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By Edgar Dunn

PART I.-DETERMINATION OF GASES IN SMELTER FLUES. IN 1907, upon arriving in Anaconda to take up work in the testing department of the Washoe Reduction Works, the. following problem was met at the car step, so to speak: complete and. exact analysis of gases, not only at the stack, but also in all departmental flues. Taken up to employ time not otherwise needed for regular testing department work, instructions were extremely liberal for a commercial plant, to the effect that accuracy should not be sacrificed to speed. In December, 1907, the work was temporarily transferred to the Great Falls Smelter, and some of the methods here given were there worked out. Differences in smelting operations at Great Falls and Anaconda, however, necessitated further investigations and the development of a new method for S03 determinations at the latter plant, where work was resumed in July, 1908, and completed about a year later. At the time of inception of the work, data (not only on percentages, but even on methods) were found to be meager in the extreme, for one or the other of two reasons: either entire lack of experiment at a large proportion of smelters, or disinclination on the part of the managements to divulge data of any description pertaining to either results or methods. In making determinations of gaseous constituents of flues, two methods are open to consideration: 1, the drawing out of a sample, and collection of the same as a whole, to be removed to the laboratory for later analysis; and 2, the absorption in situ on the flue of one certain constituent, disregarding others for the time being, or perhaps combining two or three in one determination. The first is generally the more rapid, but it is also the more inaccurate, method of analysis, even with special type absorption apparatus, being the more largely subject to error, both of reading, and also because of leakage during complicated manipulation in the laboratory. The amount used for analysis must also, because of limit of container, be small for the first method, and an average gas is very seldom obtained, necessitating for a fair average result a large number of determinations. Consequently, when we balance the time spent in a dozen determinations of short-time samples as against the time employed in making two or three long-time determinations of various constituents in situ, we are not so certain in our statement as to the relative speed of the two methods. Moreover, the method of analysis in the laboratory of 100 cc. of flue gas is satisfactory only when constituents thus determined are present in considerable quantity, results being simply approximate when determining such compounds as sulphur dioxide, sulphur trioxide, carbon monoxide and dioxide, and arsenic trioxide and water vapor, none of which are carried in all smelter flues in amounts in excess of (or even approaching) 1 per cent by volume. Special condi-

Jan 8, 1913

For the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS, NEW YORK, N. Y. PHILIP N. MOORE ST -Louis, Mo FIRST VICE-PRESIDENT C. W. GOODALE, BUTTE, MONT.. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y.

Jan 6, 1918

By M. S. Seltzer

In a previous paper1 it was shown that activation energies for steady-state creep in lead sulfide single crystals varied with the concentration of electronic defects. For n-type lead-excess crystals, values for the creep activation energy, Qc, decreased from 2.9 to 2.2 ev as the carrier concentration increased from 1017 to 1017 electrons per cu cm, while Q, increased from 1.6 to 2.3 ev for p-type sulfur-excess crystals as the concentration of holes increased from 6 X 1017 to 1018 per cu cm. It was also shown in Ref. 1 that the Q, values could best be correlated with the sum of the self-diffusion activation energies in PbS, i.e., for a given concentration of electrons or holes Q, = QPb + Qs, where Qpb and QS are the activation energies for diffusion of pb210 and s35 in PbS. This result suggests that creep rates are controlled by at least two atomic defects, one for lead migration and one controlling sulfur transport. It would be most desirable to interpret these creep energies in terms of an atomic defect disorder model for lead sulfide. Studies of creep rates as a function of sulfur pressure2 indicate that the defects controlling creep rates are singly ionized lead and sulfur vacancies, VPb and Vs. This hypothesis can be more firmly established by determination of Q, under conditions of constant atomic defect concentration rather than constant electronic defect concentration as has been previously done. Therefore, several measurements have been made of Q, on crystals whose con- centration of lead vacancies or sulfur vacancies has been fixed by equilibration under appropriate sulfur pressure and temperature. It was indicated in Ref. 2 that high-temperature isotherms are available which show how the concentrations of various atomic point defects in PbS vary with composition over the entire homogeneity range for the compound. Two such isotherms are shown in Fig. 1 for 900" and 1000°K. Utilizing these isotherms the concentration of a given defect, say Vbb, may be held constant over a particular temperature range by adjusting the sulfur pressure as the temperature is changed. Thus the concentration of one defect suspected of controlling creep rates may be held constant while other defect concentrations vary. The apparent activation energy for formation of these defects can be obtained from the isotherms giving their concentration as a function of sulfur pressure. Activation energies for creep obtained under conditions of constant defect concentration can then be compared with defect formation energies and certain possible atomic defects can be eliminated as creep-controlling species. We have performed creep experiments as a function of temperature at a stress of 244 g per sq mm under conditions which fixed the lead vacancy concentration, V', at 1016, 3.2 x 1016, and 3.2 x 1017 cm-3, and one were the sulfur vacancy concentration, Vs, was held at lo17 cm-3. The results are presented in Fig. 2 as creep rate, k, vs reciprocal of absolute temperature, 1/T. Specimens 34, 35, and 36 were deformed under constant lead vacancy concentration while specimen

