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By William S. McAleer

Two major trends in the coal industry today focus attention on the need for heat-drying equipment of a simpler, more flexible and less expensive type than has been considered standard equipment for drying coal. These trends are: I. The tremendous growth in the use of mechanical equipment to load coal both in underground mining and strip mining, which necessitates efficient mechanical cleaning of the fine as well as the coarse coal and thus means a growing tonnage of washed fine coal? with its attendant moisture problems. 2. The growing consumer demand for the smaller sizes for use as domestic stoker coal, with increasingly rigid specifications covering size, ash, and moisture analyses. ACCEPTED PRACTICE In the past, when, for example, 4 in. too coal has been washed, there was little trouble in producing a washed product 4 to o with a satisfactory resultant moisture. The 4 to 3/8-in. could be taken from dewatering screens at a surface moisture ranging from 2.5 to 3.5 per cent, depending upon the size consist. The 3/8-in. to o coal was generally dewatered satisfactorily with centrifugal driers, to final surface moistures from 5.5 to 8 per cent, again depending upon size consist. The centrifugal type of drier has definitely proved itself to be the most economical type of machine to handle coal approximately 3/8 in. to o as recovered by dewatering screens or drainage elevators with 15 to 25 per cent surface moisture and turn out a product with moistures as stated above. Sometimes such moistures (5.5 to 8.0 per cent) in the product are satisfactory. If not, an ultimate moisture, lower than 3 per cent, is seldom required and the centrifugal drier removes 70 to 85 per cent of the total moisture to be removed. In certain districts there has been a growing tendency to circumvent the use of centrifugals or other types of driers, by dewatering over screens of the wedge wire type and wasting all the finer sizes. Sometimes all the minus 28-mesh has been wasted and often the size wasted has been as large as 1/8-in. By wasting these finer sizes, a lower moisture can be obtained in the finished product, but taking into account the cost of the tonnage so lost, plus the added cost of ultimately disposing of this wasted tonnage, often the cost will be greater than the cost of heat-drying in a modern plant, which makes possible the recovery of all the tonnage. Moreover, with the moisture standards for domestic stoker equipment even these wasteful approaches to its solution do not solve the problem and there remains only the alternative of heat-drying. HEAT-DRYING Until about four years ago, heat-drying of coal at the preparation plants was confined chiefly to drying the fine sizes (approximately 3/8 in. to 0). Occasional

Jan 1, 1941

By Steven Mitchell

BACKGROUND Homestake Mining Company began milling operations at the Bulldog Mountain Mine near Creede, Colorado in 1969. The Bulldog Mill, rated at 350 tpd, produces a bulk flotation condentrate assaying about 180 oz/T Ag and 20% Pb, from heads of about 16 oz/T Ag and 2% Pb. The circuit is straightforward with two-stage grinding to 1-5% plus 65 mesh, followed by rougher and cleaner flotation. Reagents used are Z-6, Z-11, Aerofloat 242 and Aero Promoter 404, with an Aerofroth 65-MIBC mixture for a frother. Additional information on the geology, mine and mill are available in references (1) and (2). A flow sheet for the mill and CIP plant together is attached as Figure 1. Final flotation tailings normally vary from 1.5 - 2.0 oz/T Ag. These tailings are cycloned to produce sand for underground backfill. After cycloning, the sands are repulped and given a final scavenger float. This sand scavenger recovers a small additional amount of silver which recycles back to the main flotation circuit. The tailings are recycloned and pumped to the mine or, if the mine cannot accept sand, to tailings. The majority of the silver in the flotation tailings exists in the fine fractions; cycloning upgrades the slimes and lowers the assay of the sand. The sand, after scavenging, typically assays 0.5 oz/T Ag, and the slimes assay about 3.0-3.5 oz/T Ag. From 1969 to 1976 all of the slime tailings and the sand tailings not used underground were impounded in a tailings pond located about

Jan 1, 1983

By H. Conrad

The strain hardening associated with the creep of magnesium single crystals at room temperatu.Je was investigated by shear tests in which the direction of stressing was reversed a number of times after creep in a <100> direction. The strain hardening was strongly anisotropic; the largest amount occurring in the direction of flow and the least 180 deg to this. The time law for creep changed from a parabolic type to logarithmic for the first and subsequent reversals of stress. For a given stress the creep strain decreased significantly for the first and second reversals and then only slightly for subsequent reversals. The logarithmic creep constant a changed in a similar manner. A linear relationship was observed between the creep strain for a given reversal and the stress. The slope for the third reversal yielded a strain hardening coefficient 12 to 16 times greater than that observed for unidirectional flow. Al-though no recovery was observed upon resting at room temperature, the hardening resulting from stress reversals could be completely removed by heating to 450" C. PREVIOUS work1.&apos; indicated that the creep rate of magnesium single crystals tested in the temperature range of 78" to 364°K decreased with time. This was attributed to an increase in internal stress resulting from an accumulation of dislocations at internal obstacles. The object of the present investigation was to further evaluate the nature of this hardening by conducting tests in which the direction of stressing is changed after previous creep in shear in a given slip direction. Previous to 1950 three investigations indicated that a Bauschinger effect3 occurred for single crystals as well as polycrystals brass in tension compression,

