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By R. V. Vines, E. M. Wise

It is known qualitatively that the recrystallization behavior of platinum is dependent upon the amount and particularly the nature of impurities present, the amount of prior cold-work and the annealing time and temperature, but published data are limited. A study of the effects of cold-work and annealing temperature on the hardness of a sample of very pure platinum was undertaken to supply part of this information. Conclusions 1. The platinum used in the experiments had a probable platinum content of 99.99+ per cent, and had the following mechanical properties in the completely softened condition: Vickers hardness number, 39.4; ultimate tensile strength, 19,340 lb. per sq. in.; proportioilal limit, very low; elongation, 37.5 per cent in 2 inclles. 2. The effect of cold-rolling on the hardness is shown in Fig. 1. The hardness increases rapidly up to 10 to 15 per cent reduction and more slowly up to about 75 per cent reduction, beyond which it increases more rapidly. 3. The recrystallization temperatures for a 15-min. anneal, after cold-rolling 19, 39.5, 50.8, 66, 80.5 and 89.5 per cent reduction in thickness, are approximately 765°, 700°, 635°, 600°, 545' and 425°C., respectively. 4. The recrystallized grain size of this platinum is a function of the percentage of cold reduction, being larger the lower the percentage of cold-work. 5. Little or 110 grain grourtll resulted from subjecting recrystallized samples to higher temperatures or annealing for longer times. Prior Work As already mentioned, data on the recrystallization of platinum are scarce. Gmelin'sl handbook, which summarizes data published earlier than August 1938, lists values ranging from 400' to 810°C. for the minimum temperature of recrystallization of samples with rather indefinite

Jan 1, 1940

By E. M. Wise, R. V. Vines

It is known qualitatively that the recrystallization behavior of platinum is dependent upon the amount and particularly the nature of impurities present, the amount of prior cold-work and the annealing time and temperature, but published data are limited. A study of the effects of cold-work and annealing temperature on the hardness of a sample of very pure platinum was undertaken to supply part of this information. Conclusions 1. The platinum used in the experiments had a probable platinum content of 99.99+ per cent, and had the following mechanical properties in the completely softened condition: Vickers hardness number, 39.4; ultimate tensile strength, 19,340 lb. per sq. in.; proportioilal limit, very low; elongation, 37.5 per cent in 2 inclles. 2. The effect of cold-rolling on the hardness is shown in Fig. 1. The hardness increases rapidly up to 10 to 15 per cent reduction and more slowly up to about 75 per cent reduction, beyond which it increases more rapidly. 3. The recrystallization temperatures for a 15-min. anneal, after cold-rolling 19, 39.5, 50.8, 66, 80.5 and 89.5 per cent reduction in thickness, are approximately 765°, 700°, 635°, 600°, 545' and 425°C., respectively. 4. The recrystallized grain size of this platinum is a function of the percentage of cold reduction, being larger the lower the percentage of cold-work. 5. Little or 110 grain grourtll resulted from subjecting recrystallized samples to higher temperatures or annealing for longer times. Prior Work As already mentioned, data on the recrystallization of platinum are scarce. Gmelin'sl handbook, which summarizes data published earlier than August 1938, lists values ranging from 400' to 810°C. for the minimum temperature of recrystallization of samples with rather indefinite

Jan 1, 1940

By Charles Mabery

So FAR as the elementary composition of petroleum is -known, it may be briefly stated. Petroleum consists principally of a few series of hydrocarbons, with admixtures of sulfur, nitrogen, and oxygen derivatives in comparatively minute proportions, which may be regarded as impurities to be removed in the preparation Of commercial products. But as each series is represented by many homologs, in the aggregate, crude petroleum is an extremely complex mixture of hydrocarbons and their derivatives. In part, these hydrocarbons individually conform in structure to the system of synthetic hydrocarbons whose structure is well defined and -represented by the typical series CnH2n+2, CnH2n, the series CnH2n-2, CnH2n-4, the members of which have not been sufficiently studied to establish their structure, and the series CnH2n-6 composed of the aromatic group, benzene and its homologs. Hydrocarbons of greater density contained in the portions of petroleum that cannot be distilled without decomposition doubtless have less hydrogen than is represented by these formulas. Since to every hydrocarbon there is a definite temperature, even in vacuum, at which its constituent carbon and hydrogen atoms fall apart, and since for the heavier bodies this temperature is not much above 360° C. in vacuum, it is evident that some other method than distillation must be devised for their separation if anything further is to be learned concerning their individual constitution. CLASSIFICATION OF PETROLEUMS There is such a wide variation in the composition of petroleum from different fields, it would seem possible to make a classification on this basis were it not that no single variety is entirely free from hydrocarbons contained in others. Such a classification has been suggested of the exceptionally pure Pennsylvania petroleum, the sulfur oil from Trenton

Jan 2, 1920

By T. M. Anderson

From the start of production in 1915 until 1948, underground block caving operations accounted for all of the ore production of Inspiration Consolidated Copper Co. Open pit development work began in 1947, and ore production from the open pit commenced in March 1948. Thus began the transition from underground to open pit mining which continued until August 1954. Since then, open pit mining has accounted for all ore production which presently averages 105,000 tons of ore and 75,000 tons of waste rock each week. Open pit mining operations at Inspiration is carried on in two separate pits-the Live Oak Pit and the Thornton Pit. The Live Oak Pit covers an area of approximately 1500x3000 ft and the Thornton Pit, 2500x2000 ft. The geographic centers of the two pits are 4000 ft apart and, at their nearest point, the surface slopes are 500 ft apart.

