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By J. W. Hickman

INTRODUCTION RECENT work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of. these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution-type over-the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions.1 In. order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where Cu+ is 0.96Å and Ni-++ is 0.70Å, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with electrons. This composition in the copper-nickel alloys corresponds to 40 at. Pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is filled at 6o at. pct copper or 4o at. pct nickel. Mott and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel -has the-configuration: 3d8 4s2 and copper: 3 d10 4s) then at 60 at. pct copper or 4o at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may' exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. SURVEY OF LITERATURE The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1948

By E. A. Gulbransen, J. W. Hickman

Recent work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution type over the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions~i In order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where cu+ is o.,,6-,4 and ~i++ is o.,oh;, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with elec-trans. This in in the copper- nickel alloys corresponds to 40 at. pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is flied at 60 at. Pet Or or 4O at. pct nickel. Matt and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel has the configuration: 3ds 4s2 and copper: 3 dl0 4s) then at 60 at. pct copper or 40 at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. Survey OF Literature The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1949

By T. W. Healy, P. Somasundaran, D. W. Fuerstenau

The flotation behavior of quartz in the presence of alkyl ammonium acetates as a function of alkyl chain length has been interpreted in terms of hemi-micelle formation at the solid-liquid interface. The van der Waals cohesive free energy that is responsible for hemi-micelle formation has been found from these results to be 1.0 kT per CH2 group. This is in excellent agreement with literature values obtained from research on the properties of micelles in bulk systems. Collectors of the type CH3(CH2)n-2CH2-P, where P is a polar group and n is the number of carbon atoms in the straight alkyl chain, will induce flotation of an appropriate mineral at lower concentrations as n increases. This reduction in collector concentration with increasing n has been reported for such systems as xanthates on sulfides1,2 and amines on quartz.' The effect of chain length of alkyl surfactants on such solution properties as conductivity,' surface tension,' and solubility6 and such interfacial properties of solids as contact angle7 and electrokinetic potential8 have received considerable attention, but only limited quantitative descriptions of the effects have been given. The electrokinetic studies of alkyl amine salts on quartz indicated that the solution concentration of collector at which the marked change in electrokinetic potential of quartz occurs decreases systematically as the length of the alkyl chain increases. The aim of the present work was to obtain a quantitative description in terms of current theories of flotation of the effect of the hydrocarbon chain of alkyl ammonium acetates on the flotation behavior of quartz. BASIC PRINCIPLES The marked changes in electrokinetic potentials of quartz in dodecylammonium acetate (DAA) solutions were postulated to result from the association of adsorbed collector ions into two-dimensional aggregates, called hemi-micelles.9 Subsequently, the rapid increase in flotation rate of quartz was shown to coincide with hemi-micelle formation." We would like to discuss briefly the concept of hemi-micelles in terms of recent interpretations of micelles in bulk solution. Micelle hypothesis: In dilute solutions, alkyl ammonium and related salts behave as ordinary strong electrolytes, but at a certain concentration there is a marked change in physical properties of the solutions, e.g., in equivalent conductance, transport number, freezing point lowering and viscosity. To account for these phenomena, McBainl1 introduced the concept of micelles, which are aggregates of long-chain ions. It is believed that the ionic heads of the constituent ions of the micelle are in contact with water, whereas the nonpolar groups turn away from it and are in contact with each other. Work must be done to bring these charged polar groups together, but energy is gained (i.e., so called van der Waals cohesive energy) when hydrocarbon chains are expelled from the water and allowed to associate. For a given polar group, the tendency to form micelles will therefore strongly depend on the hydrocarbon chain length. Theoretical treatments of micelle formation by Shinoda12 and Phillips13 and others lead to the following expression for the concentration at which micelles form (the critical micelle concentration or cmc) in aqueous solutions of long- chain electrolytes

