Search Documents

By L. R. Plitt, E. O. Lilge

Tests carried out with both kaolin and silica slurries show that flocculants of the polyacrylamide type can be used to improve the thickening performance of hydrocyclones. This thickening improvement demonstrates that contrary to previously held theories, flocs can be formed which are capable of resisting the shear forces in a hydrocyclone. For the 1.25-in.-diam cyclone used, optimum thickening occurs when the flocculant solution is injected into the slurry stream at or near the feed inlet. Hydrocyclones offer many distinct advantages over gravity thickeners. These advantages include simplicity, low initial and operating costs, small space requirements, and flexibility of operation. In spite of these advantages hydrocyclones have not been widely used as thickeners. The main reason for their lack of application is that hydrocyclones are unable to efficiently remove semicolloidal particles (less than 5 microns) from the suspending solution. In gravity thickeners, the fine particles can be induced to form particle aggregates, or flocs, which have the settling characteristics of large particles. In the hydrocyclone, however, it was always assumed that the existence of shear would prevent the formation of flocs.1-3 Thus, if no floc structure is retained, the thickening hydrocyclone must be designed so that its separation size is below the size of the smallest particle to be recovered. To obtain a very small separation size requires the formation of very high centrifugal forces, which necessitates the use of small-diameter cyclones. Small hydrocyclones have, in turn, very low throughput capacities which render them impractical for many industrial thickening applications. Thus, if the effects of flocculation cannot be utilized, the usefulness of hydrocyclones as thickeners remains limited to pulps which contain no very fine particles. It is well established that most substances acquire a surface electric charge when brought into contact with an aqueous medium. The repulsive interactions between similarly charged particles act to prevent flocculation. One method of flocculating a dispersion is to neutralize the repulsive surface charges by the addition of an electrolyte. The reduction of the electrostatic surface charge (Zeta potential) then permits the universal van der Waals attractive forces to operate between the atoms of the various particles and form particle aggregates. The lime additions used by thickener operators promotes flocculation by this mechanism. A second method of flocculating a dispersion is by the addition of long-chain macromolecules. In this case flocculation is brought about by a bridging mechanism in which the molecules are adsorbed with part of their length on two or more particles, thus forming a molecular bridge between the particles.4,5 The molecules also form bridges between themselves when a single particle is bonded to several polymer molecules. The type of bonding between the flocculant molecule and the particle may be hydrogen bonding, chemical bonding, or electrolytic attraction.6 The flour and glue which are used as thickener additives are believed to promote flocculation in this manner. In the past decade synthetic long-chain polymers with extremely high flocculating capabilities have been developed. The flocs formed by these new polymeric flocculants are larger and more shear-resistant than those formed by the presence of electrolytes.7 The advent of these flocculants raises the question: Are the flocs formed by these synthetic polymers stable enough to resist the liquid shearing forces in a hydrocyclone? The investigations reported in this paper were carried out in order to provide some answers to this question. EXPERIMENTAL WORK For the bulk of the test work a 5% slurry of commercially available kaolin with an average particle size of 5 microns was used. An initial evaluation of the available flocculants was carried out to determine which flocculant formed the most shear-resistant flocs. A combination of the techniques used by Healy7 and Booth8 was used for this purpose. This initial study revealed that the neutral high-molecular weight polyacrylamides produced the most shear-resistant flocs. One of these flocculants, Separan MGL*, was selected and then used for all the hydrocyclone tests. The flocculant was dissolved in water and added to the hydrocyclone as a dilute solution.

Jan 1, 1968

By William B. Plank

IN my studies during the past twenty years of the enrollments in the mining and metallurgical schools of the United States and Canada, I have been struck with the great diversity in the curricula offered by these schools. In 1933 when I made my first complete study of the schools (Mining and Metallurgy, May 1934, p. 211), I discovered 19 different curricula or programs of study, leading to almost as many different bachelor degrees, in the 49 schools in the United States and the 4 schools in Canada. These were: (1) Mining Engineering, (2) Coal Mining, (3) Metal Mining, (4) General Mining, (5) Mining Administration, (6) Mining and Metallurgy, (7) Metallurgical Engineering, (8) Metallurgy, (9) Petroleum Engineering, (10) Petroleum Refining, (11) Petroleum Geology, (12) Petroleum and Natural Gas, (13) Ceramic Engineering, (14) Ceramics, (15) Geological Engineering, (16) Mining Geology, (17) Economic Geology, (18) Geo- physics, (19) Fuel Technology.