Jan 1, 1961

By Alexander L. Field

IN a previous paper,' the experimental methods used and some of the results obtained in an extensive investigation of steels containing zirconium were described. The present paper considers in greater detail one of the most interesting of these effects, namely, the elimination of " red shortness" and the occurrence in steel of a compound of zirconium and sulfur. A consideration of the actual percentages of zirconium, manganese, and sulfur in numerous steels in the light of behavior during rolling has led to new conclusions of the most practical import regarding the reciprocal relationships of these elements. The microscopic examination of high-sulfur steels containing zirconium has also been productive of interesting results. Before discussing the experimental data in question, it may be stated, briefly, that the rettetion between zirconium and sulfur in molten steel may be represented by the simple equation, Zr + 25 = ZrS², and that the zirconium sulfide thus formed occurs in the finished steel in the form of gray-colored inclusions, closely resembling manganese sulfide and, like the latter, exhibiting plasticity at rolling temperatures. Molten steel containing zirconium retains such a negligibly small amount of oxygen in solution that the foregoing reaction goes to completion. Hot-rolling Properties of High-sulfur Steels with and without Zirconium The chemical composition of twenty-eight steel ingots embracing eleven heats made in a basic-lined electric furnace is shown in Table 1. The practice followed in the manufacture of these high-sulfur steels was described in the previous paper. Table 1 also gives the behavior of the

Jan 1, 1924

August 10 to 14, 1914, inclusive Headquarters will be at the Hotel Utah. The following program of the meeting has been arranged y the Local Committees: Monday, August 10.-Members and guests will register at the Secretary's desk in Room C-38, Hotel Utah, and receive the official badges, booklets and programs of the meeting. At 2:30 P. M., there will be an organ recital at the Mormon Tabernacle, after which members and guests will be taken for a trip around Salt Lake City in sight-seeing motor cars. At 8:30 P. M., the ladies will assemble in the lobby of the Hotel Utah, where they will be met by the members of the Ladies' Entertainment Committee, and will be taken for an automobile drive about the city. At 8:30 P. M., a technical session will be held in the ballroom of the Hotel Utah. The following papers will be presented: F. W. BACORN: An Amendment to Sales's Theory of Ore Deposition. C. W. GOODALE: Drumlummon Mine, Marysville, Mont. I. B. JORALEMON: The Ajo Copper-Mining District. STUART CROASDALE: Leaching Experiments on the Ajo Ore. FRANK R. VAN HORN: The Occurrence of Bournonite, Jamesonite, and Calamine at Park City. HOWLAND BANCROFT: Dip Chart. M. N. ALLING: Ancient Auriferous Gravel Channels of Sierra County, California. B. S. BUTLER AND H. D. MCCASKEY: Copper Ores of the New London Mine. GEORGE A. PACKARD: Rope Idlers in the Raven Shaft. ARTHUR CROWFOOT: Development of the Round Table at Great Falls. FREDERICK LAIST AND A. E. WIGGIN: The Slime-Concentrating Plant at Anaconda. W, L, AUSTIN: The Treatment of Copper Ore by Leaching Methods. W. L. AUSTIN: Leaching Copper Products at the Steptoe Works.