Jan 1, 1964

By N. A. McLeod

BALL wear in wet grinding mills has been the subject of considerable discussion in the last few years. Its importance to millmen is obvious in view of the fact that ball wear may cost from 2 to 4¢ per ton of ore for the more fortunate operators and many times this cost when a refractory ore must be reduced to a fine state of comminution. Consequently, any factual information that may be obtained on the nature of ball wear may be applied to introduce changes leading to lower ball consumption and therefore also to lower costs. In 1940, while employed with the Britannia Mining and Smelting Co., Britannia Beach, B.C., I had occasion to investigate factors that might affect ball consumption. We performed a number of tests, which will be briefly described. These tests originated as a result of changing from a 3 1/2-in. ball to a 2-in. ball of different type of manufacture and were motivated by the desire to obtain the best possible type of 2-in. ball. Our testing was helped by the fact that the company operated a one-ton electric furnace, so that it was quite easy to make steel changes. It should be emphasized at the beginning that these tests produced results that in their general application to milling should be interpreted qualitatively rather than quantitatively. As will be evident in the description of the method used in testing, the balls were subjected to an intermittent batch grinding treatment, which may have produced results in rate of steel wear that may not have an accurate correlation with steel consumption in full-scale mill operation. However, with this fixed and rather arbitrary method of testing, results were obtained that may be of some interest and may stimulate further work on this subject. Unfortunately, owing to pressure of war work, our tests, which we had intended to repeat on a continuous grinding operation, had to be discontinued. METHOD OF TESTING Tests were made in a small cylindrical mill, rotating at 72 r.p.m. Internal dimensions of the mill were 10 1/2-in. dia. by 9 in. The cylindrical inner surface was lined with rubber and the two ends were formed by steel plates. A charge of 2000 grams dry feed and 2000 c.c. of water was added every 2 hr., the mill being drained of pulp before the addition of each charge, by tilting and sluicing with water. The mill was run on afternoon and night shift for daily periods of about 15 hr. total grinding time, and each test lasted from 60 to 150 hr. This batch method of testing involved a higher average pulp temperature in the mill, which undoubtedly affected comparative results in some of the tests. HARDNESS OF BALL VS. WEAR In these tests, special "eutectoid" steel balls were used, some of which were chill-cast and quenched, some sand-cast and quenched, and some sand-cast and annealed to a dead soft condition. The results obtained, using as mill feed an ore containing considerable free quartz and

Jan 1, 1945

By J. L. Meijering

Oxidation hardening of cylindrical and spherical specimens first decreases with depth below the surface, but then increases again as the center is approached. This is in agreement with the view that this change in hardness is mainly determined by the change in velocity of the oxidation boundary, which affects the dispersion of the oxide. WHEN a thick slab of silver containing 0.3 pct Mg by weight is internally oxidized, the hardness measured on a cross section is found to decrease considerably with distance from the surface.&apos; This phenomenon has been attributed to the diminution of the velocity of the oxidation boundary. The smaller this velocity is, the more slowly the free-oxygen concentration rises towards the concentration in equilibrium with the oxygen gas. And a small 0 concentration favors dissociation and thus conglomeration of the oxide. For instance, the hardness decreases more rapidly during long annealings in nitrogen than in air.&apos; Measurements by Gregory and Smith3 on sections through internally oxidized Al-silver wire showed a smaller variation in hardness, probably because the wire diameter was only 0.9 mm. Wood4 found a drop in hardness with depth in internally oxidized Al-copper strip, and also—by electron microscopy—the concomitant increase in Al2O3 particle size. Under certain circumstances internal oxidation leads to formation of rather irregular inner oxide films in the midst of dispersed oxide. This special sort of conglomeration—discussed in Ref. 5—is also favored by greater depth below the surface.3,5 In this paper hardness measurements in large diameter cylindrical and spherical specimens are described. Here the oxidation velocity* goes through ness initially decreases with depth but increases again towards the center. Normally, the diffusion coefficient D1 of oxygen is very large compared to D2, that of the dissolved metal. If, furthermore, the atomic fraction c2 of the latter is much larger than the O-solubility cl- but c2D2 << c1D1- the velocities in question are easily calculated2 to be: for the cylinder and for the sphere. Here p is the radial coordinate of the oxidation boundary and R the specimen radius, which in dilute silver alloys is constant, as no external oxidation occurs. These equations have been derived for a divalent solute; for nondivalent solutes c2 has to be multiplied by half the valency. The equations are not valid near the center. For which can be considered as a standard case,2 the Eqs [I] and [2] begin to yield U-values which are appreciably too high for p/R = 0.05 and 0.15, respectively. But at the v-minima they are still very good approximations. These minima lie at p = emlR= 0.37R in the cylinder and p = 1/2 R in the sphere. Other factors besides the velocity v will also influence the hardness. The oxide concentration cox is constant in a flat strip, apart from a narrow region in the middle,2 but in cylindrical and spherical specimens cox decreases steadily with depth. When C1 << c2 and c1D1 >> c2D2 one can calculate

