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By F. Weinberg

Lead single crystals have been deformed in tension over the temperature range of 4.2°K to the melting point. Changes in flow stress resulting from temperature cycling and strain rate cycling have been measured as a function of temperature for crystals of different orientations and purity. It was found that the flow stress ratio, after correcting for the temperature dependence of the shear modulus, decreased progressively with temperature above approximately 0.5Tm. The activation energy calculated from the high-temperature portion of the curve was found to be markedly higher than that of self-diffusion. For single glide crystals, the corrected flow stress showed an increase above 0.5 Tm before decreasitzg with temperature. This increase is attributed to static recovery occurrittg during temperature cycling. THE temperature dependence of the flow stress, based on temperature cycling and strain rate cycling, has been extensively investigated,' and on the basis of these results dislocation models of the work-hardening process have been proposed. In general, the flow stress is divided into two parts, ts, the short-range interaction term, which is only effective at low temperatures and which decreases with increasing temperature, and TG, the long-range stress term, which is independent of temperature after allowing for the temperature dependence of the shear modulus. The observations demonstrating that tG/µ is independent of temperature were generally carried out at low temperatures to minimize recovery effects. Several investigations have been reported on flow stress measurements at high temperatures2"5 which demonstrate that TG/µ does not remain constant at temperatures above 0.5Tm (where Tm is the melting temperature of the material in OK). Specifically, Hirsch and warrington3 carried out temperature cycling tests at two strain rates on single and polycrystalline aluminum up to 0.8 Tm and on polycrystalline copper. For aluminum they found that the flow stress ratio (the flow stress at temperature T2, divided by the flow stress at the reference temperature T1 in one temperature cycle) dropped progressively with increasing temperature above 0.5Tm. From the slopes of the high-temperature portions of the curves, they determined an activation energy for the deformation process of 1.6 ev (at best) which they considered was in agreement with the activation energy of self-diffusion, 1.35 ev. Calculations of the activation volume demonstrated that the deformation was not controlled by dislocation climb. They proposed a mechanism in which the rate-controlling process at high temperatures was due to the rate of move- ment of vacancies away from jogs, i.e., that of self-diffusion. Results of Lucke and Buhler4 on single crystals of aluminum confirmed this conclusion. They measured the critical resolved shear stress of aluminum over a wide range of temperature and strain rates. They found that the temperature dependence of the critical resolved shear stress was similar to that of the flow stress ratio, as determined by Hirsch and Warrington, and from their data calculated an activation energy for high-temperature deformation of 1.35 ev identical to that of self-diffusion. More recently Gallagher5 has carried out a detailed investigation of the temperature dependence of the flow stress ratio of copper, silver, and gold. In all cases, he found that the flow stress ratio, after adjusting for the shear modulus temperature change, drops at high temperatures. The activation energies he determined were found to be appreciably higher than the activation energy of self-diffusion of the material being considered. The flow stress ratio was found to be dependent on the orientation of the material, and, in addition, an anomalous increase in the flow stress ratio for copper, oriented for single glide, was observed above 0.5Tm. The purpose of the present investigation was to measure the critical resolved shear stress, the flow stress ratio, and the strain rate sensitivity of lead, primarily as a function of temperature. The results should indicate whether, following Lucke and Buhler, the critical resolved shear stress of lead has the same temperature dependence as the flow stress, and, following Hirsch and Warrington, whether the activation energy for high-temperature deformation in lead is the same as that of self-diffusion. Lead deforms as a normal fee material,6'7 is available in high-purity form, can readily be grown as single crystals, and, for this investigation, has the very considerable advantage of having a low melting point, 327°C. The observations of the critical resolved shear stress of lead have been published elsewhere.' EXPERIMENTAL PROCEDURE The experimental procedure was essentially the same as that used in the critical resolved shear stress measurements.' Single crystals of 99.999 pct (59) and 99.9999 pct (69) lead were deformed in tension with a table-model Instron in a silicone oil bath above room temperatures and in a cooled methyl alcohol or liquid-nitrogen bath below room temperatures. The test specimens were rectangular in section, 0.65 by 0.33 cm, and had a 5-cm gage length. The specimens were grown as single crystals with tapered ends, which fitted into matched tapered grips for testing. To obtain the flow stress between two temperatures, specimens were first deformed approximately 1.0 pct at the higher temperature. The test was then stopped, the load relaxed, the oil bath removed without disturbing the specimen, the grips and specimen cooled with a fan and then immersed in liquid nitro-

Jan 1, 1969

By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967

H. Van F. Furman, Denver, Colo. (communication to the Secretary): There are some statements in Dr. Carpenter's interesting paper which appear to require explanation, if not modification.

