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By C. E. Brukl, E. Rudy, St. Windisch

The ternary-alloy system Nb-Mo-C was investigated by means of X-ray, melting point, DTA, and metallo-graphic techniques; a complete phase diagram for temperatures above 1500°C was established. Above 1960°C, niobium monocarbide and the cubic (Bl) high-tenzperature phase in the Mo-C system form an uninterrupted series of solid solutions. The ternary range of the pseudocubic q MoCl-, is very restricted. Dimolyb-denum carbide dissolves up to 44 mol pct Nb2C (2240°C), whereas the maximum solid solubility of MO2C in Nb2C does not exceed 5 mol pct. The order-disorder transformation temperatures in Mo2C and Nb2C are lowered by the mutual metal exchanges. Six invariant (p = const) reactzons occur in the ternary system; three correspond to class 11-type four-phase reactions involving a liquid phase, one to a class I (eutectoid)-type, and two further isotherms are associated with limiting tie lines. The results of the Phase diagram investigation are discussed, and the thermodynamic interpretation identifies the low relative stability of the binary sub-carbides in conjunction with the large stability diflerences between niobium and molybdenum carbides as the cause for the formation of a stable equilibrium between the monocarbide and the metal phase in the ternary reson. Due to their refractoriness, the carbides of the high-melting transition metals have received increased interest in recent years as base materials in composite structures for aerospace applications at high temperatures and for the development of self-bonded cutting tool materials; other novel fields of application include power reactors, where operation at high temperatures becomes essential for attaining high power efficiencies. In these applications, the increased reaction rates at high temperatures require a close consideration of the chemical interactions between the alloy constituents. As a consequence, a detailed knowledge of the phase relationships in the alloy systems is required in order to provide a sound basis for developmental -type work. Partly as a result of the considerable experimental difficulties associated with the investigation of this high-melting alloy class, no complete studies of ternary metal-carbon systems have been performed until recently. Even the high-temperature phase relationships in the binary transition metal-carbon systems have been delineated only during the past few years to a degree of accuracy required for a more detailed study of ternary or higher-order alloys. In recent investigations of binary and ternary systems of refractory transition metals with carbon, boron, and silicon,&apos; alloys from the ternary systems Nb-Mo-C became of interest because of the demonstrated possibility2,3 of obtaining compatible composites based on metal + monocarbide combinations. In the meantime, however, studies in other, but related, ternary metal-carbon systems, such as Ta-W-C, have shown that the solid-state equilibria may change significantly toward higher temperatures (>2000°C), and that extrapolations based on low-temperature equilibrium data are, in general, not very reliable. Although the lower-temperature (<2000°C) phase relationships in the Nb-Mo-C system are similar to those found in Ta-W-C, a cursory thermodynamic analysis of the equilibria indicated4 that complete solid-solution formation between Mo2C and Nb2C should not occur at higher temperatures. The present work was conducted in order to experimentally verify these expectations and, in addition, to provide phase equilibrium data in the melting range of the alloys. In the boundary systems, niobium and molybdenum are known to form a continuous series of solid solutions.576 The continuous solubility was also confirmed by Kornilov and Polyakova,7,8 who also observed a minimum melting point at 22 at. pct Mo and 2345°C. The phase diagram investigations of the Nb-C system by Storms and Krikorian9 and Kimura and Sasaki10 were recently supplemented by Rudy et al.11,12 The system contains a high-melting monocarbide with the B1 structure, Table I, and a subcarbide, Nb2C, which exists in at least two different states of sublattice order at low temperatures47"-&apos;3 and a disordered state above approximately 2500°C.11,12 The melting-point measurements by Rudy et al .11,14 are in close confirmation of the data by Kimura and Sasaki.10 The rather complex phase relationships in the Mo-C system were only recently Clarified.15,18 The system is characterized by three congruently melting, intermediate phases, MozC, ? MoC1-x and a Mol-,, Table I, of which only Mo2C is stable at temperatures below 1650°C. Substoichiometric MozC exists in several states of sublattice order which interconvert in homogeneous phase transitions. Hyperstoichiometric compositions cannot exist in the ordered state. Upon cooling through a critical temperature range, the

Jan 1, 1968

By E. W. Newman

DURING 1943 and 1944, there was an urgent need for certain grades of optical calcite (Iceland spar) for instruments for military uses. To find a supply of this material, prospecting was carried out in Montana, California and Colorado. Although some production was obtained by the work in California, the best results were from prospecting the large calcite veins of south central Montana. The bulk of the optical calcite mined during World War II has come from that area. The Bureau of Mines took an active part in the search for optical calcite in Montana. It examined most of the known calcite veins in the 70-mile distance between Wilsall, on the Shields River, and Absarokee, on the Stillwater River, and conducted exploration on several of the deposits. The Geological Survey also took an active part by mapping many of the veins. Actual mining of the calcite was performed at first by Calcite Operators, Inc., and later by the Metals Reserve Co., through an agent. A sorting plant was established at Clyde Park, where custom material could be sold. These activities stimulated mining by private operators. To be suitable for military uses, the calcite mined had to meet rigid specifications as to both size and quality. Individual crystals had to be clear and transparent and if in the form of rhombs had to measure at least 7/8 in. on each edge. Some color and a few inclusions in the calcite were allowable, but material with incipient or developed cleavages, or showing twinning other than parallel to the base, was unacceptable. HISTORY OF DEPOSITS The existence of large veins of calcite in south central Montana has long been known, and for many years the farmers of this region have used the common vein calcite for producing grit for chicken feed. According to reports, the first optical calcite produced from Montana came from the Cartwright deposit near Greycliff,1 but until recently the mining of optical calcite in Montana has been limited to spasmodic searching for small crystals suitable for making nicol prisms for saccharimeters and microscopes, or for mineral specimens. The possible need of substantial amounts of optical calcite for military uses began to appear late in 1942 and early in 1943, therefore the Polaroid company began searching for a source of supply in Montana and California. Work on the Wade property near Clyde Park was started on a small scale in the fall of 1942, by A. H. Hansen, of Clyde Park. During the winter and spring of 1943, a modest quantity of optical calcite was mined and shipped to the Polaroid Corporation, Cambridge, Mass. Most of this was produced from the "Hansen vug," which was found close to the surface. Early in the summer of 1943, mining on the Wade property was undertaken by Calcite Operators, Inc., a company organized for mining optical calcite from the Montana and California deposits. This com-