Jan 3, 1950

By William J. Coulter

WITHIN the United States the problem of meeting maximum production by our metal mines has been solved by: (1) Conservation of man power by mechanization. (2) Increasing man-power efficiency as expressed in tons per man-shift by the adoption of new and more efficient methods. (3) Production from submarginal properties made possible by some form of government subsidy. (4) Selective mining of high-grade areas. (5) Drawing on broken ore reserves and reducing advanced development work to a minimum. (6) Making maximum use of available equipment. (7) Repairing equipment that normally would be replaced. (8) Working a seven-day week on a three-shift basis to get maximum use of equipment and man power. (9) Adoption of incentive plans to increase maximum efficiency and unit production. (10) Important advancement in metallurgy, resulting in larger recoveries. (11) Improvements in safety, health, and general working and living condi-

Jan 1, 1945

By P. M. Robinson, M. B. Beaer

The heat of formation at 0°C of the intermetallic compound AgMg as a function of composition has been determined by tin-solution calorimetry. In this technique, the heat of formation is determined as the difference in the heat effects, at infinite dilution, on dissolution of the compound and a mixture of its components added alternately to liquid tin from a reference temperature, such as 0°C. The experimental technique and method of calculation have been described elsewhere.' The compound AgMg is a 0 electron compound with a CsCl structure.2 In nonstoichiometric compositions of the compound, atoms of the excess component are substituted on the AgMg lattice.3,4 The homogeneity range is approximately 43 to 52 at. pct Mg at room temperature and 38 to 65 at. pct Mg at 500Oc.2 Single-phase alloys outside the homogeneity range at room temperature can be prepared by quenching. The specimens used in this investigation contained from 39.0 to 54.8 at. pct Mg. They were made available, together with analyses, by the Research Laboratory of the General Electric Co. Metallographic examination of the quenched specimens containing 39.0 and 54.8 at. pct Mg gave no indication of the presence of a precipitated phase. The measured heats of formation are listed in Table I. In a calorimetric run, four to six additions each of a specimen and the corresponding mixture of the components were made. One or two calorimetric runs were carried out with each composition depending on the amount of samples available. The limits stated in the table represent the experimental precision and not the absolute accuracy of the measurements. Thermodynamic investigations of the compound AgMg have been made by Trzebiatowski and Terpilowski 5 and Kachi.6,7 The heats of formation at 500°C derived from the combined electromotive-force values of these investigators8 are more exothermic than the heats of formation at 0°C reported here, Fig. 1. The differences cannot be explained by the difference in temperature. This is shown by the published heat capacity of the stoichiometric compound, which obeys the Kopp-Neumann rule from 0" to 500oC.9 The heats of formation derived from equilibrium data are generally considered to be less accurate than those determined by calorimetric methods because small errors in the change of the equilibrium values with temperature have a large effect on the calculated value of the heat of formation. The heats of formation derived from the combined published electromotive-force values reach a maximum at 56.0 at. pct Mg.8 Kachi reports a maximum of -4.7 kcal per g-atom at the stoichiometric composition.7 The present results also indicate a maximum at or near the stoichio metric composition, Fig. 1.

Jan 1, 1964

While the production of this state has not realized the early hopes that this coal would replace eastern coal on the Pacific Coast, it has been steady though small. Nearly all of the tonnages given are from Goodyear's, The Coal Mines of the Western Coast of the U. s., a carefully com- piled and accurate account of the development of the industry along the Pacific. [ ]

Jan 1, 1942

SEC. 1. The membership of the Institute shall comprise seven classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members; 7. Junior Foreign Affiliates. All shall be equally entitled to the privileges of membership, excepting that no member of any class whose residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the class of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain Members.

