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By R. A. Ritter, J. P. Batycky

A numerical technique has been developed to permit estimating the pressure gradient associated with laminar flow of thixotropic liquids through long Pipelines. For this purpose the pipeline is divided into a number of radial and longitudinal increments within which rheological properties of the fluid may be considered as constant at any time. Then, provided only that the fluid flow curve is defined at every duration of shear, it is possible to predict the instantaneous pressure gradient at any cross-section along the pipeline for each desired flow rate and pipe size. The technique consists of an iterative integration of shear rate to establish the appropriate value of the wall shear stress at each location. Consistency of fluid in the increment is determined by the flow history of that increment, while the radial flow associated with variations in velocity profile is accounted for by adjusting the width and radial position of the increment. A number of pressure profiles, computed at each of several flow rates, provide a convenient basis for pipeline design and pump selection. INTRODUCTION In recent years considerable attention has been given to predicting pressure drop associated with the isothermal laminar flow of time-independent non-Newtonian fluids in pipes and annuli. 6,11,12 The approach generally has been to develop analytical relationships between flow rate and pressure drop based on simple constitutive models which hopefully provide an approximate description of the rheological properties of the fluid. Analytical solutions are highly desirable since the influence of all pertinent parameters can be readily determined. Unfortunately, however, this approach is restricted to simple flow geometries and- frequently leads to erroneous results due to inadequacies in the model. In certain cases a solution may be obtained through applying appropriate numerical techniques.l,14 For example, a digital computer program is available for predicting the velocity profile and pressure drop encountered by any Newtonian or time-independent non-Newtonian fluid flowing under laminar conditions in a cylindrical pipe or annulus.l In this paper the consistency behavior of the fluid need only be described in terms of basic rheological data. Analyzing flow systems involving fluids with time-dependent rheological characteristics is considerably more complicated since substantial changes in consistency may occur because of sustained shear action. This sensitivity to shear frequently persists for several hours. Consequently, variations in pressure drop and/or flow rate resulting from the aging process and addition of unsheared or partially sheared fluid to the system must be considered for purposes of pipeline design. This paper outlines a numerical method for predicting the transient and steady-state laminar flow behavior of a thixotropic liquid in a pipeline of arbitrary length (i.e., at a specified constant flow rate, the instantaneous pressure gradient may be determined at any time after start up and at any location along the pipeline). Several such pressure gradient profiles, computed at several flow rates, may be combined to produce a complete portrait of the system response. This flow portrait provides a reasonable basis for pipeline design and for selecting a suitable pump characteristic. TIME-DEPENDENT RHEOLOGICAL BEHAVIOR The most familiar time-dependent rheological properties are those exhibited by thixotropic liquids. Many of these materials, particularly thixotropic crude oils, generally display an apparent yield stress in that a finite pressure gradient is required to initiate flow. Then, under the influence of sustained shear at a constant shear rate, the consistency systematically decreases to some final limiting value. The shear stress obtained at

By B. C. Wonsiewicz, G. Y. Chin

THE presence of deformation bands in cold-worked metals is known to influence the development of deformation textures1 but has not been considered in any theoretical treatments. At the present time the most rigorous theory of deformation textures appears to be based on Taylor's concept of homogeneous deformation of a crystal within a polycrystalline aggregate.' For each crystal the Taylor theory allows the operation of several equivalent combinations of five or more slip systems. Hence deformation bands can arise from the operation of a separate combination of slips in each of several portions within a crystal. On the other hand, a second type of band may occur as a consequence of slip on systems other than those selected on the basis on homogeneous deformation. This type appears to be associated with crystals of symmetrical orientations, such as the [loo] and [lll.] axial orientations in drawn wires of fcc single crystals studied by Ahlborn.3 In this note we propose a simple mechanism of deformation banding of the second type, and compare the theoretical results for wire drawing of [loo] and [Ill] with Ahlborn's observations. In outlini the model requires that the work to accomplish a given overall shape change by banding be less than or equal to the work to accomplish the same change by homogeneous deformation. While the work by homogeneous deformation, WH = ?T ;dri, can be calculated exactly by the equivalent methods of Taylor2 or of Bishop and Hill,4 the work by banding, WB, is less certain. The latter consists of 1) Wi, work by slip within a band, 2) Wb, work associated with formation of a boundary between bands, and 3) Wc, work to correct the difference in shape change arising from banding and homogeneous deformation. The Wi term can be evaluated explicitly for a band with an assumed set of slip systems, but a satisfactory analysis of Wb and Wc has not been obtained. Since WB = Wi + Wb + Wc WH, for banding to occur, however, a necessary condition is Wi = WH . Hence it seems reasonable to choose a band with the lowest value of Wi among competing bands consistent with Wi = WH, and then minimize Wb and Wc by arranging the physical configuration of the selected band. Wc is minimized by combining neighboring bands such that their net strain matches the macroscopic strain as closely as possible, and Wb is minimized by enforcing strain compatibility across the boundary between two neighboring bands, similar to the case of a grain boundary.5 It is realized that this procedure is not completely satisfactory, but it does seem to explain Ahlborn's observations reasonably well. The procedure is now outlined for the two corner orientations. a) [l00]. Fig. 1 shows a (100) stereographic projection. The results of the Taylor analysis for axi-symmetric flow by homogeneous deformation6 show that, while [loo] itself is unstable, the rotation of the tensile axis will nevertheless be confined to within about 15 deg from [loo]. Alternatively, less work may be expended by banding with slip on a pair of systems with primary-conjugate relationship, e.g., (ll1)[10l.I + (li1.)[110]. The latter represents minimum Wi for all possible bands.* Since there are four symmetrically