Jan 8, 1914

By E. T. Turkdogan, W. L. Worrell

The rate of reaction of hydrogen sulfide with ferrous sulfide was studied by measuring the initial rates of sulfidation of iron strips in hydrogen sulfide-hydrogen-argon mixtures at 670°, 800°, and 900" C. The time-dependent surface sulfur activity is derived from the instantaneous rate of sulfidation with the assumption that diffusion in the sulfide layer is in a pseudo-steady state with the gas-sulfide chemical reaction. The rate of sulfur transfer from hydrogen sulfide to the surface of iron sulfide is proportional to the partial pressure of hydrogen sulfide and inversely proportional to the activity of sulfur at the surface of the sulfide layer. The derived rate equation is based on the assumption that most of the surface sites on the chemisorbed layer of iron sulfide are occupied by sulfur atoms and that the slow rate-controlling reaction is the dissociation of hydrogen sulfide on the chemisorbed layer. The experimental results are in reasonable accord with this reaction model. 1 HE slow approach to parabolic growth rate in the sulfidation of iron in hydrogen sulfide-hydrogen mixtures is a manifestation of slow approach to surface equilibrium between the gas and the surface of the sulfide layer. For example, at 800°C and Fig. 7 in Part I, the parabolic growth rate begins after approximately 1 day of sulfidation time. With decreasing temperature and decreasing partial pressure of hydrogen sulfide, the time necessary to reach gas-sulfide surface equilibrium is much longer. These observations are similar to those reported previously by Turkdogan et al.' on the oxidation of iron to wustite in hydrogen-water vapor mixtures. The slow approach to gas-sulfide equilibrium is well-demonstrated by the results in Fig. 1 where the square of the weight gain per unit area, ( g S per sq cmI2, is plotted against time for gas mixtures having PH g//>H = 1.0 with 0, 25, 50, and 67 pct Ar at 800°C. The value of 1.5 X lo-' (g S per sq cm)' corresponds to almost complete sulfidation of the iron strip (- 0.05 cm thick) to iron sulfide. The points fall on S-shaped curves. If the inflection parts of the curves are considered to be linear, thus indicating parabolic growth rate and the establishment of gas-sulfide equilibrium, their slopes would have to be the same for a fixed ratio in the gas mixture. Such is not the case, and the slopes for the "linear" parts of the S-shaped curves are lower than the value when gas-sulfide surface equilibrium is established. The subject matter of this paper is the kinetics of the surface reaction of hydrogen sulfide with iron sulfide during the early stages of sulfidation of an iron strip. EXPERIMENTAL RESULTS The apparatus and materials used were the same as those discussed in Part I. In the present experiments of relatively short duration, a purified iron strip, 5 by 2 by 0.05 cm, which was suspended in the uniform hot zone of a vertical zircon tube, reacted with a flowing gas mixture of hydrogen sulfide-hydrogen-argon. The sample was suspended from a gold chain attached to a calibrated silica spring. The amount of sulfur picked up by the iron, which formed a layer of iron sulfide, was determined by measuring the displacement of a reference point on the silica spring, using a cathetom-eter. In all cases, the degreased sample was first annealed in a stream of oxygen-free dry hydrogen for several hours to remove any impurities such as oxygen, nitrogen, or carbon which might have been present on the surface of the sample.' The rate measurements were carried out at 670°, 800°, and 900° C in hydrogen sulfide-hydrogen-argon mixtures with pH2 s/Ph2 ratios from 4 to 0.1. In a few experiments of short duration no sulfur deposition was observed in gas mixtures with (comments concerning sulfur deposition at high pH s/ph ratios were made in Part I.) Typical examples of the results obtained are shown in Fig. 2 for two temperatures and two gas compositions. With the present experimental technique, reproducible rate data could be obtained only after a uniform

Jan 1, 1969

By D. J. Salley, M. Burke, G. L. Simard

A PREVIOUS paper1 described experiments on the interaction of dithiophosphate with galena and suggested that the process had characteristics of both chemisorption and surface chemical reaction. In order to add to this knowledge, a study has been made of the competition of a second ion with the dithiophosphate for a galena surface. Use again was made of radiotracer methods. Since radiophosphate was readily available, it was chosen as the competing ion. It is a feature of the tracer method that, in spite of similarity in the chemical behavior of the ions, the measurement of one ion in the presence of another can be made as simply as if only one ion species were present. In order to study the competition effectively, it naturally was necessary to examine the interaction of phosphate with galena alone as well as in the presence of dithiophosphate; consequently, this report consists of two parts. The first is devoted to a study of the rates, the isotherms, the desorption, and the exchange in the phosphate-galena system in the same manner as was done for the dithio-phosphate-galena system. The second portion is concerned with the studies on the competition. Flotation experiments on the three-component sys- tem are also outlined and the relationships involved are discussed briefly. The experimental method was that of the previous paper. The preparation of the galena, the radioactive and the nonradioactive dithiophosphate, and the procedures for radioactive counting, for sorp-tion, and for flotation measurements were identical to those previously employed. The radiophosphate* was used in the form of disodium phosphate solution. In the competition experiments the effect of the phosphate ion in depressing dithiophosphate uptake was followed by holding the initial concentration of nonradioactive phosphate constant while varying the initial concentration of the radioactive dithiophosphate. Counterfashion, the depression of phosphate by dithiophosphate was obtained by keeping the initial nonradioactive dithiophosphate ion concentration constant and altering the initial concentration of the radioactive phosphate ion. All solutions were buffered at a pH of 7.8 a0.1 by 20x10-' mol per cc of sodium carbonate. Measurements with radiocarbonate indicated that little or no carbonate could be sorbed in the presence of