Jan 1, 1946

SEC. 1. The membership of the Institute shall comprise seven classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members; 7. Junior Foreign Affiliates. All shall be equally entitled to the privileges of membership, excepting that no member of any class whose residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the class of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain Members.

Jan 1, 1946

By J. W. Downey, A. E. Dwight, R. A. Conner

THE MgCu2 type Laves phase has been observed in the thorium-osmium and thorium-iridium systems. Two alloys corresponding to ThOs2 and ThIr, were prepared by arc melting a 5-g charge in a water-cooled copper. crucible. Both alloys were very brittle. X-ray diffraction patterns were obtained using filtered Cu and Co radiation with a Straumanis-type DeBye-Scherrer camera. The a,, values as shown in Table I were obtained by a Nelson-Riley extrapolation. The structure belongs to space group Oh7-Fd3m. Relative intensities for each of these compounds were calculated on the assumption that 8 thorium atoms occupy (a) positions and 16 osmium or irid-ium atoms occupy (d) positions. The calculated intensities are the product of the Lorentz-polarization factor, the multiplicity factor and F', the structure factor, neglecting the absorption and temperature

Jan 1, 1959

By Y. C. Liu, R. H. Richman

From rolling textures of polycrystalline AgCl determined as a function of temperature, changes in the amounts of the individual textural components are correlated with temperature-dependent changes in glide geometry. The preferred orientations are influenced by the slip behavior as follows: 1) pencil glide, characterized by (110) slip directions and a greater participation in the deformation the higher the temperature, leads to a(012) fiber texture; 2) low-temperature deformation, primarily on (110) (110) systems, generates the {237}-(11, 9, 7) component; and 3) slip on {111}(110), comprising a significant portion of the room-temperature deformation, generates the {135}(211) and {110}(112) components. Typical re crystallization textures are also presented and briefly discussed. SPECIFIC relations between flow mechanisms in crystals and the individual orientations or components in deformation textures are necessary for a thorough understanding of the origin of such textures. Within each ordinary class of crystal struc- tures there is insufficient variety in the observed preferred orientations to permit direct and unambiguous correlation between flow mechanism and texture. A second approach to this problem is the correlation of textural changes with some known variation in glide geometry within one substance,1 In this paper, the latter approach is applied directly to a material in which there are distinct changes in the character of glide with changes in temperature. Silver chloride, although a nonmetal, is reported to exhibit slip,2,3 fiber textures,4 and rolling textures5,6 crystallographically similar to those of the well-studied fcc metals;7,8 in addition, there is a marked temperature sensitivity of the glide planes upon which flow occurs.3 Previous investigations of textures in AgCl unfortunately did not employ methods sufficiently sensitive to define possibly important minor components in the texture, nor did they utilize the temperature dependence of the glide systems. Thus, in order to clarify the effects of changes in slip mechanism, this paper reports a survey, using semiquantitative methods, of preferred orientations in rolled AgC1. Inasmuch as the influence of prior deformation texture upon preferred orientations after annealing is also of interest, some representative annealing textures are presented.

Jan 1, 1965

By Norman D. Fitz Gerald

THE growth of domestic requirements for motor fuel has been phe-nomenal, rising year after year in a fashion almost unique among com-modities, resisting depressions and forging rapidly ahead in times of prosperity. Consumption advanced from 226 millions of barrels in 1925 to 522 millions of barrels in 1938; or 130 per cent. The economic influ-ences generating and sustaining this demand are of vital concern to the petroleum industry. The general factors affecting utilization of motor fuel are well known but it is the purpose of this paper to employ the recently developed technique of economic dynamics to describe them mathematically. Such problems in economic analysis are complicated by the freedom of all the variables to fluctuate, their mutual interdependence, changing incidence upon one another, and the nonquantitative character of some of them. Economic quantities and relationships, unlike those of the physical world, are continuously changing and this dynamic characteristic is both a distinguishing and confusing feature in economic research. The com-plexities of the problems require application of the analytical devices of mathematical statistics to uncover the probable relationships between factors. The procedure employed is to formulate a logical relationship linking the dependent to the independent variables, and then simul-taneously, rather than sequentially, determine their separate effects by multiple correlation. This transformation of common knowledge to quantitative terms makes it possible to measure the probable effects of changing conditions upon requirements, assisting in the sound interpreta-tion of economic policies. The utility of the results of such dynamic analysis is in sharp contrast to the sterility of the trends and other simple empiricisms of descriptive statistics. It is not intended in this study to throw light on the reasons why any motor fuel at all is consumed; but to discover relationships explaining why more was consumed at one time than at another. Specifically the prob-lem is confined to the measurement of the influences of statistically

