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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 W. J. Romanow

RECENT papers by Williams, Sherwood, and Boothby,1 Seybolt et al.2 Heikes; and Roberts4 attest to the increasing importance of the hexagonal ferromagnetic compound MnBi. Since the magnetic properties of MnBi crystals are highly anisotropic, it is useful and necessary to have appropriate aids for determining their orientations—a (00.1) standard stereographic projection and a corresponding table of crystallographic angles for this structure. The tables of crystallographic angles for the hexagonal system available in the literature5 are computed for c/a ratios greater than that of MnBi and cannot satisfactorily be used to find the crystallographic angles of MnBi. A table of angles between the crystallographic planes (HK.L) and (hk.1) was calculated for MnBi from the formula0 F=are cos Hh+Kk+ 1/2(Hk+hK) + 3/4 (a/c)2Ll/v(H2 + K2 + HK + 3/4 (a/c)2L2) (h2+ k2+hk + 3/4 (a/c)2l2) on an IBM Type 650 Magnetic Drum Data Processing machine. The lattice constants used are listed in Table I and are those determined by Willis and Rooksby7 at 20°C. More recently published values obtained by both X-ray and neutron diffraction"' show no difference from these significant to the calculation. From the crystallographic angles between the basal plane (00.1) and the general plane (hk.1) in Table I, an (00.1) standard stereographic projection was made for MnBi which is shown in Fig. 1. Acknowledgments The author wishes to thank R. G. Treuting and J. N. Hobstetter for their technical assistance, and Miss D. P. Booth for programing the IBM machine for the calculations. He appreciates the opportunity to read the paper of B. W. Roberts of General Electric Co. prior to its publication. References 1H. J. Williams, R. C. Sherwood, and 0. L. Boothby: Bulletin Amer. Physical Soc., 1956 vol. 1, p. 132. 2 A. U. Seybolt, H. Hangen, B. W. Roberts, and P. Yurcisin: AIME Trans., 1956, vol. 206, p. 605: Journal oF Metals, May 1956. 3R. R. Heikes: Physical Review, 1955, vol. 99, p. 446. .B. W. Roberts: A Neutron Diffraction Study of the Structures of Manganese B.W.Roberts:ANeutronDiffractionBismuthide, Physical. Review, 1956, vol. 104, p. 607. 5 A. Taylor and S. Leber: AIME Trans., 1954, vol. 200, p. 190; JouRNal of Metals February 1954. « C. S. Barrett: Structure of Metals, 2nd Ed., p. 635. McGraw-Hill Book Co. New York and London, 1952. 7B. T. M. Willis and H. P. Rooksby: Proceedings Physical Soc., London, 1954, vol. 67B, p. 290.

Jan 1, 1958

By Charles R. Keyes

PAGE. I Introduction,........674 11. Occurrence............ 676 III. Geology of Death Valley BoRate-Region,....677 1. Surface.Relief ......677 2. Geologic Formations,....680 3. Geotectonics,..684 IV. FURnace Canyon Deposits..686 1. General Features..686 2. Geologic Structure..688 3. Ores.....690 4. Typical Section ...691 V. Lost Valley Deposits...693 VI. Mojave Desert Deposits..693 1. Distribution....693 2. Geologic Structure ........694 3. Ores............ 696 VII. Santa Clara Valley Deposits .699 1. Distribution....699 2. Geologic Structure..700 3. Ores.....700 VIII. Ventura County Deposits..701 IX. Geologic Occurrence of Borax .701 1. Original Sources...701 2. Solfataric Borax...702 3. Lacustrine Borax...703 4. Marsh Borax....703 5. Terranal Borax...704 X. Chemistry of Natural Borates.... 705 1. General Considerations.....705 2. Composition of Saline Waters...706 3. Solubility of Components....707 4. Time-Element in Water.Concentrations . 707 5. Effect of Temperature.....708 6. Effect of Pressure......709 XI. Occurrence of Other Commercial Salines,.... 709 I. Introduction. A complete transforrnation has taken place in the borax industry during the year 1908. A most remarkable factor in