Jan 1, 1970

By Erwin Pink

It has been pointed out in a previous publication' that, for a given strain rate, serrated yielding can be observed only at certain test temperatures. Fig. 1 shows the results obtained for polycrystalline and re-crystallized tantalum, Va group in the periodic table of elements, where serrations in the course of deformation match the decrease of total elongation. However, there was no evidence of repeated yielding when testing molybdenum or tungsten, VIa group, at similar conditions, i.e., annealed and air-cooled samples (serrations have been found in quenched tungsten2). The reason for the observed serrations in the stress-strain curve are dissolved impurities on interstitial sites of the lattice. Of importance is the concentration of oxygen, carbon, and nitrogen, which are in random solution. Two methods to calculate the limiting concentrations for serrated yielding have been evaluated and applied with more or less success in estimating the role of carbon and nitrogen in mild steel.3 J. Friedel4 has given two equations, which determine the upper and lower strain rates i for the appearance of serrations at a certain test temperature: W denotes the binding energy of the interstitial atom, -1 ev for refractory metals;5 e' the portion of continuous strain in the discontinuous stress-strain curve, measured as -3x10-3; b the Burgers vector, c the concentration, see Table 11, in atom fractions; p the dislocation density, -2 X l09 per cm2 at an average stress ?, -15 kp per mm2 at medium strain. k stands for the Boltzmann constant, T for the absolute temperature, and D for the diffusion coefficient. Table I. Eq. [1], for a given strain rate, determines the minimum temperature, and [2] the maximum temperature, below or above which no "dynamic strain-aging" can occur. According to the calculation, which uses the given quantities, serrations should only be observed within the cross-hatched temperature regions in Fig. 1, and this is in good agreement with the experiment. The effect of varying impurity concentrations is indicated schematically in Fig. 2: only Eq. [I] is affected. Setting Eq. [I] equal to [2], one can calculate the limiting concentration cmin which first causes serrations. The second method uses the aging condition by Cottrell and Bilby6,7 \£i/ \ n. a / where n(t) is the number of impurity atoms, which segregate at a dislocation line of 1 cm length after the time t (t in our case is the time between "repeated yield drops" in the serrated curve, or, the time until the above mentioned strain E' is obtained, i.e., -1 sec for medium intensity or serrations). no is the number of impurity atoms in 1 cm3 and A = Qb4ep[(1 + v)/(l - v)], derived from equations given in Ref. 7. p is the shear modulus, 18,800 kp per mm2 for tantalum, 12,200 for molybdenum, AE the tetragonal distortion caused by interstitial impurities in a bcc lattice (approximately 0.4 for both tantalum and molybdenum) and v Poisson's ratio (0.35 for tantalum, 0.30 for molybdenum). From Eq. [3], combined with the condition for a pronounced yield drop as formulated by cottrel16 (at least one impurity atom segregated at the unit length of a dislocation), again a no min, and hence the concentration Cmin can be calculated.

Jan 1, 1970

By David Cornell, Yusuf K. Sukkar

The fundamental differential equation for fluid flow has been rearranged, integrated numerically for natural gases, and the results presented in tabular and graphical form suitable for the direct calculation of vertical gas flow problems. The integration is rigorous except for the use of a constant average temperature. Both static and flowing bottom-hole pressures may be calculated by (his method without resort to trial and error procedures. INTRODUCTION Bottom-hole pressures can be determined either by direct measurement with a bottom-hole pressure gauge or by calculation. Since measurement with a bottom-hole pressure gauge is costly, calculation of bottom-hole pressures is to be preferred when possible. Calculation involves knowledge of the wellhead pressure, the properties of the gas, the depth of the well, the flow rate, the temperature of the gas, and the size of the flow line. These quantities must be combined in a suitable equation for vertical flow. Several equations have been developed for the purpose of calculating gas flow through both horizontal and vertical pipes1,2,4,5,6,7,8,9 These equations all have the basic differential equation for flow as their starting point. They differ only in the assumptions which are made in order to simplify the integration step. The bottom-hole pressures calculated using any of the better known equations are in good agreement with bottom-hole pressures calculated by a more rigorous but considerably more tedious stepwise integration method. All of these methods, however. require a trial and error solution for the calculation of flowing bottom-hole pressures. The purpose of this paper is to present a method which provides a direct solution of static and flowing bottom-hole pressures without use of a trial and error solution. At the same time the method involves fewer simplifying assumptions than any of the previous methods used, except lor the lengthy stepwise method. The derivation of any practical flow equation begins with the basic differential equation which is rigorous for almost all flow problems. The five terms in Equation 1 represent the potential energy, the potential energy of position, the kinetic energy, the shaft work done, and the energy losses due to motion of the fluid respectively. Equation 1 reduces to Bernoulli's theorem for the case of horizontal flow of an incompressible fluid, no work done, and no energy losses due to friction. In the present case, the term (v) (dv)/(g,.) can be shown to be quite negligible compared to the other terms, and is therefore neglected in the derivation. The term — dws includes work done by a pump or turbine in the system and is zero in this case. The frictional losses in the pipe are included in the term — d(lw) which is expressed in terms of the Moody friction factor as in Equation 2. (f) (v2) (dL) d(lW) = (f)(V2) (dl)/(2) (g) (d) The specific volume of a gas can be expressed in terms of the temperature, pressure, molecular weight, and compressibility factor. The velocity of the gas can be expressed in terms of the weight rate of flow, the specific volume, and the dimensions of the pipe.The reduced pressure Pr is to be used because z can be expressed as a function of Pr and Tr alone for most natural gases:

Jan 1, 1956

Time as a Factor in the Making and Treating of Steel. By John Johnston. (Howe Lecture) (T.P. 1478) Influence of Chromium and Molybdenum on Structure, Hardness and Decarburization of 0.35 Per Cent Carbon Steel. By R. F. Miller and R. F. Campbell. (T.P. 1345) Mechanical Properties of Iron-manganese Alloys. By F, M. Walters, Jr., I. R. Kramer and B. M. Loring. (T.P. 1369) The Instability of Low-expansion Iron-nickel-cobalt Alloys. By I. R. Kramer and F. M. Walters, Jr. (T.P. 1370) The S-curve of a Chromium-nickel Steel. By B. M. Loring. (T.P. 1383) A Magnetic Determination of the A3 Transformation Point in Iron. By B. A. Rogers and K. 0. Stamm. (T.P. 1388) Rapid Tension Tests Using Two-load Method. By A. V. de Forest, C. W. MacGregor and A. R. Anderson. (T.P. 1393) Effects of Scrap in the Blast-furnace Burden. By C. L. T. Edwards. (T.P. 1270) Temperature Gradients through Composite Carbon Columns and their Application to Blastfurnace Linings. By F. J. Vosburgh and M. R. HatFIeld. (T.P. 1363) Correlations of Some Coke Properties with Blast-furnace Operation. By H. W. Johnson. (T.P. 1402) The Technical Cohesive Strength and Yield Strength of Metals. By D. J. McAdam, Jr. (T.P. 1414) Effects of Eight Complex Deoxidizers on Some 0.40 Per Cent Carbon Forging Steels. By George F. Comstock. (T.P. 1417) Significance of the Bessemer End Point. By H. T. Bowman. (T.P. 1428) Structural Diagrams of Nickel Irons and Steels. By J. T. EasE and N. B. Pilling. (T.P. 1432) Carbides in Low-chromium Steel. By Walter Crafts and C. M. OFFenhauer. (T.P. 1436) Hardenability Calculated from Chemical Composition. By M. A. Grossmann. (T.P. 1437) Recrystallization of Silicon Ferrite in Terms of Rate of Nucleation and Rate of Growth. By J. K. Stanley and R. F. Mehl. (T.P. 1438) The Solubility of Carbon as Graphite in Gamma Iron. By R. W. Gurry. (T.P. 1440) An Evaluation of the Factors Affecting Iron Oxide in the Open-hearth Bath. By J. E. Gould and H. J. Hand. (T.P. 1442) Precision in Creep Testing. By J. A. Fellows, Earnshaw Cook and Howard S. Avery. (T.P. 1443) Lattice Relationships in the Decomposition of Austenite to Pearlite, Bainite and Martensite. By G. V. Smith and R. F. Mehl. (T.P. 1459) Rate of Nucleation and Rate of Growth of Pearlite. By F. C. Hull, R. A. Colton and R. F. Mehl. (T.P. 1460) Weight Change as a Criterion of Extent of Decarburization or Carburization. By R. W. Gurry. (T.P. 1470) Observations in the Making and Use of Sulphite-treated Steels. By E. L, Ramsey and L. G. Graper. (T.P. 1476) Diffusion in Metal Accompanied by Phase Change. By L. S. Darken. (T.P. 1479) Engineering Properties of Heat-resistant Alloys. By Howard S. Avery, Earnshaw Cook and J. A. Fellows. (T.P. 1480) Distribution of Manganese and of Sulphur between Slag and Metal in the Open-hearth Furnace. By L. S. Darken and B. M. Larsen. (T.P. 1481)