Jan 1, 1960

By Kenneth Cottingham

The number of wells completed in Ohio during I940 was about 20 per cent more than during the preceding year, the comparative totals being 1020 and 1228. Of the 1940 completions, 327 were oil wells, 491 gas wells, and 410 dry. The completions for the past five years, divided into oil wells, gas wells, and dry holes, are shown in Table 2. Wells drilled deeper and input wells in water-flood areas are not included in the tabulation. The annual production of oil has decreased steadily in Ohio from the maximum of 23,941,000 bbl. produced in 1896. Table 3 shows the quantities of oil produced in the last five years. In 1940, the total was 3,052,000 bbl., produced by about 25,500 wells. The number of wells and the approximate quantities by grades are shown in Table I. Table i ,—Tabulation by Grade Grade 1 2 Barrels __________________________________________________________________________________________ Pennsylvania ............. . 1,198,000 Lima.................... . 325,000 Corning................... 3,730 1,159,000 Lodi...................... T,040 350,000 Cleveland................. 30 1:1,000 Total................... 25,500 3,052,000 The prices paid for Ohio crude oil in 1940, together with dates of changes in posting, are shown in Table 4. The production of natural gas in 0hio has declined from a maximum of 79,510,032 M cu. ft. in I9I5 S to 36,469,000 M cu. ft. in 1939, the most recent year for which a figure is available. Consumption reached its peak in Ohio in the year 1916, when it was 169,480,01r M cu. ft., declining to 114,720,ooo M CU. ft. in 1939. The produc-tion and consumption of natural gas in Ohio for the past five years are shown in Table 5. TAble 2.—Completions in Ohio during Past Five Years Numbs of Wells Drilled during Year YearI, ] Oil Gas Dry Total 1936............. 263 570 324 1,157 1937............. 317 503 45I 1,271 1938............. 189 433 288 gro 1939............. I70 501 349 1,020 19391940............. 327 491 410 1,228 Total.......... 1,266 2,498 1,822 5,586 Table 6 shows the number of oil wells and the number of gas wells completed by sands during 1940, with the average initial production per well for each sand. Table 7 shows the total number of wells drilled—oil, gas and dry—by sands. Development during 1940 Szth-Trenton.—For several years, considerahle interest has been shown in a horizon lying some 500 to 700 ft. below the top of the Trenton, known to the driller in western Ohio as the "green sand," and in eastern Ohio as the St. Peter. In 1939, ten &apos;lgreen sand" tests were drilled, all in western Ohio and all dry- In 19401 eight wells were drilled to this horizon, one of which was a small oil well (one barrel) in Men county- Of the remaining seven—all of which were dry-—one in Franklin County, in central Ohio, was drilled to a depth of 2903 ft. .Another was in Medina

Jan 1, 1941

By Kenneth Cottingham

The number of wells completed in Ohio during I940 was about 20 per cent more than during the preceding year, the comparative totals being 1020 and 1228. Of the 1940 completions, 327 were oil wells, 491 gas wells, and 410 dry. The completions for the past five years, divided into oil wells, gas wells, and dry holes, are shown in Table 2. Wells drilled deeper and input wells in water-flood areas are not included in the tabulation. The annual production of oil has decreased steadily in Ohio from the maximum of 23,941,000 bbl. produced in 1896. Table 3 shows the quantities of oil produced in the last five years. In 1940, the total was 3,052,000 bbl., produced by about 25,500 wells. The number of wells and the approximate quantities by grades are shown in Table I. Table i ,—Tabulation by Grade Grade 1 2 Barrels __________________________________________________________________________________________ Pennsylvania ............. . 1,198,000 Lima.................... . 325,000 Corning................... 3,730 1,159,000 Lodi...................... T,040 350,000 Cleveland................. 30 1:1,000 Total................... 25,500 3,052,000 The prices paid for Ohio crude oil in 1940, together with dates of changes in posting, are shown in Table 4. The production of natural gas in 0hio has declined from a maximum of 79,510,032 M cu. ft. in I9I5 S to 36,469,000 M cu. ft. in 1939, the most recent year for which a figure is available. Consumption reached its peak in Ohio in the year 1916, when it was 169,480,01r M cu. ft., declining to 114,720,ooo M CU. ft. in 1939. The produc-tion and consumption of natural gas in Ohio for the past five years are shown in Table 5. TAble 2.—Completions in Ohio during Past Five Years Numbs of Wells Drilled during Year YearI, ] Oil Gas Dry Total 1936............. 263 570 324 1,157 1937............. 317 503 45I 1,271 1938............. 189 433 288 gro 1939............. I70 501 349 1,020 19391940............. 327 491 410 1,228 Total.......... 1,266 2,498 1,822 5,586 Table 6 shows the number of oil wells and the number of gas wells completed by sands during 1940, with the average initial production per well for each sand. Table 7 shows the total number of wells drilled—oil, gas and dry—by sands. Development during 1940 Szth-Trenton.—For several years, considerahle interest has been shown in a horizon lying some 500 to 700 ft. below the top of the Trenton, known to the driller in western Ohio as the "green sand," and in eastern Ohio as the St. Peter. In 1939, ten &apos;lgreen sand" tests were drilled, all in western Ohio and all dry- In 19401 eight wells were drilled to this horizon, one of which was a small oil well (one barrel) in Men county- Of the remaining seven—all of which were dry-—one in Franklin County, in central Ohio, was drilled to a depth of 2903 ft. .Another was in Medina

Jan 1, 1941

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.&apos; The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of &apos; However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-&apos; have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h&apos;) formed by the reaction where, accorhng to the notation of Kroger and Vink,6&apos;7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i&apos; and Fe3&apos; ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.&apos;-&apos; A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i&apos; and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By W. J. Feuerstein

STRUCTURAL imperfections in crystals, in recent years, have received the attention of metallurgists concerned with single-crystal properties. Certain etching solutions cause local variations in the rate of etching at dislocations.&apos; Dislocations are expected to be preferred segregation sites for impurities&apos; and Dash" has shown that precipitation of copper occurs preferentially at edge-type dislocations in silicon. Diffusion rates along dislocations are probably higher than rates through more perfect crystalline regions.&apos; These and other phenomena which may be influenced by dislocations may be studied by revealing dislocations as etch pits. This study was undertaken to develop an etch solution for silicon crystals to reveal low-angle grain boundaries associated with dislocation arrays and also etch pits with good contour definition. Additional etches have been reported by Dash," Vogel and Lovell.T rystals were sectioned on crystal lographic planes at various angles from the growth direction for microscopic examination of the etch pits. Experimental Crystals of 75-100 g mass and 3 cm diam were oriented and cut on crystallographic planes. Crystals were grown by Czochralski technique from a quartz crucible. Lapped wafers were chemically polished in a modified CP-4 etch for 1 min (bromine was deleted from the etch solution). The polished wafer was then etched* at room temperature for 5 min. The use of larger amounts of H2O and/or CH2COOH slows the reaction. The Cu(NO3),.3H2O was added to increase the reaction rate and give more definition to the etch pits developed. Some pertinent features concerning the attack of this etch on silicon can be summarized as follows:

Jan 1, 1959

By J. B. Morgan

The mechanical behavior of MgCu2 from 20 o to 725°C has been determined by "brittle-ring" tensite-test techniques, axial compression, and bending experiments. Compressive ductility begins at 450°C (0.65 T/Tm) and slowly increases with increasing temperature white the tensile ductility is characterized by an abrupt brittle-ductile transition at 600°C (0.8T/Tm). The compressive strength increases eightfold from room temperature to 400°C with a "normal" decrease as the temperature is further increased. The tensile strength goes through a rather abrupt threefold increase above 600°C with a subsequent decrease at higher temperatures. The slip system is (111)[110] and the twinning system is (111)[112]. At high temperatures MgCu2 is quite rate-sensitive, and dynamic yield points are observed that are extremely orientation-dependent. The high-temperature creep behavior under constant load is characterized by an increasing strain-rate with time. The general characteristics of the mechanical behavior make it possible to classify MgCu2 with those materials in which initial mobile dislocation density and the dislocation velocity-stress dependence are significant in determining mechanical response. Mgcu2 is the C15 prototype of the cubic Laves phase. Its range of homogeneity extends from 32.8 to 35.5 at. pct Mg at 500°C and narrows at lower temperatures. The lattice parameter is reported to vary from 7.02 to 7.05A,1 and the compound is completely ordered to the melting point of 819°C. MgCu2 has a brassy metallic appearance, is extremely brittle, and many of its physical properties are intermediate between those of the constituent elements: the electrical resistivity is 3.5 x 10-6 ohm-cm, Young&apos;s modulus is 10x 106 psi, the shear modulus is 6 x l06 psi, and the thermal coefficient of expansion is 18.7 x 10-6 cm per cm per "C from 20" to 250°C. Usually, properties of intermetallic compounds as functions of temperature have been determined by hardness, compression, or impact behavior, and almost all of these experiments have been performed on polycrystalline materials. Tammann and Dahl,2 for instance, determined the onset of ductility in a series of binary intermetallics by ball-hardness measurements and found the onset to range between 0.71 and 0.96 T/T,. Lowrie&apos;s3 investigations included some tensile properties, and he found ductility beginning around 0.65 T/Tm for most materials examined. His work did include some data on polycrystalline, nonstoichiometric MgCu2, however. The present work is an attempt to extend the examination of the particular compound MgCu2 in single-crystal form in order to aid the formation of general concepts about mechanical be-

Jan 1, 1965

By D. Turnbull, J. C. Fisher

ACCORDING to the "reaction-path" modell,2 of martensite nucleation, the shear angle of the embryonic martensite plate must be treated as a variable, and included in any calculation of nucleus critical size. Also, as can be deduced from this model, the interfacial free energy between austenite and martensite does not reach its final value until the shear is completed. It is zero for zero shear angle. However, in order to account for the kinetics of the martensite transformation, some sort of interfacial energy barrier appears to be necessary even with the reaction-path model, for otherwise the volume and the energy of formation of the critical size nucleus both collapse to zero.3 Cohen independently suggested that surface energy could be incorporated into the reaction-path model, with the overall free energy of a martensite embryo being a function of its volume and shear angle.&apos; It is possible to estimate the energy associated with the formation of a critical-size martensite nucleus starting with the reaction-path model and including a surface free-energy barrier. As the dependence of interfacial free energy upon shear angle is unknown, a simple type of dependence will be assumed, with the belief that the true dependence would not lead to appreciably different results. Consider the work required to form a lenticular martensite plate with radius r, thickness t, and shear angle 8. There are three contributions; one being the interfacial free energy, one being the free energy change in the martensite plate, and one being the free energy increase in the surrounding austenite. The interfacial free energy u is assumed to depend upon the shear angle 0 according to the relationship s=s0(?/?0)n [1] where 8, is the equilibrium shear angle and n is an exponent that may lie in the range 0 n 2. The work required to form the interfaces of a martensite plate then is W. = 2pr² s0(?/?0)n [2] The free energy change per unit volume of martensite is composed of two parts, one the ordinary volume free energy ?f1. which is negative, and the other the elastic strain energy G?m²/2, where G is the shear modulus and 7, the shear strain relative to the martensite structure. This expression for the strain energy is valid only when the shear strain ym, is sufficiently small that the martensite is within its linear elastic range. There is no doubt that ym, lies beyond the linear elastic range for embryos that are considerably subcritical. However, for critical nuclei it will be shown that ym, is 1.5 pct or less, within the linear elastic range of martensite. For embryos of nearly critical size, then, the strain energy of the martensite is correctly given by G?m²/2. The shear strain in the martensite is ym, = 8, — 8, and the work required to form the strained martensite is Wm --= (pr²t/2) [?fv + G(?O - ?)²/2] [3] The free energy change in the austenite is entirely that due to elastic distortion. The elastic strain is not uniformly distributed in the austenite, being large near the martensite plate and small elsewhere. Approximately, however, the energy corresponds to a uniform shear strain ya= (?t/2)/r [4] throughout the volume 4pr³/3 surrounding the plate. The work required to strain the surrounding austenite then is Wa = (4pr³/3) (G?a²/2) = (G?²/6) prt² [51 For simplicity, the same shear modulus G is assumed for each structure. The total free energy for forming a plate then is W = W3 + Wm + Wa. = 2pr² s0 (?/p?0)n + (pr²t/2) [?fr+G(?0-?)²/2] + (G?²6) prt2 [6] This expression is correct for nuclei and for embryos of nearly critical size, where, as will be shown, the strain energy in the martensite is correctly given by the expression G (? — ?)². Having W as a function of r, t, and 8, as in Eq. 6, there is a saddle-point where W has a stationary value, W subsequently decreasing indefinitely as the nucleus volume increases along the reaction path. The stationary value of W is the energy of the critical nucleus. The critical nucleus has radius, thickness, and shear angle such that ?W/?r - awlat: = ?W/?p? = 0. Performing these differentiations and calculating the critical nucleus energy, W* = [8192p(G?/6)²;s/27 ?fv4] [7] where a= (?/?0)3n+1[l +G(8"-8)&apos;/2af.]&apos; [7a] and where 8 is to be determined from the equation (1 + 3n/4) + G8(6O - (9)/[Af. +G(6>o-6>)72] = 0 [8] For ?f, near —200 cal per mol or —10" ergs per cc, and 8, near 1/6, as for iron-base alloys, Eq. 8 gives ?0 - ? ~ - (4 + 3n) ?f1./4G0O [9] as the difference between the equilibrium shear angle and the actual shear angle for a critical nu-

