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By J. B. Mackintosh

In a recent paper read before the Institute on this subject, Mr. G. C. Stone advances the theory that the precipitate obtained in Williams's volumetric process,* by treating the boiling nitric acid solution of a manganese salt with potassic chlorate., is not pure MnO2, but approximates more closely to the composition 10Mn02+Mn0. As the value of the process and the accuracy of our results mould depend on whether this was the fact or not, it has seemed to me, and to my associates, Messrs. Beebe and Colly, that it would be of importance to ascertain the composition of this precipitate, and to that end the following series of experiments has been undertaken. These experiments have all been based on the considerations: 1. That potassic permanganate has an oxidizing power equivalent to five atoms of oxygen for every two of manganese : K2Mn2O8 = K2O.2MnO.O5. 2. That the same amount of manganese in the state of binoxide has an oxidizing power equivalent to two atoms of oxygen : 2MnO2 = 2MnO.O2. If, then, we take a solution of permanganate of unknown strength, and reduce it to binoxide, the oxidizing power of the binoxide formed will be equal to that of two-fifths the quantity of the permanganate solution originally taken. While, if the precipitate obtained should not be binoxide, but an indefinite or definite mixture of bin- and mon- oxides, then, from its equivalent oxidizing power, we can calculate its composition. The analyses were conducted in the following manner. The amount of permanganate taken was decomposed with hydrochloric acid, and concentrated to expel the excess of water. Sufficient excess of nitric acid was now added, and the solution was boiled until all the hydrochloric acid was destroyed. The manganese was then precipitated by potassic chlorate; and, after standing some time to cool—a pre-

Jan 1, 1884

By D. I. Cameron

A graphical method has been developed and tested for separating the effects of grain boundary and lattice diffusion in polycrystalline materials. The method is based on the assumptions that for unidirectional diffusion from a plane source of radioactive material, the penetration of activity far into the specimen from the source is due solely to grain-boundary effects, and 2) pure grain-boundary penetration is described by a linear plot of log activity vs the perpendicular distance x from the source. The former is based on the fact that at any temperature the grain-boundary diffusion coefficient is always very large relative to the lattice diffusion coefficient; and the latter is based on the derivation of Fisher.1 Using these criteria along with appropriate penetration data (in this case, data for the diffusion of Cb95 in pressed and sintered UO2) one first plots the data as log activity vs x2 and as log activity vs x, as shown by curves 1 and 2, respectively, in Fig. 1. A tangent line to curve 2 for large x (curve 3) is then transferred to the x2 plot as curve 4. The subtraction of curve 4 from curve 1 yields curve 5 which represents only lattice diffusion and may therefore be related to the diffusion coefficient by using the appropriate solution to Fick's second law. It should be noted that the method has inherent inaccuracies for small and large values of x2 and only the subtraction at intermediate values can be used. For the illustrated specimen the calculated diffusion coefficient is 3.4 X 10-11 sq cm per sec at 1445°C while data using a single crystal of UO2 at the same temperature yielded a value of 2.9 x 10-11 sq cm per sec.2 The same method of subtracting grain-boundary diffusion effects to obtain lattice diffusion coefficients has been successfully used to determine self-diffusion coefficients of Th230 in polycrystal- line thoria.

Jan 1, 1962

By T. S. Lundy, J. I. Federer

A graphical method has been developed and tested for separating the effects of grain boundary and lattice diffusion in polycrystalline materials. The method is based on the assumptions that for unidirectional diffusion from a plane source of radioactive material, the penetration of activity far into the specimen from the source is due solely to grain-boundary effects, and 2) pure grain-boundary penetration is described by a linear plot of log activity vs the perpendicular distance x from the source. The former is based on the fact that at any temperature the grain-boundary diffusion coefficient is always very large relative to the lattice diffusion coefficient; and the latter is based on the derivation of Fisher.1 Using these criteria along with appropriate penetration data (in this case, data for the diffusion of Cb95 in pressed and sintered UO2) one first plots the data as log activity vs x2 and as log activity vs x, as shown by curves 1 and 2, respectively, in Fig. 1. A tangent line to curve 2 for large x (curve 3) is then transferred to the x2 plot as curve 4. The subtraction of curve 4 from curve 1 yields curve 5 which represents only lattice diffusion and may therefore be related to the diffusion coefficient by using the appropriate solution to Fick's second law. It should be noted that the method has inherent inaccuracies for small and large values of x2 and only the subtraction at intermediate values can be used. For the illustrated specimen the calculated diffusion coefficient is 3.4 X 10-11 sq cm per sec at1445°C while data using a single crystal of UO2 at the same temperature yielded a value of 2.9 x 10-11 sq cm per sec.2 The same method of subtracting grain-boundary diffusion effects to obtain lattice diffusion coefficients has been successfully used to determine self-diffusion coefficients of Th230 in polycrystalline thoria.