Jan 1, 1942

Time as a Factor in the Making and Treating of Steel. By John Johnston. (Howe Lecture) (T.P. 1478) Influence of Chromium and Molybdenum on Structure, Hardness and Decarburization of 0.35 Per Cent Carbon Steel. By R. F. Miller and R. F. Campbell. (T.P. 1345) Mechanical Properties of Iron-manganese Alloys. By F, M. Walters, Jr., I. R. Kramer and B. M. Loring. (T.P. 1369) The Instability of Low-expansion Iron-nickel-cobalt Alloys. By I. R. Kramer and F. M. Walters, Jr. (T.P. 1370) The S-curve of a Chromium-nickel Steel. By B. M. Loring. (T.P. 1383) A Magnetic Determination of the A3 Transformation Point in Iron. By B. A. Rogers and K. 0. Stamm. (T.P. 1388) Rapid Tension Tests Using Two-load Method. By A. V. de Forest, C. W. MacGregor and A. R. Anderson. (T.P. 1393) Effects of Scrap in the Blast-furnace Burden. By C. L. T. Edwards. (T.P. 1270) Temperature Gradients through Composite Carbon Columns and their Application to Blastfurnace Linings. By F. J. Vosburgh and M. R. HatFIeld. (T.P. 1363) Correlations of Some Coke Properties with Blast-furnace Operation. By H. W. Johnson. (T.P. 1402) The Technical Cohesive Strength and Yield Strength of Metals. By D. J. McAdam, Jr. (T.P. 1414) Effects of Eight Complex Deoxidizers on Some 0.40 Per Cent Carbon Forging Steels. By George F. Comstock. (T.P. 1417) Significance of the Bessemer End Point. By H. T. Bowman. (T.P. 1428) Structural Diagrams of Nickel Irons and Steels. By J. T. EasE and N. B. Pilling. (T.P. 1432) Carbides in Low-chromium Steel. By Walter Crafts and C. M. OFFenhauer. (T.P. 1436) Hardenability Calculated from Chemical Composition. By M. A. Grossmann. (T.P. 1437) Recrystallization of Silicon Ferrite in Terms of Rate of Nucleation and Rate of Growth. By J. K. Stanley and R. F. Mehl. (T.P. 1438) The Solubility of Carbon as Graphite in Gamma Iron. By R. W. Gurry. (T.P. 1440) An Evaluation of the Factors Affecting Iron Oxide in the Open-hearth Bath. By J. E. Gould and H. J. Hand. (T.P. 1442) Precision in Creep Testing. By J. A. Fellows, Earnshaw Cook and Howard S. Avery. (T.P. 1443) Lattice Relationships in the Decomposition of Austenite to Pearlite, Bainite and Martensite. By G. V. Smith and R. F. Mehl. (T.P. 1459) Rate of Nucleation and Rate of Growth of Pearlite. By F. C. Hull, R. A. Colton and R. F. Mehl. (T.P. 1460) Weight Change as a Criterion of Extent of Decarburization or Carburization. By R. W. Gurry. (T.P. 1470) Observations in the Making and Use of Sulphite-treated Steels. By E. L, Ramsey and L. G. Graper. (T.P. 1476) Diffusion in Metal Accompanied by Phase Change. By L. S. Darken. (T.P. 1479) Engineering Properties of Heat-resistant Alloys. By Howard S. Avery, Earnshaw Cook and J. A. Fellows. (T.P. 1480) Distribution of Manganese and of Sulphur between Slag and Metal in the Open-hearth Furnace. By L. S. Darken and B. M. Larsen. (T.P. 1481)

Jan 1, 1942

By J. L. Kenty, J. P. Hirth

The concept of a critical super saturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, is discussed with reference to vapor-solid nucleation. The necessary and sufficient conditions deduced for observations of this type of behavior are: 1) the nucleation rate must exhibit a sharp dependence on super saturation, 2) the growth rate must be sufficiently large that nuclei become observable in the time period of the experiment, and 3) the number of highly preferred nucleation sites must be small. Experiments reveal that the nucleation of silver on sodium chloride is visually detectable at all experimentally accessible super saturations and does not exhibit critical nucleation behavior. Failure to observe a critical super saturation is attributed to the insensitivity of nucleation rate to supersaturation as a consequence of the particular values of the contact angle and the surface free energy for this system. THE concept of a critical supersaturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, arises naturally in homogeneous nucleation theory. Experimentally this type of behavior has been found by Volmer1 and others for water and other low surface tension liquids, as reviewed by several authors.2'3 The same type of behavior has been predicted and observed for heterogeneous nucleation of solids by Yang et al.4 and others,596 as also recently reviewed.2,7,8 In the work reported here on the heterogeneous nucleation of silver on NaC1, however, no critical super-saturation was found. Similar observations have been made recently for other systems.9-11 These results led to a reexamination of nucleation theory which revealed that there are conditions for which critical behavior is not predicted, either for homogeneous or heterogeneous nucleation. Although heterogeneous nucleation is of primary importance in this paper, some insight into critical behavior for such a case can be gained by considering homogeneous nucleation. Accordingly both types of nucleation theory are reviewed briefly. The requisite conditions for critical supersaturation behavior are then considered. The experimental results for the nucleation of silver on NaCl are presented and interpreted in terms of the theoretical presentation. REVIEW OF NUCLEATION THEORY There are essentially two approaches to nucleation theory, the so-called classical theory involving the concepts of bulk thermodynamics, and the statistical mechanical theory in which nuclei are regarded as macromolecules. The classical theory is based on the work of Volmer and Weber12,13 and Becker and. Doring14 and has been extended by Pound et al.15 The crucial assumption in the classical theory is that the small clusters or nuclei can be characterized by the same thermodynamic properties as those of the stable bulk phase. Thus, the nuclei are assumed to have a surface free energy, y, and a volume free energy of formation (relative to the vapor phase), ,, identical to that of the bulk. For deposition under low super-saturation conditions, the nuclei are large and this assumption is satisfactory. However, in many cases of interest, the nuclei contain only a few atoms and this assumption is highly questionable. The statistical mechanical models originated, for the specific case of a dimer as the critical nucleus, with the work of Frenkel16 and were extended later to larger sizes by Walton,17,18 Hirth19 and, more recently, Ht Zinsmeister. These models describe the nucleus in terms of a partition function, the estimation of which is tractable for clusters of 2 to 10 atoms, but extremely difficult for clusters larger than 10 atoms. Although the classical and statistical mechanical models are expected to apply for the limiting cases of large and small nuclei, both are uncertain for intermediate sizes. In this paper we shall treat only the classical model, recognizing that it is exact only for large nucleus sizes and regarding it as a phenom-enological description for small nucleus sizes. When analyses of experimental data using bulk properties show the nucleus size to be small, the resulting parameters should be regarded as largely empirical parameters describing the relative nucleation potency of the system. Considerable justification for the continued use of classical theory is provided by its general success in predicting nucleation behavior as a function of supersaturation and temperature. We emphasize that the qualitative features of the statistical mechanical models, particularly the critical super-saturation behavior that is central to the present work, are the same as those of the classical model. Of course, potential energy terms and surface partition functions replace the volume and surface energy terms of the latter model. The most recent versions of classical nucleation theory have been extensively reviewed.2,3,7 so that only the results are presented here. For homogeneous nucleation of a condensed phase from the vapor phase, the volume free energy change is ?Gv=vrT = =^ln£ [1] where v is the molecular volume of the condensing species. The supersaturation ratio,

