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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' 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' 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 Irving Cadoff, Kurt Komarek, Edward Miller

THE lead-telluride phase diagram as compiled by ansen' has one intermetallic compound, PbTe, with solid-solubility limits extending from 22 to 45 wt pct Te (31.4 to 57.1 at. pct). Pelzel2 redetermined the solubility limits on the lead-rich side of the compound by measuring the relative areas of the two phases in samples annealed in the liquid + compound region, and obtained data that agreed with that of Hansen. Recent studies of the semiconducting properties of PbTe3 however, have indicated that addition of either lead or tellurium to PbTe does not produce samples having carrier concentrations greater than about 10 19 cm-3. Assuming that each impurity atom results in one ionized charge carrier, this carrier concentration corresponds to a solubility range of less than 0.04 at. pct. Fritts and Karrar4 have also observed two phases in samples containing from 0.15 to 3.0 pct excess Pb. To resolve the discrepancy between these data, the solid solubility limits of the compound PbTe were reinvestigated, using several other techniques. Ten 25-g samples with compositions of 1/2, 1, 3, 5, and 10 wt pct excess Pb and Te and two 100-g samples of 15 and 65 wt pct Te were prepared, sealed in evacuated quartz capsules, and melted at 950oC. The 1 pct excess Pb and Te and the 15 and 65 wt pct Te alloys were homogenized for 96 hr at 450°C; the remaining specimens were annealed 50°C below the solidus temperature reported in Hansen. The specimens were polished and etched with dilute HNO,. All the samples were two phase, the second phase appearing at grain boundaries or as spheroidized inclusions in the grains. In the case of the tellurium rich specimens, the second phase could be identified as a eutectic. Debye-Scherrer powder diffraction patterns of the i, 1, 3, 5, and 10 pct excess samples were obtained using CuKa filtered radiation. The films were indexed as the B1 or NaCl structure. The calculated lattice parameter of PbTe was the same for all the specimens, with an average of a0 = 6.460 ± 0.0005A. Lines due to excess lead or tellurium were very faint but could be clearly seen in all the films. The relative areas of the two phases in the 15 and 65 wt pct Te samples were corrected for the differences in density of Pb, Te, and PbTe, and taken as proportional to the relative volumes of the two phases. The corrected relative volumes agreed with a phase diagram having negligible solubility of both lead and tellurium in lead tellurium. The density of the two specimens was obtained to give a third independent determination of the phase limits. The specimens were broken into small pieces to eliminate any internal porosity, and adherent air bubbles were removed by vigorous shaking under water for several hours. The density of lead (11.34 g per cm3) and of tellurium (6.25 g per cm3) was taken from the International Critical Tables and that of stoichiometric PbTe (8.25 g per cm3) calculated from the lattice parameter. For the 15 wt pct Te samples, the density assuming no solubility was calculated to be 9.89 g per cm3; the observed density was 9.86 g per cm8. For the 65 wt pct Te alloy, the density calculated for the case of no solubility was 7.24 g per cm3; the measured density wag 7.22 g per cm3. These results are consistent with those of planimetry and X-ray. SUMMARY Data have been presented which show that the solid solubility of both lead and tellurium in PbTe is

Jan 1, 1961

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members) Members and guests who called at Institute headquarters during the period Feb. 10, 1917 to Mar. 10, 1917: F. H. Armstrong, Vulcan, Mich. G. Komar, Staten Island, N. Y. Franklin Bache, Philadelphia, Pa. H. M. LaFollette, LaFollette, Tenn. R. A. Bingham, W. Orange, N. J. H. Mortimer-Lamb, Montreal, Canada. G. S. Blair, Pittsburgh, Pa. J. S. Lane, New York, N. Y. Graham Bright, Pittsburgh, Pa. D. H. McLaughlin, Cambridge, Mass. C. A. Burdick, New York, N. Y. F. J. McMahon, Wilkes-Barre, Pa. Frederick P. Burrall, Dawson, Y. T. F. Oskar Martin, San Francisco, Cal. William Campbell, New York, N. Y. C. Mentzel, New York, N. Y. G. L. Carlisle, Jr., New York, N. Y. T. C. Merriman, New Haven, Conn. J. Murray Clark, Toronto, Canada. K. -A. Pauly, Schenectady, N. Y. Wayne Darlington, Philadelphia, Pa. , Francis R. Pyne, Elizabeth, N. J. Ralph W. Deacon, Elizabeth, N. J. C. S. Robinson, Youngstown, O. P. St. Jon Dixon; So. Porcupine, Canada. W. A. Scheuch, New York, N. Y. A. E. Drucker, New York, N. Y. Jesse Scobey, New York, N. Y. Lucien Eaton, Ishpeming, Mich. Dunbar D. Scott, Rochester, N. Y. W. E. Goldsborough, New York, N. Y. W. C. Smith, Elizabeth, N. J. C. Marshall Gravatt, Port Royal, Va. Charles Spearman, Mt. St. Patrick, Can. C. N. Hickok, Cleveland, O. . - Harold C: E. Spence, Duncan, Ariz. C. Vey Holman, Rockland, Me. M. M. Thompson, Morsemere, N. J. W. F. Jahn, Kirkland Lake, Canada. Benjamin F. Tibby, Salt Lake City, Utah. F. E. Johnesse, Boise, Ida. J. S. Unger, Pittsburgh, Pa. E. C. Johnson, Chicago, Ill.