Jan 1, 1969

Organization Place Date 1919 Automotive Engineers New York, N. Y. Feb. 4-6 American Institute of Mining Engineers New York, N. Y. Feb. 17-20 New England Association of Gas Engineers Boston, Mass. Feb. 19 American Institute of Electrical Engineers New York, N. Y. Feb. 19-21 National Society for the Study of Education Chicago, Ill. Feb. 25-28 American Railway Engineering Association Chicago, Ill. Mch. 18-20 American Electrochemical Society New York, N. Y. Apr. 3-5.

Jan 2, 1919

By H. R. Peiffer, R. Geckle

The silver phase of silver and finely divided alumina composites is shown to grow as single crystabs upon solidification from the melt. These crystals grow without the aid of an externally applied thermal gradient or a mold. The single-crystal growth is more readily disrupted as the alumina content varies from the optimum concentration of 20 wt pct. Pretreatment such as variation of fabrication pressure, and presintering of the specimens appear to play a lesser role in this phenomenon. In actual practice the growth of single crystals of metals from the melt is a tedious, painstaking process.' Care must be taken to insure the proper thermal gradients and rate of growth in a vibration-free environment. Excellent single crystals can be grown when these variables are controlled. When a second insoluble and finely divided phase is present in the melt the growth of single crystals is difficult, if not impossible, even under the most favorable conditions outlined above. During the past few years, a composite of silver and alumina has demonstrated an ability to resist flow even though the major phase, silver, is mo1ten. 2 A more surprising feature of this material is the ease with which single crystals of silver grow upon cooling the composite from temperatures above the melting point of silver to temperatures near room temperature. Observations have been made that demonstrate that single crystals of silver will grow even when conditions most unfavorable for growth of pure silver crystals exist. The crystals grown in this manner are imperfect in that a great deal of subgrain structure exists. It is the purpose of this manuscript to qualitatively describe this process and to attempt to isolate the influencing factors of this behavior. MATERIAL PREPARATION The composite material is prepared by powder-metallurgical techniques. Two items of great importance are the introduction of oxygen into the system and the obvious need for a thorough mixing of the metallic and refractory oxide phases. The oxygen is necessary in order that the silver wets the alumina. Without oxygen the phases separate and the material shows no unusual properties. In order to supply the needed oxygen the silver is added in the form of silver oxide which is readily decomposed to oxygen and silver upon heating. The silver oxide is readily obtained in a finely divided form that allows a uniform mixture of the alumina and silver oxide to be prepared. The correct ratio of alumina to silver oxide is mixed in the presence of alcohol in an ordinary food blender. The mixture has the consistency of a thin slurry and after mixing for approximately 20 min is dried and pressed into billets at various pressures. As is shown in Fig. 1, there is no limit to the shape of the specimens obtainable as single crystals. These billets are heated in air in a predeter-