Jan 1, 1970

By L. J. Erck

H EAVY-MEDIA separation continues to be the favored process for concentrating the coarser fractions by elimination of undesirable tailing and middling fractions. The first vessel used for heavy-media separation was the closed-top cone. Further developments then led to the Akins spiral separator which fulfilled the requirements for improving metallurgica1 separation as well as gaining mechanical advantages. During the last season there has been a substantial influx of separator designs for further improvements of metallurgical separation based on the heavy- media method as well as attempting to garner further mechanical advantages with reduction in power consumption to boot. The newest of these designs was the Hardinge counter-current separator which was introduced into the field last spring in two plants. Both Hardinge separators proved satisfactory in operation and substantiat-

Jan 1, 1950

By PAUL DYER MERICA

PAUL DYER MERICA, who has been awarded the James Douglas Gold Medal for his achievements in non-ferrous metallurgy, is a Hoosier, having been born at Warsaw, Ind., in 1889. His father, a clergyman and educator, was president of the University of Wyoming from 1908 to 1913. After graduating from the University of Wisconsin in 1908, young Merica (not yet twenty years of age) went to China, where he was professor of chemistry in Chekiang Provincial College, Hangchow, until 1911. He then went to Germany to s t u d y and was fortunate enough to receive his Ph.D. from the University of Berlin just a few months before the outbreak of the World War in 1914. Returning to America, his first position was as special investigator at the En¬gineering Experiment Station of the University of Illinois, but before the year was out he joined the staff of the U. S. Bureau of Standards as associate physicist. Since 1918, he has been superintendent of research for the International Nickel Co. His work during those years is excellently summarized in the following quotation from the statement of Zay Jeffries recommending him for the award.

Jan 1, 1929

Many of those who attended the meeting at Chicago spent the first part of the following week in Pittsburgh, when the Experiment Station of the Bureau of Mines was dedicated and the fourth annual First Aid and Mine Rescue Contests were, held. The Bureau buildings were open for inspection during the three days, Monday, Tuesday, and Wednesday. The dedicatory ceremonies were held in the Bureau of Mines main building, Monday morning, Sept. 29, Mr. T. J. Gillespie, representing the Pittsburgh Chamber of Commerce, presiding. In his address of welcome, Hon. E. V. Babcock, Mayor of Pittsburgh, said: "The reclamation work already done stands out conspicuously beneficial to industry and populace alike all over the United States. It has demonstrated methods of preservation of life and reclaiming of injured persons which are new and greatly beneficial to modern civiliza-tion. The establishment of this institution in Pittsburgh was greatly desired, and now it is here it is greatly appreciated." The response was given by First-Assistant Secretary of the Interior Vogelsang, who represented Secretary Franklin K. Lane. He said that the Bureau of Mines did more during the war for the triumph of American arms than any other institution.

Jan 11, 1919

NORTH AMERICA ALASKA Anchorage.-Strandberg, H. College.-Barber, R. J. Burns, W. T. Henricksen, R. Henton, H. M. Joesting. H. R. Comet.-Albertson, F. E. Douglas.-Cahill, W. E. Carlson, L. Fairbanks.-Andregg. J. N. Coats. R. R.