Jan 1, 1901

By P. K. Koh, H. A. Lewis, H. F. Graff

New data on the distribution of silicon between slag and carbon-saturated iron at 1600Oand 1700OC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1'700°C for slags containing up to 20 pct A12O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A12O3-SiO, slags over a range from zero pct Al2O3 to saturation with Al2O3, or CaO.2Al2O3. The upper limit of SiO2 is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/Al203 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al,O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al0 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al2O3 and of Al20,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO2 (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2. The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By Samuel S. Wyer

The following abbreviations hare been used in the text: Am. Mfr. and Iron World. American Manufacturer and Iron World, Pittsburg, Pa. Can. Min. Rez;. Canadian Mininy Review, Ottawa, Can. Cuss. Mag. Cassier's Mayazine, New York, N. Y. Col. Eng. Colliery Engineer, Scranton, Pa. Col. Guard. Colliery Guardian, London, Eog. Eng. and Min. Jour. Engineering and Mining Journal, New York, N. Y. Eng. News. Engineering News, New York, N. Y. Engr. Engineering, London, Eng. J. I. and 8. I. Journal of the Iron and Steel Institute, London, Eng. Jour. W. Soc. of Engrs. Journal Western Society of Engineers, Chicago, Ill. Lond. Eng. The Engineer, London, Eng. Mines and Min. Mines and Minerals, Scranton, Pa. North of Eng. I. M. E. North of England Institute of Mining Engineers, Newcastle-on-Tyne, England. Oester. Zeitsch f. Berg u. Hüt. Oesterreichische Zeitschrift für Berg-und Hittenwesen, Vienna, Austria. Pract. Engr. Practical Engineer, London, Eng. Proc. I. C! E. Proceedings Institution of Civil Engineers, London, Eng. Trans. A. I. M. E. Transactions American Institute of Mining Engineers, New York, N. Y. Trans. A. S. M. E. Transactions American Society Mechanical Engineers, New York, N. I!. Duns. Fed. I. M. E, Transuctions Federated Institute Mining Engineers, Newcastle-on-Tgne, England. Trans. L 31. E. Transactions Institute Mining Engineers, Newcastle-on-Tyne, England.

Jan 1, 1907

By R. E. Cuthbertson

AN early appreciation by the management that Climax ore presented a challenging problem of economic concentration was responsible for the establishment, in June 1926, of an ore-testing department at the experimental plant of the Colorado School of Mines at Golden, some ninety miles from Climax. An engineering office was later organized in the same community for the design of all ore-treatment units erected at Climax during the period of rapid growth. Work of the ore-testing and design staffs was effectively co-ordinated under a common head. The primary reason for having the ore-testing and plant design departments in Golden, was to place these activities under the able supervision of A. J. Weinig, consultant for the Climax Molybdenum Co., and director of the experimental plant. A secondary consideration was the availability of excellent facilities for research in ore dressing in a highly favorable environment. Concentration of molybdenite by flotation from an ore of simple mineral composition does not appear, superficially, to present a serious problem in ore dressing but experience belies this apparent simplicity. The molybdenite content of average Climax ore is low and it is finely

Jan 1, 1946

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication."' In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating arid distillation in the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char." Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking qualities by inspection of chemical analyses of coals.' A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: a+b+c+d Coking index = -------- 5 a equals 22/oxygen content on ash and moisture-free basis, b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/l.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above' 1.1 indicate good coking tendencies. Although generally usable, this formula 'is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct. Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1953

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication."' In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating arid distillation in the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char." Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking qualities by inspection of chemical analyses of coals.' A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: a+b+c+d Coking index = -------- 5 a equals 22/oxygen content on ash and moisture-free basis, b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/l.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above' 1.1 indicate good coking tendencies. Although generally usable, this formula 'is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct. Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1953

By L. T. Hiaains

EVEN before the surrender of Germany, a gradual reduction in output of many of the small mining iseswises in the different countries of South America had occurred. Part of this was due to restricted purchases of strategic mineral supplies, and part to economic conditions. Inflationary tendencies have keen increasing since the war started; out in the past three years they have become serious. The difficulty in obtaining supplies, and labor troubles, has also combined to reduce production in many circumstances. British Guiana The Cuyuni Goldfields, Ltd., operating he Aleck Hill mine, is increasing their yanked mill to 500 tons. This appears be one of the few important new developments in South America during recent years. Brazil The big Volta Redonda steel plant was sported as being ready to start operations. Argentina Political troubles have restricted activities during the past year, and fuel short. ges have been so acute that surplus corn as burned in some instances. Practically all the tungsten producers ther closed down entirely or reduced