Jan 1, 1964

By Bernard York, John J. Reed

J. P. Zannaras (U.S. Tungsten Corp., Congress, Ariz.) —In the investigation described in the paper by Bernard York and John J. Reed, the 8x8x8-in. square block was subjected to compressive forces from three sides, top, side, and rear. Let us refer to the stresses set up by these forces as Sz due to top pressure, Sy due to side pressure, and Sx due to rear pressure. At the section across the 2-in. hole (when failure occurred at 317 psi) the compressive stress Sy was equal to 317 x 8/6 = —422 psi, the top compressive stress S; is of the same intensity, —422 psi, and the rear compressive stress S, equals —317 psi. The true stress is T = Sy — S — S Taking as 0.2,* Taking the case when the opening was ½ in. and failure occurred at 517 psi, 8 Sy - 517 x -----= —537 psi 7.5 8 Sz = 517 x-----= —537 psi 7.5 Sx = —517 psi The true stress T = Sy — Sz — S, T - —537 + 0.2 x 537 + 0.2 x 517 = —327 psi. It can be shown that the above fundamental formula holds good not only for the above two examples but for all sizes of openings used, because when this formula is expressed in terms of the external pressure and size of the opening it agrees perfectly with the experimental results obtained by the authors and given in Fig. 12 of their paper. General formula: T = Sy — s: — S....

Jan 1, 1955

Jan 1, 1951

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Extensive solid solubilities of CdTe (zincblende-type struckre) and InTe (B37 type) in each of the rock salt-type compounds, PbTe and SnTe, have been observed. Partial phase diagrams have been determined by thermal analysis and X-ray metallography. The limiting mol fraction. X,, of the solute in the rock salt-type a phase and the corresponding eutectic temperatures, T,, are: (PbTe)l-x(CdTe)x: X,- 0.2, T, =866°C; (PbTe),-,(lnTe),: X, - 0.35, T, = 646"C; (SnTe),-,(CdTe),:X,- 0.11, T, = 784 "C; (SnTe),-,(lnTe),: X,-0.53, T, = 630°C. The lattice parameters of the a phase decrease linearly with X, even in (PbTe),-,(CdTe),, where a, (CdTe) = 6.481A > %(PbTe) = 6.459A. This is taken as proof that the cadmium atom enters an octahedral interstice of the tellurium atom sublattice; i.e., the formation of the a phase entails the direct replacement of lead by cadmium. The a, us X curve extrapolates to 6.16A at X = 1, in agreement with the value predicted for an ionic crystal of CdTe; it is also consistent with the reported lattice parameter It is well-established that the compositions of intrinsic semiconducting and semimetallic compounds conform to normal valence rules.1"5 The apparent exceptions can be explained by taking account of anion-anion covalences, as in CdSb, or of multiple cation valences, as in In Te.'This empirical generalization is the basis of the chemical approach to semiconductors2 by which the properties of an intrinsic semiconductor are rationalized in terms of the ionic-covalent bonds necessary to saturate the valence-electron complement of the anion sublattice. A fundamental shortcoming of this approach is its disregard of long-range crystal interactions. It cannot, accordingly, deal with the phenomenon of charge conduction except through the use of ad hoc postulates. As an example, a crystal of CdTe would, in the valence-bond picture: be described in terms of electron pairs, each with the same discrete energy, localized between every cadmium and tellurium atom. This is, of course, contrary to the Pauli of the high-pressure rock-salt form of CdTe, corrected for decompression from 36 kbar. The free energy of formation of the a phase of pure CdTe at room temperature is calculated from the phase diagram to be +10 kcal per g-atom, in accmd with the value calculated from the transformation pressure. The standard enthalpy is +13 kcal per g-atom, and the standard entropy is +9 eu. The latter value implies the formation of extra classical particles, such as vacancies, interstitials, or nondegenerate charge carriers, but these alternatives are not consistent with the semiconducting properties and the densities of the a phase. The extrapolated values of the lattice parameters of (PbTe),-,(lnTe), and Spectively, for the rock salt-type modification of InTe. The corresponding interatomic separation is intermediate between monovalent and trivalent indium. The qualitative implications of the results are considered from the viewpoints of both valence-band theory and energy-band theory. principle, and is corrected by methods of molecular-orbital theory in which bonds are replaced by bands of molecular orbitals whose energies, E, depend upon a crystal-momentum vector, k.7 Each band is derived from a linear combination of atomic orbitals with two electrons required to saturate each molecular orbital in the band. In a crystal of N atoms containing z atoms in its primitive unit cell, there are 2 N/z states per band which lie in a region of k space bound by the Brillouin zone. In an intrinsic semiconductor, the bands can be grouped into valence bands which are normally filled and conduction bands which are normally empty. If the highest valence band and the lowest conduction band overlap anywhere within the Brillouin zone, the material is rendered semimetallic. The quantity defines the effective mass, m*, of an electron in a conduction band (or of a hole, i.e., an electron deficiency, in the valence band) and leads directly to the concept of charge mobility through the relation \x = et/m*, where e is the electron charge and t is the lattice relaxation time.