Jan 1, 1938

By D. A. Stevenson, R. A. Burmeister

Single-phase silver antimony telluride has been prepared by zone-melting techniques using initial compositions of A new phase appears upon prolonged annealing of this material, but the reaction does not appear to be a simple eutectoid decomposition. A complete analysis of the phase equilibria is complicated by the slow kinetics involved. The Hall coefficient, magneto -resistance, electrical resistivity, and Seebeck coefficient are all sensitive to the presence of second phases. The low Hall mobilities measured for single-phase material indicate that the usual band theory is inadequate to explain the observed transport properties in the system. Density anomalies of up to 2.5 pet between measured and theoretical density were observed but are not conclusive evidence for a defect structure. COMPOSITIONS in the Ag-Sb-Te system have been studied previously by several investigators.1"18 The interest in this system arises from potential thermoelectric applications of alloys on the Ag2Te-Sb2Tes vertical section. Although the composition corresponding to the formula AgSbTe, has received most attention, it has been found to consist of more than one phase.7'8 A thorough understanding of the properties of this heterogeneous material has been impeded by both lack of knowledge of the properties of the homogeneous phases comprising it and the problem of analysis of transport properties in an inhomogeneous system. The present work describes the preparation of the homogeneous ternary phase and the corresponding electrical properties of both homogeneous and heterogeneous material. MATERIAL PREPARATION Most specimens for this investigation were prepared by encapsulating the elements in evacuated quartz tubes after which they were melted and homogenized in the liquid state. The ambient temperature was then dropped to 500°C and the resulting ingot zone melted. The growth rate, width of zone, stoichiometry, and number of passes have an effect on the resultant microstructure. Grains several centimeters in length were easily produced by this method. Other solidification techniques were also used, including uniform slow cooling of the entire specimen and rapid freezing. The microstructures of specimens produced by these techniques frequently differed appreciably from similar compositions prepared by zoning. A variety of nonequilibrium microstructures characterized by long needlelike particles resulted from the rapid-freeze method. PHASE EQUILIBRIA The lack of information on phase equilibria is a major difficulty associated with a comprehensive study of the Ag-Sb-Te system. Considerable confusion has resulted from the use of the formula AgSbTe, to identify the cubic ternary intermediate phase even though it has been established that material of this stoichiometry normally contains AgzTe as a second phase.798 In this paper, silver antimony telluride will denote the cubic ternary intermediate phase comprising the major portion of AgSbTe,. The term "single phase" will denote material which consists of only the cubic phase (as evidenced by metallographic examination and X-ray diffraction) and the term heterogeneous will describe multiphase material containing AgzTe, SbzTe3, or other phases in addition to the cubic phase. The single-phase material may actually contain a variety of inhomogeneities—gradual changes in composition on a macroscopic scale, localized fluctuations in composition, clusters or other products of early stages of the precipitation process, and a variety of point and line defects—all of which will not be detected by the present techniques for determining homogeneity. Single-phase material has been prepared from compositions close to 59 mole pct SbzTe3 21 (this notation refers to the location on the Ag,Te-Sb2TeS vertical section). Zone widths of =2 cm and growth rates 51.2 cm per hr were used. The single-phase region at elevated temperatures extends off the vertical section to a composition which can be expressed approximately as Ag,,SbzgTes,.9 The latter two compositions as well as AgSbTe, are represented in the conventional Gibbs triangle in Fig. 1. It is not presently possible to ascribe exact values to the limits of the single-phase region on a given isotherm or vertical section due to the extremely

Jan 1, 1964

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 RICHARD W HUNT 1883

Jan 1, 1917

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The microhardness of single crystals of tungsten disilicide has been investigated by the Knoop method. The average random room-temperature hardness of the WSi, matrix was 1350 kg per sq mm. Hardness crnisotropy was noted with respect to plane and indenter orientation as determined by single-crq.stal X-rny studies. Annealing at 1600" and 1800°C decreased the average hardness to 1310 and 1230 kg per sq tnm, respectively, and produced a second phase identified by X-ray diffraction and electron-microprobe analysis to be wSio.7. Ball-impact experiwzents produced rosettes at 850°C. Optical and electron microscopy showed evidence of slip and cross slip and twinning produced by microhardness indentations. Prismatic (100), [001] slip was found and cor~elated with hardness data. THE present study was undertaken to investigate the hardness anisotropy of as-grown and annealed single crystals of tungsten disilicide. The existence of the silicide WSiz in the W-Si system has been well-established and its structure thoroughly investigated zachariasen2 found WSi, to have a tetragonal C type of structure, similar to that of MoSi, with lattice parameters a = 3.212A, Kieffer et al. studied the W-Si system and measured the density and microhardness (at a 100-g load) of both polycrystalline WSi, and WSi,.,. The values found were 9.25 g per cu cm and 1090 kg per sq mm for WSi,, and 12.21 per cu cm and 770 kg per sq mm for WSi0.7, respectively. According to Samsonov et a1.5 the microhardness of polycrystalline WSi2 is 1430 kg per sq mm (at a 120-g load). EXPERIMENTAL The WSi, single-crystal boules investigated in this paper were grown by a Verneuil-type process using an electric arc by the Linde Division of the Union Carbide Corp.6 The largest specimens were 8 mm in diameter by 16 mm long. The crystals had an average density of 9.01 g per cu cm with a tungsten • silicon content of 99.9 wt pct. The major impurities were: 87 ppm O, 41 ppm N. 54 pprn C, 500 ppm Zr, 50 ppm Na, and 50 ppm Mn. The crystals were silicon-poor, the average silicon content being 22.20 pct (stoichiometric value is 23.40 pct), and tungsten-rich, the average tungsten content being 77.70 pct (stoichiometric value is 76.60 pct). As-received single crystals were ground and analyzed by powder X-ray diffraction technique using Cu Ka radiation. Laue and layer line rotation patterns were obtained on cleaved sections of WSi, single crystals. Electron-microprobe traverses of representative crystals were done using a Phillips-AMR electron microanalyzer. Carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to the metallographic examination, the specimens were mounted in Lucite and then polished for short times on polishing wheels using 9-, 3-, and 1-p diamond-grade pastes. Finally they were fine-polished with Linde A powder for 24 hr on a Syntron vibratory polisher. The samples were etched with 4H 2 O:1HF:2HNO3, which is a medium fast-acting etchant. The combination 1HF:2HNO3:5 lactic acid is also a satisfactory etchant. Annealing runs for selected specimens were made at 1600" and 1800°C for 3 hr at 1.0 to 3.0 x 10-5 mm Hg. A Brew tantalum resistance furnace with WSi2 powder for setters was used. The WSi2 powder was the same as that used for the crystal growth. Temperatures were measured with a calibrated W, W-26 pct Re thermocouple and a microoptical pyrometer. Powder X-ray diffraction, emission spectrographic, and electron-microprobe analyses were done after the annealing runs. For microhardness measurements a Tukon Microhardness Tester Type FB with a Knoop indenter was used. Although measurements were taken at loads ranging from 25 to 1000 g, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Only indentations of cracking classes 1 and 2 were considered.' DISCUSSION OF RESULTS Powder X-ray diffraction analysis showed the as-received crystals to be single-phase WSi2. Laue and layer line rotation patterns obtained on cleaved sections of WSi2 single crystals proved them to be tetragonal WS 2 2 The results also indicated that the c axis of the crystal was oriented parallel to the boule or growth axis. Electron-microprobe traverses across the matrix of the as-grown crystals showed them to be homogeneous WSi,. Optical and electron microscopy of etched crystals, however, revealed that they contained minute amounts of the "golden" and the "blue" second phases as opposed to the "white" or WSi2 phase. These two second phases were concentrated in inclusion and etch-pit