Jan 1, 1962

By G. R. Purdy, J. G. Parr

The intermetallic compound Ti2Co was studied by X-ray diffraction and metallographic techniques. The phase occurs off stoickzometric composition, with its greatest variance at high temperature. The solubility limits of the phase have been cletermined, and an amendment to the titanium-cobalt phase diagram is suggested. THE first intermetnllic compound to appear at the titanium-rich side of the titanium-cobalt system was found by Laves and wallbauml to be Ti2Co. They described this compound as isomorphous with Ti2Ni and Ti2Fe, and demonstrated that it had a face-centered-cubic structure with 96 atoms per unit cell. This contention is supported by the work of Duwez and Taylor2 and Orrell and Fontana3 who also determined the lattice parameter to be about 11.30A. Rostoker4 believed that Ti2Co did not exist, and that the phase considered by the other workers to be Ti2Co was Ti,Co20. However, Orrell and Fontana determined oxygen and nitrogen contents and found that their alloys did not contain sufficient of these elements to produce significant quantities of a stoichiometric oxygen compound. The present investigation was initiated to determine the composition limits of the phase Ti,Co.

Jan 1, 1961

By D. A. Martin, Laird Crocker, W. I. Nissen

The Federal Bureau of Mines has developed a process for removing SO2 from stack gases. The process comprises absorption of SO2 in an. aqueous solution of sodium citrate, citric acid, and sodium thiosulfate, followed by reaction of the absorbed SO2 with H2S to precipitate sulfur and regenerate the citrate solution for recycle. A pilot plant was operated at The Bunker Hill Co. lead smelter in Kellogg, Idaho, to assess the feasibility of using the process for flue gas desulfurization. Nominal capacity of the pilot plant, which treated .tail gas from the lead smelter sintering furnace, was 1699 standard meters cubed per hour (15 degrees celsius) of 0.3- to 0.7-percent-SO2 gas yielding about 272 net kilograms of sulfur per day. The pilot plant was operated for about 4500 hours and produced more than 45 net tonnes of sulfur. The operation demonstrated that (1) more than 95 percent of the SO2 could be removed from the lead smelter sintering furnace tail gases, (2) regeneration of the citrate solution with H2S and precipitation of sulfur in conventional stirred vessels was readily controlled and highly efficient, (3) the precipitated sulfur could be continuously recovered as a 99.5-percent-pure product by kerosine flotation and melting, and (4) the 77- to 79-percent-H2S gas used for sulfur precipitation could be readily produced from pilot plant product sulfur, natural gas, and steam. Projected operating costs, including capital charges, for a citrate plant, installed at a 118 000-tonne-per-year lead smelter and treating 49 271 standard meters cubed per hour of lead smelter sintering furnace tail gas, are estimated to be $384 per tonne of sulfur.

Jan 1, 1976

By R. W. Fenn, H. A. Lepper, W. R. Hibbard

THIS paper reports the results of static tension and torsion tests made on single crystals of alpha brass for the purpose of determining its elastic coefficients. 70-30 alpha brass was chosen because it has been used extensively in the study of the plastic deformation and because it has the following desirable characteristics: (1) face-centered cubic structure, (2) marked elastic anistropy, (3) low elastic modulus. In 1928 Masima and Sachs' using static methods reported the following values for the elastic coefficients of 72-28 pct alpha brass: S11 = 19.4 X 10-13' cm2 per dyne S12 = —8.35 X 10"' cm2 per dyne S44 = 13.9 X 10-13= cm2 per dyne These values were obtained from the measurements shown in fig. 1. The experimental points for both tension and torsion lie consistently below the lines drawn to represent them. Fig. 2 shows the stress-strain curves for their specimens. Only a few points in the elastic range of these curves were available to obtain their values for Young's modulus. Therefore, it was considered that a re-evaluation of these data was desirable. In addition a variation of from 1.13 to 1.485 kg per mm2 was found in the values of the critical resolved shear stress for 70-30 alpha brass reported by Burghoff,² Treuting and Brick: Martin,4 Maddin, Mathewson and Hibbard5,6 and von Goler and Sachs.' Therefore, it was desired to evaluate the conclusion of Boas and Schmid8 that a constant resolved shear stress and not a constant elastic shear initiates plastic deformation. Theoretical Considerations*: The elastic deformation of cubic crystals may be defined by three elastic coefficients (S11, S12, S44,) or three elastic parameters (C,,, C,, C,,). These coefficients or parameters are sufficient to define the stress and strain relations for cubic crystals in the generalized form of Hooke's law referred to Cartesian coordinates. Elastic parameters and coefficients in the cubic system are related by the expressions: C11 —S11+S12/(S11-S12)(S11+2 S12) C12=-S12/(S11-S12)(S11+ 2 S12) (S11 — S12) (S11 + 2 S12) [2] C44 =1/S44 PI It is possible to determine all the elastic coefficients for a cubic metal by measuring two of the three elastic constants: Young's modulus (E), torsion modulus (G), or compressibility (S). The following relations exist between crystallographic orientation and E, G and S for cylindrical crystals of the cubic system: 1/E = S11 — 2 [(S11 - S12) — Su] (?1² ?2² + ?2²?83 + ?3² ?1²) [4]