Jan 1, 1961

By Morris Muskat

It is pointed out that the application of capillary pressure curves obtained by drainage or desaturation processes to the calculation of the fluid distribution in interphase transition zones involves a number of difficulties; namely: (I) the development of very low nonwetting phase saturations appears to be in contradiction with the lack of mobility of such distributions indicated by permeability-saturation curves, (2) dispersed nonwetting phases are thermodynamically unstable, and (3) discontinuous phases should not be subject to hydrostatic equilibrium requirements. While these difficulties could be obviated by assuming that the capillary pressure drainage curve has an initial horizontal segment, they are automatically circumvented by application of the imbibition capillary pressure curve to the lower part of the water-oil transition zone. These generally show zero displacement pressure at only partial wetting-phase saturations. The countercurrent upward flow of oil into the main oil-saturated pay and downward drainage of water also suggests that wetting phase imbibition processes will control the saturation distribution immediately above the water-saturated section. Similar considerations, with a generalized interpretation of the apparent wetting-phase behavior of the oil and gas phases, provides a basis for constructing the curve for fluid distribution in the oil-gas transition zone. In the transition zones so derived, the oil begins with a nonvanishing saturation at the water-oil contact and terminates with a similar saturation at the top of the gas-oil contact. The gas-oil transition zone begins with an equivalent nonvanishing gas saturation. Introduction It has been a common assumption for some years that the nature of the fluid dis- tribution in virgin reservoirs, and in particular that in the transition zones between the oil and water and between the oil and gas sections, can be computed by a simple application of capillary pressure data. The results of such calculations appear to have been first reported by Leverett.&apos; The latter, however, indicated only the numerical values of the parameters used in the computations, without explicitly describing the procedure. Leverett&apos;s illustrative calculated transition zones are reproduced in Fig I. Although no critical study of the apparently obvious method of calculation has been published, one cannot proceed very far in the computation without encountering some rather fundamental questions not yet answered in the literature. This paper is not written under the pretense that the whole transition-zone problem has been fully and satisfactorily solved. Its purpose, rather, is to discuss suggestions for its treatment, much of it admittedly hypothetical, and emphasize the nature of the uncertainties arising therein; for the literature, as now available, gives little indication that there are any problems still outstanding. The Transition-zone Equation The basic equation, which presumably gives directly the fluid distribution without recourse to any further consideration, is: Ap = (r1 - r2)gh [1] where r1, y2 are the densities of the two contiguous fluids, h is the height above the "capillary-free" zone of complete saturation with fluid I, g the acceleration of gravity, and Ap is the capillary pressure across the average interface at the height

Jan 1, 1949

By John M. Bostwick, James C. Bradbury

Bitumen is a general term for a group of materials composed of mixtures of hydrocarbons that are fusible and soluble in carbon disulfide. Included in the group are petroleum, asphalts, asphaltites, and mineral waxes. Asphalt is a dark-colored, cementitious solid or semisolid, which generally softens on heating and resumes a more viscous or solid state when cooled. It is found in native form in fissures and pore spaces in rocks and as lakes. It is also obtained from the residues produced in petroleum refining. Asphaltites are black, naturally occurring solid bitumens. They are generally shiny and break with a conchoidal fracture. Common asphaltites are gilsonite (uintahite), grahamite, and glance pitch. Mineral waxes are solid or semisolid, relatively nonvolatile bitumens of various colors, having an unctuous feel and waxy luster, Of the native waxes, ozokerite is the best known. Montan wax is also classed as a natural wax, although it never occurs in the pure state and must be extracted from lignite or cannel coal (Ladoo, 1920). Mineral waxes may also be obtained by pyroprocessing of petroleum, lignite, and peat. Pyrobitumens are dark-colored, solid hydrocarbons that are infusible and relatively insoluble in carbon disulfide. They are so-called because they will yield liquid and gaseous hydrocarbons only when heated. Asphaltic pyrobitumens are defined as "substantially free of oxygenated bodies" and include wurtzilite (elaterite), albertite, and impsonite (Thrush, 1968). Nonasphaltic pyrobitumens contain oxygenated bodies; examples are coal and peat. The nonasphaltic type will not be discussed further. Petroleum Asphalts Asphalts refined from crude petroleum have almost completely replaced the native types. Refineries can produce asphalts in every desirable grade more economically and in greater quantity than the native types and with a variety of properties that meet the requirements of the various manufacturers using them. For all practical purposes, it is estimated that more than 95% of the asphalts consumed in the United States are refined from crude petroleum (private communication). Native Asphalts Native asphalts are dark brown or black, semisolid or solid substances that, in theory, formed by slow, natural fractionation of crude petroleum at or near the surface of the earth (Goulston, 1938). They are colloidal systems of high molecular weight components dispersed in a medium consisting of low molecular weight components (Pracy, 1954). Native asphalts may occur as lakes, as impregnations of rock (rock asphalt) or as deposits consisting of mixtures of natural asphalt and mineral matter in various proportions (Stern, 1960). Practical use of native asphalt dates to about 3000 B.C. It was mined from surface pits or lakes and used, then as now, for masonry mortar, waterproofing aqueducts and tunnels, binders for road construction, and as an article of commerce (Miller, 1938). Generally the native asphalts find little commercial use today except where they are geographically abundant, easily mined and transported, or have specific or special application. Petroleum-refined asphalt is produced by unusually economical techniques and is much less costly to use. The largest and best known of the lake deposits is that on the Island of Trinidad, where the lake covers an area of 114 acres and is 285 ft deep at its center (Stem, 1960). The lake asphalt is refined by heating to evaporate in-