Jan 1, 1940

By Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.' In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy's3 equation for nonabsorbing thin films. In Lucy's derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.' The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.'-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc's were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

By J. C. McKinnell

The appraisal of an oil lease may often be mad,? through production decline analysis, which requires description of the functional relationship between the oil production rate and either cumulative production or time. Heretofore, attempts to define the function appropriate to a given set of production data have depended to some extent on subjective procedures. The purpose here is to introduce an objective solution, obtained by combining the principle of least squares with the theory of equations. MATHEMATICAL ANALYSIS The fundamental differential equation appropriate to a general class of decline curves may be written. Solution of Eq. 1 for general boundary conditions may be written in terms of either the cumulative oil production or time: These equations constitute the mathematical expression of the so-called hyperbolic decline. Their complete description for a given set of production data requires the numerical evaluation of the three parameters1.', n, D, and (go),. For the special case of n = 0, Eq. 2 becomes q. = (q.), - DiN with the corresponding expression in terms of time being q. = (qa),e...........(5) Similarly, for the special case of n = 1, Eq. 3 becomes with the corresponding expression in terms of cumula- tive oil production being q. = (q.),e " '.......(7) Eqs. 4 and 5 constitute the mathematical description of the so-called exponential decline; Eqs. 6 and 7 are the mathematical description of the harmonic decline.',' Returning to the hyperbolic expressions, Eqs. 2 and 3 may also be written, q: = sNp + b........ (8) and where a = 1 - n; s = (n— 1)D,(q0);"; b = (go):-"; a'=-n;s/= nD,(qo);"; and b' = (go);-. Note that both Eqs. 8 and 9 are linear in either time or cumulative production with respect to an exponential function of the production rate. In other words, a straight line relationship results for both variables when associated with the appropriate power of q,. This fact is of prime importance in the application of statistical analysis. . STATISTICAL ANALYSIS For a given oil lease, the time, production rate and cumulative production are recorded records. To establish predictive formulas from Eqs. 2 and 3, it remains to determine numerical values for the three parameters [n, D, and (q,) .] through an investigation of the past history. Upon interpreting a, s and b as parameters, Eq. 8 may be expressed for every time interval of interest, i, over the past history as follows. (q,): = s(Np), + b........(10) In general, Eq. 10 will not be satisfied exactly, because of the assumptions in the expression of Eq. 1, and the errors and anomalies universally associated with production data. It will instead define the residual, s(Np), + b- CO=d......(11) Squaring both sides and summing over all the data points, m, under consideration yields