Jan 1, 1951

By R. L. Huntington, D. T. MacRoberts, Charles R. Hetherington

Since the equation of continuity governing transient flow of gases through porous media cannot be integrated mathematically into a simple usable expression free from series terms, empirical and approximate equations have been advanced relating cumulative production and future production rates from gas reservoirs with time. In order to check the accuracy of these empirical equations and to obtain an insight into the initial conditions pertinent to the solution of the fundamental equation of continuity, experimental work has been conducted on a vertical 2-in. tube, 91.6 ft. high, packed with unconsolidated Wilcox sand. The results presented in graphical form show the accuracy of the approximate relations. Data from unsteady-flow runs on the 2-in. experimental tube are presented graphically, and are applied to obtain an equation for this specific case, and are offered as an aid in future investigations of this basic equation. The close agreement between equations calculated for steady-state flow and the experiments indicates that the decline of actual gas reservoirs may be treated by an application of these equations without serious error. Introduction The steady-state flow of gas through a porous material—that is, flow wherein the boundary conditions do not vary with time—is subject to analytical solution. Muskat1 has shown that the general differential equation is simply the La Place equation in P2. Direct solutions may be at once obtained. The unsteady state, on the other hand, is not analytically reducible. Since nearly all phenomena of practical interest in gas production involve flow in the unsteady rather than in the steady state, it has been necessary to derive approximate Solutions to the general equation. The validity of such approximations has not hitherto been adequately tested. In the experiments to be described a simple, closed, linear system is substituted for the real complex gas field. The general results, however, are independent of the geometry Of the system' The problem studied is the rate of production, and the accompanying variations in pressure, when one end of a linear porous system is opened to the atmosphere and permitted to produce to exhaustion. An approximate solution to the general differential equation, based upon the assumption of an "infinite series of steady states," is then applied to the results to determine the validity of this method of dealing with actual reservoirs. Theoretical Considerations The fundamental differential equation governing the flow of a gas through a Porous medium can be derived easily from the equation of continuity, Darcy's law, Boyle's law and a statement of the thermo-dynamic nature of the flow. For isothermal flow it is: d2P2/dx2 + d2p2/dy2 + d2p2/dz2 = 2fµ/K dP-dT

Jan 1, 1942

By R. L. Huntington, D. T. MacRoberts, Charles R. Hetherington

Since the equation of continuity governing transient flow of gases through porous media cannot be integrated mathematically into a simple usable expression free from series terms, empirical and approximate equations have been advanced relating cumulative production and future production rates from gas reservoirs with time. In order to check the accuracy of these empirical equations and to obtain an insight into the initial conditions pertinent to the solution of the fundamental equation of continuity, experimental work has been conducted on a vertical 2-in. tube, 91.6 ft. high, packed with unconsolidated Wilcox sand. The results presented in graphical form show the accuracy of the approximate relations. Data from unsteady-flow runs on the 2-in. experimental tube are presented graphically, and are applied to obtain an equation for this specific case, and are offered as an aid in future investigations of this basic equation. The close agreement between equations calculated for steady-state flow and the experiments indicates that the decline of actual gas reservoirs may be treated by an application of these equations without serious error. Introduction The steady-state flow of gas through a porous material—that is, flow wherein the boundary conditions do not vary with time—is subject to analytical solution. Muskat1 has shown that the general differential equation is simply the La Place equation in P2. Direct solutions may be at once obtained. The unsteady state, on the other hand, is not analytically reducible. Since nearly all phenomena of practical interest in gas production involve flow in the unsteady rather than in the steady state, it has been necessary to derive approximate Solutions to the general equation. The validity of such approximations has not hitherto been adequately tested. In the experiments to be described a simple, closed, linear system is substituted for the real complex gas field. The general results, however, are independent of the geometry Of the system' The problem studied is the rate of production, and the accompanying variations in pressure, when one end of a linear porous system is opened to the atmosphere and permitted to produce to exhaustion. An approximate solution to the general differential equation, based upon the assumption of an "infinite series of steady states," is then applied to the results to determine the validity of this method of dealing with actual reservoirs. Theoretical Considerations The fundamental differential equation governing the flow of a gas through a Porous medium can be derived easily from the equation of continuity, Darcy's law, Boyle's law and a statement of the thermo-dynamic nature of the flow. For isothermal flow it is: d2P2/dx2 + d2p2/dy2 + d2p2/dz2 = 2fµ/K dP-dT