Jan 1, 1945

By B. V. P. Rao, H. L. Lovell, G. Simkovich

In the study described here, flotation tests were conducted on pure CaF2, on CaF2 doped at several concentration levels with either NaF or YF3, and on natural fluorite samples containing various amounts of impurities in an effort to extend previous knowledge of the influence of crystalline point imperfections on the flotation properties of solids. The results of these tests showed that although recoveries generally decreased as impurities increased, the differences in recovery were not nearly as striking as those detected in earlier experiments. A number of experimentalists have shown an interest in the way in which crystalline point imperfections affect the flotation properties of solids. As long ago as 1953, Welch hypothesized that it might be possible to control surface imperfections and thereby also control the flotation of solids.&apos; A few years later, in some rather extensive work, Plaksin and his coworkers varied the surface imperfections of a number of compounds by oxidation or reduction processes and found that significant variations in flotation properties resulted.2-4 More recently, Simkovich showed that the recovery of both AgCl and PbS could be markedly varied by adding solid-solution impurities, which acted as doping agents, to these compounds.5 Then Mular studied the flotation of ZnO as a function of the doping agents Al2O3 and Li2O.6 Once again, it was found that these impurities, even in very low concentrations, had profound effects upon flotation recoveries. From an imperfection point of view, the defect structures of the compounds tested previously are as follows:7 PbS — amphoteric semiconductor with a Frenkel-type defect structure in the cation sub-lattice.8 AgCl - ionic conductor-Frenkel type defect structure? ZnO — n-type semiconductor, zinc ion interstitials and quasi-free electrons.10 All of these works undoubtedly bear some relation to the findings that the flotation properties of seemingly identical minerals from different ore deposits often exhibit extreme variation in flotation behavior, i.e., that small amounts of analytically undetectable impurities often have a great influence upon flotation

Jan 1, 1969

By A. H. Geisler, R. F. Mehl, C. S. Barrett

The complicated nature of the property changes that accompany age-hardening has made it necessary to reconsider and to elaborate the simple dispersion theory.l It has been apparent for some time that more direct information is needed concerning the atomic mechanism of precipitation from solid solution if the theory of age-hardening is to be developed past a purely qualitative stage.‡ Fortunately, in recent years information has been developed which allows us to trace in detail the lattice changes accompanying the process of precipitation from solid solution. This information relates chiefly to the sequence of the several stages of lattice alteration by which the matrix lattice is transformed to the equilibrium precipitate lattice, and permits reasonable inferences to he drawn concerning the states of internal strain that accompany these stages. This information is most complete for the solid solution of copper in aluminum. The equilibrium precipitate is the 0 phase, "CuAl2." This forms in plates, parallel to the {100} matrix planes. The atom pattern and atom spacing on the plane in 0 lying parallel to this plane are roughly similar to those opposite it in the matrix.3 The formation of 0, however, is preceded by the formation of a transition lattice 0&apos;: which again lies parallel to the matrix {100} plane, but in this case the matching of atom pattern and spacing across the matrix-precipitate interface is nearly periect; thus there is lattice coherency across the interface and the interface is a plane of separation in only a very limited sense.&apos;8 Particles of 0&apos; may be recognized microscopically and form a well-defined Wid-manstatten figure.* The 0&apos; lattice is recognized by the occurrence of diffraction lines on powder photo-grams or of spots on Laue photograms which may be analyzed in the usual ways to determine the lattice type and the lattice spacings. Very recent research 6, 7, 1 has shown, however, that streaks occur on the Laue photogram at an earlier point in time during the aging process. These streaks have been attributed to a preferential clustering of copper atoms into small platelike elements of only a few atoms in thickness and a lew hundred atoms in diameter, probably of the composition of " CuA12," which may be designated as Guinier-Preston zones or aggregates.1 It is difficult if not impossible to determine the lattice type and lattice spacing in these aggregates. It is possible1 that these aggregates are in fact ?&apos; in a high State of dispersion; the inclination to argue this is strong, as we shall see later. Never-