By W. J. Romanow

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

Jan 1, 1958

By J. B. Cohen, O. F. Kimball

Aging of specimens of Au-20 at. pct Ni and Au-40 at. pct Ni has been followed with electron microscopy, resistance, magnetic measurements, and X-ray diffraction. The periodic structures observed by electron microscopy in Au-Ni alloys by Fisher and Embury are shown to be due to nickel-rich prepre-cipitates. Assuming this alloy system undergoes spinodal decomposition, our observations and available data on thermodynamic properties and elastic constants indicate that the gradient energy coefficient in this system is of the order of 10-5 ergs cm-1 . Shifts of X-ray peaks in this system have been found to be due primarily to residual stresses, not faulting. A large effect of applied stress during aging was detected by X-rays and electron microscopy for the Au-20 at. pct Ni alloy. The presence of a preprecipitation stage during aging of gold-rich Au-Ni alloys for short times below 300°C has been indicated by several previous investigations. Changes in electrical resistivity,1"3 elastic modulus,4 superparamagnetisrn,5 positions of X-ray diffraction peaks,6 and hardness7 have been studied. Electron diffraction and microscopic studies by Fukano8 and Fisher and Embury9 respectively showed that the precipitation process resulted in the formation of periodic composition fluctuations—perhaps spinodal decomposition. MOSS10 detected a satellite with X-rays in quenched specimens, but the wavelength was much smallerthan that found by Fukano. Recently Woodilla and Averbac11 detected a modulation similar to that found by Moss, but with electron diffraction. They suggested that the microstructures observed by Fisher and Embury may be simply due to a Moir'e effect from a back deposit of gold during electropolishing. Satellites in electron diffraction can be enhanced by small bends or tilts of a foil. Even if this were not the case, asymmetric satellites, as are found in Au-Ni are difficult to analyze. They are principally influenced by the large differences in atomic size in this system, and obtaining information on the associated composition fluctuations depends on assumptions as to whether or not there are isolated clusters or composition "waves", and in the latter case whether or not the entire specimen has decomposed. Assuming that decomposition was complete in alloys aged at low temperatures, Woodilla and Averbach suggested that the satellites indicated a composition which varied about the average value by only± 5 pct, much less than that predicted from the phase limits, Fig. 1; they attributed this small variation to a cessation of the reaction caused by the loss of mobile vacancies. In Ref. 12 it was shown that vacancies are trapped by the preprecipitate in this system. Furthermore, after reversion, aging proceeds at a much slower rate than immediately after a quench from the solution temperature,5'11,13 indicating the importance of vacancies in the kinetics. In some senses Au-Ni is a favorable system for studying preprecipitation and reversion mechanisms because of the simplicity of the equilibrium diagram14 and the availability of good thermodynamic15 and diffusion data.16,l7 The calculations necessary to relate the decomposition process to classical nucleation and growth or to spinodal decomposition, as well as those necessary for understanding reversion mechanisms, can, therefore, be made. As an example, the position of the chemical spinodal, calculated from the thermo-dynamic data of Sellars and Maak15 with the method described by Rundman and Hilliard,18 is included in Fig. 1. It is compared to the chemical spinodal calculated from the equilibrium miscibility gap by Cook and Hilliard's method.l9 Included is the coherent spinodal suggested by Golding and MOSS," using measured elastic constants for their calculations and the same ther-modynamic data. The spinodal estimated by Woodilla and Averbach,11 by determining the temperature limits for the observation of the satellites discussed above, is also given. Actually this last curve is open to question on the following grounds: As a phase boundary is approached the spacing of particles or the wavelength

Jan 1, 1970

By W. J. Parton

THE efficient recovery and preparation of small sizes of anthracite called No. 4 Buckwheat (3/3 2 by 1/3 2 in.) and No. 5 Buckwheat (1/3 2 in. by 0), present a difficult problem to the anthracite operators. In many instances preparation of these sizes, particularly No. 5 anthracite, is extremely inefficient. In many of the older preparation plants, inadequate facilities, and often none at all, were provided as an integral part of the plant for cleaning this fine anthracite. Consequently, much of the material smaller than s, 32 in. was discarded. As the demand for these sizes increased, facilities for preparing the fine sizes were often crowded into existing structures with consequent sacrifices of capacities and efficiency. In addition to this condition, the methods of preparing the finest sizes are being developed in an attempt to improve their efficiencies. Because the demand for small sizes of anthracite still is increasing, many operators would benefit by investigating and improving the cleaning equipment employed on these sizes.