Jan 1, 1964

By N. Mungan

A study was made of the effects of wettability and interfacial tension on the immiscible displacement of a Iiquid by another Iiquid from porous media. The influence of viscosity ratio was also investigated. Porous media used were polytetrafluoroethylene (TFE) cores prepared by compressing TFE powder under different pressures. lt is shown that displacement of a wetting by a nonwetting Iiquid is always less efficient than the displacement of a nonwetting by a wetting fluid, all other things being equal. In the former case, the recovery efficiency can be increased substantially by either reducing the interfacial tension or increasing the viscosity of the displacing fluid. A qualitative discussion is given on the implications of this work to the recovery of crude oil by water flooding. INTRODUCTION The high cost of oil exploration and new recovery schemes makes it imperative that waterflooding be conducted under conditions favoring most efficient oil recovery. To improve oil recovery by waterflooding, it is essential that the role played by interfacial forces in the entrapment of residual oil be studied and understood. Interfacial phenomena in natural rock, connate water and crude oil systems are very complicated because of the complexity of the natural liquids found in petroleum reservoirs, because of our inability to adequately describe the geometrical structure of the porous media and because of a lack of understanding of physical and chemical interactions between the liquids and surface of the pores. The problem becomes further complicated when one tries to elucidate the role of interfacial phenomena in fluid flow. Numerous studies of the displacement of oil by water under different interfacial tension or wet-tability conditions have been made.lm3 These studies have been performed in silica, alundum or sandstone systems using water and paraffin oil and also some surface active material to control the interfacial tension s and the contact angle 0. Unfortunately, the high energies of various interfaces involved favor adsorption and orientation of the surface active material at the interfaces. Also the surface active material concentration at the interfaces exceeds that in the bulk of the liquid phases. Such surface excess may cause the surfactant distribution, the contact angle and the interfacial tension to differ from their measured static equilibrium values and makes interpretation of the displacement experiments difficult. Furthermore, as changes in s also lead to changes in cos 0, the role played individually by one of these parameters in the displacement becomes obscured by the effect of the other. To circumvent these difficulties, a low surface energy solid and true solutions or pure liquids should be used. Use of a low surface energy solid minimizes adsorption and orientation effects at the solid-liquid interfaces. By controlling s and cos 0 through use of selected pairs of pure liquids or true solutions rather than by surfactants, the adsorption effects at liquid-liquid interfaces are eliminated. In the present study TFE cores were used as the porous media. Liquids used were water, sucrose solutions, paraffin oils and benzyl, n-butyl and isobutyl alcohols. The interfacial tension was varied from 40 to 1.1 dynes/cm by suitably choosing the liquid pair. A surface active material was added to the water-oil system only in the case where interfacial tension of 0.5 dyne/ cm was desired. No precise changes of cos 0 were attempted. However, either the displaced or the displacing liquid could be made the one which preferentially wets the TFE surface. Using sucrose solutions and blends of paraffin oils proved to be a convenient way of changing the viscosity ratio between the displaced and displacing liquids. The present investigation examines the effect of interfacial tension, wettability and viscosity ratio on the immiscible liquid-liquid displacement from porous media. Observed data permit a