Jan 1, 1941

By R. F. Mehl, C. S. Barrett, A. H. Geisler

The complicated nature of the property changes that accompany age-hardening has made it necessary to reconsider and to elaborate the simple dispersion theory.l It has been apparent for some time that more direct information is needed concerning the atomic mechanism of precipitation from solid solution if the theory of age-hardening is to be developed past a purely qualitative stage.‡ Fortunately, in recent years information has been developed which allows us to trace in detail the lattice changes accompanying the process of precipitation from solid solution. This information relates chiefly to the sequence of the several stages of lattice alteration by which the matrix lattice is transformed to the equilibrium precipitate lattice, and permits reasonable inferences to he drawn concerning the states of internal strain that accompany these stages. This information is most complete for the solid solution of copper in aluminum. The equilibrium precipitate is the 0 phase, "CuAl2." This forms in plates, parallel to the {100} matrix planes. The atom pattern and atom spacing on the plane in 0 lying parallel to this plane are roughly similar to those opposite it in the matrix.3 The formation of 0, however, is preceded by the formation of a transition lattice 0&apos;: which again lies parallel to the matrix {100} plane, but in this case the matching of atom pattern and spacing across the matrix-precipitate interface is nearly periect; thus there is lattice coherency across the interface and the interface is a plane of separation in only a very limited sense.&apos;8 Particles of 0&apos; may be recognized microscopically and form a well-defined Wid-manstatten figure.* The 0&apos; lattice is recognized by the occurrence of diffraction lines on powder photo-grams or of spots on Laue photograms which may be analyzed in the usual ways to determine the lattice type and the lattice spacings. Very recent research 6, 7, 1 has shown, however, that streaks occur on the Laue photogram at an earlier point in time during the aging process. These streaks have been attributed to a preferential clustering of copper atoms into small platelike elements of only a few atoms in thickness and a lew hundred atoms in diameter, probably of the composition of " CuA12," which may be designated as Guinier-Preston zones or aggregates.1 It is difficult if not impossible to determine the lattice type and lattice spacing in these aggregates. It is possible1 that these aggregates are in fact ?&apos; in a high State of dispersion; the inclination to argue this is strong, as we shall see later. Never-

Jan 1, 1941

EUGENE McAULIFFE, * St. Louis, Mo.-The method employed by the Engineer&apos;s Committee in arriving at a proper selling price for coal and coke represents hard painstaking effort based on a thoroughly scientific foundation; and the United States Fuel Administration can well point with pride to the work of this committee. The results so obtained placed

Jan 12, 1918

By C. H. Mathewson, H. l. Burghoff

The study of the creep of metals under conditions of prolonged loading has received the attention of many investigators for several years and almost innumerable papers have been published on the various aspects of the subject. As it appeared that much could still be learned from a study of single crystals, the present work was carried out to study the effects of temperature and conditions of loading upon the properties and deformation in tension of single crystals of alpha brass containing about 70 per cent copper and go per cent zinc. In particular, it was hoped to obtain information from tests below and above the recrys-tallization temperature of the material, so that properties such as elastic limit, yield point or critical stress, and manner of deformation might be compared for tensile tests at an ordinary loading rate and for prolonged loading. Accordingly, short-time tensile tests and creep tests were made at room temperature, 300°, 500° and 700°F. The two latter temperatures are above the lowest possible recrystallization temperature of polycrys-talline 70-30 brass. Previous Work Clarke and White1 have made creep tests of some copper-zinc alloys, including 70-30 brass, and copper-zinc-tin alloys at temperatures both below and above the recrystallization temperature of the materials considered. Hanson and Wheeler2 have studied the flow and fracture of single crystals of aluminum for short-time and prolonged tensile loading over a range of temperature extending from room temperature to 400°F., their experiments being made without consideration of the orientations of the test specimens. Extensive creep and fracture tests on single crystals of lead at room temperature have been made by Betty3 and by Baker, Betty and Moore." Results of the last-named investigation were published while the present work was in progress. Miller5 examined the elastic limit of zinc single crystals at and above room temperature by means of creep tests, while Miller and Milligan6 reported the results of tests designed to show the influence of temperature on elastic limit of single crystals of aluminum, silver and zinc. The behavior of iron crystals under static tensile loading at room temperature was reported by Gensamer and Meh17 while the present investigation was in progress. Their specimens exhibited a well-defined yield point, below which no appreciable creep could be detected. The manner of yielding proved interesting, as the shape of the creep-time curve for the iron crystals differed from the common type of crcep curves. Elongation did not begin immediately, or at least was initially very slow. The rate of elongation then increased continuously and finally decreased to zero. This S-shaped type of elongation-time

Jan 1, 1941

By H. l. Burghoff, C. H. Mathewson

The study of the creep of metals under conditions of prolonged loading has received the attention of many investigators for several years and almost innumerable papers have been published on the various aspects of the subject. As it appeared that much could still be learned from a study of single crystals, the present work was carried out to study the effects of temperature and conditions of loading upon the properties and deformation in tension of single crystals of alpha brass containing about 70 per cent copper and go per cent zinc. In particular, it was hoped to obtain information from tests below and above the recrys-tallization temperature of the material, so that properties such as elastic limit, yield point or critical stress, and manner of deformation might be compared for tensile tests at an ordinary loading rate and for prolonged loading. Accordingly, short-time tensile tests and creep tests were made at room temperature, 300°, 500° and 700°F. The two latter temperatures are above the lowest possible recrystallization temperature of polycrys-talline 70-30 brass. Previous Work Clarke and White1 have made creep tests of some copper-zinc alloys, including 70-30 brass, and copper-zinc-tin alloys at temperatures both below and above the recrystallization temperature of the materials considered. Hanson and Wheeler2 have studied the flow and fracture of single crystals of aluminum for short-time and prolonged tensile loading over a range of temperature extending from room temperature to 400°F., their experiments being made without consideration of the orientations of the test specimens. Extensive creep and fracture tests on single crystals of lead at room temperature have been made by Betty3 and by Baker, Betty and Moore." Results of the last-named investigation were published while the present work was in progress. Miller5 examined the elastic limit of zinc single crystals at and above room temperature by means of creep tests, while Miller and Milligan6 reported the results of tests designed to show the influence of temperature on elastic limit of single crystals of aluminum, silver and zinc. The behavior of iron crystals under static tensile loading at room temperature was reported by Gensamer and Meh17 while the present investigation was in progress. Their specimens exhibited a well-defined yield point, below which no appreciable creep could be detected. The manner of yielding proved interesting, as the shape of the creep-time curve for the iron crystals differed from the common type of crcep curves. Elongation did not begin immediately, or at least was initially very slow. The rate of elongation then increased continuously and finally decreased to zero. This S-shaped type of elongation-time