Jan 1, 1949

By R. E. Ogilvie, A. R. Kaufmann, S. H. Gelles

The solid-solubility limits of iron in beryllium were determined between 850o and 1200oC by analysis of differential type multiphase diffusion couples, using an X-ray absorption technique. The maximum value of the solubility limit was found to be 0.92 ± 0.02 at. pct (5.46 wt pet) at the eutectic temperature 1225°C. The solubilities of nickel and beryllium were determined between 900°and 1200°C by the same technique and the maximum solubility was found to be 4.93 + 0.01 at. pct (25.2 wt pet) at the eutectoid temperature, 1065°C. A previously unreported high-temperature phase which decomposes eutectoidally at 1065 °C was found to exist in the beryllium-nickel system at a composition of approximately 8 at. pct Ni (36 wt pet) by diffision-couple analysis. The presence of this phase was confirmed by thermal analysis and metallo-graphic analysis of the structure resulting from the eutectoid decomposition. G. V. Raynor1 has treated the solid solubilities of some of the elements in beryllium on the basis of the "Hume-Rothery" rules2 which have been modified to include ionic size and ionic distortion effects. It was predicted that the solubility of iron and nickel in beryllium should be slightly less than that of copper. The lowering of the solubility, according to Raynor, is due to a more unfavorable relative valency effect and an ionic size effect. Kaufmann and corzine3 have compiled data on the solubilities of elements in beryllium and have discussed them in the light of the Raynor paper. These authors feel that, because the elements having the greatest solubility in beryllium systematically fall in the Group VIII and IB Columns of the periodic table, the electronic structure greatly influences the maximum solid solubility of elements in beryllium. The solubility of iron in beryllium was determined by Teitel and cohen4 as part of the study of the beryllium-iron phase diagram. The determination was carried out by X-ray and thermal analysis and according to the phase diagram presented, the maximum solubility of iron in beryllium is 0.41 at. pct (2.5 wt pct) at 1225oC. However, it is estimated that the uncertainty in the position of the a-beryllium primary solid-solution boundary is about 0.5 at. pct (3wtpct). Losana and Goria3 in studying the beryllium-nickel phase diagram, determined the solid solubility of nickel in beryllium by thermal analysis. They found the maximum solubility to be between 1.65 and 2.65 at. pct (10 to 15 wt pct) at 1240°C. This value decreased rapidly with decreasing temperature. In determining approximate ranges of solubilities for different elements in beryllium, Kaufmann, et al,8 reported a value of between 1.3 and 1.7 at. pct (7.9 to 10.1 wt pct) for the solubility of nickel in beryllium. The value was obtained by metallographic examination of quenched alloys and lattice-parameter measurements. However, the authors also noted a single-phase structure for a 1.7 at. pct Ni alloy (10 wt pct) on cooling from the liquid. This would indicate a higher solubility range than was reported. ~isch,' in his X-ray studies of beryllium-copper, beryllium-nickel, and beryllium-iron intermetallic compounds, reports the disappearance of a second phase (Ni,Be2) in the beryllium primary solid solution at approximately 4 at. pct (20 wt pct). THEORY The analysis of concentration gradients in diffusion couples has proven to be a useful tool in determining phase equilibria.8-14 In this particular study the diffusion couples were chosen to straddle the expected composition range of the phase boundary, then heat treated at a given temperature and the concentration gradient evaluated. The composition of the phase boundary for a given temperature appears at a point of discontinuity of the composition gradient. Examples of typical phase diagrams and the concentration gradients which should be found in such systems are shown in Fig. 1. In the present work, gradients of the form of Fig. l(c) were obtained in diffusion couples made of pure beryllium and two-phase alloys of beryllium with either iron or nickel. The composition at the point where the gradient becomes discontinuous, Cs, corresponds to the solubility limit of either iron or nickel in beryllium. The analysis of the concentration gradients was carried out by an X-ra absorption method developed and applied by Ogilvie and later used by Moll13 and Hilliard.l4 It depends on the fact that the absorption of X-rays by matter is determined by the concentration and type of the various atomic species present. The relationship for the intensity, I, of a monochro-