Jan 1, 1954

By W. L. Doyle

SLAG weights were taken on a series of twenty-eight 6-ton bottom-pour heats. These weights varied from 573 to 1050 lb. Of these, four were chosen for study of the effect of cleaned and uncleaned foundry scrap on the variations of slag weights. Data regarding the make-up and results of the heats are given in Table I. For heat No. 3 the actual slag weight was checked, using the Mn-MnO calculation method-weight 1050 lb. [5,600 X 0.0055 = 30.80 heads and gates 6,000 X 0.004 = 27.00 plate scrap 800 X 0.0083 = 6.64 pig iron 450 X 0.0034 = 1.53 iron ore]

Jan 1, 1947

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman&apos; have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah&apos; and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

By H. A. Doerner

PROPOSALS to use hydrocarbon or natural gases for the reduction of zinc from oxide materials may be traced back through Patent Office files to the early years of the present century. Natural gas at rates cheap enough to compete with solid fuels has been available at or near one major zinc district for more than a decade. That the seemingly meritorious and economically interesting applications of these proposals have not devel-oped into workable processes for direct production of zinc by natural gas cannot be completely ascribed to the proverbial conservatism of the zinc industry. It is possible to produce spelter commercially in normal times from zinc oxide and carbonaceous reducing agents without having a very precise understanding of the chemistry of the process. The reduc-tion by hydrocarbons is not, however, in this class, and the technical complexity of this reduction metallurgy and chemistry prohibits solution of the inherent difficulties by the "hit and miss" methods that are some-times thought to be practical. In a thermodynamic study of the chemistry of zinc smelting, Maier1 made a preliminary study of the chemistry of the use of methane for reducing zinc oxide by thermodynamic means, pointing out that the following reactions, the limits of which could be theoretically predicted, were important: ZnO + CH4 = Zn(gas) + CO + 2H2 [1] CH4 = C -I- 2H2 [2] ZnO + CO = Zn(gas) + CO2 [3] ZnO + H2 = Zn(gas) + H2O [4] Other possible reactions, not discussed in the reference quoted, are: CO2 + CH4 = 2CO + 2H2 [5] H2O + CH4 = CO + 3H2 [6]

Jan 1, 1933

By Jerome J. English, Gordon W. Powell

An experimental investigation and mathematical analysis of the thermal-dilation behavior of the titanium alloy Ti-7Al-3Cb have shown that the linear dimensional changes associated with the polymorphic transformation need not be isotropic. The absolute magnitude of the linear dimensional change, which may be either positiue or negative, associated with the cr-p transformation is dependent upon the relutzve volumes of different orientations of the transformation product. It is hypothesized that the dilation irregulati-ties that have been observed during the polymorphic transformation of pure, coarse-grained titanium and other titanium-base alloys can be explained in the same manner. When titanium is heated above about 165O°F, the hcp a structure transforms to bcc 0. Thermal-dilatioh measurements have shown that the transformation is accompanied by a decrease in length of 0.16 pct.&apos; Such dilation behavior would be expected because the volume of the hcp unit cell is about 0.3 to 0.4 pct greater than that of the bcc unit cell. A recent investigation2 of the thermal-dilation behavior of an experimental a-p* titanium alloy, Ti- 7A1-3Cb, containing 0.06 wt pct 0 showed that its dilation behavior during the polymorphic transformation differed substantially from that reported for unalloyed titanium. The first time the alloy was cycled through the transformation, the dilation curve closely duplicated that of unalloyed titanium. However, upon repeated cycling through the transformation temperature range, both the magnitude and the sign of the dimensional change associated with the transformation were observed to vary with each cycle. This investigation was undertaken to obtain additional data on the dimensional changes associated with the polymorphic transformation in the Ti-7A1-3Cb alloy and to determine the cause of the dimensional irregularities. After testing, the specimens were examined metallo-graphically. In addition, Laue back-reflection patterns were obtained from selected sections taken perpendicular to the specimen axes to determine the a orientations present in these sections. White radiation from a tungsten target and a 0.1-mm-diam collimator were used to produce the diffraction patterns. RESULTS Dilation Curves. Three types of thermal-dilation curves were obtained when the a-8 titanium alloy was heated and cooled through the transformation temperature range. These three types of curves are illustrated in Fig. 1. The type I curve represents what is considered normal behavior, because the dilation change is what would be expected on the basis of the volumes of the unit cells of a and p. The Type I1 curve is the inverse of Type I. Normal behavior is characterized by an expansion on cooling through the transformation, whereas a contraction takes place in the Type 11 curve. With Type ni behavior, no clearly distinguishable length change occurs during the transformation. No other anomalies that might be indicative of other phase transformations were observed in the dilation curves at lower temperatures. Apparently, the cooling rate was low enough for equilibrium to be reached during the 0 to a transformation. Table I lists the types of dilation curves observed during the polymorphic transformation as a function of the direction of measurement and cycle number. The A1 value was determined by extrapolating the low-temperature (a + 5 pct p) and high-temperature (100 pct p) segments of the dilation curves to a common temperature and measuring the difference in the or-dinates at that temperature, see Fig. 1. The transformation occurs over a temperature range in this alloy, so the magnitude of A1 is not an absolute value but depends on the choice of temperature. A mean temperature, T,, within the transformation temperature range was selected for the measurement. T, on cooling occurred about 100°C lower than T, on heating. The first time each of the three dilation specimens was heated to above the temperature, that is, Cycle 2, normal Type I behavior was observed. In Cycle 3, two deviations from normal behavior occurred. First, during cooling of the longitudinal specimen, a substantially larger expansion, +0.21 pct, was measured as 0 transformed to a compared with +0.03 pct in Cycle 2. Second, the thickness specimen was observed to undergo a contraction instead of the anticipated expansion on cooling. Continued cycling of the three specimens from room temperature to 2500°F produced additional changes in the dilation behavior. These changes did not seem to be related to the fabrication direction of the alloy because the values of a1 for the longitudinal, transverse, and thickness specimens varied unpredictably in magnitude and sign. Furthermore, both the longitudinal and transverse specimens showed all three types of dilation curves at least once during the six cycles that they received. Fig. 2 is a sketch of the transverse specimen after

