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By P. G. Shewmon

Radioactive MgZA has been used to study the rate of self-diffusion in oriented single crystals of magnesium in the temperature range 468O to 635OC. The diffusion coefficients parallel and perpendicular to the c-axis are: Dl, = 1.0 exp (—32,200IRT) cm2 per sec and Dl = 1.5 exp (—32,500IR T) cm Qer sec. The ratio Dl/Dll was found to vary from 1.13 at 468 to 1.24 at 575 C. Assuming a vacancy mechanism, an explanation of this aniso-tropy of diffusion follows from a consideration of the difference in the saddle points for diffusion in and out of the basal plane. RECENT discovery of radioactive Mg2"'-' has made possible the study of self-diffusion in magnesium. The experimental procedure and the results of a study of diffusion in polycrystalline magnesium have been described in an earlier paper.V he present work is an application of the same techniques to the study of self-diffusion in oriented single crystals of magnesium. In the general diffusion problem the diffusion coefficient is a second order tensor relating the two vectors, the diffusion flux, and the concentration gradient. In a hexagonal lattice, such as magnesium, the complete determination of the diffusion coefficient D as a function of direction in the lattice requires a knowledge of D,, and D,, i.e., the diffusion coefficients parallel and perpendicular to the c-axis, respectively. It can be proven quite generally that in a hexagonal lattice D is independent of direction in the basal plane, and that out of the basal plane it varies with 0, the angle between the c-axis and the direction of diffusion, according to the equation D(B) = D,,cos2B + D,sin2B. [I] The proof of Eq. 1 depends only upon the symmetry elements of the hexagonal lattice and upon the transformation properties of a second order tensor." Therefore, Eq. 1 holds for any mechanism of diffusion and any c/a ratio. Experimental Procedure The experimental procedure used with polycrystalline specimens can be briefly outlined as follows. Radioactive Mg" was produced by bombarding a NaCl crystal with 350 mev protons and was chemically separated from the target as MgO. The Mg" was then vapor deposited on a specially cleaned magnesium specimen by heating the MgO on a tantalum ribbon in a vacuum. During the diffusion treatment, oxidation and vapor loss of the radioactive material were minimized by annealing the samples in pairs with the active faces in contact, each pair being inside a magnesium container, which was in turn surrounded by an argon atmosphere in a sealed Pyrex tube. The distance-activity profiles were obtained by measuring the activity of thin sections cut parallel to the original interface with a lathe. The only technique which was peculiar to this work was the preparation and orientation of the single crystal specimens. The single crystals used in this work were grown by E. C. Burke of the Dow Chemical Co., using a modified Bridgman method, in which the furnace and specimen were stationary while the temperature gradient moved.' In growing these crystals the starting material was distilled magnesium, the crucibles were machined from Acheson electrode graphite, and the furnace atmosphere was tank argon. The crystals were grown from sublimed magnesium with the following analysis: 0.0002 pct Al, 0.0017 pct Fe, 0.0009 pct Mn, 0.0001 pct Ni, 0.0006 pct Pb, and less than 0.01 pct Ca, 0.0001 pct Cu, 0.001 pct Si, 0.001 pct Sn, and 0.02 pct Zn. The two crystals used were roughly lh in. diam and eight in. long. The c-axis made angles of about 7" and 78", respectively, with the specimen axes. If the values of D obtained by the use of these two crystals are taken equal to D,, and D,, respectively, the error introduced by this assumption is less than 1 pct. This can be shown by combining Eq. 1, the identity sin% + cos'8 = 1, and the experimental fact that DJDn in magnesium was always less than 1.25.