Jan 1, 1960

By Elmars Ence, Harold Margolin

The titanium-aluminum system has been investigated in the composition region 0 to 34 pct Al in the temperature range 800" to 1450°C. The phases encountered in this region were: a,ß, TiAl3, The reactions observed are as follows: 13 ; L - 6T. A1, 0 (15 pct Al) + 6 (18 pct Al) - yTi Al (16.5 pct Al) at -1170°C andP (7 pctpct Al) + y (9.2 pet Al) - ah(9 pct Al) at - 1060°C. A eutectoid reaction: y — a +d belm 700°C is postulated. THE Ti-A1 system has been the sub.ect of a number of investigations. Several of these1-3 have indicated extensive solubility of A1 in both a and ß titanium. Ence and Margolin, as a result of work on the Ti-A1-0 system:'5 have shown that the a solubility ofalumi-num is considerably restricted, and found that a compound, Ti2A1 existed in the region formerly designated as Q a This structure was identified as hexagonal with c/a = 0.803. Pietrokowsky confirmed the existence of this phase7 and pointed out that the structure was isomorphous with Ti3Sn.8 Although the existence of Ti,A1 has been confirmed by others,9-12 there has been considerable disagreement regarding the composition and mode of formation. A detailed reinvestigation of the Ti-A1 system has been published by Sagel et al.13 The tentative diagram indicated two phases, a, and e, occurring in the former all a region. The a, phase has the same structure as Ti2A1 and was indicated as having a broad region of solubility. Epsilon, a tetragonal phase, was shown to form within the a, solubility region. AS a result of unpublished work,14 Ence and Mugy3 olin disagreed with the interpretation of Sage1 et al., although some common features existed. The present study was conducted in an attempt to clarify prevailing uncertainties. EXPERIMENTAL PROCEDURE Alloy Preparation—Alloys were prepared from iodide titanium (99.9 pct Ti with less than 0.01 pct Zr) or Bureau of Mines electrolytic titanium (BHN-73) and high purity aluminum (99.99 pct). Alloys were arc-melted in argon or helium atmosphere as 15-g buttons in the composition range up to 34 pct Al. Depending on need, alloys were made in increments varying from 0.25 to 2 pct Al. Up to five 15-g buttons of some compositions were made. Weight losses during melting did not exceed about 1 pct of the charge and chemical analysis revealed that both titanium and aluminum were evaporated. In general, nominal and analyzed compositions agreed within 0.5 pct and therefore nominal compositions were used in plotting the data. Unavoidably, some overlap of composition occurred, particularly where small increments of A1 were used. The small increments were primarily used to obtain alloys which would fall into the narrow a -, r region and this purpose was achieved. In general, the data obtained from Bureau of Mines base titanium and iodide titanium alloys were in agreement. Forging—Both as-cast and forged samples were employed. Samples were heated for hand forging by an oxygen-hydrogen torch to the region 1200" to 1300°C. A titanium anvil and cover plate were used to prevent any iron pick-up and consequent formation of a low melting point compound. Frequent reheating kept the temperature in the desired range. Under these conditions, alloys containing up to 15.5 pct could be successfully forged. To check on the depth of contamination, forged alloys were heated slightlybelow the ß transformation temperature. Metal was removed to a depth below the contaminated surface so revealed, and the subsequent results obtained from these samples agreed closely with those secured from as-cast material. Heat Treatment—Prior to heat treatment, all alloys were vacuum annealed to remove hydrogen. Samples