Jan 1, 1983

By D. Geiselman, A. G. Guy

Single cvystals were grown from high-purity magnesium containing known amounts of nitvogen in the range 0.0008 to 0.0048 wt pet. Crystals of known ovientation were tested in tension in an Instron ma chine to determine the yield strength and to obsevue wheather a yield point occurred. Slowly cooled crystals or those given a solution heat treatment did not show a yield point. However, crystals that were aged following a solution treatment showed a yield point for all of the nitrogen contents studied. It was concluded that nitrogen caused the yield point by the Cottrell mechanism. NITROGEN has been shown to produce sharp yield points in single crystals of cadmium, zinc,2&apos;3 ß-brass,4 and iron,5,6 as well as in polycrystalline iron7 and molybdenum.8,9 Since magnesium has a structure similar to zinc and cadmium, it seemed reasonable that magnesium should also exhibit a sharp yield point provided it contained sufficient nitrogen. Bobalek and Shrader10 reported a total nitrogen content of 0.002 to 0.0065 wt pct in com- mercial magnesium alloys, an amount well in excess of that required by theory. However. magnesium differs from cadmium and zinc in that it forms a stable nitride, Mg3N2, which has a standard free energy of formation of -95,480 cal per mole at 25" c." If rather than being in solid solution, the nitrogen were predominantly combined as the nitride, it could not act to produce a yield point. This type of behavior is the basis for the elimination of strain aging and a yield point in steel by the addition of strong nitride formers such as titanium,12 columbium,13 aluminum,14 vanadium,15 and boron.16,17 Thus, there appeared to be factors both favorable and unfavorable to the production by nitrogen of a sharp yield point in magnesium, and the purpose of this investigation was to determine the actual behavior of magnesium crystals containing known amounts of nitrogen.

Jan 1, 1960

By Granville S. Borden

The fruits of industry are divided between capital, labor, and governments. Capital takes its redemption and remuneration through profits or dividends; labor takes its share through wages; governments take their share through taxes. Each must have a just share, and the question of what is a just share and the question of who-shall make the allocation are vital current political and economic issues. Certain political philosophies con- tend that government should take all the fruits and that some dictator or politician should have irrevocable discretion and power to distribute the fruits. Believers in democracy and free enterprise adhere to the view that capital is entitled to redemption and fair remuneration; that labor shall have a fair wage; and that governments shall make equitable levies. But since all human beings, both individually and in groups, are inherently selfish, there are many variable views in regard to the question of what ratios shall be applied in a division of the fruits and who shall have the power to fix these ratios. Perhaps all parties should devote more energy to means of increasing the crop, and not so much time to quarreling over a division of the existing crop. Moreover, all three parties must guard against killing the goose that lays the mineral eggs. For example, if the tax burden becomes oppressive and the taxpayer refuses to carry it, then business stagnates, with consequent unemployment, reduction of profits, and curtailment of government revenue. If a producer assumes the increased tax burden, marginal operations must be closed down, and again the consequences are increased unemployment and diminished government revenue. Quite often an increase in a rate of tax results in a reduction of government revenue. Perhaps the worst detrimental feature of selfishness and greed on the part of any one of the three distributees of the fruits of industry is the retardation of expansion of the enterprise. Growth means new jobs, more government revenue, better trade, and better standards of living. Explorations and discoveries have resulted in tremendous contributions

Jan 1, 1959

By Joel H. Watkins

The terms kaolin, china clay, ball clay, and paper clay are more or less loosely and interchangeably applied to a large class of white-burning clays. These clays are made up chiefly of hydrous amorphous (colloidal) aluminum silicates with variable amounts of free silica and other impurities in small quantities. Occasionally also the term kaolinite is wrongly applied to a white-burning clay, for kaolinite is a mineral of definite chemical composition and definite crystalline form which occurs but sparingly in nature. It is not the purpose of this paper, however, to define or classify clays, or to enter into a discussion of the chemistry of clays. It is rather a general description of the occurrence and methods of mining of a kindred group of clays, and a discussion of their future economic aspect. In the Southern Appalachian States, the mining of white-burning clays has in recent years become an important industry. Although these clays are of several distinct types, which occur in as many localities under different geologic conditions, they are for the most part primarily of the same origin. They are essentially the same in elementary constituents, and are largely consumed in the game industrial arts. From the standpoint of a mining engineer, therefore, and for convenience in comparison and correlation, it should be interesting to discuss them under one heading. Kinds of Clay The most important types of clay which are now being actively mined in the Southern Appalachian States and with which this paper is particularly concerned are the North Carolina, Virginia, and Georgia kaolins or china clays (residual); the South Carolina and Georgia kaolins or paper clays (sedimentary); and the Florida and Tennessee plastic kaolins or ball clays (sedimentary). Other varieties which are interesting but which are as yet of little importance are the pocket deposits of white clay in Augusta County, Virginia, the bauxitic kaolins of Tennessee,