Jan 1, 1957

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

Solid-solubility limits at 1500°, l000q and 500°C for carbon, nitrogen, and oxygen in high-purity tantalum were determined by X-ray lattice-parameter methods. For carbon, the solubility was found to be 0.17 at. pct at 1500°C, and less than 0.07 at. pct at 1000°C. A nitrogen solubility of 3.70 at. pct at 1500° C decreases linearly with temperature to 2.75 at. pct at 1000°C, and 1.8 at. pct at 500°C. In the case of oxygen, the solubility was found to be 3.65 at. pct at 1500°C, 2.95 at. pct at 1000°C, and 2.5 at. pct at 500°C. The phases Ta2C, the low-temperature modification of Ta205, and Ta,N of unknown composition but which has a superlattice structure based upon the original bcc tantalum lattice have been identified as the initial precipitates in the respective systems. Metallographic methods were employed to verify the X-ray analyses. The etching behavior of Ta is discussed in terms of lattice i?rzperfections and precipitate phases. The excellent fabricability, high melting point, and nuclear properties of tantalum are responsible for interest in this refractory metal. Data on the solid solubility of the interstitial elements (oxygen, nitrogen, and carbon) in tantalum and on the precipitate phases are somewhat limited. The significant contributions are discussed below. Because the purity of electron-beam melted tantalum (only recently available) is considerably higher than that used in previous studies, the present investigation was initiated. Gebhardt et all-3 have investigated the tantalum-oxygen and tantalum-nitrogen systems with particular reference to the changes in physical properties and to the rates of reaction between these gases and the metal. The solubility of oxygen in tantalum was reported2 to be 3.7 at. pet at 1500°, 2.3 at. pet at 100O°C, and 1.4 at. pct at 750°C. Schonberg4 reported that several oxide phases (Ta40, Ta,O, TaO and Ta,05) exist while X-ray studies by Gebhardtl showed only two oxides, Ta,05 and an unidentified phase which was associated with a platelet-type precipitate. La-gergren and Magneli,' however, questioned the existence of compounds other than the two allotropic modifications of Ta,05 for the tantalum-oxygen system. In the case of nitrogen, the solubility was estab- lished by Gebhardt3 to be of the order of 7 at. pct at 1800°c. The solubility was reported to decrease rapidly with temperature, and, although no limits were established, a precipitate phase was observed by Gebhardt except when the high-nitrogen specimens were cooled very rapidly from the reaction temperature of 1800c. He reported the initial precipitate phase to be a tetragonal distortion of the bcc tantalum lattice while Schonberg6 reported the phase lowest in nitrogen Jo be a cubic super-lattice with a cell size of 10.11 A. Two other nitride phases, Ta,N and TaN, were reported; these appear to be isomor-phous with the carbides of tantalum. The tantalum-carbon system was investigated by Ellinger7 and by Lesser and Braurer. Two compounds, Ta,C and TaC, were reported to exist, each with a range of composition. The solubility of carbon in tantalum was found to be practically nil at all temperatures. Thus, of the interstitial elements which are present in small amounts in high-purity tantalum, carbon might be expected to form precipitates. The present investigation was initiated to obtain additional data on the solid-solubility limits of these interstitials at 1500°, 1000°, and 500' with particular emphasis on the distribution and the identification of the precipitate phases. EXPERIMENTAL WORK AND RESULTS In the present investigations of the solid solubility and of the precipitate phases in the systems tantalum-nitrogen, -oxygen, and -carbon, high-purity tantalum was reacted with high-purity gases, homogenized at 1800°c, and annealed at and quenched from 1500°, 1000,

Jan 1, 1962

By Leo Dana

INTRODUCTION THE object of this paper is to discuss the factors and conditions that affect the observed values of the melting points of refractory materials and to describe practical methods for the determination of these points. While it appeared to be necessary to discuss some of the general properties of silicates and refractories, these subjects have been entered into only in so far as they relate to the melting point and its determination. Refractory materials such as fireclays, firebricks, and minerals generally, may be considered to be composed of compounds of metallic oxides, solid solutions of the oxides, the pure oxides, or mixtures of the three classes together with small amounts of a variety of chemical compounds. The oxides of silica and alumina occur most commonly in refractory materials; in combination with. these, oxides of the alkali earth, the alkali, the iron group, and the rare earth metals are frequently found.