Jan 1, 1910

By A. E. Dwight, A. F. Berndt

ThE published U-Ru equilibrium diagram indicates the existence of six intermetallic compounds in this system.' The structure of only two of the compounds, u2Ru2,3 and URU3,4 have been identified. This communication reports on the crystal structure and density of Uau3, which is formed by a peritectoid transformation at 1025° ± 5°C: U3Ru4 + U3Ru5 = U2Ru3. An alloy with the stoichiometric formula U2Ru3 was prepared by arc melting electrolytic uranium and ruthenium of 99.9 pct purity on a water-cooled copper hearth under an argon atmosphere. After homo-genization at 1000°C for 3 days, a metallographic examination revealed that the peritectoid transformation was complete and less than 5 pct of a second phase was present. A powdered sample, obtained by crushing the brittle compound, was annealed for 1 hr at 1000°C and air-cooled. Debye-Scherrer patterns were obtained with filtered CrKa, FeKa, CoKa, or CuKa radiation. The X-ray patterns of U2Ru3 weFe indexed as an fcc structure with a. = 12.895 0.00lA. The unit-cell constant and its standard deviation were calculated by a computer program described by Mueller, Heaton, and Miller.5 The density, measured by an immersion method, was 14.45 g cm-3. A calculated density of 14.48 g cm-3 was obtained on the assumption that twenty-four formula units (120 atoms) comprise a unit cell. The space group is either oh7 Fd3m, or the less symmetric, T4h, Fd3, since reflections indexed as hk0 with h + k + 4n are absent. All values of h2 + k2 + 12 permitted by both space groups are listed in Table I together with dc, do, and I. values. The calculated d spacings were obtained by the computer program of Mueller, Meyer, and simonsen.6 The observed d spacings above 0.77A were obtained from X-ray" patterns prepared with CuKa radiation, above 0.90A with CoKa radiaaion, above 0.98A with FeKa radiation, and above 1.16A with CrKa radiation. An attempt was made to identify the crystal structure of U2Ru3 by comparison with published data on other A2B3 compounds. A recent compilation7 of intermetallic compounds lists thirty-two structure types with the A2B3 stoichiometry. Only two of the structure types are fcc and they are Sb2O3(r), senarmontite, with 16 Sb2O3 per unit cell, and In2Te3 for which several structures have been proposed.8 However, the two cases cited do not have twenty-four formula units in the unit cell. We therefore, cannot identify UPRU3 with any of the other known A2B3 compounds. Ternary alloys were made in which 5 at. pct Os, Rh, or A1 were substituted for 5 pct of the Ru in U2Ru3. The osmium substitution increased the unit cell constant to 12.899 * .001A, which is to be expected since the atomic volume of osmium is slightly larger than

Jan 1, 1969

By S. H. Cathcart

Price, production and drilling operations exceeded any year since 1930. A top price for crude of $2.55 was maintained from May 1 to November 6 and increased activity about coincides with that period. The average crude price for the year was: Bradford, $2.46; Kane-Butler, $2.34; Southwest Pennsylvania, $2.13. Production for the year exceeded 15 million barrels, an increase of about 2 million barrels over 1933. That this increase was more than justified by market demand is indicated by a reduction of 892,000 bbl. in stocks for the year. Two classes of data appear on Table 1, which are differentiated by footnote references. Where possible the .figures were obtained from individuals and companies that, from long acquaintance and varied contacts, are most capable of supplying an estimate where an estimate is necessary. The remaining data represent a rather careful compilation from all available published records (see p. 378). Drilling operations and production as summarized by the Oil City Derrick are as shown on Table 2.

Jan 1, 1935

By Lombard Squires, W. K. Lewis, W. I. Thompson

Clays consist predominantly of hydrated silicates of alumina. The formula is frequently assumed to be A1203 . 2Si02 . 2H20,'and certain of I. North Carolina. Low plasticity. 11. Same as I, after washing. Low plasticity. III. Tennessee. Good plasticity. IV. Pennsylvania flint fireclay. Low plasticity. V. Laredo, Texas. Very plastic. CaO/Na2O corrected for GO2. VI. San Antonio, Texas. Fine grained, highly plastic. Moisture and CO2 were determined together at 18.8 per cent. VII. Selected crude bentonite, California. " Data from R. Ries: Clays. John Wiley & Sons, New York, 1927. them undoubtedly have substantially this composition, but in general the ratio of silica to alumina is considerably higher. However, they always contain water of chemical constitution, as shown by Table 1.