Jan 4, 1917

By J. W. Stewart

THE aim of this paper is to point out the various ways in which design is taught in standard four-year mining engineering curricula in American colleges and universities; to discuss the reasons apparently justifying the great diversity of procedure that exists along this line; and to indicate possible solutions to the difficulties now attending the teaching of design. A study was made of typical four-year mining engineering curricula in 15 colleges and universities of the United States (Table I). Great diversity in content of the various design courses, if taught as described, became apparent immediately. It appeared that it might be both interesting and instructive if the cause for this colorful variety could be found. Was the cause local mining conditions, departmental individuality, or actual necessity? Study of the school catalogues revealed that the various design courses could be classified into two fairly distinct types; namely, (I) those dealing with mine equipment or structures, and (2) those dealing with underground layout of mine workings. It seemed reasonable to label the first type of course "mining design" and the second type "mine design." Some such distinction must have been in the minds of mining educators, for we find both names (i.e., mine design and mining design) used to designate the design courses included in the various mining curricula. Unhappily, the name and the apparent content of such courses do not, in all instances, conform to the classification made here, although in most instances such conformation does obtain (Table I), It is possible that in the exceptional case the method of teaching a design course, and consequently the content of it, may have been changed at some time without change in the name of the course. Apparently only 3 of the I5 schools made an effort to cover both types of design in their curricula (Table I). Two other schools did not list or describe any course of study that could with certainty be taken as a design course. Of the remaining 10 schools, 9 gave a mining-design type of course and one gave a strictly mine-design type. Obviously, the preponderance of design courses afforded are of the mining-design type. Why? To answer this question, it is necessary to make a study of the prerequisites for the two types of design courses taught. In all schools the design courses were taught in the senior year; in eight, design was taught throughout both semesters; in two, it was taught during the first semester only; and in three it was taught during the second semester only. Consequently, excepting the last three cases noted, it is obvious that all prerequisites for a design course should be completed by the end of the junior year. PREREQUISITES What are the probable prerequisites for the different kinds of design courses as they appear to be taught? Let us take first the case of the mine-design type of course, having to do with layout of underground workings. Here it would seem that logical

Jan 1, 1941

By T. L. Joseph

A study is made of the amount of solution loss necessary to maintain the reducing power of the gas stream in the blast furnace. Curves are presented to show the effect of solution loss, moisture in the blast, and carbon dioxide from the flux on the nitrogen in the THE blast furnace process is based upon the counter flow of gases and solids. As CO, N, and H, flow upward from the combustion zones, oxygen is acquired from the descending charge. In the reduction of iron ore, a portion of CO is converted to CO, and similarly a portion of H, is converted to water vapor. The inert N,, from the air used in combustion, passes through the furnace with little change. Its concentration is, however, decreased by reactions such as direct reduction and solution loss which increase the volume of CO in the gas stream; Similarly the evolution of C02 from the limestone also dilutes the nitrogen. he purpose of this paper is to illustrate an idealized and simplified method of studying furnace processes by following changes in the gas phase between the tuyeres and the stock line. A more specific objective is to evaluate the effect of solution loss upon the CO/CO, ratio in that region of the furnace in which FeO is reduced to metallic iron. This last stage of reduction requires relatively high CO/CO, ratios to exceed the equilibrium requirements. Solution loss or the reaction of COZ with C to produce CO has a pronounced effect upon the ratio of the carbon gases and is necessary to maintain the reducing power of the gas stream if the consumption of coke is low. It will be explained later that indirect reduction followed by solution loss is stoichiometri-cally equivalent to direct reduction. Calculations will be made to show how the composition of the gas in the region of the mantle varies with coke consumption and with different amounts of solution loss. Such calculations show the condi- tions under which gasification of C with oxygen in the charge is needed to maintain the reducing power of the gas. Equilibrium conditions for FeO and the carbon gases will be used to establish a minimum CO/CO, ratio below which reduction will not proceed. The manner in which carbon is gasified in the furnace, at the tuyeres with oxygen in the air or above the tuyeres with oxygen from the charge, will be a basic feature of all calculations. It is hoped that greater interest in the use of top gas as a means of following furnace reactions will be aroused by the calculations and generalized curves which are presented. Bosh Gas Equations Subject to some alteration by the amount of moisture in the blast and by direct reduction, the gas leaving the combustion zones of a blast furnace has a definite composition. Because a relatively small amount of oxygen is acquired from the charge in the bosh and in the crucible, the products of combustion undergo little change until they enter the shaft. Bosh gas is, therefore, essentially the products of combustion of carbon in a deep fuel bed with air. The relative weights and volumes of reacting materials are expressed by the equation: 2~ + 0? + 3.76N, = 2C0 $ 3.76NZ [I] Air Bosh Gas -air = 79% N? = 3.76) 21% 02 Starting with a known mass of C consumed largely by air, Eq 1, but partly by water vapor, Eq 2, the volume and C + H2O = CO $ H? [21 composition of the bosh gas can be calculated and subsequent changes followed as reactions take place at various elevations in the furnace. As shown in