Jan 1, 1915

By Albert Ladd Colby

PAGE I. Introduction,...........577 11. PRocess of Manufacture. 1. American Specifications. 2. Foreign Specifications, . ......... 580 III. Chemical Properties. I. Chemical Composition: (a) American Specifications ; (b) Foreign Specifications. 2. Chemical Analysis: (a) American Specifications ; (b) Foreign Specifications ; (c) Number of Analyses Required ; (d) Sample for Analysis ; (e) Check-Analyses Impracticable ; (f) Rejection Solely on Variation in Com-&apos; position,............581 IV. Physical Properties. 1. Drop-Test and Drop-Testing Hachine: (a) American Specifications ; (b) Foreign Specifications ; (c) Limits in Deflection. 2. Tensile Test: (a) American Specifications; (b) Foreign Specifications ; (c) Test-Pieces are not Representative ; (d) Specified Tensile Strength is Affected by the Section ; (e) BpeciBed Tensile Strength is Often Inconsistent with Specified Chemistry ; (f) Specified Tensile Strength is Often Inconsistent with Specified Elongation ; (g) Amount of Tensile Testing Required is Excessive ; (11) Conclusions. 3. Dead-Weight Test: (a) American Specifications; (b) Foreign Specifications; (c) Number of Tests Specified. 4. Bending-Test: ((1) American Specifications ; (b) Foreign Specifications,..........589 V. Section. 1. American Specifications. 2. Foreign Specifications: (a) Templets ; (b) Sample Piece of Rail; (c) Allowable Variation from Templet,...........601 VI. Weight. 1. American Specifications. 2. Foreign Specifications,. . 603 VII. Length. 1. American Specifications. 2. Foreign Specifications, . . 604 VIII. Drilling. 1. American Specifications. 2. Foreign Specifications, . 604 IX. Finish. 1. American Specifications. 2. Foreign Specifications, . . 50.5 X. Branding. 1. American Specifications. 2. Foreign Specifications : (a) Data to be Rolled in Raised Letters on Web of Rail ; (b) Marking of the Blow-Number on Each Rail; (c) Additional Marking and Painting of Rails,........605 XI. Inspection. 1. American Specifications. 2. Foreign Specifications: (a) Prior Notice of Rolling; (b) Free Access to the Works ; (c) Cost of Inspection, Analyses and Tests to be Borne by the Manufacturer ; (d) Rails after Inspection by Manufacturer to be Sorted into Lots Prior to Inspection by the Engineer ; (e) Disposition of Rejected

Jan 1, 1907

By D. E. Etter, J. E. Selle

The Pu-Ce phase diagram was determined by differential thermal analysis, metallography, and elechm-nricroprobe analysis. The dingram is chararterized by a eutectic with extensive solid solubility in the cubic Phases of both cerium and plutonium. No intermediate phases were found. Cerium is soluble in e plutonium to 16.0 at. pet Ce at 626OC nnd in d plcltoniurn to 23.0 at. pet at 613 "C, decreasing to 17.5 at. pet at room temperature. No solubility in the a, ß, or ? phases was jound, and the mininum cerium required to stabilize 5 plutonium to room temperature is 3.2 at. pet. The maximum solubility of plutonium in 6 cerium is 19.5 at. pet at 721OC, and the maximum soluhility of plutonium in ? cerium is 34.5 at. pet. Invariant points in the system are: a) eutectic at 626oC, L16.5 = E Pu16.0 + y Ce65.5; b) peritectoid at613oC, e Pu13.5 -y Ce65.5- d Pu23.0. AS part of a program aimed at the determination of the phase equilibria in the Pu-Ce-Cu ternary system, preliminary investigations were made of the three binary systems. A survey of the Pu-Ce binary system by differential therma1 analysis indi- cated several areas of disagreement with the published diagram,&apos; primarily in the shape of the liquidus surface. Consequently, a thorough investigation of the system was undertaken, and this report presents the results of the study. EXPERIMENTAL PROCEDURE Three methods of investigation were used: differential thermal analysis (DTA), metallography, and analysis with electron-microprobe X-ray analyzer (EMX). The EMX analysis was particularly useful for the determination of solvus lines. The DTA method was most useful for the determination of the liquidus curves. Metallography complemented both of these techniques. Materials. The cerium metal used for most of this work had a freezing point of 805°C. This material showed 15°C premelting, and was found metallographically to contain some unidentified in~lusions.2 The temperature of premelting is defined as the point at which the DTA curve breaks away from the base line, analogous to a curve obtained from a solid-solution alloy. Several compositions were prepared near the cerium end of the diagram with higher-purity material which had a freezing point of 800°C. etallographic analysis showed this material to be relatively free of inclusions and only 8°C premelting was observed. Major impurities were found by spectrographic