Jan 1, 1967

By W. E. Mitchell

The ore that is being treated by the present plant lies between the leached zone, or capping, and the mixed sulfide and oxide zone. The principal copper minerals are chalcanthite (CuS04.5H20), brochantite (CuSO4.3Cu (OH)2 and atacamite, (CuC12.3Cu (OH)2). There are, in addition, some other minerals such as cuprite and kröhnkite (CuS04. Na2S04.2H20). These minerals, with many others, occur in a greatly crushed granodiorite rock. most of the copper-bearing minerals occur in the cracks and veinlets, but there are disseminated values and it is probably the relative proportion of these that accounts for some otherwise unexplainable variations in extraction. The entire mineralization of the ore is complex and varies with depth. This variation, the problems presented thereby, and the effect of various constituents of the ore will be taken up in detail. An analysis of :in unweighted composite of the ore treated during 1927 follows: I&apos;Lr Cent. Per Cent. Per Cent. Cu............... 1.58 S................. 2.10 Mo............ 0.01 SiO? ............. 66.10 HNO3 ........0.03 As............ 0.005 Fe.......... 1.41 C1 .............. 0.05 Sb............. 0.005 CnO ..... 0.20 Na................ 0.80 Ba............ 0.01 A1203 .......... 17.70 KI.............. 4.80 H20............ 0.70 mgO.............. 0.68 Mn............... 0.07 0 in sulfates. . . . 3.94 Total..... 100.19 The most important constituents of the ore, as indicated by experience to date, are: (1) The total copper content; (2) the acid-insoluble copper; (3) the acid-making copper mineral, mainly the chalcanthite; (4) the chlorine; (5) the nitrates; (6) the soluble iron; (7) the soluble molybdenum. The total copper content needs no discussion. In Table 1, the values are weighted averages calculated from individual charge analyses. The acid-insoluble copper directly affects the extraction, as the present leach recovers practically no acid-insoluble copper. In Table 1 the values are unweighted averages of the analyses of monthly composite samples. The acid-making copper mineral affects the amount of copper that can be dissolved from the ore without neutralizing acid in the solution. The