Jan 1, 1967

By D. J. Barrett, M. A. Sochocky

INTRODUCTION Summary of Factors Influencing Comminution Circuit Design The selection of an appropriate comminution circuit for a specific ore is one of the most important decisions in the design of a processing plant. The importance is related to the fact that the capital and operating costs for crushing and grinding plant generally represent, as is well known, the major portion of the plant costs. This chapter will, therefore, identify as many as possible of the factors which influence the selection of a comminution circuit. The number of factors which will have to be considered for any comminution project will depend, among other things, on the type of project. If, for example, the project is an entirely new mining development, then most, if not all, the factors identified will have to be analyzed. If the project is an expansion of a developed mining operation or if the new orebody is adjacent to a viable operation, then the existing operation will influence the choice of factors or design constraints which need to be considered. The existing infrastructure or supporting systems may be quite adequate to accommodate the requirements of any expansion or new development. Hence, those factors may not have to be considered. To cover, however, the widest spectrum of projects, the factors which have been identified in this chapter are those which will have to be considered for the most complex of projects, that of developing an entirely new mining operation. The range of factors is as broad as the range of different ore types. Thus, each development must be treated with individualized care. The most important step in the development is the analysis and understanding of the ore characteristics. The hardness of the ore, its abrasiveness, friability, moisture content, grade, mineralization including gangue mineralization, liberation size, chemistry, and other characteristics should be the first to be analyzed in the investigation. The next should be the determination of factors such as plant size, throughput, location, climate, accessibility, and availability of water. The selection of samples for initial bench scale work and bulk sampling (when needed) for further

Jan 1, 1982

By A. Satter, J. M. Campbell

Reported herein are the results of a careful and detailed study of the non-ideal behavior of pure gases and their mixtures. Included are: (1) new data on five ternary systems composed of methane, ethane and H2 S; (2) a simple compressibility factor correlation that is inherently superior to present correlations, particularly for gases containing H2S and CO2; and(3) a detailed study of combination rules and the effect of system composition on the choice thereof. This study makes use of the rather large mass of data already available in the literature. A complete re-examination of the data and ideas presented in the last 25 years was considered desirable as a prelude to our basic concern — the effect of diluents on gas behavior. A consideration of both the macroscopic and microscopic properties of gases provides a better insight which, in turn, gives a firmer basis for improved correlation techniques. Such a study has shown that expressing the compressibility factor Z as a function of acentric factor w, as well as reduced temperature and pressure, yields a correlation that is broader in scope. The study of various combination rules has shown that better results are obtained by "tailoring" the rule used to the system composition. To do so improves the basic reality of results by overcoming some of the anomalies often found when using Kay's rule alone. Tentative recommendations are made regarding the most reliable combination rule for use with a given class of gas. The data presented are useful for estimating the direction and magnitude of the expected deviation when using a given rule. Although more work is needed, particularly around the critical region and with CO2 mixtures, the advantage of the classification scheme proposed is apparent. INTRODUCTION When one attempts to write a PVT equation to fit the data for actual gases, greater precision is obtained by the use of a multiple number of empirical constants. This has lead to multiple-constant equations such as Benedict-Webb-Rubin, Beattie-Bridgman, Keyes, etc., which are capable of yielding very precise results for pure gases in a range for which data to get the constants are available. As a matter of practicality, though, the use of such equations for gas mixtures is limited. Because of the infinite number of gas analyses available, any attempt to compile the constants needed requires a prohibitive amount of experimental data. This could be overcome by the use of a combination rule, but there is no real advantage in doing so because the end result offers no practical impovement over the Z factor correlation. The most widely used method of predicting the volumetric properties of pure gases is based upon the "theorem of corresponding states". According to this theorem, "all pure substances have corresponding molal volume at corresponding temperature and pressure if the reference point of correspondence is the critical point". Generalized compressibility charts for gases were prepared first by Cope and associates1 in 1931 and later by Brown and co-workers2 in 1932. However, the most commonly used charts are those of Dodge,3 Nelson and Obert,4 Hougen and atsson: and Standing and Katz.6 The work of Katz and co-workers has provided us with basic data for the hydrocarbons most widely used today. Their original chart6 was compared with a relatively large amount of multi-component data for gases consisting almost entirely of normal paraffin hydrocarbons. A deviation of only + 1.2 per cent was obtained.39 In the 20 years following publication of this work it has been found that the behavior of most mixtures of paraffin hydrocarbons could be predicted by this correlation within at least 5 per cent. Where difficulty has been encountered it has largely involved one or more of the following circumstances: pressures above 4,000 psig, mixtures containing large amounts of heavy ends and/or aromatics, systems in the critical region and mixtures containing polar compounds and/or CO2. The abnormal error sometimes found with such gases, not too unexpected for this method, is