Jan 1, 1935

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was ('Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By J. H. Palm

Experiments have shown12 that the formula -S = St - (St - Se')e ne [1] expresses very well the relation between the true stress S and the true form monotonic deformation of plastic metals in single tension and compression (Fig 1). St (asymptotic or final stress), Se' (threshold stress) and ne (characteristic or specific strain) are constants, the significance of which immediately follows from Fig 1. Only at the initial stages of deformation the experimental curve runs below the theoretical curve. This may be due, at least partly, to the uneven stress distribution caused by the anisotropy of the crystals. It is now obvious that a similar formula H = Ht- (Ht- He)e ne' [2] might be valid for the relation between the hardness and the strain. The hardness can be only a function of the strain and must therefore be independent on the hydrostatic tension present in the neck during straining. Hence, if Eq 2 is correct it will also represent the relation between hardness and strain in the middle section of the neck, the strain of which is generally assumed to be almost or fully homogeneous. For aluminum, copper, and several copper alloys it is indeed observed that Eq 2 agrees very well with the experimental Vickers hardness-strain relation from zero strain on up to the strain at fracture. Moreover nc' is, for several metals fairly equal to nc- Hence H = C1 + C2S [3] C1 and C2 are constants during uniform uniaxial tension. Eq 3 was also obtained for copper by Voce.3 According to Hencky's theory4 the ratio of the Brinell or Vickers hardness and the yieldstress (expressed in kg per mm2) of a non-strainhardening metal is approximately equal to 2.8. If Eq 1, 2 and 3 are correct the ratio Ht/S, must accordingly be the same for all plastic metals and be equal to 2.8. It is now experimentally established that this ratio varies between 2.7 and 3.1 with a mean value of 2.9. Taking into account that Ht and especially St can be obtained only by extrapolation from the range of rather low strains, the agreement with the theory is very satisfactory. References 1. J. H. Palm: Appl. Sci. Res. Al (1948) 198. 2. E. Voce: Jnl. Inst. of Met. (1948) 74, II, 537. 3. E. Voce: Metal Treatment (1948) 15, 53. 4. H. Hencky: Zlsch. f. angew. Math. and Mech. (1923) 3, 241.

Jan 1, 1950

By John B. Goddard, David R. Brosnahan

Leaching of uranium in situ from sandstone deposits with ammonium carbonate solution containing dissolved oxygen occurs rapidly compared with the leaching of the bulk of the sulfur present as FeS2. However, because of their high reducing capacity and their relative abundance, the FeS2 minerals consume the bulk of the oxidant. A pressure leach apparatus was constructed that permitted measuring oxygen consumption by FeS2, best described by a first-order reaction. The experimental rate constants for various cores are roughly proportional to their FeS2 contents.

Jan 1, 1983

By Paul M. Tyler

MINOR industrial minerals included in this chapter are: the alum minerals, bromine, calcium chloride, epsomite and other natural magnesium salts, iodine, meerschaum, quartz, industrial crystals other than quartz (Iceland spar, tourmaline, fluorite, selenite, mica), and nonfuel gases (air, helium, carbon dioxide). ALUM MINERALS The alums comprise a series of double sulphates (or selenates) isomorphous with potash alum, which, according to a ruling of the Pennsylvania courts, is the only product commercially described simply as "alum." Common alum occurs in nature as kalinite (K2SO4- A12 (SO4) 324H2O). The mineral mendozite (Na2S04) 3.A12 (SO4)3- 24H2O) is soda alum; tschennigite (NH4)2SO4.Al2 (SO4)3.24H2O) is ammonium alum; and there are about a dozen other native alums and related double sulphates. Alunite (alumstone or alum rock) has the formula Al2(SO4) 3.K2S04.4A1 (OH)3 and alunogen, Al2(So4) 3.18H20. Saline residues, found wherever natural water is evaporated, may contain sulphate of alumina, which for most uses is the essential ingredient of alum. Mineral wells and springs that emerge from beds of pyritiferous shale are typically astringent and at times form local deposits of alum, generally as incrustations. Acid waters acting upon aluminous rocks may form sulphates of alumina. The alums of commerce, as well as aluminum sulphate (concentrated alum), are produced principally by treating bauxite with acid, but they have been made also on a substantial scale from clay, cryolite, pyritic slates, schists, lignites, alunite, and leucite. Alum shale-chiefly clay, pyrite, and (usually) carbonaceous matter-was extensively used in England as a source of alum for more than two centuries. In France, pyritic lignites mixed with sand and clay were burned in heaps to red ash, the leach Liquors from which, after treatment with ammonia, yielded alum and copperas. Processes have been developed for making alum or aluminum sulphate from such diverse materials as feldspar, aluminous phosphate minerals, greensand, and mixtures of mica and