Jan 1, 1930

Trans. No. Place Date Vol. Page 1. Wilkes-Barre Pa......May.71 1 3 2. Bethlehem, Pa.........Aug., &apos;71 I 10 3. Troy, N.Y............Nov..: 71 1 13 4. Philadelphia, Pa........Feb., 72.. 1 17 5. New York. N. Y.*......May, &apos;72.. 1 20 6. Pittsburgh. Pa.........Oct..&apos; 72.. 1 25 7. Boston, Mesa..........Feb., &apos;73.. 1 28 8. Philadelhia, Pa.*......May, &apos;73.. 2 3 9. Easton, is............Oct..&apos; 73.. 2 7 10. New York, N. Y.......Feb..&apos; 74 . . 2 11 11. St. Louie. Mo.*........May,&apos; 74 . . 3 3 12. Hazleton, Pa...........Oct., &apos;74.. 3 8 13. New Haven Conn......Feb., &apos;75.. 3 15 14. Dover,N.J.*..........May, 75.. 4 3 15. Cleveland,O...........Oct. 75. 4 0 16. Washington D. C......Feb.&apos;&apos; 76.: 4 18 17. philadelphia, Pa.......June,: 76.. 5 3 18. Philadelphia Pa........Oct 76.. 5 19 19. New York, N. Y.......Feb: &apos;77.. 5 27 20. Wilkes-Barre. Pa.*.....Mag :77.. 0 3 21. Amenia N. Y..........Oct. 77.. 6 10 22. Philadeiphia Pa........Feb.;&apos; 78. . 6 18 23. Chattanooga&apos; Term.*. . . May&apos; 78. . 7 3 24. Lake George: N. Y....: Oct. 78. . 7 103 25. Baltimore, Md.*.......Feb:&apos; 79.. 7 217 26. ~ittsburgi, Pa.........~a;&apos; 79.. 6 3 27. Montreal, Canada......~ept.;&apos; 79.. 8 121 28. New York, N. Y.*......Feb., &apos;80.. 8 275 29. Lake Superior, Mich....Aug., &apos;80. . 9 1 30. Philadelphia, Pa.*......Feb., &apos;81. 9 275 31. Staunton, Va..........May, &apos;81. .10 1 32. Harrisburg, Pa.........Oct.. &apos;81..10 119 33. Washington, I). C.*....Feb., &apos;82. . 10 226 34. Denver. Colo..........Aug.. &apos;82. . ll 1 35. Boston. Mass.*.........Feb.. &apos;83..11 217 38. Roanoke, Va...........June, &apos;83.. 12 3 37. Troy, N. Y...........Oct.. &apos;83. .12 175 38. Cincinnati. O.*.... Feb, &apos;84..12 4 39. Chicago Ill............May, &apos;84. . 13 1 40. philadelphia, Pa........Sept., &apos;84. . 13 285 41. New York, N. Y.*......Feb., &apos;85. . 13 586 42. Chattanooga, Tenn.....May, &apos;85..14 1 43. Halifax, N. S..........Sept., &apos;85.. 14 307 44. Pittsburgh, Pa.*........Feb.. &apos;86 . . 14 587 45. Bethlehem. Pa.........May, &apos;86 .. 15 Ixiii. 46. St. Louis, Mo..........Oct, 86.. 15 Ixx. 47. Scranton, Pa.*.........Feb.&apos;, &apos;87. . 15 lxxvi 48. Utah and Montana.....July &apos;87.. 16 xvii. 49. Duluth, Minn...........July&apos; &apos;87. -16 xxiv. 50. Boston. Mass.*.........Feb.: &apos;88. . 16 xxviii. 51. Birmingham, Ala.......May, &apos;88. .17 xix. 52. Buffalo N. Y..........Oct. &apos;88.. 17 xxiv. 53. New york, N.Y........feb.&apos; ;89 . . 17 xxxi. 54. Colorado..............June&apos; 89 . . 18 xvii. 55. Ottawa, Canada........Oct., 89. . 18 xxiv. 56. Washington, I). C.*. . . Feb. 90. .18 xxx. 57. New York, N. Y........sept:, &apos;93. .19 vii. 58. New York, N. Y.*......Feb. &apos;91. . 19 xxv. 59. Cleveland, O.......... June, :91 . .a xvi. 60. Glen Summit, Pa.......Oct, 111. . 20 lxi. 61. Baltimore, Md.*.......Feb.: &apos;92. .21 xix. 62. Plattsburg, N. Y.......June, &apos;02. . 21 xxxiii. 03. Reading. Pa...........Oct., :92. .21 xliv. 64. Montreal. Canada*.....Feb. 93..21 65. Chicago, Ill............aug.: &apos;93..22 XI. 66. Virginia Reach. Va.*. ...Feb., &apos;04. .24 xwl. 67. Bridgeport Coon.......Oct., &apos;94..24 xxx?. 08. Florida ...&apos;............Mar., &apos;95. .25 xix 69 Atlanta. Ga......... Oct 95. 25 xi 70. Pittsburgh. Pa.*........Feb., &apos;96.. 26 xvii. Trans. No. Place Date Vol. Page 71. Colorado..............Sept. &apos;96. .26 xxix. 72. Chicago, Ill............Feb.. "97.. 27 xvii. 73. Lake Superior..........July &apos;97. .27 xxx. 74. Atlantic City, N. J.*. ..Feb.: :98. .28 xvii. 75. Buffalo N. Y..........Oct. 08. .28 XXXVI. 76. New York,N. Y.*......Feb.: &apos;99. .29 xvii. 77. California.............Sept., ;99. . 29 xlix. 78. Washington, D. C.*.....Feb., 00. .30 xix. 79. Canada...............Aug.. &apos;00. .30 xlv. 80. Richmond. Va.*........Feb.. &apos;01. . 31 xix. 81. Mexico................Nov..&apos;01.. 32 cxviii. 82. Philadelphia Pa. $......May, :02. . 33 xxxv. 83. New Haven, Conn......Oct.. 02.. 33 xlvii. 84. Albany N. Y.*........Feb &apos;03. .34 xxiii. 85. New York, N. Y........Oct.&apos;: &apos;03. .34 xi. 86. Atlantic City. N. J.*....Feb., &apos;04. .35 XXIII. 87. Lake Superior..........Sept.&apos;04. .35 dii. 88. Washington. D. C......May&apos; &apos;05. .36 xlii. 89. British Columbia.......July, &apos;05. . 36 90. Bethlehem. Pa.........Feb. &apos;06. .37 xli. 91. London, England.......July: &apos;06. .37 xlviii. 92. New York, N. Y........April, &apos;07. . 38 lii. 93. Toronto, Canada.......July. &apos;07. .38 lix. 94. New York, N. Y........Feb., :08. .39 xli. 95. Chattanooga, Tenn.....Oct.. 08..39 xlviii. 06. New Haven Conn......Feb. &apos;09. .40 xli. 97. Spokane,Wash.........Sept:.&apos;09. .40 xlviii. 98. Pittsburgh, Pa.........Mar.,&apos;10. .41 xxxviii. 99. Canal Zone............Nov.,&apos;10. .41 dv. 100. Wilkes-Barre, Pa.......June. &apos; 11. . 42 xxxiv. 101. San Francisco, Cal......Oct.. &apos;11..42 xliv. 102. New York. N. Y.*......Feb 12. .43 Ixxvii. 103. Cleveland, Ohio........0ct;&apos; &apos;12.. 44 wii. 104. New York, N. Y.*......Feb.. &apos;13. .45 xv. 105. Butte, Mont...........Aug., &apos;13. .46 ?&apos; 108. New York, N. Y........Oct., 13..47 vii 107. New York. N. Y.*......Feb.. &apos;14..48 xv. 108 Salt Lake City. Otah Aug. :l. 49 5: 109. Pittsburgh, Pa.........Oct., 14. .50 vii. 110. New York, N. Y.*......Feb., &apos;15. .51 xvi. 111. San Francisco, Cal......Sept., &apos;15. .52 xii. 112. New York,N. Y.*......Feb., &apos;16..54 xvi. 1 Arizona...............Sept.,&apos;l6. .55 VII 114. New York, N. Y.*......Feb., &apos;17: .56 vii. 115. St. Louis, Mo..........Oct.. &apos;17..57 vii. 116. NewYork,N. Y.*......Feb.. &apos;18..59 xvii 117. Colorado.....:........Sept.,&apos;18. .60 vii. 118. Milwaukee, Wis........Oct.. &apos;18. .60 x:!: 119. NewYork,N. Y.*......Feb., &apos;19..61 xi. 120. Chicago...............Sept.,&apos; l9.. 62 VII. 121. New York, N. T.*......Feb., &apos;20..63 ix. 122. Lake Superior District. .Aug., &apos;20.. 66 ix. 123. New York, N. Y.*......Feb., &apos;21. .66 xiii. 124. Wilkes-Barre, Pa...... Sept.. : 21.. 66 xix. 125. New York, N. Y.*......Feb., 22. .67 ix. 126. San Francisco. Cal......Sept.,:22. .68 xxix. 127. New York, N.Y.*.....Feb., 23. .69 xxix 128. Canada...............Aug., &apos;23. .69 xxxv! 128.129. New York, N. Y.*......Feb., ;24. .70 xxxi. 130. Birmingham, Ala.......Oct. 24. .71 xxxiii 131. NewYork.N Y.*......Feb.: &apos;25.. 71 xxxviii. 132. 131.Salt Lake City, Utah .. .Sept., &apos;25. .73 xvi 133. New York, N. Y.*......Feb., &apos;26. .73 xxii. 134. Pittsburgh Pa ....... Oct.. &apos;26. .74 xv. 135. New York,&apos; N. Y.*............Feb., &apos;27. .75 x::: 135.136. NewYork,N. Y.*......Feb., &apos;28..76 104 137 NewYork.N. Y.*......Feb., &apos;29. .291 116 138.San FranciscoYork,N.Y. Cal..........Oct. 29..308 406 139. New York, N. Y.*...Feb., &apos;30..30H 1321