Jan 9, 1919

By G. F. Jenkins

ASBESTOS is a general term embracing the fibrous varieties of a number of minerals. Of these, the hydrous magnesium silicate, chrysotile (H4Mg3Si209), a variety of serpentine, is the most abundant and useful to industry. All other types of asbestos belong to the amphibole group of minerals and are classified as: crocidolite, NaFe(SiO3), FeSiO3; anthophyllite, (MgFe)SiO3; amosite, also a ferromagnesium silicate but with iron content higher than that of anthophyllite; tremolite, CaMg3(SiO3)4; and, actinolite, Ca (MgFe)3(SiO3)4. PROPERTIES The commercial value of asbestos depends largely on the physical property that permits it to be readily separated into fine filaments of high tensile strength and flexibility, which, coupled with the fact that it has the quality of incombustibility of a mineral-in distinction to vegetable and animal fibers-makes it of unique usefulness for many purposes. To some extent, the value depends upon the length of the fiber, although extreme length is neither necessary nor desirable for most purposes. Chrysotile occurs as cross-fiber veins, in which the asbestos fibers are approximately' at right angles to the vein walls, with vein width- or fiber length-seldom exceeding 2 or 3 in.; also as slip-fiber, in which the fibers 'lie in the same plane as the vein or on slippage planes. A cleanly broken vein of cross-fiber has a pearly luster and may range from a deep green or brown color to light shades of yellowish green or cream. When of good quality, the fiber filaments forming the vein may be easily drawn away from their neighbors and exhibit a fine silkiness and pure white color. They may be twisted into a thread and when flexed between thumb and fingers are found to be strong and pliable. Chrysotile withstands comparatively high temperatures without breaking down completely or fusing but begins to lose water of crystalliza-

Jan 1, 1949

By F. R. Cattoir, R. W. Kimball, C. T. Anderson

ONE of the principal impurities in all steels is sulphur. Sulphur-bearing, manganese-free steels exhibit hot shortness. Manganese is added to steel to improve the hot-working properties. If no sulphur were present in steel, it is probable that hot shortness would be nonexistent. This paper is the first of a series to be issued by this Laboratory reporting the measurements of hot forgeability tests and the physical properties of Fe-C alloys to which additions of various alloying elements have been made. The present paper describes the results- obtained by the addition of varying amounts of sulphur to Fe-C alloys. To obtain control over residual elements in the various charges melted in the arc furnace, it was considered advantageous to use sponge iron from one source as the melting stock rather than scrap metal having an unknown history. Small amounts of unwanted alloying elements might be introduced into the charge when scrap was used, thereby influencing the results of the various heats. A sponge iron having a high silica-lime ratio was used. Ore from Sunrise, Wyo., had been reduced to sponge iron and briquetted at the Bureau of Mines sponge-iron plant at Laramie, Wyo. The briquettes were 5 in. in diam and 2 to 3 in. in thickness, and weighed about 10 lb each. The chemical analysis of the sponge iron is as follows: C, 0.67 pct; Mn, 0.10; SiO2, 4.75; CaO, 1.4; P, 0.044; S, 0.72; MgO, 0.4; A12O3, 1.1; total Fe, 87.5; Fe metallic, 79.2; and reduction, 90.5 pct. Where a reducing agent was required, crushed graphite electrodes usually were used. The charcoal available contained 0.20 pct S. An analysis of the available coke showed it to contain 0.70 pct S. Where high sulphur heats were required, elemental sulphur additions were made to the ladle. Limestone of good quality was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2, 3.0; and P2O5, 0.014. Melting Procedure Sponge iron was melted to produce metal stock for the experimental alloys in a silica-lined, three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating. Fig. 1 shows this furnace installation. About 25 tons of sponge iron was melted in 75 heats, averaging 927 lb of sponge iron to the heat. An addition of carbon was required to complete the reduction of a portion of the iron oxide remaining in the sponge to prevent high losses of iron oxide in the slag and a low carbon content in the resulting metal. As reducing agents in preparing the melting stock, charcoal, coke, and a carbon product resulting from the thermal decomposition of natural gas were used. The quantity varied from 20 to 60 Ib per furnace charge, with an average of 38 lb. An average analysis of the metal obtained gave 0.52 pct C, about 0.01 pct Mn, 0.070 pct P, and 0.092 pct S. The average yield of metal was 647 lb with 241 1b of slag, the sponge-iron recovery being 70 pct. The metal obtained in melting the sponge iron was cast into pigs weighing about 20 lb each to facilitate recharging into the furnace for further refining. The pouring of the pigs is shown in Fig. 2. The average power consumption for the production of the 24 tons of metal obtained was 1704 kw-hr per ton.