Jan 1, 1952

By E. A. Gulbransen, K. F. Andrew

In a recent communication14 we have reported on the kinetics of the reactions of zirconium with O2, N2 and H2 as a function of the time, temperature and pressure variables. A systematic study was made and the results correlated with fundamental theories of gas-metal reactions. This paper will present a similar study for titanium. Titanium and zirconium are members of the IV group of the periodic table and possess many similar physical and chemical properties as a result of their similar electronic configuration for the outer electrons. The two metals are relatively inert to both gas and liquid phase corrosion at room temperature. However, at moderate temperatures the metals become active and react readily with the common gases including O2, N2 and H2 which are of interest in this study. A study of the kinetics of these gas-metal reactions is of interest for three reasons: (1) to understand the rate of reaction of titanium and its role in the behavior of high temperature alloys; (2) to understand the practical difficulties of the reduction, refining and working of titanium; and (3) to correlate the data with fundamental theories of gas-metal reactions and crystal structure predictions. Literature Survey Several review papers8 and books4243 exist on the preparation and properties of titanium and its alloys. THE METAL Titanium has, at room temperature, a hexagonal lattice of the zinc type. Hagg19 gives a value of 2.953A for the (a) axis, a value of 4.729 for the (c) axis and a density of 4.427 at 20°C. Burgers and Jacobs6 have observed the transformation of the hexagonal to the body-centered cubic structure at 880°C and have established a value of 3.31 for the cube edge and a density of 4.31. TITANIUM-OXYGEN Carpenter and Reavell6 using a pressure change method have studied the reaction at temperatures of 742° and 1000°C and for a pressure of one-fifth of an atmosphere. The probabilities for reaction are calculated from kinetic theory and they report a value of 10-5 for O2 at 1000°C and 10-6 at 740°C. The titanium-oxygen system has been investigated by Ehrlich.10,11 Five phases are observed. Between (TiO2 and TiO1.90) an alpha-phase, consisting ofarutile lattice, is found. A beta-phase is observed between (TiO1.80 and TiO1.70). A gamma-phase is homogeneous between (TiO1.56 and TiO1.46) and has a structure of the corundum type. The delta-phase exists between TiO1.25 and TiO0.6 and has a sodium chloride structure. From TiO0.42 to Ti the metal structure is observed. The surface oxide films have been studied by Hickman and Gulbransen.20 The rutile structure is observed in the temperature range studied, 300 to 700°C. Three crystalline modifications of TiO2 exist: rutile and anatase which are tetragonal and brookite which has an orthorhombic structure. Anatase is reported36 to exist in two forms: I and II. Anatase II changes to anatase I at 642°C. Anatase I is stable up to 915°C where rutile becomes the stable modification. At 1300°C rutile transforms to brookite which melts at 1900°C. The monoxide, TiO, may be prepared from the dioxide by high temperature reduction with carbon or magnesium. Its melting point is 1750°C. TITANIUM-NITROGEN Carpenter and Reavell6 report that at 1000°C a linear rate law is observed. The probability of reaction is given as 10-8 at 1000°C. Fast12 has studied the solubility of nitrogen and its effect on the mechanical properties of the metal. The crystal structure of TiN has been shown by several workers2'21'44 to follow the sodium chloride structure. However, the calculated density is found to differ from the pycnometric value. This is studied by Brager3,4 in detail. He has suggested that the titanium sites in the lattice are only partially filled at low temperatures. As the temperature of preparation is raised the vacant sites become occupied which expands the lattice and increases the hardness and density. An (a) value of 4.22Å is given for room temperature. TITANIUM-HYDROGEN The solubility and the crystal structures observed in this system have been reviewed in a recent book by Smith.40

Jan 1, 1950

THE National Safety Council will hold the following ses-sions in the Waldorf-Astoria Hotel, New York, N. Y., on Oct. 2, 3 and 4: Oct. 2. 9.30 A. M. 1. Report of past year committees, by Chairman 2. "Safety Pays," by Howard I. Young, Vice-President, American Zinc, Lead and Smelting Co., Mascot, Tenn. (Discussion) 3. Entertainment 4. "Methods and Results of Improved Foremanship Conferences," by H. A. Gilbertson, Director of Per-sonnel, Lehigh Coal and Navigation Co., Lansford, Pa. (Discussion) 5. Appointment of election and resolutions committees Oct. 3, 9.30 A. M.

Jan 9, 1928

[ ] S. H. Ash (Mining Industry Continues with Lower Fatal-Injury Rates, P. 257) was born in Roslyn, Wash. and attended Lehigh University and University of Washington. He received a B.S. and E.M. degree in mining engineering. Mr. Ash was supervising engineer in charge of work of Safety Div., Bureau of Mines, eastern Pennsylvania and the states of N. Y., Del., N. J. and the New England states. He was appointed chief engineer of Metal and Nonmetal Mining Section of the Mineral Production Security Div., Bureau of Mines, July 1942. At present he is chief engineer, Safety Branch, U. S. Bureau of Mines. Besides holding membership in AIME, he is a member of National Honorary Engineering Society, Society of American Military Engineers, Tau Beta Pi and many other societies.