Jan 1, 1942

By S. S. Lisnyak, B. D. Lichter

An important question in the study of the "hot corrosion" phenomenon (i.e., accelerated oxidation of Ni-Cr-base and Co-Cr-base "superalloys" in the presence of sulfur) is the condition of formation and physico-chemical properties of different sulfides in the system Ni-Co-Cr-S. seyboltl has observed the presence of ((chromium-rich" sulfides of compositions M3S4, and M2S3 in the scales of superalloys after hot corrosion; however, as he points out, much confusion exists as to the identity of sulfides found on Ni-Cr and Co-Cr alloys. According to the literature,&apos; ternary sulfides, e.g., NiCr2S4, (monoclinic structure) and CoCr2S4 (spinel structure) exist in these systems. Therefore, it is likely that these compounds are found in the scale of alloys undergoing hot corrosion. At present this possibility has not been discussed in the literature. Accordingly, we have begun investigation on the properties of ternary sulfides and their mutual interaction. The magnetic and electrical properties of pure NiCr2S4 and pure CoCr2S2 have been previously determined."-&apos; In the present work we have studied the interaction between these sulfides at high temperatures by means of X-ray diffraction and magnetic susceptibility. The measurements were carried out at room temperature after appropriate thermai treatment of samples at high temperatures. For alloys containing the three elements nickel, chromium, and cobalt this interaction may be of importance in the study of the hot corrosion phenomenon. The compounds NiCr2S4 and CoCr2S4 were prepared from stoichiometric amounts of the elements and CoS in the case of CoCr2S4. Samples were mixed and sealed in evacuated silica tubes, slowly heated to 900&apos; to 100O°C, and held at temperature for a total of 120 hr (NiCr2S4) or 80 hr (CoCr2S4) with intermediate re-grinding~. X-ray diffraction showed a pure spinel structure for CoCr2S4 and a monoclinic structure for NiCr2S4. Samples of mixtures of the two ternary sulfides were prepared with different compositions, see Table I. Samples were heated for a total of 80 hr at 900&apos;C in evacuated silica tubes, with one intermediate regrind-ing. The capsules were slow-cooled to room temperature in the furnace. Samples for X-ray diffraction were prepared by placing powder on a glass slide with vaseline. Dif- fractometer traces were obtained on a G.E. XRD-5 diffractometer using a chromium tube and vanadium filter (40 kv and 31 ma). The size of the spinel unit cell was determined from the eight highest angle peaks (80 deg < 2b < 160 deg). Calculated lattice parameters were plotted vs cos B . ctn 0 and extrapolated to 6 = 90 deg. Measurements of the magnetic susceptibility were carried out at room temperature using the Faraday method in a magnetic field of 3000 G and using a Cahn RG automatic microbalance. The system was calibrated from the well-established susceptibilities of platinum and palladium: (Xpt = 0.968 x 10-6 g-1 and Xpd 7 5.04 x 10~6 g-1). The weight of samples were approximately 0.200 g. X-ray diffraction patterns for unsintered mixtures showed Bragg peaks from both the spinel (CoCr2S4) and monoclinic (NiCr2S4) structures. After sintering no monoclinic peaks were observed in samples containing up to 40 mol pct NiCr2S4. However, the spinel peaks were displaced to higher angles with increasing

Jan 1, 1970

By P. T. Carter, A. B. Murad, H. B. Bell

The distribution of manganese and oxygen between molten iron and FeO-MnO-SiO2 slags not saturated with SiO2 has been determined and used to calculate activities of MnO and SiO2 in MnO-SiO2 slags. These were found to be intermediate between the corresponding activities in FeO-SiO2 and CaO-SiO2 slags. THE equilibrium constant for the reaction between molten iron containing manganese and slags containing FeO and MnO, namely: FeO(slag) + Mn = MnO (slag) + Fe(1iquid) is most conveniently represented by: (MnO) Kmn== (FeOHMn] [Fe] is omitted, since for dilute solutions of manganese in iron, afe is approximately constant. When activities are used for (MnO), (FeO) and [Mn], Kmn is a true equilibrium constant and will apply to all types of slags, but when weight percentages are used, the values obtained for Kmn for different slags vary considerably. The equilibrium between iron containing manganese and relatively pure FeO-MnO slags has been investigated by several workers;1-4 the most recent investigation reported is that of Chipman, Gero, and Winkler.4 Their results, corresponding to slags containing up to 4 pct SiO2, were represented by the equation: 6440 log KMn = +2.95 In this case both slag and metal may be assumed to be ideal solutions, therefore the values of Kmn so derived represent the true constant for the manganese reaction. As the molecular weights of MnO and FeO are almost equal, weight concentration of these oxides may also be used in the above expression. Acidic oxides such as SiO2 and P2O5 affect the activities of FeO and MnO differently, so that when total concentrations by weight of FeO and MnO are used in the above expression for Kmn the values obtained are no longer constant. These will be denoted by K&apos;mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK&apos;mn =3.172 This corresponds to Kmn values much higher than those obtained for pure oxide slags. The results of Körber and Oelsen, and Chipman, Gero, and Winkler are summarized in Table I. In the present investigation it was decided to study the manganese reaction using iron-manganese-silicate slags not saturated with silica, and which fell mainly between the orthosilicate join 2FeO . SiO2 - 2MnO.SiO2 and the FeO-MnO side of the ternary system FeO-MnO-SiO2. It has been shown" that the phases present in solidified slags of this part of the diagram are (FeO, MnO) and (2Fe0.Si02, 2Mn0-SiO,) solid solutions. Such an investigation would be of interest in deoxidation and also gives information on activities in liquid slags. This equilibrium has not as yet been investigated successfully. Hilty and Crafts7 attempted to examine this reaction in a rotating crucible furnace, but were unable to obtain suitable slag samples. In the present investigation one series of experiments was carried out in a rotating crucible furnace, because the success of Taylor and Chipman8 with such a furnace in their study of oxygen distribution between molten iron and (CaO, MgO) — FeO-Si0, slags suggested that it would minimize contamination of the slag by the crucible material. A second series was carried out using a wire-wound resistance furnace. Rotating Crucible Furnace Experiments In all cases the metallic charge consisted of 800 to 1000 g Armco iron containing 0.02 pct C, 0.03 pct Mn, and traces of Si. Manganese and silicon additions consisted of electrolytic manganese (99.9 pct)