Jan 1, 1964

By R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-C and Fe-Ni solid-solution alloys has been investigated at 25°C. It is found that the rate of solid-solution strengthening is dependent upon the strain at which the yield stress is measured, the macroyield stress being much more concentration-dependent than the microyield stress. In fact the addition of nickel does not lead to any increase in the microyield stress of iron. The primary effect of increasing the carbon or nickel content is to increase the slope of the stress-strain curve in the microyield region; this effect has been correlated, by means of transmission electron microscopy, with a decreased ability of the dislocations to cross-slip. It is concluded that the Mott-Nabarro theory is a good description of true solid-solution hardening in these and other iron-base alloys. A.LL theories of the solid-solution strengthening1-4 indicate that the flow stress of an alloy increases both with solute concentration and "misfit" between the solvent and solute atoms. The functional relationship between strength, solute concentration, C, and misfit depends upon the particular theory. Mott and Nabarro1,2 and Schoeck and Seeger3 both predict a linear increase in strength with concentration, while Fleischer4 indicates that the strength should be proportional to C1/2; there are in the literature experimental observations to support both these compositional dependencies.1&apos;8 The experimental evidence used to support the theories is the change in macroscopic yield stress (strain, e, = 10-3) with composition. However, recent investigations have revealed that solid-solution strengthening in a Cu-Al single crystals7 and in Fe-V polycrystal-line" alloys depends upon the strain at which the flow stress is measured; a flow stress in the microplastic range (e = 10-6 to 10-5) is much less concentration-dependent than the macroyield stress. Since the theories of solid-solution strengthening are concerned in particular with the stress to move a dislocation in a dislocation-free matrix, they should only be compared with microyield-stress data; it will be shown that in a material deforming homogeneously the microyield stress (e = 10-6) is approximately the stress to move through the matrix those dislocations which have been nucleated by stress concentrations such as particles or grain boundary ledges.9-11 In contrast, the macro-yield stress is more complex in that it is affected by several phenomena: dislocation multiplication, dislocation interactions, and the ease of propagating slip across grain boundaries. For example, it is experimentally observed that when long-range order12&apos;13 or solute effects10 restrict cross alip the grain boundary

Jan 1, 1967

By J. L. Swedlow, M. L. Williams

Two standard techniques for assessing fracture initiatlon in sheet specimens involve measurements of 1) the applied load of fracture which, via linear fuacture mechanics, is used to find the fracture tough/less SC (or SIC), and 2) the velative displacement of fracture of the opposite free faces of the crack (COD). In the past, the quantitative association between these two parameters has not been determined in detail, owing to the mathematical difficulties of computing. the stress and strain fields in the combined elasto-plastic flow near the crack. Using a numerical technique Irecently developed and applied to a 7075- TO&apos; aluminum plane stress specimern, the two parameters noted have been determined and associated quantitatirely. CONSIDERABLE effort has been expended in selecting a rigorous yet practical manner for predicting fracture. The usual point of departure is the modified Griffith criterion in which the mechanism of energy dissipation is reflected in Sc (or SIC), the parameter of "fracture toughness". Sc. differs from the surface energy used by Griffith in perfectly brittle fracture in that it includes the effect of plastic flow in the vicinity of the crack tip. Because plastic flow alters the stresses and displacements predicted from the usual linear theory of fracture mechanics, and because analysis of the nonlinear stress-strain field has presented great obstacles: only estimates of several pertinent quantities have heretofore been available. Nevertheless, two parameters have often been measured experimentally althougll usually just at the point of fracture. These are the energy release rate, or fracture toughness 9, (or I,), and the crack-opening displacement (COD). Such observations have been used in connection with frarture criteria and have been most helpful in design, although their application requires care with respect to changes in geometrical configuration from that upon which the criteria were based 1,2 Recently, however, a reasonably accurate and comprehensive method for analyzing the elasto-plastic flow has been devised and applied to plane stress specimens having arbitrary octahedral stress-strain curves.3 It thus becomes feasible to compute, albeit numerically, both the fracture toughness and crack opening as functions of the applied tensile loading on a typical specimen geometry. As a result, it is now possible to associate these two parameters quantitatively, and thereby to associate data obtained by one method with data pertaining to the other. ELASTIC ANALYSIS For the case of linear elasticity, it is relatively easy to deduce the connection between various measures of crack deformation. Using, for example, the singularity analysis, it is found that the leading term of the Airy stress function x f°r symmetrically applied loadings on an isotropic medium is

Jan 1, 1968

By Enid C. Plante, K. L. Sutherland

PRACTICAL metallurgists are unanimous in stating that oxidation of mined sulphide ore adversely affects separation of the constituent minerals under standard conditions in a mill. Frequently, the need for different operating conditions in different plants is attributed either to the extent of oxidation of the mineral surfaces or to soluble oxidation products. The investigations reported in this paper study the effect of oxidation on the primary condition necessary for flotation, namely that of adhesion of an air bubble to the mineral. OXIDATION PRODUCTS FROM SULPHIDE MINERALS Weinig and Carpenter1 state that the relative rates of oxidation of some sulphides are: FeAsS > FeS2 > CuFeS2 > ZnS >PbS > Cu2S tetrahedrite. They also show that oxidation is rapid at first, that sulphides of older geological formations are more stable than those of recent date and that mixtures oxidize more rapidly than any one mineral alone. The more rapid oxidation of mixtures is borne out by results of Gottschalk and Buehler2 who found that PbS, ZnS and CuS oxidized 8 to 20 times faster when pyrite was present. Only the end products of oxidation, sulphate and the metal ion, were identified in these tests. Gaudin3 states that pyrite is difficult to oxidize in the laboratory. Winchell,4 using pyrite containing 99.98 pct FeS2, allowed water to percolate through a bed of this ground material. At the end of three months only a trace of Fe +++and S04- were found. Even after 10 months the quantity of Fe+++ was only 7.8 mg and S04- 25.5 mg per liter of percolating solution. Carmichael5 confirmed Winchell&apos;s results on the slow oxidation of pyrite. Usually the oxidation of sulphide surfaces has been conducted in neutral or acid solutions, the acidity being caused by the oxidation products. Eliseev and Nagirnyak6 found that treatment of pure pyrite with lime gave only thiosulphate, but considered it possible that thiosulphate was obtained not by oxidation of the pyrite itself, but by oxidation of calcium disulphide. Mitrofanov7 suggested that thiosulphate was formed by the following process: oxidation of sulphide to give free sulphur (this frequently happens with marcasite), followed by oxidation of the sulphur to sulphur dioxide and reaction of the sulphur dioxide with sulphur to give thiosulphate. Ferric and ferrous hydroxides, or similar compounds, were shown to be present. The Research Staff of the United Verde Copper Co.8 treated ore from the United Verde mine with lime. Thiosulphate, sulphide and polysulphides were stated to be