Jan 1, 1952

By P. A. Beck, Hsun Hu

As described by means of quantitative pole figures, the annealing texture of highly rolled aluminum consists of the four retained components of the rolling texture near (123) [121], rather more sharply developed, and of a cube texture component. Local reorientation corresponds fairly well to 40 rotation around a [111] axis. In copper strip rolled 96 pct, the annealing texture is mainly the cube texture, with the four twin orientations as minor components. The annealing texture of highly rolled brass strip consists of four components of the (225) [734] type. REVIEWS by Wassermann,' Barrett,' Dunn,3 and Richards' give detailed accounts of the numerous publications dealing with annealing textures in rolled polycrystalline metals. Although a considerable amount of information of an empirical nature has been available for many years, even relatively recently the state of recrystallization-texture theory was considered uncertain. The reviews referred to above deal mainly with the description of experimental results, without developing generally applicable principles, suitable for explaining the observed annealing textures. The investigations of Burgers and Louwerse5 and Barrett6 showed that in deformed single crystals of aluminum the orientation of the recrystallized grains deviates drastically from that of the deformed matrix. According to Barrett and to Beck and Hu,7 the relationship between the two orientations can be best described as a rotation of about 40° around a [111] axis. Recent investigations led to similar orientation relationships for various face-centered cubic metals with a simple texture, regardless of whether the annealing process was recrystallization (strain-free grains growing in a highly deformed large crystal of aluminum' or copper: or in deformed cube texture copper") or coarsening (strain-free grains growing at the expense of an essentially strain-free, fine grained, polycrystalline matrix of single orientation texture copper,'" aluminum,' or nickel-iron). Barrett" pointed out the possibility that this orientation relationship may be a result of the orientation dependence of the rate of grain boundary migration. More recently, considerable evidence became available in favor of this view.12,13 In apparent contradiction to the above results, it has been known for a long time that the recrystallization texture of polycrystalline metals is often similar to the deformation texture. This was found, in particular, for the fiber textures obtained by wire drawing, compression, or compression rolling.' Following a suggestion by Barrett,2 Kronberg and Wilson and Beck and Hu7 described a mechanism by which a [Ill] fiber texture, resulting from plastic deformation, may be retained upon recrystallization, even though the orientation of individual recrystallized grains differs from that of the local area of the matrix in which they grow. This mechanism assumes that the reorientation corresponds to a rotation around the [1ll] axis, which is also the fiber axis. The present investigation was undertaken to examine in detail the orientation relationship between deformation texture and recrystallization texture in rolled face-centered cubic metals, using the quantitative methods of texture determination that have recently become available.", '" Quantitative pole figures for the rolling textures of such metals were reported recently." Quantitative pole figures for annealing textures are given in the present paper. It was planned to investigate whether or not the orientation relationship previously found for the recrystallization of deformed single crystals, and for coarsening of single-orientation texture material, is capable of accounting for the observed, often complex, annealing textures in rolled polycrystalline metals. The question whether local reorientation is predominant, even in the early phases of the annealing process, was to be studied with high purity aluminum. by making use of an oxide film and sensitive tint illum-

Jan 1, 1953

By Arnulf Muan, Klaus Schwerdtfeger

Equilibrium ratios C02/C0 of a gas phase coexisting with selected phase assemblages of the system Fe-Mn-0 have been determined in the temperature range 1000" to 1300°C. The oxygen pressure for the "hfnO" +hfn30, equilibrium and for the "(Fe,hTn)O" + (Fe,Mnh 0* equilibrium at high manganese contents has been determined by electromotive force measurements using stabilized zirconia as a solid electrolyte. The notstoichometry 01' "hTnO" and of "(Fe, iM1z)O" solid solutions has been determined by ther-mog-/avi?netry and by wet-chemical analysis. The data obtained are used to derive activity-composition relations in "(Fe,hfn)O" and (Fe,Mn),O4 solid solutions. WUSTITE "FeO" and manganosite "MnO" form a continuous series of solid solution at high temperatures,' and so do magnetite Fe304 and the high-temperature, cubic modification of Mn304 (Ref. 2) (high hausmannite, -1170). The oxides "FeO" and "MnO" are cation-deficient phases.495 The nonstoi-chiometry of "(Fe,Mn)O" solid solutions has been studied by Engell and ~ohl' at two selected C02/C0 ratios at 1250°C. The two oxide end members of the spinel solid solution, FesO4 and Mn,04, however, are known to be close to stoichiometric under the experimental conditions used in the present investigation.''' The oxygen pressures of "(Fe,Mn)07' solid solutions in equilibrium with iron have been determined by Schenck and coworkers,8 by Foster and welch," and by ~n~e1l.l' The two former groups equilibrated the condensed phases in C02-CO atmospheres of lmown compositions, whereas Engell" used a galvanic cell with stabilized zirconia as a solid electrolyte. The results of these investigators are not in good agreement. Activities of FeO in manganowiistite as calculated from the results of Foster and Welch show ideal behavior, those of Engell yield a pronounced positive deviation, and those of Schenck et 01. show a moderate positive deviation from ideality. In the present work oxygen pressures for the iron + manganowiistite and manganowustite + spinel equilibria and the nonstoichiometry of manganowiistites have been measured. The data were used to calculate activities in the manganowiistite and spinel solid solutions. EXPERIMENTAL METHODS The COz/CO ratios at which manganowustite and iron are in equilibrium were determined by thermo-gravimetric and quenching methods. Experimental details are described in a previous publication.'2 In the thermogravimetric technique, incipient reduction of manganowiistite pellets to metallic iron was observed as a break in the weight vs log COZ/CO curve. In the quenching technique, manganowiistite samples were partially reduced to metallic iron, or the metallic iron of manganowustite + metallic iron mixtures was partially oxidized to manganowustite, in atmospheres of constant C02/CO ratios. After quenching the composition of the oxide phase was determined by X-ray lattice parameter measurements and comparison with a standard curve obtained from oxide solid solutions of known compositions. The nonstoichiometry of "MnO" and "(Fe,Mn)07' solid solutions was determined by chemical analysis of samples equilibrated in C02-CO atmospheres and quenched to room temperature, as well as thermo-gravimetrically by reducing (Fe,Mn),04 or Mn304 to manganowiistite or manganosite. The equilibrium between manganowiistite and (Fe,Mn),04 was measured thermogravimetrically by reducing (Fe,Mn),04 solid solutions having composition in the range of %„ l(NFe +NM) from 0 to 0.63. No experiments could be performed with this technique at higher manganese contents, because the equilibrium C02/C0 ratios are too large for accurate control. An additional difficulty arises at the higher manganese contents due to the strong increase in oxygen content of the manganowustite phase with increasing log Py near the manganowiistite-spinel boundary. Consequently a sharp break in the weight loss vs log C02/CO curve cannot be observed at the phase boundary. At high manganese contents of the manganowiistite, e.g., (NMn/(NF~ + NMn) > 0.9, electromotive force measurements with stabilized zirconia as a solid electrolyte were made to determine the equilibrium oxygen partial pressure. Experimental details are described in a previous paper.* Mixtures of "(Fe,Mn)O" and (Fe,Mn),04 were pressed to pellets, and the oxygen pressure of the equilibrated samples was compared to that of Ni + NiO mixtures in the cell The composition of the manganowiistite in the equilibrated two-phase mixture was determined by lattice parameter measurements and comparison with known standards. The oxygen pressure for the Ni + NiO equilibrium was taken from available data.l3~l4 No reliable results were obtained with the electromotive force technique on iron-rich oxides. The electromotive force drifted strongly with time in this composition range. An additional difficulty arises from the partial de-