Jan 1, 1941

By H. l. Burghoff, C. H. Mathewson

THE study of the creep of metals under conditions of prolonged loading has received the attention of many investigators for several years and almost innumerable papers have been published on the various aspects of the subject. As it appeared that much could still be learned from a study of single crystals, the present work was carried out to study the effects of temperature and conditions of loading upon the properties and deformation in tension of single crystals of alpha brass containing about 70 per cent copper and 30 per cent zinc. In particular, it was hoped to obtain information from tests below and above the recrystallization temperature of the material, so that properties such as elastic limit, yield point or critical stress, and manner of deformation might be compared for tensile tests at an ordinary loading rate and for prolonged. loading. Accordingly, short-time tensile tests and creep tests were made at room temperature, 300º, 500° and 700°F. The two latter temperatures are above the lowest possible recrystallization temperature of polycrystalline 70-30 brass. PREVIOUS WORK Clarke and White1 have made creep tests of some copper-zinc alloys, including 70-30 brass, and copper-zinc-tin alloys at temperatures both below and above the recrystallization temperature of the materials considered. Hanson and Wheeler have studied the flow and fracture of single crystals of aluminum for short-time and prolonged tensile loading over a range of temperature extending from room temperature to 400°F., their experiments being made without consideration of the orientations of the test specimens. Extensive creep and fracture tests on single crystals of lead at room temperature have been made by Betty3 and by Baker, Betty & Moore.4 Results of the last-named investigation were published while the present work was in progress. Millers examined the elastic limit of zinc single crystals at and above room temperature by means of creep tests, while Miller and Milligan6 reported the results of tests designed to show the influence of temperature on elastic limit of single crystals of aluminum, silver and zinc. The behavior, of iron crystals under static tensile loading at room temperature was reported by Gensamer and Mehl7 while the present investigation was in progress. Their specimens exhibited a well-defined yield point, below which no appreciable creep could be detected. The manner of yielding proved interesting, as the shape of the creep-time curve for the iron crystals differed from the common type of creep curves. Elongation did not begin immediately, or at least was initially very slow. The rate of elongation then increased continuously and finally decreased to zero. This S-shaped type of elongation-time

Jan 1, 1941

By J. Eric Belford

The Kidd Creek orebody is a massive base metal sulphide deposit with surface dimensions of 168 m by 670 m. The steeply dipping ore- body has been evaluated to a depth of 1 524 m. To date, the mining of the orebody has been divided into three stages. The first stage of mining was an open pit operation which supplied ore from 1966 until 1977 when a depth of 219 m was reached at the widest or north end of the orebody. The second stage of mining, called No.1 Mine, was the development of an underground mine to replace the pit and recover the ore from the floor of the pit to a depth of 792 m. Development of the underground mine started in 1969. Full production of 273 000 tonnes per month was attained in 1977. The third stage of mining called No.2 Mine, was initiated to accommodate a production expansion and included the development of a second underground mining operation to recover the ore from the bottom of No.1 Mine, i.e. the 2600 level; to a depth as yet undetermined but most likely the 4600 foot level. Development of the No.2 Mine began in 1974. Full production of 91 000 tonnes per month will be achieved in 1982. The choice of the 2800 level as the partition between the two underground mines was based on the following factors: The 2600 level is the lowest level which can conveniently be mined through the No.1 Mine crusher on the 2800 level. Development and trial stoping methods for mining at depth could be evaluated in the 2600 to 2800 block utilizing the existing hoisting facilities of No.1 Mine. Early development of the ore in the 2600 to 2800 block would provide additional mill feed sooner than could be achieved by developing from No.2 Shaft. The underground mining plan then is to mine from the pit floor down to the 2600 foot level and at the same time mine from the 2800 level down to at least the 4600 foot level. PLANNING The Kidd Creek operations are designed to follow a logical mining sequence. The grade of ore supplied to the concentrator is the result of following the mining plan. The philosophy of mining has been to mine downward in horizontal slices. In the case of No.1 Mine the slices are 122 m thick while in No.2 Mine the slices will be 183 m thick. The point of this approach is to mine the pillars immediately after creating them rather than allowing them to stand, deteriorate and generate uncontrollable situations. Two types of ore are handled separately to optimize recoverable values in concentrates. The &apos;A&apos; type ore is a copper zinc ore with some silver and little lead. The &apos;C&apos; type ore is a zinc silver ore with some lead and copper