Jan 1, 1953

By E. Parthe, J. P. Pemsler

TWO references can be found in the literature concerning the ternary system uranium-tantalum -carbon. C. H. Schramm, P. Gordon, and A. R. Kaufmam reported in this Journal1 on the existence of the ternary carbide "UTa10C4." They also report a second face-centered-cubic carbide phase in the system U-Ta-C, which they denote as "white" phase. The publication includes a reproduction of a Debye-Scherrer powder photograph of "UTa10C4" and a list of the sin2 0 values of this compound. H. Nowotny, R. Kieffer, F. Benesovsky, and E. Laube2 report the complete solid solubility between TaC and UC with a B1 structure. Since the ternary phase "UTa10C4" lies very close to the binary system Ta-C, and the established phase Ta2C with a C27 structure had not been mentioned by Schramm et al., it was thought worthwhile to compare the patterns of "UTa10C4" with Ta2C. The strong lines of the given pattern were indexed on a hexagonal unit cell with the approximate cell parameters a = 3.09A and c = 4.93A. These are the values reported for Ta2C in the literature.3 The correspondence between reported and calculated sin2 8 values may be studied in columns 4 and 5 of Table I. The agreement is fair, but there remain weak lines which cannot be assigned to the hexagonal unit cell. The extinctions correspond to those of Ta2C, but a comparison of the calculated and observed intensities of the Ta2C lines (columns 2 and 3) with those of the corresponding lines of "UTa10C4" (column 6) show occasional deviations. To clarify this situation, four new samples were prepared. The compositions of these samples were chosen in such a way as to observe any existing ternary phase in the system TaC-UC-U-Ta. The samples were arc melted in an inert atmosphere and annealed at 1100°C for 36 to 72 hr. Compositions of the samples determined by chemical analysis are given along with the results of X-ray investigations in Table 11. The following conclusions may be drawn from these data: a) No ternary compounds occur in the section TaC-UC-U-Ta of the ternary system Ta-U-C. The "white" phase reported by Schramm et al. corresponds to a solid solution between TaC and UC. Only one three-phase field exists: C27-B1-A2. (Both tantalum and ? uranium have body-centered-cubic A2 structures.) The a uranium observed in sample 4 transformed from the high-temperature ? phase on cooling. b) The phase Ta2C with a C27 structure extends into the ternary system. "UTa10C4" is, therefore, a uranium-enriched Ta2C. Good agreement is ob-

Jan 1, 1960

ZAY JEFFRIES, Cleveland, Ohio (written discussion?).-The authors conclude that there is a certain average size of precipitated CuAl2 par-ticle which produces maximum strength and hardness in duralumin; that when the size of particle is smaller or larger than this particular size the hardness decreases. The writer agrees with this conclusion, because it seems to he directly indicated by the facts. Why does duralumin present this apparent discrepancy? Let us con-sider some physical aspects of the precipitation of CuAl2 from a saturated solution on cooling. When a molecule of CuAI3 is removed from the solvent, or matrix, and added to another group of CuAl2 molecules, as is known to occur on slow cooling, the forces of adhesion between the CuAl2 molecule and the solvent have been exceeded. Since a. change in tem-perature only is sufficient to cause precipitation, it must also be sufficient to cause the loss of adhesion bonds between the excess CuAl2 molecules and the solvent, or matrix. Lost adhesion bonds means loss of cohesion of the mass as a whole. When duralumin is cooled from 500° in a furnace, globules of CuAl2, large enough to be seen easily with a high-power microscope, are formed. There are, however, globules so small as to be hardly distinguishable, and others too small to be resolved are suggested by the non-uniformity of the surface appearance of the section. As the smallest globule of CuAl2 resolvable with a high-power microscope contains about 2,000,-000,000 molecules, it is evident that with rapid cooling submicroscopic particles of CuAl2 must be present in large numbers; in fact, after quench-

Jan 12, 1919

By P. Chiotti, G. R. Kilp

IN the study of zinc-zirconium1 and zinc-uranium2 systems, vapor-pressure measurements were made in order to establish the equilibrium phase diagrams for a pressure of 1 atm. In each of these systems, only zinc has an appreciable vapor pressure over the temperature range investigated. The zinc pressure was measured over a sufficiently wide temperature and composition range to permit calculation of the standard free energy, enthalpy, and entropy of formation for the compounds ZrZn, ZrZn2, ZrZn3, ZrZn6, ZrZn14 , and U2Zn17. In these calculations the compounds were treated as line compounds. Although the exact composition range was not determined, metallographic and thermal data indicate that the solubility range for these compounds is small. It is to be noted that the compound initially reported to correspond to the formula UZn9, 2 has been shown by the crystal structure work of Makarov and vinogradov3 to correspond to the formula U2Zn17,. The crystal structure is similar to that for the compounds Th2M17, investigated by Florio,4 et al; here M represents iron, cobalt, or nickel. Therefore, thermodynamic calculations are based on the formpla U2Zn17 EXPERIMENTAL The dew-point method employed to measure the vapor pressure of zinc over uranium-zinc alloys has been described previously.2 The same procedure and apparatus were used in measuring the zinc pressure over zinc-zirconium alloys. In the case of alloys in the two-phase region consisting of a zirconium and the compound ZrZn, the Knudsen effusion method was employed to obtain a few values in the temperature range 600" to 560°C. In most cases, tantalum crucibles were used to contain the zirconium alloys. THERMODYNAMIC PROPERTIES OFU2Zn17 A least-squares treatment of the vapor-pressure data obtained for 35 and 65 wt pct U alloys in the temperature range 650° to 940°C gave lOg10PAtm = 7,713/T + 6.33 Here, as in following equations, T represents degrees kelvin and P represents the zinc vapor pressure in atmospheres. The probable errors for the two constants were calculated to be 60.68 and 0.0563, respectively. This relation represents the equilibrium dissociation pressure for the reaction U2Zn17 (s) - 2U(s) + 17Zn(v) The solubility of zinc in solid uranium is negligible and the only additional information required to calculate the free energy of formation of U2Zn17 is the free energy of vaporization of pure zinc. K. K. Kelley5 gives the relations, AF°= 30,902 + 6.03Tlog T + 0.275 X 10-3T2 - 45.03T