By W. T. Jr. Thom

IN PREVIOUS classifications of coal, it has been customary to regard moisture eliminated from coal samples between 20° and 100° C. as extraneous matter, rather than as a constituent part of the coal. It seems, however, that the physical character and use properties of the low-rank coals are directly related to the amount of such moisture present, and recent chemical work has shown1 that such coals contain unstable groupings which decompose between 20° C. and temperatures somewhat above 100° C., with the splitting off of moisture. According to this view, the moisture eliminated from air-dried coal below boiling point is similar in all essential respects to moisture eliminated above 100° C., and is produced by analogous reactions; and inasmuch as the moisture given off above 100° C. has always been treated as a constituent of the volatile matter of coal, it would seem that consistent usage would include as a part of the volatile matter all moisture present as an essential component of the coal as it occurs in nature. As a matter of experience, it seems clear that the general physical and chemical characteristics of the low-rank coals are largely determined by or related to the moisture, whether chemically or physically combined, present in air-dried coal; it is also demonstrable by trial that the low-rank coals cannot be satisfactorily classified on a purely chemical basis by using the moisture free form of analysis. The low-rank coals of the western United States include numerous well-defined types, many of which were referred to in a classification proposed by Ashley,2 in which the physical and use properties of the coals were made the primary basis for their systematic grouping. When testing this classification by replotting analyses of these type coals according to the Seyler scheme of classification,3 a satisfactory parallelism between use properties and chemical constitution of the dry coal was found among

Jan 5, 1925

By Rossiter W. Raymond

The formal outline of Mr. Hague's life and work is embraced in the following statement, chiefly based upon data furnished by him, at my request, shortly before his death. At that time the probability that I would survive to record his death was apparently small; but I urged upon him the duty of providing, whether for me or for my successor as Secretary of the Institute, trustworthy material for the notice which somebody would some day have to write—and which might otherwise be incomplete or incorrect. Mr. Hague, with characteristic promptness and freedom from affectation, did what I asked of him; and I am therefore able to present an authoritative sketch—concerning the details of which I shall add my own comments, and some particulars obtained from friends. James Duncan Hague was born Feb. 24, 1836, at Boston, Maes., where his father, Rev. William Hague, D.D.,an eminent clergyman, then resided. After a preliminary education in private schools, he studied in 1854 at the Lawrence Scientific School of Harvard University; in 1855 and 1856 at the University of Göttingen, Hanover; and from 1856 to 1858 at the Royal Mining Academy of Freiberg, Saxony. In 1859-1861 he was attached as chemist to a South Sea exploring expedition, sent by W. H. Webb, of New York, to examine Jarvis, Baker, and other islands for phosphate-deposits. After the outbreak of the Civil War, he entered the U. 5. Navy, serving for a year as Judge Advocate to the fleet stationed at Port Royal, S. C. In 1863 he became Superintendent of the Albany and Boston copper-mine, in the Lake Superior region, where he was also connected with the earliest development of the Calumet and Hecla property. In 1867 he became the First Assistant Geologist in Clarence King's famous Exploration of