Jan 1, 1946

By L. C. Morganroth

Magnesite both Massive and Crystalline MAGNESITES are. of two general classes-massive and crystalline. Massive magnesite occurs in serpentine, being formed by the breaking down or decay of serpentine-making minerals or rocks as olivine, etc. (All the magnesia contained by the olivine is not liberated, as a portion goes to make up the serpentine; the breaking up of this serpentine later forms more magnesite.) Serpentine in various stages of transformation is found in the vicinity of magnesite deposits. Massive magnesite is very widely distributed. It is found in Greece, . California, Africa, India, Australia, Mexico, South America, and deposits of varying sizes occur in several of the European countries. Those on the Island of Euboea, Greece, are probable the most important deposits of this character of magnesite. They have been worked for a number of years, the principal quarries or mines being 3 miles in the interior from the village of St. George. (St. George is on the west coast of the island, between the towns of Limni and Khalkis.) (Figs. 1 and 2). -The magnesite occurs in veins or lenses in serpentine. Some of these lenses are very large; one worked several years ago was approximately, 50 ft. in thickness, 75 to 100 ft. high and 300 ft. or more in length. The magnesite is pure white and makes a very prominent feature of the landscape. While massive magnesite is widely scattered over the world, many of the deposits are in veins too thin to work. The usual mode of occurrence is in the form of stock work, the deposits in Venezuela, Mexico, and many of those in California, being of this form. The veins vary in thickness from the thinness of paper up to several inches, running in all directions, occasionally leading to a mass or nucleus of some,size. The spaces between the veins are filled with a disintegrated serpentine in the form of sand. Several of the deposits in California would probably be workable, if they were more favorably situated with reference to transportation, but by far the majority of the deposits are too poor to work. At one deposit,

Jan 9, 1914

By C. M. White

CITIZENSHIP is a rather abstract subject on which a great deal could be said-a subject on which a great deal is said -and still one which too many of us seldom think about and seldom work at. Too many of us engineers and business men have but a vague idea of citizenship. We think that if we go to the polls on election day and obey the laws scrupulously, with the exception of an occasional traffic violation, we are pretty good citizens and are doing our duty by our city, state, and nation. But when you think it over, that's a very passive observance of the important right of counting oneself a citizen of a country. There is nothing very positive in that attitude. There is nothing that indicates that we have sufficient interest to really go out and do a job for the -welfare of our country, forgetting any personal advantages or inconveniences that might arise. In other words, this type of voting-on-election- day, law-abiding citizenship does not keep us awake a single minute; it does not take any particular thought or require the expenditure of any time or energy.

Jan 1, 1939

By Irwin Roman

NUMEROUS results and formulas have been published for analyzing seismic records, but most of them apply only to large-scale phenomena such as are encountered in studying earthquakes. In a few cases,1 formulas have been published for some of the simpler structures. In the present paper, an attempt will be made to analyze several types of struc-tures without using methods more advanced than those of a first course in calculus. In, tracing a disturbance through a medium, it is almost always possible to base the analysis on Fermat's Principle of Extreme Time, which states that waves of displacement travel between points in such a manner as to make the time of travel an extremum with respect to all neighboring paths. In the simpler cases, comprising most of those used in optics or geophysical prospecting, this time is a minimum and the principle is often referred to as the Principle of Least Time. Within a homogeneous medium, having a uniform speed of transmission of the disturbance in all directions and throughout the medium, the paths are straight and are refracted at the interfaces in accordance with the Snell law of refraction, which states that the ratio of the sine of the angle, made by the ray with the normal to the interface, to the speed of trans-mission is the same on both sides of the interface. Thus, in any medium composed of homogeneous sections, this same ratio has a constant value at all points. In particular, if all interfaces are horizontal, it is apparent that the angles of incidence are the angles made by the ray with the vertical direction. Furthermore, the incident ray, the refracted ray and the normal to the interface are all in the same plane at each refraction;