Jan 1, 1954

By I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3' have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,' Rosenberg and Cadoff,9 and Bilello and cadoff' have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff'6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-' and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

Jan 1, 1964

By T. P. Meloy

Economic constraints require that the optimum mineral processing circuit be chosen for a given ore and then the circuit be optimized. Meloy (1983) developed a general methodology for finding the best circuit for a given ore. This analysis, however, did not specify a way to optimize the best circuit once it has been found. To optimize a given circuit, it is necessary to find the optimum set points for each unit operation in the circuit. Developed in this paper is a simple, general equation which, when applied, defines the optimum separation set point for the maximum mineral grade. This general equation, Equation (4), applies not only to simple ores, but also to complex ores containing variable and locked particles. Currently, the optimum set point can be calculated only for heavy media and cyclone circuits, because they are the only unit operations for which the necessary data has been measured.

Jan 1, 1984

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.' They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,' it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,' the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:' = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By R. G. Treuting

Germanium single crystals strained in tension at 600°C slip on the {Ill} plane and, macroscopically at least, in the <110> direction. Deformation is in homogeneous: various localized rotations are observed, as is a banding consistent with secondary slip banding. The structure after deformation is polygonized with a domain size of about 2x1O-3 cm. In relaxation tests, an incubation period prior to flow is observed, of duration inversely related to temperature and applied stress. Under continuous loading, there is a sharp first yield point. A critical resolved shear stress therefore must be cited with respect both to temperature and to rate of loading. At 600°C, when loading proceeds at 2900 psi per min, it is 1310 psi. The yield point phenomenon is suggestive of Cottrell&apos;s solute atom atmosphere theory and five points of qualitative agreement with this theory are found. PLASTICITY of germanium at elevated temperatures has been reported by Gallagher,&apos; who ascribed it to slip on {Ill) planes and described some associated effects. Preliminary experiments with single crystals of silicon and germanium loaded as simple beams confirmed {ill) as the slip plane of both materials.V his was demonstrated by the standard technique employing traces on two surfaces of known angle on a deformed crystal of known orientation.3 These experiments did not fix the slip direction, since more than one glide system operated. Uniaxial tensile straining is preferred for this purpose in order to restrict slip to one predominant system and to provide an unequivocal determination of the orientation change with respect to the stress axis. Experimental Method Specimens were diamond-sawed from germanium crystals containing about 5x10-5 wt pct Sb prepared by the zone-leveling process described by Pfann and Olsen;4 these specimens measured about 81/2 in. long, 0.20 in. wide, and were of various thicknesses from 0.035 to 0.060 in. Prior to testing, a specimen was coated over 1 in. or more of length at each end with Apiezon wax, chemically polished (in a solution of 15 ml HF, 25 ml HNO,, 15 ml CH3COOH, and 3 to 4 drops Br2), and dewaxed in warm xylene. A brief re-etching after scribing through a complete wax coating with vernier dividers provided gage marks at 0.200 in. intervals on the polished surface. A specimen with grips soft soldered to the ends was passed through the furnace tube and the grips pinned to the tensile machine in series with a stress gage. The Schopper testing machine is best described by reference to the illustration on p. 107 of Schmid and Boas5 and is operated with the pendulum arm locked, fixing the upper head. Load is applied through the screw-driven lower head, manually or by reduced speed motor. The furnace is 21/2 in. long surrounding a 4x7/16 in. ID quartz tube and was positioned about the specimen to permit free motion. The inert or reducing atmosphere required was sufficiently provided by a flow of helium introduced at the center of the furnace tube, with the tube ends loosely plugged with asbestos paper. Surface corrosion was slight. The stress gage employs a Be-Cu strip with SR-4 units incorporated in a simple bridge network with provision for balancing and calibrating. The bridge output on loading is fed through a Leeds and North-rup dc amplifier to a Speedomax 10 mv recorder, and calibration is obtained by dead loading. Experiments of two types have been conducted. Most have been in relaxation at constant elongation. One stress-strain curve has been taken with the machine continuously driven. Following extension of a specimen, Laue X-ray photographs were taken to obtain the orientation change between deformed and undeformed regions, recorded on a single film by translating the specimen in a plane normal to the beam between exposures. Sequences of such multiple exposures were made on some specimens to include the entire orientation range on one film. Slip Direction To obtain a maximum orientation change with a single slip system, crystals of very closely <110> axial orientation were used. The classic determination of slip direction rests on establishing that direc-