Jan 1, 1952

By C. G. Dunn

Identification of the kinds of orientation relationships that may exist among crystals is an important problem in the metallurgical field. As an aid to its solution standard orientations of several orders of twins would be very useful for rapid analyses to discover high-order as well as low-order twin relationships. Although data have been published that give orientations for three generations of twins, these data are not readily useful in the form presented; i.e., in a stereo-graphic projection with one pole per orientation.' However, accurate data based on calculations of the positions of all {1001 planes for such groups would be very useful when presented in tabular form. Therefore, calculations have been made for a group of four orders of twins and the data are listed in Table 3. Illustrative applications are considered briefly, with the idea of pointing out what may be done with large groups of orientations. Method of Computing Orientation OF a Twin It is common practice to describe the orientation of a crystal in terms of the positions on a stereographic net of the poles of certain planes of the crystal. A single position on a net may be given in terms of two angle variables, two sets of which appear in the following equations: Polar Net Wulff Net x = , sin ?p cos Fbp x = r COS ?w y = r sin ?p sin Fp y = r sin ?w cos Fw % = r cos ?p z = r sin ?w, sin +, The three numbers z, y and z determine a length r as well as a direction (0, 4) in an X, Y, Z coordinate system. In the present case, r will be set equal to (h2 + k2 + L2)1/2, where h, k and I are the usual Miller indices for a crystallographic plane, a restriction that facilitates determination of the positions of poles of new planes from those of old or known ones,2 as will become evident later. Furthermore, since twinned lattices have certain planes in common, it is an easy matter to determine the orientation of a twin of a crystal if the orientation of the crystal itself is known. We start therefore with a crystal of known orientation (positions of three {Ioo} poles given) and determine where the cube poles occur in first, second, third and fourth-order twins. Methods for identifying twinned lattices and for making the calculations to find the orientation of a twin have been published.3,4' Reference 4 will be illustrated in the calculation of the orientation of a twin, even though this method differs from the one used by the writer in obtaining the following data on four orders of twins. Consider a crystal S and its twin A1, A' being one of the four {112} or {III} type* first-order twills of S. The orientation of S—i.e., the positions of poles of (I00)

Jan 1, 1945

By H. N. Treaftis, J. W. Cahn

THE previous determinations of the solvus of tin in solid lead disagree with one another by as much as 40°C or almost 10 at. pct. Even determinations that appear to be careful differ considerably in both the solubility and its temperature coefficient. Recent kinetic workl -3 on the rate of precipitation of tin from lead-tin alloys and thermodynamic work4 on the heat of solution of tin in lead have given some insight into the time necessary to reach equilibrium in this system. As this time is longer than that used in almost all previous determinations of the solvus, these determinations are questionable. Since the interpretation of recent kinetic results requires accurate values of the equilibrium solubility the present work was undertaken. DISCUSSION OF PREVIOUS RESULTS The methods used in previous studies may be placed into three classes: 1) Several alloys covering a range of compositions are allowed to reach "equilibrium" at a certain temperature.5-7 Some property, such as the X-ray lattice parameter of the lead-rich phase or the re- sistivity of the alloy, is then measured as a function of composition. The solubility limit for that temperature is taken to be that composition at which a discontinuity in the property occurs. However, the recent kinetic work has shown that tin precipitates in two stages. The first stage is rapid but leaves the lead still supersaturated. The second stage is very slow, and it seems from the equilibration times quoted by the investigators of the solvus that the end of the first stage of precipitation was usually mistaken for equilibrium. This is especially true at temperatures below 100°C where the first reaction is still quite rapid (from minutes to months), but where the second stage is so slow that very long holding times are required to reach equilibrium. Alternatively micrographic work8 on several alloys of different compositions seems to have given good results if done carefully. 2) The beginning of precipitation in a homogenized alloy is measured as it cools slowly8-10. Since reactions in solids undercool easily, such determinations will always give too low a temperature for the solvus. 3) Some property of an alloy is measured as a function of temperature while the alloy is above the solvus.5,9,11 The range of temperature can usually be extended slightly into the two phase region. Then the alloy is precipitated at a much lower temperature and slowly reheated. The solvus is taken to be the lowest temperature where the property of the reheated alloy is equal to that previously determined for the homogeneous alloy. Usually one also expects a discontinuity at the solvus in the temperature variation of the property for the reheated alloy. The difficulty in this method is the sluggishness of the dissolution process, and this method may give too high a solvus temperature. EXPERIMENTAL The phase boundary or solvus temperature was determined by a modification of method 3 for a series of chemically analyzed high-purity alloys, ranging from 5.1 to 26.4 at. pct Sn. The resistance, as a function of temperature, of a sample of homogenized alloy (which could easily be undercooled) was compared with the equilibrium resistance which that alloy sample attained after precipitation at room temperature followed by long isothermal anneals at various temperatures. Before each anneal the sample was rehomogenized and reprecipitated. The solvus temperature could be located to within 1°C as the intersection of the resistance vs temperature curves for the homogenized and equilibrium alloys. No attempt was made to locate the phase boundary more accurately since the limiting factor was the precision with which the alloys could be analyzed. This precision was ±0.1 wt pct Sn and corresponds to an error of 1 deg in temperature. This use of isothermal anneals differs from some of the previous investigations in which method 3 was used with baths of slowly rising temperatures. It was found early in the investigation that solvus temperatures tended to be high if the latter method was used even at extremely slow heating rates. For example a