Jan 1, 1949

By H. Margolin, E. Ence

A. J. Goldak and J. Gordon Parr University of Alberta) —Margolin and Ence's paper reached us only a few days after we had submitted a paper on the structure of Ti2Cu to the AIME. Here, however, we only wish to point out an error in the paper (page 321): "Karlsson has reported the crystal structure of the first intermediate phase occurring in the Ti-rich portion of the Ti-Cu system to be face-centered tetragonal." Karlsson actually reported the structure of Ti3Cu (i.e., "the first intermediate phase") to be primitive tetragonal with four atoms per lattice point: Cu at 0, 0, 0; and Ti at 1/2, 1/2, 0; 0, 1/2, 1/2; and 1/2, 0, 1/2. Thus, Karlsson suggests a primitive lattice with an ordered arrangement of atoms located at corners and face-centers: Ence and Margolin suggest a random body-centered tetragonal structure—-with which our results agree. E. Ence and H. Margolin (azlt1zo.l-s' reply)— We do not agree that Karlsson has not reported the structure of Ti3Cu as face-centered tetragonal. The fact that Cu atoms are located at the corners and titanium at the face-centers does not indicate that the lattice is not face-centered. We are pleased that the discussers' results agree with our own.

Jan 1, 1962

By M. G. Benz, J. F. Elliott

A. J. Goldak and J. Gordon Parr (U)iuersity of Alberta) —Margolin and Ence's paper reached us only a few days after we had submitted a paper on the structure of Ti2Cu to the AIME. Here, however, we only wish to point out an error in the paper (page 321): "Karlsson has reported the crystal structure of the first intermediate phase occurring in the Ti-rich portion of the Ti-Cu system to be face-centered tetragonal." Karlsson actually reported the structure of Ti3Cu (i.e., "the first intermediate phase") to be primitive tetragonal with four atoms per lattice point: Cu at 0, 0, 0; and Ti at 1/2, 1/2, 0; 0, 1/2, 1/2; and 1/2, 0, 1/2. Thus, Karlsson suggests a primitive lattice with an ordered arrangement of atoms located at corners and face-centers: Ence and Margolin suggest a random body-centered tetragonal structure—-with which our results agree. E. Ence and H. Margolin (authors' reply)— We do not agree that Karlsson has not reported the structure of Ti3Cu as face-centered tetragonal. The fact that Cu atoms are located at the corners and titanium at the face-centers does not indicate that the lattice is not face-centered. We are pleased that the discussers' results agree with our own.

Jan 1, 1962

By A. U. Seybolt, D. H. Haman

The rate of oxidation of the lowest nitride of chromium, Cr2N, was measured to be equal to the rate of oxidation of chromium metal. It was found that, while the presence of Cr2N in chromium does not affect the oxidation mechanism, a long exposure at high temperature affects the morphology of Cr2N in chromium, causing a massive internal nitriding along chromium pain boundaries. Marker expen' -ments showed that the rate of oxidation of Cr2N layers on chromium is determined by the rate of chromium diffusion through Cr,03. The rate of formation of Cr2N is determined by diffusion rate of nitrogen through Cr2N. This rate at 1000°C is around thirty times faster than the rate of oxiahtion. Evidence is presented which suggests that nitrogen from the air reaches the chromium through the Cr2O9 by migration through pores or cracks rather than by a diffusive process. IT has long been recognized that, when chromium or alloys containing substantial amounts of chromium are oxidized in air, some chromium nitride (Cr2N) is formed under the oxide scale. Although the presence of this nitride layer has often been described, there appears to have been no systematic study of the role played by the nitride during the oxidation process. Indeed, there have been conflicting re-ports'92 on the kinetics of oxidation of chromium and chromium alloys in air and in oxygen. However, it is now well-established'-5 that the rate-controlling process during the parabolic oxidation of chromium to Cr2O3 is chromium-ion diffusion through Cr2O3. Because of the importance of chromium-containing alloys as oxidation-resistant materials, it seemed desirable to investigate the behavior of chromium during oxidation with and without the presence of chromium nitride. Since a semicontinuous Cr2N layer forms relatively early during the oxidation of chromium in the air, chromium atoms must either pass out of or through the Cr2N layer to become incorporated in the growing Cr2O3 scale. Therefore, it seemed desirable to examine the oxidation behavior of the pure nitride. MATERIALS AND EXPERIMENTAL PROCEDURE The chromium used in this investigation consisted of slices of an ingot made from "five-nine" iodide chromium which had been argon-atmosphere melted in a Y2O 3-stabilized ZrO2 crucible in an induction furnace. The only impurity of any significance was 625 ppm of 0, which was usually reduced to a microscopically invisible amount by hydrogen annealing at 1400°C. However, one sample of chromium was used with the as-cast oxygen level as explained below. The samples were used after abrading through 600 Sic paper and then washing in toluene and alcohol. Both nitriding and oxidation experiments were performed in a vertical tube furnace connected to a glass vacuum system. 'This system was equipped with pressure measuring instruments for the range of 10 p to 1 atm, and a cartesian-diver pressure-control device was used in conjunction with a needle valve to allow control of pressure in the range of about 10 to 760 mm. The nitrogen or hydrogen gas was purified by passing through hot copper chips at 600°C, anhydrous calcium sulfate (Drierite), and liquid nitrogen. Oxygen gas was dried through the Drierite column and a dry-ice trap (-78°C). Changes in specimen weight were followed by a Pyrex helix used in conjunction with a cathetometer which could reproducibly be read to +0.001 cm, yielding an accuracy of about +0.2 mg. The spring was maintained in the cool upper part of the furnace tube where the temperature did not rise above about 35°C. The nitride in equilibrium with metallic chro-