Jan 1, 1956

[Alphabetic Section (Page 689): The letter immediately following the member&apos;s name indicates grade: M-Member, A-Associate, J-Junior. The numerals following member&apos;s grade indicate year of election. The letter following year of election indicates primary Divisional affiliation: A-Mining & Exploration F-Coal B-Minerals Beneficiation G-Petroleum C-Iron and Steel H-Industrial Minerals D-Extractive Metallurgy J-Council o f Education E-Institute of Metals K-Council o f Economics]

Jan 1, 1961

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na&apos; and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°&apos;K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°&apos;K and

Jan 1, 1968

By J. H. Swislzer

TWO-LIQUID miscibility gaps have been found to exist in both the CaO-SiO, system above 1705 and the Cr,03 system above 2200"c. Glasser and 0sborn3 studied the extension of these miscibility gaps into the Ca0-Si0,-Crz03 ternary system and reported that the two-liquid region is not present at temperatures below the monotectic temperature of 1705°C in the CaO-SiO, system. The present authors, in connection with other work on surface-tension measurements and foam stabilities in the same ternary system,4 observed that the miscibility gap exists at temperatures as low as 1600°C. A brief experimental study was devoted to deter- mining tie-line positions in the two-phase region. The technique used was to obtain a separation of phases at 1600°C, then to quench-in the high-temperature phases and obtain a chemical analysis of each phase. It was necessary to take special precautions in obtaining a phase separation because of a tendency toward emulsification of the two liquids. The procedure followed is described in the schematic drawing in Fig. 1. A small platinum crucible containing several pinholes on its sides was placed inside a larger platinum crucible. An excess of Crz03 was placed in the outer crucible, together with a prefused binary CaO-Si02 mixture, and the Cr203 was allowed to diffuse through the pinholes and saturate the same binary CaO-SiOl mixture in the smaller crucible. After equilibration at 1600°C, the inner crucible contained only the lighter liquid (liquid A) saturated with Cr203. The outer crucible contained layers of both liquids. Experimental data were obtained by analyzing the entire contents of the inner crucible and only the bottom layer of the larger crucible (liquid B). The upper layer of the outer crucible was not suitable for chemical-analysis purposes because dispersions of the second phase sometimes were found in the samples. The technique is described in more detail in Ref. 4. The same method was used by Grieveson and urkdoan&apos; to study a miscibility gap in sulfate-ferrite melts, where the liquids were difficult to separate because of similarities in density. In addition to the phase-separation experiments, a few others were conducted to obtain information

Jan 1, 1964

By Luke L. Y. Chang, Bert Phillips

ThE tendency toward further oxidation of the intermediate oxides and the high volatilization rates of the higher oxides have prevented direct attainment of equilibrium data for the system tungsten-oxygen. As a result, St. Pierre et al.1 have proposed a phase diagram (to 800°C) based on thermody-namic data to 1200°C for the known tungsten oxides (WO2z, W18O49, W20O58, and WO3) and a report on a tungsten suboxide W3O.2 Recent modification of a technique previously described3 5 now permits adequate preservation of compositions of mixtures of metallic tungsten and metal oxides (e.g., of tungsten, cobalt, calcium, samarium, titanium) in order that condensed phase relations may be established to 1700 This method has been applied to study the high-temperature stability of tungsten oxides. In the method used, the desired compositions were sealed in nonreactive containers such that only a small gas volume remained. Each sample then established its own equilibrium atmosphere at temperature. This method has advantages in the study of systems of the W-0 type where knowledge of the condensed phases is desirable but for which composition and pressure of the gas phase are not readily attainable because of oxide volatility. Mixtures of 99.99 pct tungsten metal powder and purified tungsten anhydride (WO3) or in some cases W18O49* were equilibrated in pellet form in sealed