Jan 1, 1961

By M. Semchyshen, G. A. Timmons

The predominant orientation in both straight-rolled and cross-rolled molybdenum is the {100} [110] texture. Upon complete recrystallization, this same texture predominates, but there is less spread about the ideal orientation. A secondary orientation about the [111] direction as the axis develops in cross-rolled sheet. Compression-rolled sheet exhibits random orientation in the plane of the sheet. Some mechanical properties were measured at varying angles to the rolling direction to determine the effect of preferred orientation on anisotropy in molybdenum sheet which had been straight, cross, or compression rolled. THE development of the arc-cast process has made available large ingots of molybdenum from which it is possible to roll sheet of considerable size. It is anticipated that such sheet will be further fabricated by spinning, drawing, stamping, or forming. Anisotropy of physical properties caused by the preferred orientation developed in the sheet during rolling may be expected to affect the behavior of the metal when subjected to these fabricating operations. To produce a sheet which will be most amenable to the fabrication of a given shape by a particular operation, consideration should be given to the directions and magnitudes of plastic deformations produced in the operation. When possible, the rolling schedule should be controlled to develop a texture which favors the required deformation. The existence of preferred orientations in rolled molybdenum sheet has been reported by Jeffries,' Konobejewsky,' Fujiwara," Goss,' and Ransley and Rooksby." None of these investigators obtained sufficient X-ray data to permit the construction of pole figures; instead, they based their conclusions upon Debye-Scherrer patterns of a limited number of positions. Ransley and Rooksby devoted some attention to transcrystalline cleavage at 45" to the rolling direction, indicating that it is appreciable in polycrystalline material only when the crystals are in the ideally preferred condition, and that this condition is only approached if the metal has been rolled successively in two perpendicular directions. In a recent paper, Custers and Riemersmao introduced the first pole figures to describe the textures of straight-rolled and cross-rolled molybdenum sheet. To increase the knowledge concerning the generation and effects of preferred orientations in molybdenum sheet, an investigation was undertaken to determine the effects of variations in rolling schedule and annealing treatments on preferred orientation, and to correlate preferred orientations with some mechanical properties. The orientations of straight-rolled, cross-rolled, and compression-rolled sheet have been determined by X-ray analysis, both as-rolled and after recrystallization. Pole figures have been constructed to describe the textures produced by these various rolling procedures. Texture of Cast Molybdenum Ingots In the arc-cast process, molybdenum powder is pressed into a vertical column which is sintered to increase its strength as it proceeds downward into a water-cooled mold, where the metal is melted in an alternating-current arc established between the end of the formed powder electrode and the metal bath at the top of the growing ingot. Since the solid-liquid interface moves continuously upward in the mold, the crystal axes are not normal to the cold surface of the mold but have the curvature shown in Fig. la. X-ray analysis reveals that the cube axis is the fiber axis and that it is normal to the cold surface of the mold; that is, the [loo] direction is parallel to the longitudinal axis of the ingot. This substantiates recent work by

Jan 1, 1953

By H. E. Hostetter

Grossmann's method1 for calculating the hardenability of steel from the composition and grain size has gained wide acceptance, and when properly used, has been well proved in practical application, both for estimating the hardenability of known compositions and for selecting compositions to meet known hardenability requirements. The Grossmann method uses as the criterion of hardenadility the "ideal critical diameter," DI, which is the' size round that will just harden to a structure of 50 per cent martensite at the center when given the theoretically fastest quench, or "ideal quench." The DI can be related to actual quenching practice if the severity of quench is known; or the DI can be correlated with hardenability as determined by the Jominy end-quench method.2 The effect on hardenability of each element present in a steel can be represented by a multiplying factor, the value of which depends on the amount of the element present and the degree of effectiveness of the particular element. (The value of the factor for a given carbon content varies with the grain size.) When the factors for all elements present in a steel have been determined from charts, they are multiplied, and the resultant product is the DI of the steel. The validity of Grossmann's scheme of multiplying factors has been confirmed in a number of other investigations.3-6 It can be appreciated that a certain desired level of hardenability can be obtained by adding chromium, molybdenum, nickel and vanadium to a base composition containing carbon, manganese, silicon and the usual impurities. Many of the ranges of hardenability used commercially can be obtained by any of the foregoing alloying elements used singly in the base composition. The same hardenability levels also can be obtained through use of any of a great number of multiple element combinations of these alloying elements. In this report a method will be presented for determining what one combination is the most efficient (based on hardenability and cost of added alloy) for a given level of hardenability. It should not be assumed from the emphasis given to hardenability, that hardenability is the only criterion for the selection of an alloy composition. Such properties as the hot-working characteristics, machinability, carburizing characteristics, amount of distortion during quenching and the retention of austenite may be considerations of importance in many applications. However, hardenability is one of the most important properties of an alloy steel and one that must be considered in almost all cases involving heat-treatment by quenching. Therefore, a method for determining the lowest-cost alloy combination should be of considerable value. Determination of Most Efficient Combinations For comparing the alloying elements on standards of cost and hardenability, it