Jan 1, 1964

By Michel Elle, John Chipman

The equilibrium of gaseous H20-H2 mixtures with liquid iron-columbium alloys in the range 0.2 to 2.4 pct Cb shows that the activity coefficient of oxygen is strongly diminished by Cb. The oxide in equilibvium with the melt is identified as CbO2. The equi-librium constant at 1600 deg C is [%Cb][fo. % 0]2 = 2.9 x 10-4 where log fo= —0.14 [%Cb]. The deoxidizing power is comparable to that of vanadium, COLUMBIUM (niobium) is finding increasing use as an alloying element in steel. It forms several stable oxides and is removed from the steel bath by oxidizing slags. The specific oxide formed in steel-making is not known although Sazanov snd Shvarts-man,' in their study of its partition between slag and metal, have assumed this to be Cb2O5 It is the purpose of this study to determine its deoxidation equilibrium at 1600°c, the nature of the oxide formed and the interaction between columbium and oxygen in the melt. The investigation was based on the reaction H2 + O=H2O; Kl=ph2o/(pH2[%O]) [1] in which 0 signifies oxygen dissolved in the liquid Fe-Cb alloy. The method and equipment of recent studies2,3 were utilized. In brief, the molten alloy, contained in a small crucible, is held in a controlled mixture of steam, hydrogen, and argon until equilibrium is reached. It is then cooled quickly in a stream of helium and analyzed for columbium and oxygen, the latter by vacuum fusion.4 The solubility of the oxide in liquid iron is determined by visual observation of scum formation on the surface of the melt. Crucibles of MgO proved unsatisfactory because of partial reduction at the metal interface. Pure A12O3 crucibles were heavily blackened by the melt and could not be used at high concentrations of columbium. Silica crucibles were more satisfactory but these introduced some silicon into the melt thus necessitating an uncertain but small correction for its effect on the activities of the other solutes. In silica it was possible to observe the scum formation when the melt became saturated and there was no apparent reaction between scum and crucible. The procedure for saturated melts was as follows. The alloy charge composed of electrolytic iron and columbium grain was melted and held at constant temperature. The gas ratio H2O:H2 was progressively increased by raising the saturator temperature until a point was reached at which a bright film appeared on the surface and covered it completely. This film could be dissolved by raising the temperature of the melt and it reappeared when the temperature was lowered. Under a partial film covering, utilizing bare areas for temperature measurement, the melt was brought to equilibrium with the atmosphere by holding at temperature for about 1 hr as suggested by Dastur.5 INTERACTION IN THE MELT Several experiments were made without columbium to establish a base in silica crucibles. The results are shown in Table I. Except for one run, they agreed well with Floridis1 comparable results in other crucibles. The value of log K1 is taken from Table I as 0.58. This is slightly larger than Floridis' result, probably because of less elaborate safeguards against thermal diffusion. Results obtained in the Fe-Cb-0 series in which no scum formed are shown in Table 11. The equilibrium ratio Kl is defined as ph2o/(ph2[%O]). It is related to the equilibrium constant K1 as follows:

Jan 1, 1962

By J. W. Downey, R. A. Morris, M. V. Nevitt

An experimental survey has determined the occurrence of Ti2 Ni-type phases in binary and ternary alloys of Ti, Zr, or Hf with first, second, or third long-period transition metals and also in ternary systems in which 0 is the third component. The existence of eleven previously unreported isomorphs is cited and some approximate phase boundaries are given. Lattice parameters are reported for the new phases. The periodic table relationships involved in the occurrence of the phase are discussed. A previous paper' reported the occurrence of a group of Ti2Ni-type phases (structure-type E93) containing Zr in combination with Rh, Ir, and Pt, and Hf in combination with Rh, Pd, Ir, and Pt, and cited evidence to show that all of the Zr phases and the Hf-Pd phase are not binary phases but occur only when 0 is present. More recently one of the present authors found that in the ternary systems of Ti and 0 with Cr, Mn, Fe, Co, and Ni the occurrence of the Ti2Ni-type phase could be correlated qualitatively with valency electron concentration, and that the role of 0 appeared to be that of an electron acceptor.' This paper describes the results of a broader investigation of the occurrence of Ti2Ni-type phases in binary and ternary systems containing Ti, Zr, or Hf. EXPERIMENTAL PROCEDURE Alloys were prepared by arc melting. The purity of the metals Zr, Rh, Hf, Ir, Pd, and Pt was given in the previous paper.' The additional materials used for this work were metals with a minimum purity of 99.9 pct and reagent grade ZrO2, TiO2, Cr2O3, and NiO. Chemical analysis of several alloys in each system indicated good agreement between intended compositions and cast-button compositions. For the heat treatment precautions were taken to avoid oxygen contamination. The specimens were wrapped in Mo foil and sealed in fused quartz tubes at a room temperature pressure of 1 x mm of Hg. These capsules were then annealed in a vacuum furnace at an external pressure of 5 X mm of Hg. Since the major constituent in most of the alloys studied was the brittle Ti2Ni-type phase, Debye-Scherrer patterns with sharp lines could be obtained with powder crushed from the annealed solid samples without being reannealed. Metallographic, X-ray diffraction, and density determination techniques previously described1, 2 were used. RESULTS AND DISCUSSION Zr-Rh-O, Zr-Ir-Oand Zr-Pt-O Systems-Figs. 1 through 3 show the approximate boundaries of the Ti2Ni-type phase fields at the temperatures indicated in the ternary systems Zr-Rh-O, Zr-Ir-O and Zr-Pt-0. In each isothermal section the Ti2Ni-type phase field is labeled E and the unidentified binary phase found in the previous work' is labeled ?. The dotted lines, which are not phase boundaries, correspond to the composition (Zr2 B)1-xOx. In each system the Ti2Ni-type phase field is displaced to the high-Zr side of this composition line. However, the departures from Zr2B stoichiometry for the metal components are not as high as Zr3B, as was inferred from the previous work. Lattice parameters of the Ti2Ni-type phases in the alloys shown as triangular data points in Figs. 1 through 3 are given in Table IA. The probable compositions of the Ti2Ni-type phases have been estimated from the isothermal sections. Although there are a few exceptions that probably result from uncertainties in phase boundary location and from the effect of variation of oxygen content, the generalization can be

Jan 1, 1961

By W. L. Austin

AT the Steptoe metallurgical plant, where ore of the Nevada Consolidated Copper Co. is beneficiated, a small copper-leaching annex has been in operation treating flue dust from roasting-furnace dust chambers, together with a siliceous oxidized ore. This leaching plant was designed to obviate smelting low-grade siliceous flue dust, which interfered with the operation of the reverberatories by forming a blanket on the charge The major portion of the copper content of the flue dust accumulating in the upper chambers of the. roaster flue, and at the stack, is water soluble, and also contains much free sulphuric acid and soluble sulphate It was found that sufficient acid could be obtained by mixing this material with water to provide a lixiviant for leaching the siliceous copper o mentioned. This was the sole source of the lixiviant used in the operatic to be described. An analysis of the flue dust showed it to be composed as follows: Per Cent. Copper 3.00 SiO2 23.41 Fe : 4.08 CaO + MgO : 2:72 Al203 6.07 Free H2SO4 19.94 S03 combined as sulphate 25.10 H2O combined With the sulphates 10.67 0 2.50 Total 97.49 Copper soluble in dilute H2SO4 2,56