Jan 1, 1964

By F. W. Jessen, James N. Howell

INTRODUCTION The determination of cloud points has to date been limited to rather transparent oils, visual observation of the formation of a solid phase being the criterion for the standard ASTM D 97-47 method. The need for a quiclc and simple method for determining cloud points under dynamic conditions for opaque crude oils became necessary in a study of fundamental aspects of paraffin deposition from crude oils. PREVIOUS WORK The determination of cloud points in opaque oils by viscosity temperature curves is fairly new, Young&apos; described a method employing the capillary tube principle. No information exists relative to the determination of cloud points of crude or refined oils under dynamic conditions. Shock&apos; noticed that deposition of paraffin from crude oils took place at temperatures at or below the temperature at which a sharp inflection point occurred in the viscosity-temperature curve. This observation indicates a possible correlation between this temperature and the cloud point of the crude oil. Reistle and Vietti1 have reported that when crude oils containing small amounts of asphaltic materials were heated to temperatures sufficiently high to solubilize these materials and immediately cooled the pour point of the crude oil was lowered as much as 70°F. Sachanen\ asribes this effect to the action of colloidal asphaltenes in preventing the formation of the crystalline structure necessary to maintain the oil in a rigid state. At high temperatures, asphaltenes are peptized, and the paraffin crystals formed at these temperatures adsorb the colloidal asphaltenes on their surface thereby hindering further growth of the crystals. Reistle" found, however, that such heating and cooling of crude oils had no effect upon the cloud points. This latter work dealt with a crude oil of fixed composition, and the question immediately arises as to the effect of varying the concentration of asphaltic materials on the cloud point. APPARATUS AND PROCEDURE All viscosity measurements were made with a Bendix Ultra-Viscoson. The Bendix Ultra-Viscoson, which consists of a vibrating probe and an electronic computer. measures viscosity by exciting a thin alloy steel blade on the end of a probe by short electrical pulses in damped oscillation at 28 kilocycles. The blade vibrates longitudinally with an amplilude of less than 55 micron or 20 millionths of an inch. Energy to protlucc this excitation is generated in he computer and transferred to the probe through the connecting cable. The oscillating blade is magnetostric-tive, i.e., it is capable of transforming electrical energy to mechanical energy in the ultrasonic range. Ultrasonic waves are produced in the material surrounding the blade by the oscillating motion of the blade causing layers of the material to slip back and forth over one another at a known frequency. The electronic computer calculates the energy required to produce the sliding motion which is in turn proportional to the viscosity of the material. Actual values of viscosity times density (centi-poise X grams/cc) are indicated on the computer and a continuous D-C signal is provided which is fed into a type 153 Electronic Recorder (manufactured by Brown Instruments Div. of Minneapolis-Honeywell Regulator Co.) The liquid sample container was fabricated from a Lucite cylinder and jacketed by a Luicite water bath. Early experiments using glass and steel sample containers were not satisfactory. since the Ultra-Viscoson was apparently affected by the alterzltion of the magnetic fields surrounding the probe by stresses set LIP in the glass and steel as it cooled. The procedure for determining viscosity-temperature curves was relatively simple. The temperature ot the sample was raised sufficiently high to solubilize all paraffin and asphalts present. After heating, the oil sample was immediately transferred