Jan 1, 1968

By P. Bolsaitis, L. Skolnick

A model of metallic solutions is postulated which explains the energy of formation of alloys on the basis of changes in electron density around solute and solvent atoms and changes in pairwise interactions between atoms. The model is based on the Wigner-Seitz cell model of metals, with the electronegativities of the metals as the parameter for the electron-attracting power of the constituent atoms. In contrast to models based on the description of cohesive energy in terms of pairwise interactions only, which require an empirical, adjustable correction parameter to the Berthe-lot relations in order to predict negative energies of formation, the electron cell model accounts for both negative and positive energies on the basis of parameters of the pure components. Calculated heats of mixing based on published parameters of the pure metals are found to compare favorably to experimental values, despite the absence of any adjustable parameters in the model. THE formulation of an "exact" quantum mechanical model for the energy of cohesion of metals reduces ultimately to the many-body problem and for a complete solution would require the knowledge of wave functions and energy levels of all the particles in the system. The case of alloys is further complicated by the fact that the potential fields around the constituent atoms are different and the matching of boundary conditions in terms of the resulting wave functions is still an unresolved mathematical problem. It appears that in spite of the numerous investigations that have led to an elucidation of many properties of the metallic state, the formulation of the Hume-Rothery rules in 1931 marks the lone accomplishment toward simple, qualitative prediction of the energy of formation of alloys. More recently Friedel'' and Arafa have utilized the modern concepts of the electronic structure in metals in combination with the Hume-Rothery rules to arrive at quantitative estimates of the energy of formation of alloys with low solute contents. The relative success of the Hume-Rothery rules and Friedel's and Arafa's studies encouraged broaching the subject of formulation of a model based on realistic physical parameters and of conceptual and mathematical simplicity that could be applied to alloys regardless of concentration. On the basis of the free-electron theory, the cohesive energy of pure metals can be expressed as a function of "valence" (number of free electrons per atom), lattice parameter (or density), and the ioniza-tion energy. In addition to the electronic contributions to cohesion, one has to consider the pairwise exchange interaction energy between neighboring ion cores and the contribution from van der Waals forces. The energy changes upon alloying are viewed as resulting primarily from a redistribution of electron densities around the ions (a simplification of the more basic concept of a change of the wave functions of the electrons in the presence of a perturbing potential field). In addition there is a change in the pairwise interactions between neighboring ions which is usually the only factor taken into account in commonly used adaptations of the quasichemical theory. The electronegativities of the metals forming the alloy are used as the measure of the electron-attracting power of the ions in the alloy and the difference in electronegativities as the driving force for changes in electron energy on alloying. The interplay of pairwise interactions and electronic forces results in positive or negative energies of formation of alloys. Results obtained for systems to which the free electron model is best applicable are in good agreement with experimental values. 1) COHESIVE ENERGY OF METALS IN TERMS OF THE ELECTRON CELL MODEL The simplest physical model of a metal is that of a lattice of positive charges immersed in a sea of uniform, negative charge distribution represented by the