Jan 1, 1947

By H. E. Hostetter

Grossmann's method1 for calculating the hardenability of steel from the composition and grain size has gained wide acceptance, and when properly used, has been well proved in practical application, both for estimating the hardenability of known compositions and for selecting compositions to meet known hardenability requirements. The Grossmann method uses as the criterion of hardenadility the "ideal critical diameter," DI, which is the' size round that will just harden to a structure of 50 per cent martensite at the center when given the theoretically fastest quench, or "ideal quench." The DI can be related to actual quenching practice if the severity of quench is known; or the DI can be correlated with hardenability as determined by the Jominy end-quench method.2 The effect on hardenability of each element present in a steel can be represented by a multiplying factor, the value of which depends on the amount of the element present and the degree of effectiveness of the particular element. (The value of the factor for a given carbon content varies with the grain size.) When the factors for all elements present in a steel have been determined from charts, they are multiplied, and the resultant product is the DI of the steel. The validity of Grossmann's scheme of multiplying factors has been confirmed in a number of other investigations.3-6 It can be appreciated that a certain desired level of hardenability can be obtained by adding chromium, molybdenum, nickel and vanadium to a base composition containing carbon, manganese, silicon and the usual impurities. Many of the ranges of hardenability used commercially can be obtained by any of the foregoing alloying elements used singly in the base composition. The same hardenability levels also can be obtained through use of any of a great number of multiple element combinations of these alloying elements. In this report a method will be presented for determining what one combination is the most efficient (based on hardenability and cost of added alloy) for a given level of hardenability. It should not be assumed from the emphasis given to hardenability, that hardenability is the only criterion for the selection of an alloy composition. Such properties as the hot-working characteristics, machinability, carburizing characteristics, amount of distortion during quenching and the retention of austenite may be considerations of importance in many applications. However, hardenability is one of the most important properties of an alloy steel and one that must be considered in almost all cases involving heat-treatment by quenching. Therefore, a method for determining the lowest-cost alloy combination should be of considerable value. Determination of Most Efficient Combinations For comparing the alloying elements on standards of cost and hardenability, it

Jan 1, 1947

By Arthur T. Allen

THE Kingsport formation, a part of the Knox dolomite of Ordovician age, is composed of 538 ft of dolomitc and limestone. Numerous bands, layers and nodules of chert, arenaceous and shale zones are present. The characteristics displayed by these features have been useful in mapping, prospecting and mining. Perhaps a better understanding of the origin of these zones will increase their usefulness. Introduction The presence of numerous bands, nodules, and irregular bodies of chert within the Kingsport formation in the Mascot locality has long been recognized. Oder and Miller1 mention the general characteristics, but do not deal with the chert occurrences in detail. When the occurrence of chert is studied in fresh exposures underground, a variety of characteristics is noted which has been useful in correlation and in detailing the sub-surface stratigraphy. Although the writer has no desire to enter into a controversy over the origin of chert, many observations have been made of its local characterigtics. A detailed stratigraphic section is included which shows the position of the individual horizons discussed in the following paragraphs. The term "chertification" has been adopted from Fowler and Lyden2 for use here. It refers to the replacement of lime- stone by introduced silicic acid. The writer uses it to refer to the occurrencc of introduced or original chert in limestone and dolomite. In this writing "syngenetic chert" refers to chert which has been deposited contemporaneously with the enclosing limestone or dolomite. Also, it is considered to include interstitial silica shown by chemical analysis and insoluble residues. The term "epigenetic" is applied to all chert which has been introduced after consolidation of the rocks in which it occurs, regardless of the nature of the depositing solutions. Syngenetic Chert It is the belief of the author that a large percentage of the chert found in the Kingsport formation is syngenetic. The widespread occurrence of similar nodules and bands of chert in the same horizon far from one another and far from areas of deformation or alteration of the enclosing rocks is difficult to explain by infiltration of the silica after compaction of the enclosing rocks. When chert of this type does occur near zones of movement it is likely to be involved in faulting and brecciation which indicates that it was deposited prior to deformation. Older Epigenetic Chert There are several occurrences of nodules in the Kingsport which seem to be epigenetic as pointed out in the following examples: A cherty zone occurs 26 ft above the o bed (Fig =). This is not always present but is found in the greater part of mine work-

Jan 1, 1949

By Arthur T. Allen

THE Kingsport formation, a part of the Knox dolomite of Ordovician age, is composed of 538 ft of dolomitc and limestone. Numerous bands, layers and nodules of chert, arenaceous and shale zones are present. The characteristics displayed by these features have been useful in mapping, prospecting and mining. Perhaps a better understanding of the origin of these zones will increase their usefulness. Introduction The presence of numerous bands, nodules, and irregular bodies of chert within the Kingsport formation in the Mascot locality has long been recognized. Oder and Miller1 mention the general characteristics, but do not deal with the chert occurrences in detail. When the occurrence of chert is studied in fresh exposures underground, a variety of characteristics is noted which has been useful in correlation and in detailing the sub-surface stratigraphy. Although the writer has no desire to enter into a controversy over the origin of chert, many observations have been made of its local characterigtics. A detailed stratigraphic section is included which shows the position of the individual horizons discussed in the following paragraphs. The term "chertification" has been adopted from Fowler and Lyden2 for use here. It refers to the replacement of lime- stone by introduced silicic acid. The writer uses it to refer to the occurrencc of introduced or original chert in limestone and dolomite. In this writing "syngenetic chert" refers to chert which has been deposited contemporaneously with the enclosing limestone or dolomite. Also, it is considered to include interstitial silica shown by chemical analysis and insoluble residues. The term "epigenetic" is applied to all chert which has been introduced after consolidation of the rocks in which it occurs, regardless of the nature of the depositing solutions. Syngenetic Chert It is the belief of the author that a large percentage of the chert found in the Kingsport formation is syngenetic. The widespread occurrence of similar nodules and bands of chert in the same horizon far from one another and far from areas of deformation or alteration of the enclosing rocks is difficult to explain by infiltration of the silica after compaction of the enclosing rocks. When chert of this type does occur near zones of movement it is likely to be involved in faulting and brecciation which indicates that it was deposited prior to deformation. Older Epigenetic Chert There are several occurrences of nodules in the Kingsport which seem to be epigenetic as pointed out in the following examples: A cherty zone occurs 26 ft above the o bed (Fig =). This is not always present but is found in the greater part of mine work-