Jan 1, 1947

By Enid C. Plante, K. L. Sutherland

Practical metallurgists are unanimous in stating that oxidation of mined sulphide ore adversely affects separation of the constituent minerals under standard conditions in a mill. Frequently, the need for different operating conditions in different plants is attributed either to the extent of oxidation of the mineral surfaces or to soluble oxidation products. The investigations reported in this paper study the effect of oxidation on the primary condition necessary for flotation, namely that of adhesion of an air bubble to the mineral. Oxidation Products from Sulphide Minerals Weinig and Carpenter1 state that the relative rates of oxidation of some sulphides are: FeAsS > FeS2 > CuFeS2 > ZnS > pbS > Cu2S tetrahedrite. They also show that oxidation is rapid at first, that sulphides of older geological formations are more stable than those of recent date and that mixtures oxidize more rapidly than any one mineral alone. The more rapid oxidation of mixtures is borne out by results of Gottschalk and Buehler2 who found that PbS, zns and cus oxidized 8 to 20 times faster when pyrite was present. Only the end products of oxidation, sulphate and the metal ion, were identified in these tests. Gaudin3 states that pyrite is difficult to oxidize in the laboratory. Winchell,4 using pyrite containing 99.98 pct FeS2, allowed water to percolate through a bed of this ground material. At the end of three months only a trace of Fe+++and So4- were found. Even after 10 months the quantity of Fe+++ was only 7.8 mg and SO4- 25.5 mg per liter of percolating solution. Car-michael5 confirmed Winchell&apos;s results on the slow oxidation of pyrite. Usually the oxidation of sulphide surfaces has been conducted in neutral or acid solutions, the acidity being caused by the oxidation products. Eliseev and Nagir-nyaka found that treatment of pure pyrite with lime gave only thiosulphate, but considered it possible that thiosulphate was obtained not by oxidation of the pyrite itself, but by oxidation of calcium disul-hide. Mitrofanov7 suggested that thiO~ulphate was formed by the following process: oxidation of sulphide to give free sulphur (this frequently happens with marcasite), followed by oxidation of the sulphur to sulphur dioxide and reaction of the sulphur dioxide with sulphur to give thiosulphate. Ferric and ferrous hydroxides, or similar compounds, were shown to be present. The Research Staff of the United Verde Copper Co.8 treated ore from the United verde mine with lime. Thiosulphate, sulphide and polysulphides were stated to be

Jan 1, 1949

By J. Charles Miller

NATURAL carbon dioxide has recently been exploited in the United States in consequence of oil and gas developments in the Western States and the growing demand by transcontinental and transoceanic shippers for solid carbon dioxide. The discovery by drilling of commercial deposits resulted in consideration of its geographic and geologic distribution and occurrence. Its wide distribution in nature is evidenced by its occurrence in the atmosphere, hydrosphere and lithosphere. The question of origin of carbon dioxide involves consideration of theories similar to those concerning natural hydrocarbons, although available evidence favors an inorganic rather than an organic source. Areas favorable to development of commercial production appear to be those in proximity to igneous rocks or in the vicinity of decadent volcanic activity, where, it has long been known, the gas is evolved either free or dissolved in the waters of fumaroles, geysers or mud pots. Structure contour maps are presented showing the Wagon Mound anticline in New Mexico and the Farnham anticline, Utah. A well drilled on the latter supplies gas to a 20-ton plant manufacturing solid carbon dioxide at Wellington, Utah, on the Denver and Rio Grande R.R., whence it is shipped to surrounding territory and to the West Coast. Before funds are invested in a plant for the manufacture of liquid or solid carbon dioxide, whether supplied by wells or springs, an effort to ascertain the volume of gas available is advisable. The use of present methods of estimation of gas reserves with modifications to account for the quantity absorbed by any water present in the producing formation is recommended, The Farnham anticline is used as an example and cornputationa are made of the probable volume of gas originally present in the structure. No attempt was made to compute reserves in the Niland area, California, for the reason that in such areas it is believed the volume is indeterminate. INTRODUCTION Carbon dioxide, in liquid and solid form, has found a wide variety of uses other than its primary application in carbonating beverages. It is now used in more than 40 different ways, ranging from cooling or freezing to use in gas or liquid form for mechanical purposes, chemical industry, explosive, fire extinction, and tire manufacturing. Undoubtedly the chief supply of carbon dioxide is obtained from industrial plants or artificial sources and until recently natural deposits of the gas have received little consideration. Few will question the utility and perhaps dependability of artificial sources, which possess the advantage over