Jan 1, 1930

In the special number of the magazine Ocl und Kohle (Oct. 22, 1940) dedicated to the petroleum industry of southeastern Europe, there appeared several articles relating to Yugos1avia.t In the first article the author calls attention to the fact that there are two fields in Yugoslavia that have been explored and exploited by more than 100 wells at variable depths during the last 50 years. These are on the Island of Mura, at the confluence of the Mura and the Drave. Additional exploration drilling in various other parts of the country has been without result, but certain ones of these explorations have revealed the existence of gas horizons that have some value, which are being used for industrial purposes. Table I shows the production of oil and gas between the years 1900 and 1939. TaBle —Production of Oil ad Gas in Yugoslavia . n,i Natural Natural Years oil Years Gas, Cu. Years Gas, Cu. Meters Meters T900-1929 10,000 1923 507,000 1934 1,388,000 1930 277 1924 567,000 1935 1,401,000 1931 202 I92S 691,000 I936 1,483,000 t932 289 19261 1.472,000 1937 1,841,000 1933 629 1927! 1,732,000 193s 2,431,000 1934 324 1928 2,515,000 1939 2,628,000 1935 260 1929 4,700,000 1936 137 I93O 5.345,200 1937 463 1931 6,376,153 1938 1,091 1932 1,661,737 1939 1,114 1933 959,574 The number of wells drilled from 1884 to the present time was in the neighborhood of zoo and the total footage drilled was 65,000 m. up to July I940 They may be divided roughly as follows: 12 wells in the region produce natural gas; 134 wells in the two old fields of the Island of Mura and about zo wells for the exploration of the zone of the Flysch, in Bosnia. The depths of 50 of these wells was roo to 200 m.; the depths of 50 wells oil the Island of Mura ran from zoo to 500 m.; of 2 ; wells, 500 to I000 m.; of ro wells from rooo to 2000 meters. The deepest well drilling in Yugoslavia has reached 2000 in. In the Valley of Morave, in the region of Selnica, I00 km. south of Nish, there have been discovered asphalt-bearing limestones, which contain about 15 per cent asphalt and are associated with bituminous clays. Later, at Paclenica, important deposits of natural gas were found. A zone rich in gas and oil seepages runs through Pracec, Miklenska, Bujavica, etc. The author studied these regions from the point of view of stratigraphy and tectonics. The anticlines and gas-bearing domes are concentrated in two zones: the region of the Drave (Island of Mura) and the region of the Save, southeast of zagreb, which contains the gas field in exploitation in the region of Bujavica. A full description of the productive region of the Island of Mura has been given by Egon Bohm, a geologist, in the second article mentioned. This includes a history of the exploration and exploitation that took place under Hungarian rule in this region. The most important exploration was effected between 1884 and 1885 by Stavenov and Stinger, of Vienna. In 1927 work was done in the same region by Anton Raky, a well-known explorer who makes work of this kind his specialty.