Jan 1, 1949

By Thomas C. Wilder

The activities of both components and the partial and integral molar thermodynamic properties of mixing for the liquid Al-Ge system at 1200°K and for the gertnanium-rich Al-Ge liquidus have been determined from data for eighteen alloys of compositions in the range 0.0593 < 0.880 using the reuersible gal-vanic. cell in the temperature interval 9320 to 1258°K. The liqui-dus compositions above 93 2 °K loere also ve determined by observing the discontinuities in the C us T plots for the high-melting alloys. This system shows moderate negative deviation from ideality throughout, the values for y° being 0.212 and 0.189 for aluminum and germanium, respectively, at 1200°K. Pavtial molar Properties of aluminum on the germanium-rich solidus and at infinite dilution in Ge(s) oboue 932°K were estimated from the foregozng measurements and the equlibrium data of previous investzgators. RECENT compilations of data1" have shown an increasing demand for knowledge of the thermodynamic properties of mixing of metallic alloy systems. In the case of binary-liquid systems where one of the components is a semiconductor this information is useful because, primarily, properties of the second (dopant) component on the liquidus, solidus, and at infinite dilution may be determined more accurately than from calculations based on the phase diagram. In this investigation a reversible galvanic cell was used to determine the chemical potential of aluminum in the two-phase region, liquid + [Ge], on the germanium-rich side of the A1-Ge system in the temperature range 932" to 1193°K. In addition, similar measurements for homogeneous liquid A1-Ge alloys for the entire composition range were obtained for the temperature interval 932" to 1258°K. The cell used was: The experimental technique and the treatment of the data were essentially the same as described earlier394 and are elaborated upon only briefly here. Each cell consisted of a liquid aluminum anode and three A1-Ge alloy cathodes of different composition which were held in Morganite alumina crucibles. The alloys were made up from aluminum and germanium weighed to the nearest 0.1 mg to a total weight of 5 to 10 g. Aluminum was a gift of Aluminum Co. of America and had a purity of 99.995+ pct. Germanium of transistor grade was a gift of Bell Telephone Laboratories. The four electrodes were contained in a larger alumina crucible which also held the prepurified fused chloride electrolyte. Contact to the electrodes was made by tantalum wire leads sheathed in alumina. The tantalum leads were centered in the electrodes by suitable positioning of an alumina radiation shield which fitted on the top of the - alulnina crucible. Two chrome l-alumel thermocouples, sheathed in quartz wells, completed the internal cell arrangement. The entire assembly was enclosed in an alumina tube, fitted with a water-cooled copper head so the system could be evacuated and then flushed with purified argon. *

Jan 1, 1967

By Hans Lundberg

IN ORDER to comprehend the help and information that may be expected from electrical prospecting, it is necessary to have at least a general knowledge of the methods and principles involved in preparing and interpreting results obtained in the field. Electrical prospecting is rather complicated, both in theory and practice, and in order to make a brief description clear to the practical mining man it has been necessary to idealize and generalize the problems, at the risk of having such simplification criticized by the theoretical man. This simplification must not be misinterpreted as showing a lack of theoretical knowledge. FIG. 1.-FLOW OF CURRENT IN AND AROUND A CONDUCTING BODY. For its operation, electrical prospecting mainly, depends on the fact that most metallic ores conduct an electric current much more readily than barren rocks. If an electric current flows through a block of ground within which a body of chalcopyrite is enclosed in country rock of. schist, the current will find less resistance to its passage through the chalcopyrite than through the schist, even though the passage through the latter be much shorter. This is because the longer path through the chalcopyrite offers less resistance, owing to the superior electrical conductivity of the chalcopyrite (Fig. 1).