Jan 1, 1961

By J. Stuart Warner

The reaction COSO4(c)?CoO(c) + So3(g)was investigated from 950° to 1170OK by two different methods. The sulfate was decomposed in a previously evacuated space and Pso3 calculated from the measured total pressure on the assumption that Pso2 = 2P02. The sulfate was also decomposed under conditions of controlled oxygen pressure. The difference in the results obtained by these experimental techniques is attributed to the effects of thermal diffusion. The standard free energy change for the reaction is given by ?F° = 66,292 + 17.273T log T — 102.57 T (±300 cal/mole). It was found by DTA and X-ray diffraction studies that CoS04 undergoes a transformation at 617°± 4°C. THE metal sulfates may decompose directly to the oxide or pass through one or more intermediate basic sulfates. Provided the oxidation state of the cation does not change in the course of the reaction, the decompositions may be described in general as follows: One of the major objectives of this work was to determine the validity of Eq. [3] as much of the existing sulfate data has been calculated from decomposition pressures by Eq. [5]. The type of apparatus generally used for these measurements consists of a reaction vessel at high temperature which communicates with a manometer at room temperature. A temperature gradient is thus imposed on the gas phase causing thermal diffusion which brings about a partial separation of the different gaseous species present in an initially uniform mixture. The basic theory and experimental facts associated with this phenomenon are summarized elsewhere1 and it will suffice to state here that the heavier gaseous species diffuses down the temperature gradient. Since thermal diffusion destroys the homogeneity of the gas phase, it is not necessarily true that Pso2 = 2Po2 in any particular volume element of the gas phase even though there are twice as many molecules of SO, as of 0, in the gas phase considered as a whole. Under these conditions, the decomposing sulfate gives off SO, which dissociates to SO, and 0, and all three species are distributed throughout the system by thermal diffusion. However, the sulfate will continue to dissociate until the equilibrium value of PSo3 is established on the hot zone. Thermal diffusion may distribute SO2 and O2 throughout the gas phase in any way so long as Eq. [2b] is satisfied in the hot zone; i.e. Pso2(Po2)1/2=K3pso3. When a steady state is reached, we can characterize Pso2 in that

Jan 1, 1962

By Harry M. Mikami, Harold A. Heiligman

The term chromite is often used to cover all chrome ores and concentrates which are the designations actually employed by most industrial users and producers. Chromite is, of course, the predominant mineral in chrome ores which are aggregates of chromite and gangue minerals, most commonly magnesian silicates. Most chrome ores now used are petrographically chromitites which is a rock, rather than an individual mineral term. The title of this chapter, following past usage, is meant in the broad sense. Chromite is the only primary commercial source of chromium. This book is intended to deal only with nonmetallic minerals and rocks. Chromite uses are both metallic (ferroalloys) and nonmetallic (refractories and chemicals), but any discussion of mineralogy, geology, and mining is common for all types. A number of the major commercial ores are interchangeable, and their uses are determined by economic considerations. Mineralogy COMPOSITION [Chromite is a term embracing a wide range of chromium-bearing spinel*-group minerals the compositions of which can be expressed as (Mg,Fe2+)0.(Cr,AI,Fe3+ )203.t This can be further generalized to R2+O.R23+03 and the molecular RO: R,03 ratio is generally close to one. The exact composition may be arbitrarily expressed as a solid solution of six end-members, MgAI2O4, MgCr2O4, MgFe2O4 FeCr2O4, FeA12O4, and Fe2+.Fe23+04 with the proportions of each stated or plotted in the six-cornered prism of Johnston and Stevens61 or this scheme may be simplified to comprise only three endmembers making up a composition triangle, Fig 1. [ ] FIG 1-Triaxial composition diagram showing molecular compositions of chromites listed in Table 1. The RO.Fe2O3 corner includes Ti02 norms listed in the table. Note that the high-alumina chromites (1, 2, 3, 9), form a cluster well apart from the high-Cr2O3 chromites. There is a tendency for high-iron chromites to be higher in Fe2O3 + TiO2 but it is not a consistent or systematic relationship. The MgO/RO ratio must also be known to characterize the chromite chemically. Simplest and most convenient method is Thayer&apos;s&apos; in which a chromite such as (Mg.65Fe.352+)O.(Cr.40Al.50Fe.103+)203 would be written as (Mge,) Cr eAlo. The molecular pro- portions of ferrous and ferric oxides can be seen at a glance as the divalent and trivalent oxides]