Jan 1, 1957

By J. J. Taber, W. K. Meyer

Experiments on consolidated sandstones have shown that a variety of conditions are responsible for the wide range of behavior observed when oil and water are displaced simultaneously by a solvent which is miscible with both. The type of displacement is influenced most strongly by the relation between the plait point of the ternary phase diagram and the composition path followed by the system as it achieves mis-cibility. Neglecting viscosity, the displacement becomes less efficient as the distance between the composition path and plait point is increased in either direction so that a very wide spectrum of displacements is possible with different alcohol, oil and brine systems. It is possible by choosing various composition paths as miscibility is achieved to exercise some control over the actual displacement mechanism. Control over the composition path is exercised by adding oil or water in specific amounts to the alcohol prior to its injection into the porous medium. This technique apparently makes it possible to obtain piston-like displacements with systems which are usually characterized by the efficient displacement of only one of the two phases i.e., either oil or water, while the other phase lags behind. However, the simultaneous displacement of oil and water is not as efficient as other miscible displacements at a similar mobility ratio. The evidence indicates that both oil and water "leak" into the alcohol "piston" in compensating amounts. With oils of low viscosities the displacement is inefficient because the low oil saturation in the stabilized bank causes oil to be trapped by water before miscibility is attained. INTRODUCTION The simultaneous displacement of oil and water by solvents such as alcohol has been investigated in the laboratory and in the field. The laboratorv workers investigating all-liquid miscible systems have recognized the great importance that the nature of the traingular phase diagram exerts on the efficiency of the miscible displacement. Gatlin and Slobod pointed out that displacement efficiency will be improved if miscibility can be retained for long periods and that this behavior tends to be followed if the applicable phase diagrams have very low binodal curves. In their unconsolidated sand tests the alcohol was considered an ideal miscible piston displacing both oil and water phases. Later workers have pointed out that an important feature of the phase diagram as far as oil recovery is concerned is the location of the plait point. This is particularly true in the case of consolidated Sandstone.3 Since the original discussion of this effect, the importance of plait-point location has been confirmed and discussed by other author The early workers394 recognized that the position of the plait point could be altered by changing the oil or the alcohol used in an experiment. In addition, recent work has demonstrated that the plait point can be shifted by altering the nature and concentration of dissolved salts in the aqueous phase. However, the entire scope of the relationship between displacement and plait point has not been discussed previously and a technique for changing the composition path as miscibility is achieved in a particular ternary system, i.e., oil, water and solvent, has not been demonstrated. * The importance of oil viscosity on the efficiency of oil displacement by alcohol has not previously been observed, probably because the range of viscosities used in earlier experiments was too restricted. It is the object of this paper to describe the relationships between the ternary phase diagram, fluid properties and the displacement achieved. A technique for controlling the nature of the displacement is also presented. THEORY AND DEFINITIONS PISTON-LIKE THEORY The theory of alcohol flooding has been discussed in some detail.2-4 The concept was advanced that

Jan 1, 1965

By Charles L. Thomas

A novel, highly sensitive, and reproducible nzetlzod for the determination of hydrogen in solid materials is presented. The procedure requires equilibration of the specimen with hydrogen gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subse-quent quantitative analysis by mass spectroscopy. Good linearity is obtained for the Arrl~enius plots of the investigated metals. The advantages in the use of this method over that of Sieverts aye discussed. The solubility data for copper are in reasonable agveewzent with a considerable number of other inuestigations, wllile those fov silver are considerably lower than previously reported. The first known solubility data for gold are presented. Solubility equations and heats of MUCH of the data which are available on the solubility of hydrogen in various metals and alloys have been obtained by the classical Sieverts method.&apos; The method involves the measurement of a decrease in pressure of a gas in a calibrated system, and the calculated contraction in volume is attributed to the solubility of the gas in the metal sample. The procedure requires several corrections, such as the solubility of the gas in the container walls and the diffusion of the gas through these walls, as noted by Steacie and .Johnson2 and others. In addition, errors may be incurred due to reactions between metal surface impurities, such as oxides, and the saturating gas. The precise calibration of the measuring system where large thermal gradients exist can present additional difficulties. Also, accurate volumetric measurements of small quantities of gas are difficult. Many of the objections to the Sieverts method were overcome on solid materials by Ransley and ~eufeld,~ who first saturated the metal with hydrogen and performed a subsequent extraction and measurement of the gas by chemical means. Eichenauer and pebler4 and Eichenauer, Kiinzig, and pebler5 measured the diffusion coefficient and solubility by following the degasification of a sample as a function of a rate of increase in pressure in a previously evacuated system. Here again, however, the procedure involves many of the corrections of the Sie-verts method. The present investigation deals with the solubility of hydrogen in solid copper, silver, and gold by a technique which eliminates many of the aforementioned corrections and possible errors. This procedure requires equilibration of the specimen with gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subsequent quantitative analysis by mass spectroscopy. EXPERIMENTAL Two completely separate systems were employed to accomplish first, the equilibrium saturation of the sample and second, the extraction of the dissolved gas. Saturation Apparatus. The saturation apparatus, illustrated in Fig. l, consisted of a vertically mounted quartz tube with a three-way valve for vacuum or hydrogen near the top and an outlet near the bottom leading to a butyl phthalate seal. The bottom end of the tube was terminated with a joint accommodating an O-ring sealed "Asco Stirring Gland" (The Emil Greiner Co.). This gland facilitated movement of the thermocouple without introduction of air into the system. The upper portion of the tube (above the furnace) was water-jacketed. A Welsh 1405-B mechanical pump provided the necessary system evacu-