Jan 1, 1981

By Alexander B. Morris

In a recent paper on the intermittent injection of gas in gas-lift operations as opposed to continuous injection, Morgan Walker presented a comparative table showing the effect on oil and gas production from the same wells under the two methods of operation.&apos; This table carried a column showing the formational gas-oil ratios under each method, computed by deducting the volume of input gas from the volume of trap gas. During the entire spring and summer of 1928, the present writer had been engaged on some extensive test car tests of rich gas in Glenpool, seeking, primarily, for an explanation of the apparent loss of gasoline during the summer season between the field meters and the plant master meter. Tests at several of the field meters where the richest gas was obtained regularly failed to check with other tests on the same gas made farther along the line, and the difference was not made up by the quantity of drip gasoline collected between the points. In the course of these tests, the final outcome of which is immaterial to the present purpose, an attempt was made to construct a curve representing the relationship between gasoline content of the gas in gallons per thousand cubic feet and the shrinkage in the volume of gas treated as a result of removing the condensible fractions. Such a curve was made, expressed in units of gallons per thousand cubic feet on the abcissa and the ratio vapor volume to liquid volume on the ordinate. This curve is a rectangular hyperbola and shows that 3 gal. of gasoline taken from 1000 cu. ft. of raw gas as a vapor occupied much less space, per gallon, than did 1 gal. of gasoline taken from 1000 cu. ft. of another sample of gas. This is, in general, corroborated by converting to the same units the residue settlement curves prepared by the Tidal Oil Co. and by the Natural Gasoline Manufacturers Assn., though the three curves, when plotted together, occupy entirely different positions on the paper, as shown in Fig. 1. The bearing of all this on Mr. Walker&apos;s discussion of gas-lift is this: if the formational gas is to be computed by deducting the input gas from the trap gas, some correction must be made for the vapor volume

Jan 1, 1930

By A. T. English

X-ray dif action techniques were used to investigate ordering and domain coalescence for the B2 (CsC1) superlattice in this alloy. Essentially complete disorder is obtainable by drastic quenching. isothertmal ordering occurs very rapidly at temperatures between 565° and 680°C, only a few seconds being required for development of substantial long-range order. A very fine antiphase dormain structure, found in samples annealed for short times, undergoes coalescence with further annealing. Domain "size" is found proportional to (t)1/2 . This Yate law can be derived by adapting the formalism of Hillert&apos;s analysis 01- metallurgical grain growth. For this Purpose the material is descvibed in terms of a "Swiss-cheese " structure, consisting of two multiply connected, mutually intertwined domain volumes. The observed activation enevgy for coalescence, 70 kcal per g-atom, agrees with an estit~lated value ,for volume diffusion in disordered rrzaterial. It is suggesled that the experimental value vejlects the substantially disordered environment of mobile vacancies located in the moving antiphase domain boundary. The alloy Fe-Co-2V is bcc below about 900&apos;C and orders into a B2 (CsC1) superlattice below about 730c It has important applications in magnetic components, including many requiring extensive cold rolling.* example, Marcinkowski and Brown6 observed a re1atively small as-quenched domain size of about 250Å in B2 Fe3A1. Since there appear to be no published data on domain coalescence in B2 alloys, this process was studied in detail. MATERIALS AND EXPERIMENTAL TECHNIQUES A commercial high-purity alloy, nominally 49 Fe-49Co-2V, was obtained from the Arnold Engineering Co. in the form of cold-rolled sheet 0.004 in. thick. Samples were annealed for 1 hr at 800°C in dry H2 to produce disorder and quenched into iced brine. They were then annealed in a nitrate-nitrite salt bath for various times at temperatures between 525° and 625°C. Estimates of the LRO parameter S and the APD size D were made using established X-ray diffraction techniques. Superlattice peaks are best observed using CoKa radiation, for which the value of (fFe-fCo) is maximized. Peak-to-background intensity ratio was improved by filtering CoKß from the incident beam to eliminate sample fluorescence, and by using a pulse-height analyzer. The LRO parameter S was computed from the ratio of integrated intensities I 100/I 200- Owing presumably to systematic errors associated with the presence of crystallographic texture and X-ray extinction, only rough agreement was obtained between experimental and theoretical (absolute) intensity ratios. For this reason certain experimental refinements (e.g., use of balanced filters) were considered superfluous and were omitted. Emphasis was placed on maximizing intensity in order to reduce the time taken to accurately determine the contour of the very small (loo), peak. This was done by point counting 105 counts at appropriate intervals. Background intensity averaged about 1200 cps.