Jan 1, 1933

By E. H. Jr. Dix

THE consideration of alloying elements for aluminum has led to a series of investigations of the equilibrium relations between aluminum and those alloying elements. Therefore, the aluminum end of the aluminum-antimony diagram has been studied. The general form of the aluminum-antimony equilibrium diagram has been worked out by Campbell and Mathews1 and by Tammann.2 Campbell and Mathews described principally the beginning of solidification. They found the curve of beginning of solidification to rise gradually from the melting point of pure aluminum to a maximum at about 67 per cent. aluminum. After a slight lowering of the curve at a little greater antimony concentration the curve again rises to a maximum at 18.4 per cent. aluminum, which corresponds to the compound AlSb. The curve then drops to the melting point of pure antimony. Tammann explained the maximum occurring at about 67 per cent. aluminum as the result of the slow formation of the single compound AlSb. The space lattice of the compound AlSb, according to Owen and Preston,3 is face-centered cubic, the antimony atoms being intermeshed with an identical aluminum lattice. Very little, if any, work has been done on aluminum alloys containing small amounts of antimony.

Jan 1, 1930

By RUSSELL C. FLEMING

THE important advances that have been made of recent years in mining and milling methods and in mechanical equipment at mines need no re- telling, but there has been a remarkable growth in one type of equipment which has gone nearly unnoticed. That is the increasing use of storage-battery locomotives underground. Since the war the number of these locomotives and their field of use have increased tremendously; their growing acceptance represents an al- most complete reversal of opinion from an earlier period when they were generally looked upon as in- adequate for the strain of mine service. At the time when storage-battery powered units were first making their bid for recognition, the use of power in haulage had already passed through several phases; hand tramming, rope haulage, compressed air locomotives, even gasoline locomotives, had all been used, ending finally in the general adoption of the electric trolley locomotive for practically all power-haulage requirements. It was, and is, conceded that the trolley loco- motive met more adequately the varied and severe conditions of mine service than any previous type of haul- age unit. Subsequent developments have had to endure comparison and surpass in performance that type of haulage before changes would be considered.

Jan 1, 1930

By D. L. McElroy, J. L. Schroder

Although the earliest use of rubber-tired haulage was in Illinois in 1936, the first unit of this type of equipment used in West Virginia was shipped into the state in 1938. All units placed in West Virginia mines have been of the shuttle-car type. The Katherine Coal Mining Co., at Lumberport, W. Va., was the second company in the United States to install shuttle cars and the Gay Coal and Coke Co., at Mt. Gay, W. Va., was the first company in the country to install the thin-bed type of shuttle car. On Oct. 8, 1940, nine companies in the state were using 41 shuttle cars, of which 10 cars at three mines were of the thin-bed type. All shuttle cars of the low type were in the southern fields and all of the high type were in northern West Virginia. At that time several units were in the process of delivery. The data in this paper were collected in the field by Mr. Schroder in connection with graduate work on mechanical loading of coal in West Virginia by mobile loaders. In the course of his field work he visited five mines in the state that were using shuttle cars. All of these mines were in high-volatile coal beds of strong structure. The more pertinent data obtained at the mines visited are given in Table I. The maximum distance of shuttle-car haul is the distance between the transfer station and the farthermost place. Tonnage per loading unit per foot of bed thickness is to some degree a measure of relative efficiency, especially if the different operations are working the same bed or have somewhat similar conditions. The thin-bed operation is well up in the higher bracket of the afore-mentioned column, which is as

Jan 1, 1942

By J. L. Schroder, D. L. McElroy

Although the earliest use of rubber-tired haulage was in Illinois in 1936, the first unit of this type of equipment used in West Virginia was shipped into the state in 1938. All units placed in West Virginia mines have been of the shuttle-car type. The Katherine Coal Mining Co., at Lumberport, W. Va., was the second company in the United States to install shuttle cars and the Gay Coal and Coke Co., at Mt. Gay, W. Va., was the first company in the country to install the thin-bed type of shuttle car. On Oct. 8, 1940, nine companies in the state were using 41 shuttle cars, of which 10 cars at three mines were of the thin-bed type. All shuttle cars of the low type were in the southern fields and all of the high type were in northern West Virginia. At that time several units were in the process of delivery. The data in this paper were collected in the field by Mr. Schroder in connection with graduate work on mechanical loading of coal in West Virginia by mobile loaders. In the course of his field work he visited five mines in the state that were using shuttle cars. All of these mines were in high-volatile coal beds of strong structure. The more pertinent data obtained at the mines visited are given in Table I. The maximum distance of shuttle-car haul is the distance between the transfer station and the farthermost place. Tonnage per loading unit per foot of bed thickness is to some degree a measure of relative efficiency, especially if the different operations are working the same bed or have somewhat similar conditions. The thin-bed operation is well up in the higher bracket of the afore-mentioned column, which is as