Jan 1, 1969

By John B. Campbell, George G. Binder, Loren H. Jenks

Conventional methods of producing crude oil generally leave in the depleted reservoir 1 to 3 bbl of oil for every barrel brought to the surface. This paper describes a field test which explores the possibility of using gas-driven liquid propane to improve oil recovery efficiency. Laboratory theoretical and experimental studies leading to the field test indicated that low residual oil values could be obtained using limited amounts of propane driven by gas. The field test involved (I) repressuring the reservoir to the vapor pressure of liquid propane, (2) injecting the liquid propane, and (3) injecting dry natural gas to drive the propane and oil to the producing wells. Considerable preliminary work, including new drilling, work-overs, and a pressure survey was necessary. During the test, oil production rates have averaged about nine times the final primary rates. The field average GOR is still below the pre-test value. Oil recovery to date is 112,000 STB. About one-third of the 143,-000 bbl of propane injected has been produced to date. Results of the C-2 block test are encouraging and larger, more definitive field projects ore indicated. INTRODUCTION The cost of finding new crude oil reservoirs continues to increase. Today the oil industry is drilling more and deeper wells and making fewer big discoveries. Nevertheless, the demand for oil and oil products increases each year. It is natural that oil companies, faced with this situation, concentrate on recovering more of the oil existing in our known crude oil reservoirs. There is room for much improvement. For every barrel of oil brought to the surface by present day methods of producing crude oil, generally 1 to 3 bbl are left behind in the depleted reservoirs. The "unrecoverable" oil in petroleum reservoirs is largely "trapped" by capillarity. Since flushing with a solvent is exceedingly effective in combatting oil loss due to capillarity, much effort in this direction has been made in recent years1,2,3,4,5. Liquefied petroleum gas (LPG) has been suggested as a relatively inexpensive. abundant, easily recoverable solvent for crude. Some operators have observed striking responses in oil recovery at production wells offsetting input wells in LPG storage reservoirs6,7,8. In spite of the low unit cost of LPG, however, it is uneconomic in general to inject a volume of LPG into a reservoir to remove a like volume of oil. A modification of solvent flushing in which a limited quantity of liquid propane is gas driven through a reservoir appears capable of recovering much more than 1 bbl of oil per barrel of propane injected. Also, most of the propane injected should be recoverable for sale or re-use. Since such a process could well have widespread and profitable application, The Carter Oil Co. is making an extensive evaluation of the technique's possibilities. Laboratory development of the gas-driven propane recovery technique was sufficiently encouraging to justify testing in the field. Since 1952, the Production and Research Departments of The Carter Oil Co. have cooperated in a field test in the C-2 Block leases of the

Jan 1, 1958

By John T. Ryan

FOR the first ten months of 1942, on which data are available at the time this is written, the coal-mining industry achieved a most creditable safety record, and ha1 figures for the year may show a record surpassing that of 1941 in which the industry reached the best accident rate in its history. The ten- month accident rate for both bituminous and anthracite mining in 1942 was 2.197 fatalities per million tons of coal mined, compared with a revised rate of 2.271 for the same months of 1941. The bituminous rate decreased from 2.139 in 1941 to 2.039 for ten months of this year, and the anthracite rate shows a reduction from 3.707 to 3.699 for the same period.

Jan 1, 1943

By F. W. Gibson

A detailed description of the smelting and refining operations of the Amax-Homestake Lead Toller's smelter at Buick, Missouri. This is one of two completely new lead smelting and refining operations to go into operation in the United States in over forty years. Incorporated into the operation are the new methods and equipment which have been developed and lend themselves to the particular metallurgy of this plant. The text, as well as the statistical data presented, represent actual current practice after 22 months of operation, and although the metallurgy is considered to be relatively simple, several metallurgical problems unique to Missouri concentrates are discussed.