Jan 1, 1968

By A. A. Smith, J. S. Smart, A. J. Phillips

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By A. J. Phillips, A. A. Smith, J. S. Smart

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By William Marsh Baldwin

TWO of the most useful and important equations available to the metallurgist for the study of plastic deformation of metals are the Huber-von Mises-Henckyl-~ and the St. Venant7-10 equations. Huber-von Mises-Hengky Equation The Huber-von Mises-Hencky equation answers the question: When does plastic flow occur in metal that is subjected to a multi-axial stress? It occurs, according to this equation, when the three principal stresses,t UI, u2, and u3 satisfy the equation: (<ri - <r2)2 + (<r2 - <rsY + (ff! - <r3)* = 2Ki [i] Here K is the yield strength of the material as determined in an ordinary tensile test. If the quantities ul, 52, andas are assigned to the coordinates of a Cartesian three-dimensional system, this expression describes a cylinder whose axis of symmetry is inclined at equal angles to the three coordinate axes4s6 (Fig. I). The radius of this cylinder is .\/%K. For the purpose of simplicity, it is sometimes advantageous to ascribe the values al/K = sl, az/K = s2, UD/K = SJ to the three coordinate axes instead of the principal stress alone. In this case, Eq. I becomes (*i - s*)1 + (s2 - S3)2 + (si - SiY = 2 [2] and the radius of the cylinder becomes \/%. In the latter method of representation, a point lying inside the cylinder indicates that the metal will react elasti-cally, whereas a point lying on the cylindrical surface indicates that the metal will behave plastically. Some of the geometric features of this cylinder are worthy of study. Let us inquire first as to what interpretation may be placed upon what we will choose to call the "circles of latitude" of the cylinder (L in Fig. I) and the "meridians" of the cylinder (M in Fig. I). Circles of Latitude Circles of latitude are formed by allowing a plane, passing perpendicular to the cylinder axis, to intersect with the cylinder. Any point, P, on this circle is presumed to have the coordinates sl, SZ, and s3. The coordinates of the point resulting from the intersection of the plane and the cylinder axis will be a, a, and a (since the cylinder axis is equally inclined to the three coordinate axes). L?t US now pass a line through the point on the circle and the point on the axis.

Jan 1, 1946

By William Marsh Baldwin

TWO of the most useful and important equations available to the metallurgist for the study of plastic deformation of metals are the Huber-von Mises-Henckyl-~ and the St. Venant7-10 equations. Huber-von Mises-Hengky Equation The Huber-von Mises-Hencky equation answers the question: When does plastic flow occur in metal that is subjected to a multi-axial stress? It occurs, according to this equation, when the three principal stresses,t UI, u2, and u3 satisfy the equation: (<ri - <r2)2 + (<r2 - <rsY + (ff! - <r3)* = 2Ki [i] Here K is the yield strength of the material as determined in an ordinary tensile test. If the quantities ul, 52, andas are assigned to the coordinates of a Cartesian three-dimensional system, this expression describes a cylinder whose axis of symmetry is inclined at equal angles to the three coordinate axes4s6 (Fig. I). The radius of this cylinder is .\/%K. For the purpose of simplicity, it is sometimes advantageous to ascribe the values al/K = sl, az/K = s2, UD/K = SJ to the three coordinate axes instead of the principal stress alone. In this case, Eq. I becomes (*i - s*)1 + (s2 - S3)2 + (si - SiY = 2 [2] and the radius of the cylinder becomes \/%. In the latter method of representation, a point lying inside the cylinder indicates that the metal will react elasti-cally, whereas a point lying on the cylindrical surface indicates that the metal will behave plastically. Some of the geometric features of this cylinder are worthy of study. Let us inquire first as to what interpretation may be placed upon what we will choose to call the "circles of latitude" of the cylinder (L in Fig. I) and the "meridians" of the cylinder (M in Fig. I). Circles of Latitude Circles of latitude are formed by allowing a plane, passing perpendicular to the cylinder axis, to intersect with the cylinder. Any point, P, on this circle is presumed to have the coordinates sl, SZ, and s3. The coordinates of the point resulting from the intersection of the plane and the cylinder axis will be a, a, and a (since the cylinder axis is equally inclined to the three coordinate axes). L?t US now pass a line through the point on the circle and the point on the axis.

Jan 1, 1946