Jan 1, 1941

In the special number of the magazine Ocl und Kohle (Oct. 22, 1940) dedicated to the petroleum industry of southeastern Europe, there appeared several articles relating to Yugos1avia.t In the first article the author calls attention to the fact that there are two fields in Yugoslavia that have been explored and exploited by more than 100 wells at variable depths during the last 50 years. These are on the Island of Mura, at the confluence of the Mura and the Drave. Additional exploration drilling in various other parts of the country has been without result, but certain ones of these explorations have revealed the existence of gas horizons that have some value, which are being used for industrial purposes. Table I shows the production of oil and gas between the years 1900 and 1939. TaBle —Production of Oil ad Gas in Yugoslavia . n,i Natural Natural Years oil Years Gas, Cu. Years Gas, Cu. Meters Meters T900-1929 10,000 1923 507,000 1934 1,388,000 1930 277 1924 567,000 1935 1,401,000 1931 202 I92S 691,000 I936 1,483,000 t932 289 19261 1.472,000 1937 1,841,000 1933 629 1927! 1,732,000 193s 2,431,000 1934 324 1928 2,515,000 1939 2,628,000 1935 260 1929 4,700,000 1936 137 I93O 5.345,200 1937 463 1931 6,376,153 1938 1,091 1932 1,661,737 1939 1,114 1933 959,574 The number of wells drilled from 1884 to the present time was in the neighborhood of zoo and the total footage drilled was 65,000 m. up to July I940 They may be divided roughly as follows: 12 wells in the region produce natural gas; 134 wells in the two old fields of the Island of Mura and about zo wells for the exploration of the zone of the Flysch, in Bosnia. The depths of 50 of these wells was roo to 200 m.; the depths of 50 wells oil the Island of Mura ran from zoo to 500 m.; of 2 ; wells, 500 to I000 m.; of ro wells from rooo to 2000 meters. The deepest well drilling in Yugoslavia has reached 2000 in. In the Valley of Morave, in the region of Selnica, I00 km. south of Nish, there have been discovered asphalt-bearing limestones, which contain about 15 per cent asphalt and are associated with bituminous clays. Later, at Paclenica, important deposits of natural gas were found. A zone rich in gas and oil seepages runs through Pracec, Miklenska, Bujavica, etc. The author studied these regions from the point of view of stratigraphy and tectonics. The anticlines and gas-bearing domes are concentrated in two zones: the region of the Drave (Island of Mura) and the region of the Save, southeast of zagreb, which contains the gas field in exploitation in the region of Bujavica. A full description of the productive region of the Island of Mura has been given by Egon Bohm, a geologist, in the second article mentioned. This includes a history of the exploration and exploitation that took place under Hungarian rule in this region. The most important exploration was effected between 1884 and 1885 by Stavenov and Stinger, of Vienna. In 1927 work was done in the same region by Anton Raky, a well-known explorer who makes work of this kind his specialty.

Jan 1, 1941

By J. Chipman, J. B. Gero, T. B. Winkler

D. C. Hilty—This paper is a useful and timely addition to our store of quantitative data relating to manganese distribution between slag and metal in steel-making processes. For some time, many of us have suspected that the values of Kmn derived by Körber and Oelsen might be too low, and this paper now appears to confirm that suspicion. Application of the new constant to openhearth data should prove interesting. The manganese deoxidation curves of fig. 4 agree fairly well with direct measurements of isothermal solubilities of oxygen in liquid iron containing manganese that have recently been made at the Union Carbide and Carbon Research Labs., Inc. According to the solubility data just mentioned, however, the curves for 1550" and 1600°C lie much closer to each other than the authors have indicated. In other words, the solubility measurements suggest that the logarithm of the oxygen solubility is not a linear function of the reciprocal of the absolute temperature, as the authors have assumed for their calculations. It seems possible that this discrepancy may be due in part to the authors&apos; use of the distribution coefficient, L,,, obtained from Taylor and Chipman&apos;s curve for the solubility of oxygen in iron as shown in fig. 2. Taylor and Chipman gave the equation of this curve as —6320 Log % 0 - ---T + 2.734 Their data, however, can be fitted equally well by a curve having the equation: 13.23 x104 1.18x10" Log % O = 36.350 -13.23x10 Moreover, this curve also fits the authors&apos; oxygen distribution data somewhat better than does the linear curve of Taylor and Chipman. Its use in the derivation of Lo for calculation of the deoxidation curves by the authors&apos; eq 15 causes the effect of temperature on the calculated curves of fig. 4 to agree quite well with the temperature effect that has been observed. An experimental determination of the temperature coefficient of the manganese reaction appears to be desirable. J. E. Stukel—Because the authors have done such an excellent job, my comments will be confined to additional information. Very shortly Professor T. L. Joseph and I will publish the results of a study of the reaction between molten manganese and silica. It was found that electrolytic manganese, melted in silica crucibles, reacted with the silica to form a silico-manganese alloy containing 18 pct silicon (1500°C) and a silica saturated MnO-SiO, slag. Therefore, the presence of silicon and its oxides in the Fe-Mn-0 system will affect the equilibrium. Carbon is also an important factor. The higher the carbon content of the iron the less ability manganese has to reduce silica. As a matter of interest, recently a study of the manganese equilibrium in carbon saturated iron and blast furnace slags was completed at Carnegie Institute of Technology. As a comparison to the present study, 2 to 5 hr were required to reach equilibrium and temperature was a much more important factor than slag composition in determining the (Mn)/(MnO) ratio. These results will also be published in the near future. It can be seen, therefore, that the results of this paper cannot be applied directly to openhearth studies without a degree of flexibility. J. Chipman (authors&apos; reply)—With regard to the effect of silicon on the manganese constant, this effect is, of course, known. Much more data is needed in order to establish it accurately, and I hope we can look forward to having some accurate data on that. Mr. Hilty suggests that a three-term expression for the Taylor-Chipman solubility of oxygen in liquid iron might fit a little better than the two-term equation. I think that it would be too great a compliment to the precision of the data to employ a three-term equation, and I would still recommend the simple, two-term expression.

Jan 1, 1951

By V. Rajaram

The oil shales located in the Appalachian Basin cover an eight-state area of the eastern US and are referred to as Devonian (black) shales. These shales have been exploited for their gas potential for several years. The Institute of Gas Technology (IGT) has conducted research since 1972 on the production of shale oil from the Devonian shales. This resulted in the development of the HYTORT process. This process demonstrated that the yield from the Eastern oil shales can be greater than the value indicated by the Fischer assay method. IGT estimates that 67 Gm3 (423 billion bbl) of oil could be recovered by HYTORT processing of surface minable eastern US shales. Recently, American Syncrude Corp. and Southern Pacific Petroleum NL have proposed oil shale projects in Kentucky. This paper will describe the surface mining and retorting techniques that have been studied for exploitation of the Devonian shales, and enumerate the problems that have to be overcome before commercial production can be realized.

Jan 1, 1986