Jan 1, 1960

By A. D. Zunkel, A. H. Larson

Equilibrium arsenic contents of Pb-As alloys in contact with PbO-As2O3 slags containing less than 30 mol pct As2O3, were determined at 650°, 700: and 750 C in an inert at?rzosphere. In this temperature range, the arsenic content of the alloy increased with increasing temperature in the single-phase liquid slag region and decreased with increasing temperature in the two-phase slag region and the single-phase solid-solution slag region. The PbO-As2O3 phase diagram below 22 mol pct As2O3 was determined by thertrzal analysis and by application of a log ?As2O3/?PbO vS log XAs2o3 /x3pbO plot determined from the equilibrium actiuity data. The resulting phase diagram was not well-defined since the eutectic temperature was not detected in the thermal analysis experiments, although a region of terminal solid solubility of As2O3 was found. Results from the phase diagram determination are compared with an existing diagram in the literature. THIS experimental investigation is an extension of a study by the authors1 on the slag-metal equilibria in the systems concerned with commercial lead refining processes such as softening and dross fuming. The first part of this investigation was a study of the slag-metal equilibria in the Pb-PbO-Sb2O3 system. The only experimental work previously done on the Pb-PbO-As2O3 system was by Pelzel2,3 in which the phase diagram for the PbO-As2O3 system was determined below 50 wt pct As2O3 and the equilibrium constant for the reaction 3Pb + As2O3 + 3PbO + 2As was determined as a function of temperature. No slag-metal equilibrium data have been determined. It is due to the scarcity of information regarding the Pb-PbO-As203 system that this work was undertaken. This paper describes the determination of the slag-metal equilibria in the Pb-PbO-As203 system by equilibrating Pb-As alloys with PbO-As2O3 slags in an inert atmosphere, the effect of 1 wt pct additions of bismuth and copper on the slag-metal equilibria, and the PbO-As2O3 phase diagram both by thermal analysis and the use of the slag-metal equilibria data. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade and assayed as follows: 1) 99.8 pct PbO (0.014 pct insoluble in CHJCOOH, 0.02 pct not precipitated by H2S, 0.1 pct CaO, and 0.08 pct SiO2); 2) 99.95 pct As2O3; 3) 99.99 pct Pb; 4) 99.0 pct As; 5) 99.99 pct Cu; and 6) 99.97 pct Bi. Room-temperature X-ray patterns revealed no detectable impurities in any of these materials. Apparatus for Equilibrium and Thermal-Analysis Determinations. The resistance-heated crucible furnace used in this investigation employed nichrome elements and was mounted so that it could be raised to surround the reaction tube during each experiment and, subsequently, lowered. A schematic diagram of the apparatus is shown in Fig. 1. Each charge was heated in a 3+-in.-OD by 31/2-in.-high 416 stainless-steel crucible placed in a 41/4-in.-1D by 18-in.-long fused-silica reaction tube which was closed at one end. On a shoulder around the crucible was placed a 3: -in.-OD by 12-in.-long open-end fused-silica condenser tube. The open end of the reaction tube was covered by a water-cooled brass cap with ports for 1) admitting an inert atmosphere to the system through a stopcock, 2) introducing a stainless-steel, motor-driven, paddle stirrer into the crucible, 3) evacuating the system with a mechanical vacuum pump, and 4) sampling the melt with Vycor sampling tubes. The brass cap was fitted to the open end of the reaction tube with a silicone gasket and collar clamp. The furnace temperature was controlled by a Barber-Coleman Capacitrol controller and a chromel-alumel thermocouple. Due to the corrosiveness of the melt, the controlling thermocouple also served as the measuring thermocouple. The temperature of the melt was calibrated against the controller temperature and was checked periodically during each test with a Vycor-enclosed calibrated chromel-alumel thermocouple. The temperature measurement and control can be considered accurate to ±3°C. Procedure. The charge placed in the crucible for each experiment consisted of 1000 g of Pb-As alloy and 300 g of PbO-As2O3 slag. The crucible was then placed in the reaction tube, the condenser tube was placed on the shoulder of the crucible, the silicone gasket and brass cap were fitted on the open end of the reaction tube, and the entire system was evacuated and filled with argon ten times. After the last flushing, a positive argon pressure of 1 psig was impressed on the system. The furnace was then raised to sur-

Jan 1, 1968

CONTENTS PAGE BARTON, D. C.-The Eötvös Torsion Balance Method of mapping Geologic Structure (T. P. No. 50) 1 GEORGE, P. W.-Experiments with Eötvös Torsion Balance in the Tri-State Zinc and Lead District (T. P. No. 65). 15 LANCASTER-JONES, E.-The Computation of Eötvös Gravity Effects (T. P. No.75) HEILAND, C. A.-A Cartographic Correction for the Eötvös Torsion Balance-(T. P. No. 52) 17 SLICHTER; L. B.-Certain Aspects of Magnetic Surveying (T. P. No. 120). . . . 18 WEAVER, W.-Certain Applications of the Surface Potential Method (T. P. No.121) LUNDBERG, H.-Recent Results in Electrical Prospecting for Ore (T. P. No. 98). . 20 HOTCHKISS, W. 0., ROONEY, W. J. and FISHER, J.-Earth-resistivity Measure-ments in the Lake Superior Copper Country (T. P. No. 82) 21 LEONARDON, E. G. and KELLY, S. F.-Some Applications of Potential Methods to Structural Studies (T. P. No. 115) 23 MASON, M.-Geophysical Exploration for Ores (T. P. No. 45) 25 The Eötvös. Torsion Balance Method of Mapping Geologic Structure Discussion of the paper of D. C.. Barton, issued as Technical Publication No. 50 with Mining and, Metallurgy, February, 1928. D. C. BARTON.-The field surveys which I have been privileged to use as illustrations for this paper were done for Mr. DeGolyer&apos;s companies and were released through his favor. W. J. MILLARD, Tulsa, Okla.-Has any oil been found by the torsion balance in West Texas? D. C. BARTON.-NO new oilfield has been discovered on the basis of torsion balance work. It has had some part in controlling the policy of certain companies in playing the extension of known oil fields. A number of "T. B." structures have been drilled and dry holes obtained. Of those known to the writer, one apparently was a structural high, one is a broad general high but locally low and probably is a deep-seated structural high, one seems normal although the control is poor, and one was considered structurally low but is now suspected by some geologists of being structurally high. E. L. DEGOLYER, New York, N. Y.-A large gravity structure, generally referred to, I believe, as the Crosby County Structure, has been found in West Texas. This structure is perfectly symmetrical with the arrows all pointing toward a common center, very much like the Nash salt-dome pattern in Dr. Barton&apos;s paper (Fig. 9). One of the peculiar things about it, from the standpoint of the gravity high, is that it is so