Jan 7, 1914

By W. L. Austin

At the Steptoe metallurgical plant, where ore of the Nevada Consolidated Copper Co. is beneficiated, a small copper-leaching annex has been in operation treating flue dust from roasting-furnace dust chambers, together with a siliceous oxidized ore. This leaching plant was designed to obviate smelting low-grade siliceous flue dust, which interfered with the operation of the reverberatories by forming a blanket on the charge. The major portion of the copper content of the flue dust accumulating in the upper chambers of the roaster flue, and at the stack, is water soluble, and also contains much free sulphuric acid and soluble sulphates. It was found that sufficient acid could be obtained by mixing this material with water to provide a lixiviant for leaching the siliceous copper ore mentioned. This was the sole source of the lixiviant used in the operation to be described. An analysis of the flue dust showed it to be composed as follows : Per Cent. Copper.............................................. 3.00 siO2................................................. 23.41 Fe................................................... 4.08 CaO + MgO......................................... 2.72 Al203................................................ 0.07 Free H2S04........................................... 19.94 SO3 combined as sulphate.............................. 25.10 H2O combined with the sulphates....................... 10.67 0................................................... 2.50 Total................................... 97.49 Copper soluble in dilute H2SO4.......................... 2.56 The oxidized ore, locally known as carbonate, has the following composition:

Jan 1, 1915

By A. G. Guy

IN the course of a research on steady-state diffusion it became necessary to make diffusion calculations for a finite solid. This problem was found to be sufficiently different from the corresponding problem for the semi-infinite solid for an entirely new approach to be necessary in obtaining a useful solution. The assumption of an exponential variation of the diffusion coefficient with concentration' was no longer a practical necessity, so that the new solution offered the possibility of handling diffusion in semi-infinite solids for arbitrary variations of the diffusion coefficient with concentration. In discussing the principle on which this method of calculation is based, it is convenient to consider the relatively simple problem of one dimensional diffusion into a matrix that initially contains none of the diffusing substance. The solution of the set- ond Fick Law,?C/?t=D0?2C/?x2, for diffusion into a semi-infinite solid is3 C/C=1-F(x/2vD0t [1] where C is the concentration of the diffusing substance at a depth x cm below the surface after dif- A. G. GUY, Member AIME, and M. GOLOMB are Professor of Metollurgicol Engineering and Professor of Mathematics, respectively, Purdue University, Lafayette, Ind., A. S. YUE, formerly with Purdue University, is now with the Research Laboratory, Dow Chemical Co., Midland, Mich. TP 4505E. Manuscript, July 18,1956. fusion has occurred for t seconds; C, is the concentration of the diffusing substance at the surface of the matrix; Do is the diffusion constant, expressed in sq cm per sec; and + represents the Gauss error function. The corresponding solution for diffusion into a finite solid of thickness, 1, is conveniently written for the change in concentration, C+, at a point midway through the matrix and for times, t, great enough for the following equation to be used4 c1/2/C1=(1/2-2/?e-?2D0t/l2) [2] In Eqs. 1 and 2 the diffusion coefficient is represented by the symbol Do (rather than by D) to emphasize that these equations are valid only for constant values of D. To understand how these equations can be modified to take account of actual variations of D, such as that shown in Fig. 1, first consider the fact that for a given time of diffusion theconcentration at a given point is determined, not by the D value alone, but by the ratio x/vD0 in Eq. 1 and by a similar ratio, l2/D0 in Eq. 2. Even though in fact D varies, it is possible to keep this ratio constant by using a special coordinate system, x,, that varies with D in the appropriate manner. The necessary character of this special coordinate system can be easily visualized by imagining that