Jan 1, 1962

By V. Kondic, W. M. Rumball

HUNT and Jackson' have recently suggested that binary eutectics might be classified according to the entropy of fusion of the component phases. Such a classification was in fact proposed2 some time ago by the authors and the purpose of this communication is to present some supporting evidence. As pointed out by Hunt and Jackson' typical metals of low entropy of fusion, ?S, tend to form normal eutectics (using Scheil's terminology3). Where one phase is metallic (low ?S) and the other nonmetallic (high AS) then anomalous structures are formed. These anomalous structures may either be regular (e.g., Bi-Sn)or irregular (e.g., A1-Si). Finally Hunt and Jackson suggest that where both phases are of high ?S regular faceted structures are formed. In the proposed classification2 the ratio of the entropies of fusion is taken as the quantitative parameter, i.e., ?Sa/?SB = E, where e > 1.0. An extensive literature survey has been carried out2,4 for reliable photomicrographs of eutectic structures. The structures, numbering 151, have been classified into two classes, viz., normal (i.e., lamellar and rodlike) and anomalous. The latter group has been arbitrarily subdivided into regular and irregular anomalous eutectics. Details and sources of the structures are given elsewhere.2,4 In the absence of better thermodynamic data the value of E has been determined for each of the systems making the following assumptions and approximations: l) The entropy of fusion of solid solutions may be calculated additively;5 ii) Inter metallic compounds are treated similarly but with the addition of the following term for fully ordered structures.5 -4.573(Ni lOg10 Nl + N2 log10 N2) where Nl and N2 are the atomic fractions. It might be argued that the entropies of fusion are meaningless as the eutectic phases form at some temperature (T,°K) below their true melting point (Ta or Tb). As AS, = Lo/To if La the latent heat of fusion of a, is assumed independent of temperature, the actual entropy change AS& is given by La/Te. The ratio of entropies of fusion then becomes Fig. 1 shows E' plotted against cumulative totals for normal and anomalous systems from which it is seen that normal eutectics predominate at low values of E'; e.g., some 90 pct of normal systems lie below E' = 1.5 with 65 pct of anomalous systems above this value. Fig. 1 also shows that the regular anomalous structures occur mostly at low values of c' possibly suggesting growth more akin to normal than anomalous growth. The choice of c as a classification parameter was based on nucleation concepts, it being observed that metals widely separated in Sundquist and Mondolfo's8 nucleation series were anomalous and those close together normal. The basis of these classification views is really outside the intended scope of this communication but it is hoped to explain them fully in the near future.7 Having arrived at this entropy of fusion classification by nucleation considerations it is interesting to note that Hunt and Jackson's ideas are based on growth considerations. Elsewhere one of the authors4 has shown that an even better classification of the metallographic structures reviewed is obtained from purely conventional heterogeneous nucleation concepts. It has been found that systems having a value of the parameter +b less than 0.28 are almost certainly normal and above this anomalous: V, is the gram atomic volume. This parameter is nevertheless closely related to c and c', these being an approximation of p. The parameter is also related to the other classification3,8,9 which have met with any success in the past. All these classifications are to be reviewed shortly by the authorsU7 A significant thing about the classifications based on

Jan 1, 1968

By J. D. Meakin

J. D. Meakin (The Franklin Institute Laboratories)— In a recent paper Garofalo12 has shown that a number of experimental creep results can be represented by the empirical relation In this expression ? is the steady creep rate, s is the applied stress, and A is a constant at a given temperature; a and n are adjustable parameters. Garofalo has shown that Expression [6] approximates to a power function at low stresses and a simple exponential function at high stresses. Among the data used by Garofalo are the results we published for creep of copper." For these results we found that the best correlation was an exponential law with different parameters in the low-and high-stress region, respectively. That is, i = A exp qs where A and q have different values above and below a critical stress a,. In Ref. 13 are listed a variety of observations which support the proposal that different mechanisms are operative at stresses above and below a,, and it is not felt appropriate to repeat those observations here. The purpose of this note is to demonstrate that, although the representation used by Garofalo does fit the experimental data very well, this fit cannot be used to conclude that only one mechanism is rate-controlling. The argument is best made graphically and is illustrated in Fig. 9. The continuous curves 2 and 3 represent pairs of simple exponential functions which intersect at i = 10-5. The curve 2 closely resembles the copper results in that a change of slope of 2:1 occurs at i = 10-5; the two functions shown are in fact: e = 10-7 exp (1.150) and ? = 10-6&apos; exp (0.576s) For purposes of comparison, curve 3 represents two exponential functions with a change of exponent of 3:1 and curve 1 has the exponent 1.150 throughout. It is quite clear that a satisfactory straight-line fit is obtained on a Garofalo plot for all three curves. The curves represent processes which have either a single stress exponent or two ex- ponents in a ratio as high as 3:l. It must, therefore, be concluded that the ability to obtain a linear dependence between log i and log (sinh cyo) cannot be taken as evidence for a single activated process. In fact, to some extent the way the experimental points quoted by Garofalo lie about a best fit straight line on the log (sinh as) plot indicates that two processes are indeed occurring. This is seen in Figs. 7(c) and 8(c) of Ref. 12 where it is particularly evident that the experimental points deviate from the straight line in a manner similar to curves 2 and 3 of Fig. 9. It is, of course, recognized that the generally used exponential form is an approximation to the hyperbolic sine function which is not valid for exponents of less than 1.2, e.g., qs < 1.2. The only curve in Ref. 12 which is affected by this restriction is Fig. 6(b) where the deviation from a In ? vs s

Jan 1, 1964