Jan 1, 1965

By Henry Rumfelt

8.1-1. History and Description of Shovels. The history of excavating machinery is not clearly defined but the machines seem to have been originally developed for dredging activities, principally involving rivers and harbors. The first, as far as can be determined, was a steam "spoon dredge" developed by Grimshaw of Boulton and Watt of Sunderland, England, in 1796. The land machine forerunner of the present-day power shovel was not developed until 1835. It was invented by William Smith Otis, a young partner of a Philadelphia contracting firm by the name of Carmichael and Fairbanks. The moving force behind this invention was the heavy activity in railroad construction. From this early start the power shovel has developed from steam powering to internal-combution-engine powering and to electric powering. In both directions it has developed to its present state of a finely engineered and precision-built tool. Through the interim the railroad-type shovel, about a half-swing arrangement designed especially for making railroad cuts and mounted on rails, was developed. The rail-mounted shovel gradually gave way to the full revolving shovel. It was high on the list in 1912 and was practically extinct by 1927. From the beginning, a few of the small revolving shovels designed primarily for the general contractors' market had found their way into quarry and mining operations. During this same period, the stripping shovel had been introduced-a 2 ½ cu. yd., 100-ton, full revolving stripping machine with a 41 ft boom. Although this shovel was designed especially for stripping, it was also used for heavy-duty, open pit mining service. In 1925 the heavy-duty, full revolving quarry and mine machine was developed. Strip mining shovels evolved through a somewhat separate path. Hand digging plows and mule-drawn slip scrapers were first reported used by Kirkland, Blakeney and Groves near Danville, Illinois for strip mining

Jan 1, 1968

By J. R. Thoenen

Six or seven years ago the United States Bureau of Mines started development of instruments for the purpose of accurately measuring the vibrational movement of the earth in the vicinity of quarry blasts. For this work a new type of seismometer has been developed. A number of these have been constructed, the accessory field equipment has been assembled, and approximately 200 field tests of actual quarry, blasts have been made. The results of some of these tests have been published 2/ and others are the subject of two manuscripts now in preparation. So far the attention of the investigation has been centered on ascertaining the characteristics and behavior of the ground vibrations. Occasionally, when opportunity arose, measurements of the vibrations occurring in houses or other structures caused by-quarry blasts were made, but without any attempt at direct correlation or interpretation. During 1936 the National Bureau of Standards conducted some experiments to determine the normal vibrations to which the wells and floors of buildings are subject. Cooperation of the Bureau of Mines was requested in measuring the displace-ment. This afforded an opportunity to study the affect of mechanically induced vibrations end make limited comparison with previous records of vibrations from blasting. This paper deals with the experiments made in cooperation with the Bureau of Standards and includes some comparisons with effects from quarry shots. The results are in the nature of a progress report only, and are not intended to draw definite conclusions. These tests were concerned with the determination of the maximum amplitudes of vibration possible in the floors and walls of a typical dwelling when subjected to commonly experienced vibrations. The dwelling tested was obtained by the National Bureau of Standards. It was a large four-story stucco building, 41 ft. south of the southerly curb of Park Road, in Washington, D.C., which was constructed about 1900 and was supported on overburden. The basement floor elevation was approximately that of the pavement of Park Road, Park Road runs east and west; the front door of the house faced north.