Jan 1, 1928

By Irving Cadoff, Kurt Komarek, Edward Miller

Barium can be purified by equilibration with titanium. The melting point of barium was found to be 726.2° i 0.5 °C. The room-temperature lattice parameters of BaTe and Bask are 7.004 * 0.002A and 6.600 * 0.002A. Melting points for BaTe and Base were found to be 1510° * 30°C and 1830° ± 50°C, respectively. HIGH-purity barium and its compounds are difficult to prepare because of the reactivity of barium with the atmosphere and the large heats of formation of the compounds. Purification of barium by vacuum distillation,&apos; and the preparation and properties of barium oxide2 and barium sulfide3 have been reported. However, little has been done on the homologous compounds barium selenide and telluride. PURIFICATION OF BARIUM Distilled barium obtained from King Laboratories was used as the starting material. The analysis supplied with the metal showed the presence of: 0.4 wt pct Sr, 0.001 pct Mg, 0.02 pct F, 0.003 pct Cu, 0.005 pct Na and less than 5 x 10-3 wt pct of any other metallic impurity. Analyses for oxygen and nitrogen were not available. Since there is evidence4 that any barium nitride present in the starting material may decompose on distillation producing nitrogen which can contaminate the distillate, further purification was performed. At elevated temperatures, any nitrogen and oxygen present in barium should be removed by reaction with titanium. Assuming that the solubility of oxygen in liquid barium is negligible near the melting point of barium, any oxygen present will be in the form of BaO. Removal of oxygen from molten barium is expressed by the equation: BaO(S)+ TixOy(S) = Ba(l)+ TixO(y+1)(s) where Ti,Oy and TixO(y+1) are solid solutions of oxygen in titanium. At 1000°C, the change in free energy for this reaction is negative for (y+1)/x +y+1) x (100) 17.5 at. pct O.5 Since reaction with commercially pure titanium (containing 0.07 wt pct oxygen) results in a free energy change for the reaction of -19 kcal per g-atom, slight solubility of oxygen in barium would not hinder the oxygen removal. Since comparable thermodynamic data are not available to permit calculation of the partition of nitrogen between liquid barium and titanium, a similar quantitative relationship cannot be obtained. However, on the basis of work by Kubaschewski and Dench,5 complete removal of nitrogen from liquid barium can be expected. Since the melting point of barium is depressed markedly by small additions of nitrogen,&apos; the change in melting point during reaction of barium with titanium was used to follow the purification reaction. MELTING POINT OF BARIUM A 50-g sample of barium was sealed by arc welding under argon into an all titanium crucible provided with a thermocouple well. The melting point of the sample was determined by thermal analysis, using a Pt/Pt-10 pct Rh thermocouple which was calibrated according to National Bureau of Standards specification6. The crucible was then heated for 48 hr at 950°C in vacuum and the melting point redetermined. This procedure was repeated until three successive thermal analyses agreed within ±0.5oC, the limits of error of the analysis. The melting point increased from an initial value of 720.0°C to a final value of 726.2°C. Analysis on samples quenched from 950°C gave a solubility value of 0.004 wt. pct Ti. Assuming that the titanium-barium phase diagram is similar to those of titanium-magnesium7 and titanium-calcium,8 the solubility of titanium in liquid barium decreases with decreasing temperature. Therefore, the solubility of titanium in liquid barium should be less than 0.004 wt. pctat the melting point (726oC), and the effect of dissolved titanium on the melting point would be negligible. Addition of up to 3 wt pct Sr does not significantly change the melting point of barium,7 so that the effect of the 0.4 wt pct Sr in the starting material will also be negligible. The value of 726.2" ± 0.5C obtained for the melting point of barium can be compared .with a determination carried out by Keller and coworkers in low-carbon steel crucibles,&apos; who obtained a value of 725± 1C, using barium purified by fractional distillation. The higher value obtained in the present investigation is indicative of the effectiveness of titanium in removing traces of nitrogen. PREPARATION OF BaTe AND Base The compounds were prepared by direct reaction

Jan 1, 1961

By N. H. Emmons

In the United States the value of gold- and silver-ores is everywhere reckoned in ounces troy of the metal per " short ton " (2000 lbs. avoird.) of the ore. In the case of silver, which fluctuates in market value, the New York quotation on a given day must be known, in order to determine the gross value of an ore at that date. In Mexico the assay is reported &apos;in kilogrammes of silver or grammes of gold per metric ton. As everyone is aware, this is practically a percentage system, 1 kg. of silver per metric toll (1000 kg.) being 0.1 per cent., and 1 gramme of gold per metric ton, 0.0001 per cent. The notation is simple and convenient for both assayer and miner.* The Mexican government purchases at an unvarying price for silver, payable in silver, and at a fixed price for gold, payable in gold if the seller insists, but preferably in silver at about the rate of exchange between U. S. gold coin and Mesican silver coin. The value of silver is $40.915 per kilogramme in Mexican silver dollars. That of gold is $675.416 per kilogramme in gold coin. The mints do not, as a rule, issue gold dollars, as the government keeps them to pay the interest on the national debt. Almost all bullion containing a considerable percentage of gold is shipped to foreign countries (principally the United States) to be refined. The Mexican mint receives for refining and coining no bullion which is not at least .950 fine in gold and silver, separately or

Jan 1, 1902

By M. J. Duggin

Evidence is produced below to show that the carbide "Mn,C," reported by Kw,and ersson&apos; is really a mixture of two carbides. One is an Fe-Mn carbide which is probably isomorphous with hexagonal Mn15C4, reported by Bouchand and Pruchart.&apos; The othev is a tetragonul Fe-Mn carbide with cell dzmensions close to those reported previously by the author3 for an Fe0.1Mno. carbide. IN a recent investigation several Fe-Mn carbide specimens, each weighing about 5 g, were prepared in a manner previously reported.3 Debye-Scherrer X-ray photographs were taken of at least two samples from different parts of each specimen using a 114.6-mm-diam camera. The exposure time was 2 hr using filtered chromium radiation, a tube voltage of 35 kv and a tube current of 10 ma. In the case of one specimen, which contained nominal weight percentages of iron, manganese, and carbon of 9.40, 84. 6,, and 6.0, respectively, duplicate chemical analyses indicated f1.2 and 5.5 wt pct C to be present in the two samples taken of the specimen: no graphitic carbon was detected. One powder-diffraction pattern of this specimen indicated the presence of the tetragons: carbide reported earlier,3 (a = 6.772A, c = 9.427A), plus cementite (O), plus an unknown structure. The second powder-