Jan 1, 1967

By H. A. Jr. Koch, C. A. Hutchinson

Miscible phase displacement of oil from reservoirs has been emphasized in the past few years. The reason for this emphasis lies in the high oil recovery attainable by this process. Removal of capillary effects in the reservoir leads to recoveries approaching 100 per cent in the area contacted by the miscible phase. The miscible slug process is one means of obtaining a miscible displacement. Here a band or slug of I,PG is injected into the reservoir prior to gas injection. The idea is to maintain the band of LPG "wedged" between the gas and oil phases and thus achieve a miscible phase displacement. A second method lor achieving miscibility is through the injection of a gas which is not miscible with the reservoir fluid but which develops a zone of miscibility in [he reservoir through mass trans-ier with the reservoir oil.&apos; This mass transfer results in either an enrichment of the lean injected gas by intermediates from the oil or an enrichment of the oil by intermediates from a rich injection gas or one that has been enriched on the surface by LPG addition. We are interested here in discussing the process in which miscibility is developed at the displacement front by the evaporation of interrnediatcs from the oil phase into the gas phase. This process "builds up" its own slug of miscible material at the displacement front and therefore does not require the injection of LPG to obtain miscibil-ily. Each process has its own area of applicability. Generally, the high pressure gas process is applicable only with reservoir fluids which con-!ain a high concentration of inter- mediates. If the high pressure gas process is technically feasible at pressures less than 4,500 psi, it is probably more desirable economically than the slug process. The slug process has broad applicability in the shallower reservoirs and with reservoir fluids which contain a relatively low concentration of LPG and natural gasoline constituents. This paper deals with some new concepts of the high pressure gas injection process where it is proposed that flue gas can be substituted for hydrocarbon gas without sacrificing our goal of miscibility. MECHANISM Introduction Considerable effort has been devoted to study of the mechanics ot the high pressure gas injection proc-one generalization result-ing from some of these studies was that the composition of the injected gas is relatively unimportant in establishing the miscibility pressure* for a given reservoir fluid. This generalization is correct for the composition range of gases typically encountered in the field. Two such gases are a gasoline plant tail gas containing 85 per cent methane and 15 per cent ethane, and a field separator gas containing 70 per cent methane and 30 per cent heavier components. The most important factor which sets the miscibility pressure in the operation is the reservoir fluid composition, particularly the concentration of LPG-natural gasoline constituents. The injected gas is the agent by which the LPG-natural gasoline constituents are concentrated at the displacing front to create a miscible displacement. Based on these results, it appeared feasible that some inexpensive gas, such as flue gas, might be substituted for hydrocarbon gas for use in the high pressure gas process. A re-examination of the phase relations of the high pressure gas injection process should clarify the principle behind using flue gas (essentially nitrogen) as an injection gas. Three Component Diagram The phase relations of the high pressure gas injection process have been illustrated by the use of the three component diagrams.&apos;," In Fig. 1 we have arbitrarily represented the multi-component reservoir system by three components; methane, ethane through hexane, and heptanes plus. The solid curve ABC is the phase boundary curve. It represents the locus of compositions which have fixed saturation pressure at a fixed temperature; the lower branch AB shows bubble point compositions, the upper branch BC, the dew point compositions. Point B is the coniposition of the critical mixture at this temperature and pressure. The dashed lines (tie lines) connect vapor and liquid compositions which are in equilibrium. Let us consider Reservoir Fluid D which we wish to displace in 21 miscible manner by gas injection. Let us further restrict the discussion to the case where miscibility between an injection gas and the reservoir fluid at the displacement front is developed by gas enrichment in the reservoir. For this case, any gas whose composition lies between Points C and E on the right side of the three component diagram can be used to give a miscible displacement of Reservoir Fluid D. This is true because the more mobile injected gas moves faster than the displaced oil and is in continuous contact with virgin oil at the displacement front. This leads to a continuing enrichment 01&apos; the gas at the displacement front by evaporation of the C, - C,

By Robert W. Hunt

The memorable features of American history have been making fast during the last century, and notably so since 1860; and they are by no means confined to political or to any one branch of scientific development. Of all the industrial arts, none show a greater change or &apos;a mightier progress than the Bessemer manufacture. And this year, while we are celebrating the first centennial of our national life, we can also celebrate the first decennial of American Bessemer practice. While not forgetting or undervaluing what has been done in other countries, I have thought that a brief history of the introduction and development of the Pneumatic or Bessemer process in America would be of interest. In 1863 the Kelly Pneumatic Process Company was formed and an arrangement entered into with William Kelly, who had taken out letters-patent of the United States, Nos. 16,444; 17,628, reissued as 505; 18,910, dated January loth, 1857; June 23d, 1857; November 36, 1857; and December 22d, 1867, respectively. This association mas composed of the Cambria Iron Company, E. B. Ward, Park Brothers & Co., Lyon, Shorb & Co., Z. S. Durfee, and, later, Chouteau, Harrison & Valle joined the combination. Not satisfied with possessing the control of the Kelly patent, they sent Mr. 2. S. Durfee to England, to secure for this country Mushet&apos;s patent on recarburization, No. 17,389, dated May 26th, 1857, the same having been taken out in England on September 22d, 1856. In this Mr. Durfee was successful. Previous to the application of William Kelly for a patent, Henry Bessemer, of England, had taken out patents dated February 12th, 1856, and August 25th, 1856, in this country. Kelly claimed priority in the discovery of the principles of the process, and the Patent-office allowed his claim by granting him his patents. In the autumn of 1862 Mr. Alexander L. Holley, while in England, was impressed with the importance of Mr. Bessemer&apos;s invention, and so fully foresaw its future, that, upon his return to the United States, he induced Messrs. John A. Griswold and John F. Winslow, of Troy, New York, to join him in endeavoring to possess Bessemer&apos;s American patents. Mr. Holley returned to England in