Jan 1, 1928

By F. B. Foley

A description of tests made by a committee of the Division of Engineering of the National Research Council to determine whether velocity of impact affects the formation of Neumann bands. FOREWORD Not infrequently, in the case of the failure of a metal structure, such as a bridge, tank, airplane, gun carriage, etc., a doubt arises whether the failure was due, among other causes, to the effect of an overburden or of an explosive maliciously or accidentally exploded in contact with it. As few means of discriminating between the effects of these causes have been known and these means were of a rough qualitative character, it was surprising to find in the record of an inquiry into the failure of a structure, the statement that, by observations on the Neumann bands in the structure, it was possible to determine the speed of breakage in the metal and to distinguish between a fracture caused by an explosion and one caused by an ordinary mechanical strain. Such a criterion, if well proved, was of value to the explosives experts of the Bureau of Mines, the Ordnance Department of the United States Army and the Bureau of Ordnance of the United States Navy, but search showed no record of it in the literature nor did any of the metallurgists and metallographers consulted know of any data on which such a criterion could be based having been assembled and critically studied. However, it was universally held that there was promise in the idea and that there existed unique facilities at the Bureau of Mines Experiment Station at Pittsburgh for the preparation, under definitely known conditions, of material for study by metal-lographers, and that material of value might also be obtained from the proving grounds of the Army and Navy. Therefore, with the approval of the Director of the Bureau of Mines and the Chiefs of Ordnance of the War and Navy Departments, the Chairman of the Division of Engineering of the National Research Council, on April 12, 1919, appointed a Committee on the Investigation of Neumann Bands, which has since been engaged in this study and which, after some slight change in its personnel, consists now of the following: Dr. William Campbell, Advisory Metallurgist, Bureau of Ordnance, Navy Department. F. B. Foley, Metallurgist, Bureau of Mines. S P. Howell, Explosives Engineer, Bureau of Mines. Comdr. O. M. Hustvedt, U. S. N., Bureau of Ordnance, Navy Department. Dr. Charles E. Munroe, Chief Explosives Chemist, Bureau of Mines.

Jan 9, 1922

By G. F. Tagg

In an earlier paper1, the author described a method of interpreting earth-resistivity curves, based on the theoretical investigation of a single horizontal underlying stratum. If the four-electrode system of Wenner is employed, the resistivity in a homogeneous soil is given by the formula p = 2paR [1] where a is the electrode separation and R is the resistance of the earth between the two inner electrodes. If the earth is not perfectly homo¬geneous, the application of this formula gives an apparent specific resistance varying with the electrode separation. In the special case of the single horizontal underlying stratum, there is a surface layer of thickness h and resistivity pi and a lower layer, extend-ing to infinity, of resistivity p2. It has been shown by Lancaster-Jones2 that the apparent resistivity, obtained by an application of equation 1 is related to the true resistivities, the depth h and the electrode separation a by an expression of the form pa/p1 = 1 + 4F [2] where Pa is the apparent resistivity and F is a function (actually an infinite series), of the ratio h/a, and a reflection coefficient k = (p2 - p1)/(p2 + p1). For given values of h/a and k, the right-hand side of equation 2 can be calculated, and curves drawn showing the relationship between Pa/P1, h/a and k. Such a set of curves for the case when pi > P2 is given in Fig. 1.

Jan 1, 1937

By W. J. Wrazej

THE measurements on the formation of multi-layered scales on pure iron1 and the metal -lographic examination of the produced layer of FeO, Fe,O,, and Fe2O3 shown in micrographs2 throw much interesting light on this apparently well-known subject. Professor Paidassi announced2 that in a few months7 time further results are going to be published with regard to the growth of Fe2O3 and Fe2O3 layers on an Armco iron as a function of temperature. Because of the very thin layers of Fe2O3 which are shown by Paidassi (Fig. 10 of ref. 2) when samples were scaled in air at 700°C for 4 hr and because this is not in agreement with the present author&apos;s previous observations, the following experiment was recently carried out. Polished cylindrical samples 13/64 in. in diam and 1/4 in. long from electrolytic iron used for spectro-graphic work (Hilger, H.S. Iron rods, F.693) and an Armco iron sample 1/4 in. in diam of the same length were suspended in a muffle furnace on Nichrome wire and annealed in air for 4 hr at 700°C 5OC. Because of the known easy peeling off of the Fe2O3 layer which is mainly in the form of powder (purple red dust on the surface) the samples were protected against any draft and shock. After annealing, the samples were cooled in air and placed in the mount-

Jan 1, 1954