Jan 1, 1970

By W. D. Lowry

As most of the industrial activity of Oregon is centered in the Portland area, the foundries there consume the bulk of the foundry sand produced in Oregon. Although a number of the larger towns scattered throughout the state have gray-iron foundries, the sand used by most of them is of local origin: The yearly consumption of foundry sand of all types for the past few war years in Oregon is estimated to have been approximately 40,000 tons valued at about $285,000, of which an estimated 18,000 tons was shipped in from the Ottawa, Ill., district for use largely by the steel foundries. Until 1945 much of the silica sand consumed by the steel foundries in the Pacific Northwest, approximately 50,000 tons in 1944, came from Ottawa, Ill. and surrounding regions. Although some silica sand was shipped in from Belgium in the past, none is known to have been imported in recent years. Early in 1945, a very promising high-grade silica sand being produced near Eugene, Oregon, was introduced, and all but two of the Portland steel foundries are using this new sand. Until a few years ago, the search for good local (Oregon) foundry sands was carried on largely by the foundry supply houses. Recently the Oregon Department of Geology and Mineral Industries has investigated a number of deposits and has carried on and fostered research on the most promising deposit near Eugene, about 120 miles south of Portland. High-grade silica foundry sand from this deposit is now being marketed in Oregon, Washington, and British Columbia. The Eugene sand is one of the very few outstanding western steel-foundry sands. Field investigations by the Oregon Department show that there are relatively few deposits of sand in Oregon suitable for foundry use. A knowledge of the geology of the state makes this readily understandable. The only major primary sources of the quartz present in sandstones in Oregon are the intrusive masses of granite, granodiorite, and quartz diorite of late Jurassic or early Cretaceous age found in the Siskiyou Mountains of southwestetn Oregon, a part of the old Klamath Mountain highland, and in the Blue Mountains of northeastern Oregon. Transportation militates against the development of any possible deposits of foundry sand found east of the Cascade Mountains in central and eastern Oregon because few railroads traverse that area. East of the Cascades, which separate western from eastern Oregon, many of the older sediments of Paleozoic and Mesozoic age have either been metamorphosed or contain much volcanic eruptive material, and even if some of the Mesozoic sediments are highly quartzose in places, they are in relatively inaccessible areas. All the Tertiary sediments there are of continental origin and contain much ash and other volcanic debris, for there was great volcanic activity during much of that period. In western Oregon much the same is true of the Paleozoic and Mesozoic rocks

Jan 1, 1947

By Milton E. Wadsworth, Edward M. Eyring

BETTER understanding of solid surfaces and their associated adsorption products is of both academic and practical value. The study of detergents and their behavior in cleaning surfaces is fundamentally related to the nature of the products adsorbed and their ability to compete for certain surfaces. Similarly in flotation, the nature of the adsorbate before and after adsorption is basic to clear understanding of the process. The recently developed pellet technique1,2 employing infrared spectroscopy provides a powerful tool for the study of solid surfaces. Absorption bands, which are infrared-active, may be observed for adsorbed products. Also any changes in the surface substrate that occur as a result of adsorption may be detected by means of differential spectra. In applying the pellet technique to solids of large surface area, French and his coworkers3 have surveyed the adsorption of organic flocculants on clay minerals, oleic acid on fluorite, and ammonia on cracking catalysts. Recent work on application of differential infrared spectroscopy to the study of solid surfaces' has demonstrated that the difference between a sample and a reference can be obtained with double-beam instrumentation. In this way displacement of surface products, adsorption of new products, and differences in the substrate, if any, may be detected. Experimental Procedure: Potassium iodide pellets were used in this study, prepared from recrystallized analytical reagent grade KI. Grinding was carried out in a Fisher mechanical agate mortar. Two-gram plates containing the solid under study were pressed in a special evacuated die constructed in the laboratory at the University of Utah." Concentration depended on the solid in question. Zinc sulfide and willemite are sufficiently transpar- ent in the infrared region for concentrations as high as 20 mg of mineral in 2g of KI to be used. Zinc oxide is even more transparent, permitting concentrations as high as 60 mg in a 2-g plate. For non-differential operation, however, much lower concentrations (2 to 10mg/2g KI) had to be used. Spectra were obtained on a Per kin-Elmer 21 double-beam recording infrared spectrophotometer. A sodium chloride prism was used giving a spectral range of approximately 2 to 15 v wave length. For differential runs a resolution of 1000 was used and the scanning speed was controlled commensurate with instrument response. The response was checked continuously and each spectrum was repeated several times. For nondifferential runs a resolution of 927 was used. Zinc oxide used was analytical grade oxide fume. The zinc sulfide was precipitated from solution with analytical grade zinc sulfate and sodium sulfide. The precipitate was washed and centrifuged several times and dried. Before use the precipitate was washed in dilute HCl and then treated with saturated NH4Cl to remove any bulk oxides and sulfates. X-ray patterns of the precipitate were comparable to that of the natural mineral sphalerite. The precipitate was much more satisfactory than finely ground natural ZnS because of its very large surface

Jan 1, 1957

By H. W. Morse

INTRODUCTION THE experimental work on the oxidized copper ore at the New Cornelia mine at Ajo, Ariz., ended on Jan. 12, 1916. On that date final decision was made on the general nature of the process to be used in the 5,000-ton leaching plant, and on many of the details, as far as experience on a40-ton scale could decide them. With the approval of the Board of Directors and the General Manager, John C. Greenway, we have compiled what seem to be the most interesting data on the results obtained during the experimental period. The most important part of the data resulted from the operation of a 1-ton and a 40-ton plant at Ajo. Experimental work on Cornelia oxidized ore dates back to April, 1912, and has been going on nearly continuously since that time. A good many variations from the original idea have been tried, but the process finally decided upon is in principle and in all of its details a simple one. The history of the leaching work on this ore has been brought down to about a year ago in papers presented to this Institute by Stuart Croasdale1 and Dr. L. D. Ricketts.2 The present paper will, therefore, deal principally with the results obtained during the last year of the work.

Jan 9, 1916