Jan 1, 1958

By C. C. Hatch, C. R. Larsen, A. L. Mular

INTRODUCTION As part of a general project to simulate a concentrator, the Brenda Mines Limited secondary crushing plant, located near Peachland, B. C., was sampled during the summer/winter of 1975 and during the summer of 1978 to develop a digital crushing plant simulator specific to the Brenda operation. The purpose of this simulator was to study the influence of manipulable process variables on important responses, to permit study of alternative circuit configurations if desired and to perform off-line optimization. This chapter describes the methodology employed to develop the simulator (1,2) along with typical applications thereof. SECONDARY CRUSHING PLANT FLOWSHEET Figure 1 is a schematic diagram of the Brenda Mines Ltd. secondary crushing plant circuit. The 41,000 tonne coarse ore stockpile(a) is -17.8 cm oversize (3B belt) from two 2.4 m x 6.1 m double deck vibrating screens (not shown). The screens are fed by 2 conveyor belts operated in series with two 198 cm apron feeders that handle discharge from a 152 cm x 226 cm primary gyratory crusher(520 KW). The primary crusher (not shown) treats up to 2725 tonne/hr of run of mine ore. Minus 1.9 cm undersize from the primary screens (#19 belt), referred to as the primary fines, joins secondary screen undersize (#18 belt) for conveyance to fine ore bins (not shown). Feed from the coarse ore stockpile is transferred by means of vibrating feeders and two 120 cm conveyors (#6 and #7) to transfer belts #8 and #9 (Figure 1). The belts feed two secondary 2.1 m standard heavy duty cone crushers (bl and b2). Each crusher is equipped with a modified coarse mantle liner and a standard coarse bowl liner. Mantle throw is 9.2 cm; nominal close side set is 3.2 cm. Crusher .countershafts (443 rpm) are driven by single 260 KW synchronous motors (710 rpm). Discharge from the secondary cone crushers joins discharge from four 2.1 m tertiary heavy duty shorthead cone crushers (fl, f2, f3 and f4). With the exception of the cavity (modified medium mantle liner and standard coarse bowl liner; close side set is nominal .84 cm) and motor (224 KW), these machines are similar to the secondary crushers. The combined discharge is transferred from a 183 cm conveyor to #14 belt which empties into a 1452 tonne secondary screen surge bin (c). Vibrating feeders beneath the bins feed five 2.4 m x 6.1 m double deck vibrating screens (dl, d2, d3, d4 and d5) sloped at 200 from the horizontal. The upper decks are punched plates with 2.7 cm x 7.6 cm slots. Lower decks are woven wire (1.27 cm diameter) sections with

Jan 1, 1982

By S. C. Sircar, B. K. Dhindaw

KINETICS and mechanism of sulfation reactions have been studied extensively. Qualitative and quantitative data are reported for the kinetics and mechanism of sulfation reaction of copper oxide pellets;''2 yet it remains a controversial Subject. The mechanism and kinetics of the sulfation of zinc oxide powder (B.D.H. analar quality) were studied by gravimetric technique. A spring of high-carbon steel wire with accuracy well within 0.2 mg was used for measuring weight change. The sample was taken in a Pyrex glass bucket, hanging freely inside a Pyrex glass tube reactor, with a gold wire attached to the spring, the reactor being surrounded by a movable furnace (double wound type) with a temperature control within *5"C. Flow of oxygen, 60 cu cm per min, and sulfur dioxide, 45 cu cm per min, were measured through calibrated flowmeters and the mixture dried over PZ05 before entering the reactor. The experimental results are presented in Figs. 1 and 2. The plot of weight change of zinc oxide, giving the amount of zinc sulfate formed, was found to be linear over the temperature range of 500" to 700° C and up to a conversion of approximately 60 pct, as beyond it they divert from linearity.' The rate of sulfation was found to be affected by total flow rate of gases at a fixed ratio of SO2/O2, up to 60 cu cm per min, and was found to be linearly dependent on quantity of total powdered sample taken. The plot of rate of sulfation of zinc oxide, 70 mg, with varying amounts of vanadium pentoxide, at a constant ratio of gases as mentioned above, and at a constant temperature of 625"C, was also found to be linear as seen in Fig. 2. Extrapolation to zero V2O5 addition gives the same rate of sulfation, as in case of pure zinc oxide, 70 mg. Vz05 was prepared by heating ammonium vanadate at 600°C for 15 min in a muffle furnace. The available literature points out that the theory of sulfation that has received the maximum support postulates the following mechanism for sulfation of ZnS: 2ZnS + 30, = 2Zn0 + 2SOZ; the ZnO formed acts as a catalyst for the reaction, 2 S02 + O2 = 2S03. This SO3 reacts with ZnO to give zinc sulfate. It is suggested here that the above widely supported mechanism is operative in the sulfation reaction and that the rate-controlling step in the sulfation reaction of ZnO is the formation of SO3 from SO, and 0,. The authors are carrying on further work in this line, and the details will be published later. The authors wish to acknowledge the facilities provided and the help extended by Prof. P. R. Dhar, Head, Department of Metallurgical Engineering, and the permission granted to publish this note by the Director, I. I. T., Kharagpur.

Jan 1, 1969