Jan 1, 1937

By Wheeler O. North

The United Eastern Mining Co.'s property is in the Oatman, Gold Roads mining district of Mohave County, Ariz. The mine and mill are 26 mi. (41.8 km.) southwest of Kingman, the nearest railway connection. The ore consists of a mixture of calcite and quartz with some andesite. The values, which are mainly gold, alloyed with approximately 34 per cent., by weight, of silver, are extremely fine so that fine grinding is a most important factor in extraction. The milling process, briefly, consists of single-stage, coarse-crushing, two-stage ball milling in cyanide solution, followed by combined mechanical and air agitation, and by straight counter-current decantation. The Merrill zinc-dust precipitation method is used to recover the values, and is preceded by the Crowe vacuum treatment of the solution. The most notable features of the plant are the absence of filters, and the use of short peb mills loaded with steel balls, for fine grinding. As originally designed, the capacity of the mill was to be 200 tons per day, although the grinding end was to be capable of handling double that amount. By adding extra agitators and thickeners and by some alterations to the grinding end, the daily capacity has been raised to 285 tons. This, it is hoped, may be increased to 300 tons during the warm months of the present year. Tonnage Milled per Day 1917 average....... 234; maximum month.... 272; minimum month..... 146 1918 average....... 253; maximum month,... 276; minimum month..... 217 As this article primarily deals with plant operations, those interested in the mechanical description are referred to the article by Mr. Otto Wartenweiler,1 the designing engineer, which gives the details and costs of design and construction. The following changes have been made since that article was published: Two special simplex Dorr classifiers have been substituted for the two duplex Callow screens and bucket elevator, which classified the Marcy discharge and returned the oversize for regrinding. Three Dorr

Jan 1, 1920

By E. V. Foran

The repressuring of oil-producing formations during the flush stage of production, although requiring primarily the same procedure as operations on formations where the gas pressure has been depleted, offers several advantages of major importance, the value of which has not heretofore been demonstrated. It is the purpose of this paper to present an account of some recent operations of this character and the economic effects on the properties where they were applied. The principal objective in all repressuring operations is to secure an effective diffusion of the input energy to all parts of the producing sand. If this can be accomplished, success is assured during the remainder of the life of the property; if not, it will be temporary only and will be followed by difficulties, .and the maximum possible recovery will not be obtained. During the past year in Texas, the Cook pool in Shackelford County, and the Turbeville pool in Archer County, while still in their flush stage of production, have been subjected to repressuring operations to observe their reaction to this process during the early stage of their productive periods. The repressuring operations carried on in each of these pools will be discussed separately in this paper in order to show peculiarities which were present in one pool but were not observed in the other. Turbeville Pool The Turbeville pool is in Archer County, about 30 rniles south of Wichita Falls. The productive sand varies in thickness from 10 to 30 ft., the average being about 16 ft. The depth of the sand varies from 1450 to 1530 ft. The developed productive area to date is approximately 200 acres, but the limits of the pool have not yet been proved. The sand varies considerably in different parts of the pool with respect to both porosity and permeability. The gravity of the oil varies from 39 to 41° A. P. I. There were some wells which flowed for a few days after completion but during 1927 all production was secured by pumping. The

Jan 1, 1928

Prof. G. W. MAYNARD, New York City (communication to the Secretary): Prof. Christy, in his admirable paper on "The Growth of American Mining Schools," has overlooked the work done by the Rensselaer Polytechnic Institute in its department of mining and metallurgy. This oversight is naturally due to the fact that the department was, for lack of money, discontinued in 1871. It was organized by the writer in 1867, starting with ten students, who had already completed the first two years of the civil engineering course in the Institute. The course covered two years, specifically devoted to mining, metallurgy and assaying, which, in connection with the two years' drill in the civil engineering department made a four years' course. During the four years of the existence of the department, thirty-five students took the course, of whom twentyfive graduated; and of this number eight have been members of the Institute of Mining Engineers, and the majority of them have occupied high positions in the profession. The equipment of the department was, at that time, second only to that of the Columbia School of Mines. As Prof. Christy has cited other institutions which are not distinctively mining schools, but in which the ruining course was subordinate to other courses, it seems to me that the work in this line carried out by the oldest engineering school in the country may very properly be referred to. In addition to the regular mining course, a special course in assaying was given; and many young men were here prepared for positions in the mines and metallurgical works of the west. PROF. George F. Swain, Boston, Mass.: I have listened with great interest to Prof. Christy's valuable paper, but there is one conclusion at which he arrives that appears to me entirely unjustifiable, and to which I desire to take exception. Prof. Christy finds that of the total wage-earners in the United States in 1880,10.41 per cent. were employed in " trade and transport;" 20.24 per cent. in " manufactures and mechanics," and 1.83

Jan 1, 1894

By H. S. Geismer

INTRODUCTION. THERE are three general methods available for obtaining commercial brown iron-ore : hand-screening; washing; and washing and concentrating. Hand-screening has produced a large tonnage of ore in the past, but is rapidly falling into disuse, except as a preliminary step, largely because modern furnace-practice requires all foreign material to be separated from ores before they are delivered to the furnace, and hand-screened ores can rarely be made to fulfill that requirement. Another argument against hand-screening is, that the waste-pile often contains as much ore as the screen recovers. The operation known as hand-screening consists of throwing the ore-bearing material against a stationary inclined screen of 0.5- to 0.75-in. mesh, similar in construction to the screens employed in sand-pits. The recently-prospected brown-ore deposits of Cuba seem to offer possibilities for hand-screening not possessed by the average American deposit, since these ores are not associated with worthless clays. Washing, and washing and concentrating, may be discussed together, since concentrating is never practical on brown iron-ore, except to treat ores that have already been washed. (Strictly speaking, washing might be classed as concentrating, but it is never so designated by brown-ore men.) The various steps of removing ore-bearing material and converting it into ore suitable for blast-furnace use, may be grouped under five heads: loading for transportation ; transporting ; feeding into the washer; washing; and concentrating. These five subjects will be considered in consecutive order. Each of these successive steps may be accomplished in a number of different ways, the choice depending entirely upon the character of the ore-bearing material to be treated.

Aug 1, 1911