Jan 1, 1909

By Joseph A. Holmes

(Pittsburg Meeting, March, 1910.) AT the Mining Experiment Station of the U. S. Geological Survey, in Pittsburg, an investigation of the process of combustion is being carried on in a specially-designed furnace having an unusually long combustion-chamber. This work is conducted by a committee consisting of H. Kreisinger, mechanical engineer; Dr. J. C. W. Frazer, chemist; and Dr. J. K. Clement, physicist. The problem, essentially one of physical chemistry, is extremely interesting to all who are concerned in the burning of coal or the construction of furnaces. The main object of these experiments is to ascertain the relation between the amount of the volatile combustible driven from the coal and the combustion-spaces necessary to burn it completely. Our best steam-coals vary from 15 to 45 per cent. of fixed combustible. The greater part of the latter is burned on the grate; but the volatile combustible leaves the freshly-charged coal and must be burned in the combustion-space. If this space is not large enough, the volatile combustible will leave the furnace only partly burned, and the result will be a considerable heat-loss and a smoky stack. Strictly speaking, the factor which determines the completeness of combustion of the volatile matter, after it has been mixed with a certain amount of air, is the length of time the mixture is allowed to remain in the combustion-space; but this length of time depends on the extent of the space itself. Let us suppose, for instance, that, when a given coal is burned at a certain standard rate, the volume of the volatile combustible driven off per second is 10 cu. ft. Adding, say, 10 cu. ft. of air, the volume of the resulting burning mixture is increased to 20 cu. ft. If the combustion-space is 20 cu. ft., the burning mixture will stay in it,

May 1, 1910

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400' to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,' in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886'C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By H. M. Chance

Probably no other prosperous mining district is so little known as the Black Hills. The name leads one to assume that the district is a rolling country, consisting of more or less insignificant hills. Nothing could be more untrue, as the Black Hills is an elevated region rising to heights of 7000 and 8000 feet above sea-level, and broken by deep gorges and ravines. It is, in fact, a mountainous country in all that that term implies ; but the cañons and gorges are of such a character that the country is easily penetrated by railroad-lines, and good wdgon-roads exist to-day, affording access to every portion of it. Aside from the stampede to the Black Hills country in 1876, when gold-placers were discovered, and 15,000 or 20,000 people became infected with the mining fever, the region has never had a mining " boom." Quartz-mining commenced in 1877 or 1878, and has been successfully prosecuted ever since; the output of gold steadily growing, until at present the yield is about $7,000,000 annually. This great production is about equally divided between two entirely different classes of deposits. The first class, comprising the so-called quartz or free-milling ores (of which the Homestake mine is the principal producer), are veins of generally steep dip, in the older metamorphosed rocks, and similar to the veins worked in other mining districts. The second class of mines is located in what is known as the " siliceous gold-belt." The Siliceous Gold-Belt. This belt, more particularly to be described in this paper, lies in the immediate vicinity of Deadwood and Lead City, and covers an area 6 or 7 miles in length by 3 or 4 miles in width. The formation in which the siliceous ores are found is a nearly horizontal series of sandstones and shales, generally

Jan 1, 1901

By H. M. St. John

MAINTAINING a satisfactory structure in brass and bronze castings has always been a foundry problem of great practical importance. While metallurgists and scientific investigators have not entirely ignored this matter, it has received less of their attention than has been given to iron, steel and the wrought copper and aluminum alloys. Investigation in this field has probably been discouraged to some extent by the complicated nature of the alloys involved. Hundreds of alloys are in more or less common use, most of them containing copper, zinc, lead and tin in-widely varying proportions. They also contain appreciable percentages of iron and antimony as impurities, and often phosphorus, which has been added as a deoxidizer and fluidifier. Small amounts of sulfur are usually present. It is not uncommon to find nickel, sometimes in rather substantial quantities. Traces of other metals are frequently present. So complicated and variable a mixture obviously offers difficulties in. any investigation of the various factors that influence the structure and other properties of the casting.

Jan 1, 1930

By C. M. Warner

In both the Flat River district of southeast Missouri and the Joplin district of southwest Missouri the lead concentrates are of very high grade, free of arsenic, antimony and bismuth, and contain no gold and very little silver. The general practice in both districts is to smelt the concentrates containing 70 to 85 per cent lead on Scotch hearths, to recover 70 to 85 per cent of the lead, and then smelt in a blast furnace the slag formed in the Scotch hearths to bring the total recovery of lead from lead concentrates to over 97.5 per cent. At the lead smelter of the St. Joseph Lead Co. at Herculaneum, Mo., no Scotch hearths are used. In the other smelters in the district the blast furnace plays a minor role to the Scotch hearth . The concentrates produced from the Flat River district are either table concentrates or flotation concentrates containing: Both types of concentrates are received at Herculaneum in box cars after being sampled. Great care is taken in weighing and sampling of cars of concentrates and in the determination of moisture and lead contents. The concentrates are unloaded into bins by an adaptation of scoop grain unloader. Four men unload and sweep a 40 to 45-ton box car of concentrates in 30 minutes. The same grade of concentrates is received each day and no metal-bearing fluxes are available. The problem is to get as high a recovery as possible as cheaply as possible from the high-grade lead concentrates produced by the company's concentrating mills. Sintering The bulk of the sulphur is removed from the concentrates and the fine concentrate particles are agglomerated by double roasting on typical Dwight and Lloyd sintering machines.