By F. L. Robertson, C. H. Bacon, J. W. Till

A description is given of the development of a process for making low sulphur steel on furnaces fired with 2 1/2 pet sulphur oil. Slag and metal are analyzed at melt. Slag weight is estimated. A simple method for calculating necessary lime additions for making 0.025 and 0.035 pct sulphur steel is given. DURING the last 15 years John Summers & Sons have been confronted increasingly by the problem of producing a low sulphur steel from high sulphur materials. The principles adopted, the processes used, the data collected on a furnace specially set aside to study this problem, and speculation on future developments are dealt with in this paper. This study is limited to two melting shops which make sheet steel only, of the following analysis: C, 0.06 pct; Mn, 0.33; S, 0.04, 0.035, 0.03, and 0.025; and P, 0.02 and 0.015. All the processes described have reference to the manufacturing of this steel and are not necessarily applicable, without modification, to other steels. The raw materials used are given in Table I. Development of Process About 1934, Schenck&apos;s work on phosphorus was applied to frame quantitative rules for the removal of phosphorus, with great success. We could however, neither in our own work nor in the voluminous literature, find any assistance to frame quantitative furnace rules to remove sulphur. Perhaps, we should have persevered with Schenck&apos;s outstanding chapter on sulphur in The Physical Chemistry of Steelmaking, but we missed the importance of one (Ss) sentence on p. 478. "Evidently this ratio -------- is [S] the important quantity to be considered from the point of view of chemical reaction; it is clear that the sulphur content of the steel alone, as frequently given in the literature cannot suffice for judging the success of the reaction unless special details are given regarding the sulphur charge and the amount of slag."&apos; We were not however very successful in getting values for Schenck&apos;s "n" that agreed with (S) arrived at by our direct analysis. [S] In addition to Schenck&apos;s work much attention was given to V value. The formula selected for V was: (SCaO) — 1.57 (2 P2O5) (S SiO2) After plotting many charges a curve was obtained, based upon the relationship between the percentage sulphur in the finished steel and V value, Fig. 1. For a long time this was used as standard with about a 60 to 70 pct success on producer-gas fired furnaces, if all uprising scrap was used and no bought scrap used. An inspection of this curve shows clearly that it is not a quantitative manufacturing process, and that it was not sure enough to go to the trouble and expense of doing stage analysis for P,O,,

Jan 1, 1952

. F. W. SPERR, JR.,* Pittsburgh, Pa.--Mr. Malcolmson states that the Carbocoal process produces ammonium sulfate in excess of that normally recovered in the ordinary byproduct coke process. Table 3 indicates that 20,000 to 25,000 lb. of sulfate of ammonia are obtained in carbonizing 1000 tons of Clinchfield coal. This is a high-grade coal and yields from 26 to 28 lb. of ammonium sulfate per ton in a modern byproduct coke oven. On the next page, 21 lb. is stated as the yield of ammonium sulfate per short ton of raw coal; this is less than the average production from any well operated byproduct coke-oven plant treating coal of the character usually coked, in Pennsylvania and Ohio. The statement as to the comparative yields of light oil is somewhat misleading in view of the results obtained during the past year or two by the more modern byproduct coke plants. The plants put in operation by the H. Koppers Co., during the past two years, are producing about 3.5 gal. of light oil per short ton of coal, and several of these plants are producing more than 4 gal. per ton. The yield of pure toluene runs from 0.45 gal. to 0.55 gal. per ton. .The quality of the light oil .obtained from the Carbocoal process is of much greater importance than would be inferred by one not closely familiar with the subject. The presence of paraffins in the benzol and toluol fractions seriously detracts from their commercial value; the benzol and toluol fractions derived fro in the Carbocoal process contain about 50 per cent, of paraffins. It should be thoroughly understood what these paraffins are. They are simply hydrocarbons that go to make up ordinary petroleum, and if a successful method for the removal of paraffins from benzol and toluol has been developed, this can at once be applied to several well known processes by which benzol and toluol can be made directly from petroleum, which have as yet been total failures on account of the contamination of these products by paraffins.

Jan 11, 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&apos;, 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

By Edna A. Dancy, Ronald L. Pastorek, Gerhard J. Derge

In an earlier study1 in this laboratory, it was found that there is a minimum in the specific conductance of Ni-S melts in the region of the stoichiometric composition, Ni3S2. This and similar observations on other sulfide1 and telluride2 systems suggest that short-range order exists in the molten phase for several hundred degrees above the melting point, and a qualitative energy-band model has been proposed, with intrinsic semiconduction at the stoichiometric composition and degenerate electron and hole conduction at metal- and tellurium-rich compositions. This suggestion has been substantiated for the telluride systems by Seebeck coefficient measurements which showed a change in sign from negative on the metal-rich side to positive on the tellurium-rich side. In the present investigation, in order to substantiate still further the proposed model, Seebeck coefficient determinations have been extended to the Ni-S system over a composition range in the vicinity of Ni3S2. The experimental method was essentially the same as that used for the telluride systems, with minor modifications on cells for high sulfur melts to permit the use of tungsten wires and W— W-Re th~rmocouples instead of the chrome1 or alumel wires and chromel-alumel thermocouples originally used. Chrome1 and alumel both deteriorate very rapidly in atmospheres containing sulfur. The Ni-S alloys were prepared as described in the conductivity paper. Initially, a portion of the solidified melt was analyzed at the end of a run, but after this was found to be inaccurate because of segregation during cooling, the whole sample was analyzed. The nickel content, only, was determined, the sulfur content being obtained by difference. The results are summarized graphically in Fig. 1, and clearly show a change in the sign of the Seebeck coefficient in the region of the stoichiometric composition. This change of sign near Ni3S2, coupled with the minimum in the conductivity, is suggestive of an intrinsic semiconductor at the stoichiometric composition, with degenerate electron and hole conduction on either side of this composition, in keeping with the proposed model. The negative temperature coefficient of conductivity, normally indicative of metallic conduction, is not inconsistent with this model. In the completely degenerate region it would be expected, while in the vicinity of Ni3S2 the suggestion originally made by Argyriades, Derge, and pound3 for the Fe-S system can probably be applied. They proposed that the forbidden gap between the valence band and the conduction band is small, and that the increase in the number of the conducting species with increase in temperature is not large enough to compensate for the loss of mobility through thermal scattering. The research was sponsored by the Office of Naval Research under Contract NONR-760(22) Project NR 039-081. &apos;E. A. Dancy and G. J. Derge: Trans. Met. Soc. Aime, 1963, vol. 227, pp. 1034-38. &apos;E. A. Dancy: Trans. Vet. soc. AIME. 1964, vol. 233, pp. 270-77. &apos;D. Argyriades, G. Derge, and G. M. Pound: Trans. Met. Soc. . 1959, vol. 215, pp. 909-12.