Jan 1, 1970

By C. E. Shoenfelt

Wildcat drilling in the Rocky Mountain region did not suffer as large a decline in 1942 as was anticipated. The drilling program laid out by the Government at the beginning of the year stressed wild-catting operations and called for reduction of drilling in proved fields. The increased wildcatting campaign did not yield a great many new discoveries, nor important extensions to old fields. Several interesting wildcat wells were drilled in Colorado in 1942 but no new fields were discovered. The Wilson Creek field was extended and about 400 acres added to its reserves. In Montana two new oil fields and two small gas fields were discovered. The developments in the marketing situation had improved, however, making the prospects especially bright for 1943, as will be shown presently in the section on Montana in this report. In New Mexico eight wells were completed, which constituted discoveries ol either oil or gas but none of these was of major proportions. In Wyoming one new oil field and one new gas field were discovered, and one old oil field and one old gas field were extended. Most important was the disco-very of prolific oil producers in deeper sands in three old oil fields, of which one at least, Elk Basin, probably is of major proportions. Government Action On Dec. 26, 1942, President Roosevelt signed the O&apos;Mahoney bill, calling for a flat 12.5 per cent royalty on lands in the public domain. It is expected that the enactment of this bill will encourage wildcatting in the public land states. Opportunity for a full discussion of the problems of reserves and production was afforded at the hearings conducted on the O&apos;Mahoney bill by the minerals subcommittee of the Senate Committee on Public Lands and the statements submitted at these hearings last fall placed the situation, its causes and the logical remedy, clearly on record. It was established at the hearings that for several years the volume of oil discovered per wildcat well drilled has steadily declined; new fields discovered have not been of major proportions; drilling costs have advanced rapidly; a sharp decline in exploratory drilling took place in 1942, while the proportion of dry holes increased; the inescapable conclusion is that to find new reserves the search for oil must be intensified and much more wildcat drilling &apos; must be done. To ensure an adequate drilling campaign, the Petroleum Industry War Council, the Interstate Compact Commission and other representative oil organizations have voiced by resolution their opinion that an upward revision of crude prices is necessary to provide an incentive to the prospector to undertake the hazards of wildcat drilling, since statistics prove that only ope in five or six wells drilled results in actual production. Former Price Administrator Henderson rejected the recommendations for price increases and declared himself unalterably opposed to a general price advance, On the ground that such advances would contribute to inflation. Now that Mr. Hender-

Jan 1, 1943

By C. E. Shoenfelt

Wildcat drilling in the Rocky Mountain region did not suffer as large a decline in 1942 as was anticipated. The drilling program laid out by the Government at the beginning of the year stressed wild-catting operations and called for reduction of drilling in proved fields. The increased wildcatting campaign did not yield a great many new discoveries, nor important extensions to old fields. Several interesting wildcat wells were drilled in Colorado in 1942 but no new fields were discovered. The Wilson Creek field was extended and about 400 acres added to its reserves. In Montana two new oil fields and two small gas fields were discovered. The developments in the marketing situation had improved, however, making the prospects especially bright for 1943, as will be shown presently in the section on Montana in this report. In New Mexico eight wells were completed, which constituted discoveries ol either oil or gas but none of these was of major proportions. In Wyoming one new oil field and one new gas field were discovered, and one old oil field and one old gas field were extended. Most important was the disco-very of prolific oil producers in deeper sands in three old oil fields, of which one at least, Elk Basin, probably is of major proportions. Government Action On Dec. 26, 1942, President Roosevelt signed the O&apos;Mahoney bill, calling for a flat 12.5 per cent royalty on lands in the public domain. It is expected that the enactment of this bill will encourage wildcatting in the public land states. Opportunity for a full discussion of the problems of reserves and production was afforded at the hearings conducted on the O&apos;Mahoney bill by the minerals subcommittee of the Senate Committee on Public Lands and the statements submitted at these hearings last fall placed the situation, its causes and the logical remedy, clearly on record. It was established at the hearings that for several years the volume of oil discovered per wildcat well drilled has steadily declined; new fields discovered have not been of major proportions; drilling costs have advanced rapidly; a sharp decline in exploratory drilling took place in 1942, while the proportion of dry holes increased; the inescapable conclusion is that to find new reserves the search for oil must be intensified and much more wildcat drilling &apos; must be done. To ensure an adequate drilling campaign, the Petroleum Industry War Council, the Interstate Compact Commission and other representative oil organizations have voiced by resolution their opinion that an upward revision of crude prices is necessary to provide an incentive to the prospector to undertake the hazards of wildcat drilling, since statistics prove that only ope in five or six wells drilled results in actual production. Former Price Administrator Henderson rejected the recommendations for price increases and declared himself unalterably opposed to a general price advance, On the ground that such advances would contribute to inflation. Now that Mr. Hender-

Jan 1, 1943

By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemisorption.

Jan 5, 1950