Jan 1, 1937

By C. A. Edwards

Following a brief introduction, an outline is given of the four main conditions in which gases may be associated with metals; namely, (1) adsorbed gases, (2) dissolved gases, (3) gases in chemical combination, (4) gases entrapped in blowholes or cavities. Adsorption is essentially a surface phenomenon and is regarded as the attachment of outside molecules or atoms to the exposed free valencies of the atoms comprising the surface layers. In many cases where adsorbed films of gas are formed this is accompanied by a process of diffusion of the gas into the metal itself. This is particularly true in respect to iron and hydrogen, and experiments have shown that there is no difference between the rate at which hydrogen diffuses through a single crystal of iron arid through the same material after it has been recrystal-lized into a mass of small crystals. This does not prevent a somewhat greater concentration of gas at the boundaries of adjacent crystals, nor does it mean that the effect of the gas will be the same at the boundaries as it is within the body of the crystals. Indeed, under certain conditions, iron is rendered very brittle at the crystal boundaries, as shown in experiments by Pfeil with samples of almost pure iron. Much work has been done by many investigators concerning the temperature and conditions under which dissolved hydrogen, in particular, can be at least partially removed from different metals. With iron, the hydrogen that has diffused into the metal as a result of acid attack by pickling or by electrolytic deposition of the gas on the metal is partly removed by exposing the metal to the atmosphere at ordinary temperatures. Considerably more can be eliminated by raising the temperature, and even greater quantities by jointly raising the temperature and reducing the pressure. Annealing at suitable temperatures completely removes the bad effects of excessive mounts of hydrogen dissolved in or associated with iron. This is shown by the data plotted in Fig. 1, giving values for electrolytic iron sheets after annealing at temperatures between 250" and 950" C. The hydrogen brittleness is rapidly diminished at

Jan 1, 1935

By C. A. Edwards

Following a brief introduction, an outline is given of the four main conditions in which gases may be associated with metals; namely, (1) adsorbed gases, (2) dissolved gases, (3) gases in chemical combination, (4) gases entrapped in blowholes or cavities. Adsorption is essentially a surface phenomenon and is regarded as the attachment of outside molecules or atoms to the exposed free valencies of the atoms comprising the surface layers. In many cases where adsorbed films of gas are formed this is accompanied by a process of diffusion of the gas into the metal itself. This is particularly true in respect to iron and hydrogen, and experiments have shown that there is no difference between the rate at which hydrogen diffuses through a single crystal of iron arid through the same material after it has been recrystal-lized into a mass of small crystals. This does not prevent a somewhat greater concentration of gas at the boundaries of adjacent crystals, nor does it mean that the effect of the gas will be the same at the boundaries as it is within the body of the crystals. Indeed, under certain conditions, iron is rendered very brittle at the crystal boundaries, as shown in experiments by Pfeil with samples of almost pure iron. Much work has been done by many investigators concerning the temperature and conditions under which dissolved hydrogen, in particular, can be at least partially removed from different metals. With iron, the hydrogen that has diffused into the metal as a result of acid attack by pickling or by electrolytic deposition of the gas on the metal is partly removed by exposing the metal to the atmosphere at ordinary temperatures. Considerably more can be eliminated by raising the temperature, and even greater quantities by jointly raising the temperature and reducing the pressure. Annealing at suitable temperatures completely removes the bad effects of excessive mounts of hydrogen dissolved in or associated with iron. This is shown by the data plotted in Fig. 1, giving values for electrolytic iron sheets after annealing at temperatures between 250" and 950" C. The hydrogen brittleness is rapidly diminished at

Jan 1, 1935