Jan 1, 1965

By Cuppam Dasarathy

THE object of this note is to report briefly certain results of investigations on the Fe-In phase diagram. BISRA-high purity H-iron and 99.9 pct pure indium were used to prepare the alloys. The experimental techniques consisted of thermal analysis, optical metallography, and X-ray diffraction. A phase diagram based on the present results as well as those reported earlier by the author&apos; is shown in Fig. 1. It is seen that the liquidus points fall on a smooth line which meets the monotectic isotherm at 1470°C. The liquidus extends up to 3.4 at. pct In. The phase boundary separating the two liquidus L1 and L2 is shown dotted. The experimental solidus meets the monotectic isotherm at -0.9 at. pct In. The 6/6 + L2 boundary drops steeply to the 6 + La/y + L2 boundary at -1350°C. In this region, it is impossible to detect satisfactory thermal arrests because of the steep phase boundary. The present diagram shows that indium lowers the temperature of the d/y transforma-tion and raises the temperature of the y/a transfor-mation. The y +d region is found to be very narrow. Indium gives rise to a restricted y field when alloyed with iron. The width of this field is between 0.4 and 0.5 at. pct In. Details of the alloys containing 40 and 50 at. pct In have already been reported by the author&apos; and the transformation temperatures of these alloys are included in Fig. 1. It appeared from optical metallography and X-ray diffraction that the room temperature solubility of indium in a iron is less than 0.28 at. pct since alloys of 0.28 at. pct In and above, slow cooled to room temperature, contained dark etching second phase particles situated both in the matrix and grain boundaries of the a-grains, see Figs. 2 and 3. These particles were identified to be unalloyed indium by X-ray diffraction. The lattice parameter of the a phase reached a maximum of 2.8672A at the indium level of -0.28 at. pct. The present diagram, Fig. 1, is in substantial agreement with that of Stadelmaier and Fiedler&apos; except for certain differences in detail. For example, they found the monotectic composition and temperature to be 7.0 at. pct In and 1443oC, respectively, while the present work indicates them to be 3.4 at. pct In and 1470°C. The 6 + L2/y + L2 transformation is indicated in the present work to occur at -1350°C, whereas Stadelmaier and Fiedler find this to occur at -1320°C. They also claim that the width of the y field is 0.2 at. pct In while the present work shows the width to be between 0.4 and 0.5 at. pct In. 1) Indium, when alloyed with iron, gives rise to a restricted y field, the width being >0.5 at. pct In.

Jan 1, 1970

Levi Holbrook was born in Westboro, Mass., March 7, 1836. He was a descendant of John Holbrook, who came from England in 1660 and settled in the Massachusetts Bay Colony. Mr. Holbrook was prepared for college at Williston Seminary, East-hampton, Mass., and after one year spent in the West, he entered Yale. He was a, member of Phi Beta Kappa and of Linonia. During the six months following his graduation he was in Boston, under medical treatment for his cyes; then he took a horseback trip across the Rocky Mountains to the Columbia River and back, and resided in Danville, Va., for a time. From 1860 to 1863, as his eyes permitted, he was a student of modern languages and literature in Cambridge, Mass., part of the time being a resident graduate at Harvard University. Finally, however, he was obliged to abandon the idea of a literary life and from 1864 to 1867 he was engaged in financial business in Boston. The following year, he spent in New York, and then traveled for a year in Europe, Egypt and Asia Minor. In 1871, he returned to New York City. Mr. Holbrook was a member of the New England Historic Gcncalogical Society, the Society of Colonial Wars, and the Sons of the Revolution, was registrar general of the Order of the Founders and Patriots of America from 1915 to 1920, and had been governor of the New York society of that order. He was also a member of the American Fine Arts Society, the Order of the Cincinnati, the American Geographical Society (of which he was a councillor and secretary). and the Geographical Society of America. He joined the American Institute of Mining Engineers in 1878, and served as manager from 1895 to 1897. Mr. Holbrook died on July 26, 1922, from organic heart trouble, at his residence in Center Harbor, N. H. He was married Dec. 27, 1871, in Newark, N. Y., to Viola, daughter of John A, and Elizabeth (Failing)Vowers, who died on Sept. 10, less than six weeks after her husband. His two children, Clark Holbrook of Red Bank, N. J., and Mrs. Julian P. Smith, survive him

Jan 1, 1923