Jan 1, 1937

By Norman Weiss

The need for more efficient utilization of labor in the metal-mining industry has been the subject of several recent editorials in the mining press, and one attractive possibility for such improvement lies in the designing of future milling plants particularly with economy of manpower in mind. We are accustomed to think of mill design as the selection and coordinated arrangement of process equipment, but if labor is to be efficiently utilized it must be given early consideration in planning the new mill. There are three good reasons for economizing in labor: (I) to reduce costs, not only in the form of wages but also in housing, hospital, welfare, and other obligations that a company accepts when a new man is added to the payroll; (2) to prepare for recurrent periods of manpower shortage, during which a well-designed plant can manage to get along with skeleton crews; (3) because a milling plant that must depend upon an inordinately large labor force for its operation and maintenance is certain to be inefficient in other respects, for many of the shortcomings in design that make necessary the excessive use of labor are generally not corrected merely by having too many men. A simple example of this is a poorly designed ore-feeding system : if this is inadequate to the extent that one man must be constantly unclogging feed chutes, it may help the situation to put two men or three at this task instead of one, but the feed rate will still be inconstant. First of the factors that affect labor saving is the location of the mill. This is often determined by transportation costs alone, and as a result the mill may be placed close to the mine regardless of the nature of the terrain. The designer must then adapt his layout to the conditions, favorable or not. This happens often at small properties, where capital investment may seem more important than operating expense. In most instances, however, a mill site carefully selected for the advantages it gives the designer in laying out the plant is the most economical in the long run, even if it involves a slight increase in cost of ore haulage. Given some freedom of choice, the design engineer may be able to find just the piece of ground that provides the proper gradient for the needs of the flowsheet, permits installation of essential yards and trackage, and perhaps supplies an excellent site for a tailing dam. Further justification for having placed the mill not too close to the mine sometimes emerges only years later as an opportunity to treat ores from other properties. When it is known from the beginning that the new mill will serve a number of scattered mines, a free choice of mill site is naturally stimulated. The most important single factor in limiting the labor requirements of a mill is its materials-handling system for bring-

Jan 1, 1947

By R. W. Gurry

In the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and III0°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon conteDt of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched, The mean result of concordant ments-—taeats-is-^that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C .(i755°F.) and 1.89 per cent at III0°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutec-toid temperature (738°C. or I360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature II35°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. Experimental Procedure The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.&apos; In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (I6°F.) but at a given location the temperature remained within +o.5°C. (o.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (I760°F.) and III0°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with toluene; this quickly produced on the

Jan 1, 1942

By Norman Weiss

THE need for more efficient utilization of labor in the metal-mining industry has been the subject of several recent editorials in the mining press, and one attractive possibility for such improvement lies in the designing of future milling plants particularly with economy of man-power in mind. We are accustomed to think of mill design as the selection and coordinated arrangement of process equipment, but if labor is to be efficiently utilized it must be given early consideration in planning the new mill. There are three good reasons for economizing in labor: (I) to reduce costs, not only in the form of wages but also in housing, hospital, welfare, and other obligations that a company accepts when a new man is added to the payroll; (2) to prepare for recurrent periods of manpower shortage, during which a well-designed plant can manage to get along with skeleton crews; (3) because a milling plant that must depend upon an inordinately large labor force for its operation and maintenance is certain to be inefficient in other respects, for many of the shortcomings in design that make necessary the excessive use of labor are generally not corrected merely by having too many men. A simple example of this is a poorly designed ore-feeding system: if this is inadequate to the extent that one man must be constantly unclogging feed chutes, it may help the situation to put two men or three at this task instead of one, but the feed rate will still be inconstant. First of the factors that affect labor saving is the location of the mill. This is often determined by transportation costs alone, and as a result the mill may be placed close to the mine regardless of the nature of the terrain. The designer must then adapt his layout to the conditions, favorable or not. This happens often at small properties, where capital investment may seem more important than operating expense. In most instances, however, a mill site carefully selected for the advantages it gives the designer in laying out the plant is the most economical in the long run, even if it involves a slight increase in cost of ore haulage. Given some freedom of choice, the design engineer may be able to find just the piece of ground that provides the proper gradient for the needs of the flowsheet, permits installation of essential yards and trackage, and perhaps supplies an excellent site for a tailing dam. Further justification for having placed the mill not too close to the mine sometimes emerges only years later as an opportunity to treat ores from other properties. When it is known from the beginning that the new mill will serve a number of scattered mines, a free choice of mill site is naturally stimulated. The most important single factor in limiting the labor requirements of a mill is its materials-handling system for bring-

Jan 1, 1946