium was reached among solid, liquid, and gas phases. The sample was then quenched to room temperature, the phases present identified, and, for the most significant runs, the composition was determined by chemical analysis. The corresponding partial pressure of 0, was calculated from known equilibrium constants of the gas reactions occuring in the furnace atmosphere. Materials: Starting materials were oxides of commercially highest available purity; cp silicic acid was dehydrated by heating to 1350°C for 6 hr and cp Fe2O3 was dried at 400° C for the same length of time. Samples of 10 g were made up by mixing

Jan 1, 1956

By J. T. Williams

The equilibria in the V-Zr alloy system were investigated by solidus temperature determinations, thermal analysis, dilatometry, electrical resistance measurements, microscopic examination, and X-ray diffraction analysis. There is a eutectic reaction at 1230°C between a compound, V2Zr, and a solid solution containing 10 pct V in ß zirconium. V2Zr decomposes at 1300°C into liquid and a solid solution containing about 10 pct Zr in vanadium. The eutectic composition is probably about 30 pct V. A eutectoid reaction between V2 Zr and a zirconium takes place at 777°C at a very high rate. The eutectoid composition is 5 wt pct V. The limit of solubility of zirconium in vanadium was estimated to be 5 pct at 600°C. No attempt was made to determine the liquidus for the system. THE recent availability of large quantities of high purity zirconium has stimulated the study of zirconium binary systems. The equilibrium diagram for the V-Zr system has received little attention, however. Wallbauml appears to have made the first report concerning the equilibria in these alloys. He reported the existence of a compound, V2Zr, having the MgZn2 ((214) type of structure with a, = 5.277 kX and c° = 8.647 kX. Anderson, Hayes, Roberson, and Kroll2 made a survey of some potentially useful zirconium binary alloys and found that zirconium probably dissolves a small amount of vanadium. They reported the probable existence of a compound between the two elements and suggested that the zirconium-rich solid solution undergoes a eutectic reaction with this compound. Pfeil," in a critical review of the existing information, estimated that the solubility of vanadium in zirconium is less than 4.7 pct and probably less than 1.8 pct. Rostoker and Yamamoto&apos; proposed a partial diagram for the V-Zr system in a survey paper on vanadium binary alloys. Their diagram indicates the compound, V,Zr, a eutectic reaction at 1360°C, a peritectic reaction at 1740°C, and a limit of solubility of zirconium in vanadium of about 3 pct. They obtained no information on the equilibria in the zirconium-rich alloys. In view of the potential utility of the V-Zr alloys and the incomplete knowledge concerning the equilibria in the system, an attempt was made to establish the constitutional diagram. Preparation of the Alloys Raw Materials: The vanadium for making up these alloys came from the Electro Metallurgical Corp. Zirconium came from two sources. In the beginning of the investigation, sponge zirconium from the Bureau of Mines was used in making some of the alloys. Later, iodide metal made at the Westinghouse Atomic Power Development Laboratories became available. This material was used in the preparation of all the dilatometric and resistance specimens and about two-thirds of the solidus temperature specimens. A typical manufacturer&apos;s analysis of the vanadium is shown in Table I. No other analysis of the vanadium was made. The metal contained a dispersed second phase and did not have a sharp melting point. Typical results of spectrographic analysis of the Westinghouse zirconium are shown in Table 11. These data indicate a very high purity. The Bureau of Mines sponge metal was probably less pure but had good ductility. Melting: All of the alloys used in the investigation were made by melting pieces of vanadium and zirconium together in a dc electric arc furnace similar to those of Geach and Summers-Smith, craighead, Simmons, and Eastwood," and others. Melting was done in an atmosphere of helium scavenged of residual air by the preliminary melting of a separate charge of zirconium. Each ingot was turned over and melted at least three more times before removal from the furnace to aid in the attainment of homogeneity. Alloys prepared for use in the investigation are listed with the results of solidus determinations in Table III with the exception of the following compositions upon which no solidus determinations were made: 0.29, 0.54, 4.57, and 5.55 pct V. Analysis: The weight of each ingot made from iodide zirconium was within 0.1 g of the total weight of the initial charge, about 90 g. Since each component of each charge was weighed to the nearest 20 mg for amounts less than 10 g and to the nearest 0.1 g otherwise, the gross composition of an ingot could be calculated accurately. Chemical analysis for the vanadium content of several alloys agreed

Jan 1, 1956