Jan 1, 1942

By John L. Schroder, D. L. McElroy

ALTHOUGH the earliest use of rubber-tired haulage was in Illinois in 1936, the first unit of this type of equipment used in West Virginia was shipped into the state in 1938. All units placed in West Virginia mines have been of the shuttle-car type. The Katherine Coal Mining Co., at Lumberport, W. Va., was the second company in the United States to install shuttle cars and the Gay Coal and' Coke Co., at [ ] Mt. Gay, W. Va., was the first company in the country to install the thin-bed type of shuttle car. On Oct. 8, 1940, nine companies in the state were using 41 shuttle cars, of which 10 cars at three mines were of the thin-bed type. All shuttle cars of the low type were in the southern fields and all of the high type were in northern West Virginia. At that time several units were in the process of delivery. The data in this paper were collected in the field by Mr. Schroder in connection with graduate work on mechanical loading of coal in West Virginia by mobile loaders. In the course of his field work he visited five mines in the state that were using shuttle cars. All of these mines were in high-volatile coal beds of strong structure. [ ] The more pertinent data obtained at the mines visited are given in Table I. The maximum distance of shuttle-car haul is the distance between the transfer station and the farthermost place. Tonnage per loading unit per foot of bed thickness is to some degree a measure of relative efficiency, especially if the different operations are working the same bed or have somewhat similar conditions. The thin-bed operation is well up in the higher bracket of the afore-mentioned column, which is as

Jan 1, 1941

By C. Land, R. Hultgren

Heat contents of four Cr-Ni alloys were determined in a diphenyl ethev calorimeter. Aside from ferromagnetic effects, Kopp's law of additivity of heat capacities is approximately fol-lowed, in disagreement with earlier results of A. W. Foster. In 1934 Foster1 reported heat-capacity measurements of dilute solutions of chromium in nickel, primarily as a study of the effect of alloying on the ferromagnetic Curie temperature. He found that, apart from the Curie temperature effect, the general level of heat capacities was reduced 10 pct by the addition of 1 pct Cr; 20 pct by the addition of 2 pct Cr. His measurements of pure nickel essentially agreed with accepted values. These results indicate that small amounts of dissolved chromium cause an increase in the Debye temperature of nickel, presupposing a change of frequency of interatomic bonding vibrations which is much larger than should be expected. If Foster's results were verified, therefore, they would have important implications for bonding theory. The only other heat-capacity measurements in this system seem to be those of Taylor and Hinton,' who studied anomalies which they attributed to super-lattice formation at 25 at. pct Cr. At temperatures above the anomaly, Taylor and Hinton found heat capacities at this composition were quite normal, approximately obeying Kopp's law of additivity. EXPERIMENTAL WORK In order to verify or disprove the remarkable results of Foster, the heat contents of four dilute solid solutions of chromiunn in nickel were measured in a diphenyl ether calorimeter. This instrument, described elsewhere,, operates on the principle of the Bunsen ice calorimeter, but uses diphenyl ether as the working substance. Diphenyl ether melts at the convenient temperature of 26.S°C and supplies a more sensitive measure of heat than ice. The hot sample, in an atmosphere of argon, is dropped from a furnace at a measured temperature into a chamber which is surrounded by a mixture of solid and liquid diphenyl ether. The heat from the hot specimen melts some of the solid without chang- ing the temperature of the calorimeter. The amount of solid melted, and therefore the number of calories released by the specimen, is measured from the increase of volume of the mixture, which pushes mercury down a graduated capillary tube. The apparatus has been standardized against the known heat content of pure platinum. Heat loss during the dropping of the specimen was estimated by comparing the heat content of an empty platinum capsule with a solid platinum ball of the same radius and degree of polish of the surface. Repeated tests demonstrate the precision of measurement to be closer than *0.3 pct. Smoothed experimental results are listed in Table I. The tabulated values for pure nickel are taken from kelley, several measurements were made which agreed closely with this tabulation. For chromium, however, no similar agreement was found. The values tabulated were taken from a thorough study of chromium with the diphenyl ether calorimeter which will be published elsewhere.= Suitable plots of the data showed the expected ferromagnetic anomalies in the low-chromium alloys, while the 11 pct alloy shows no ferromagnetic anomaly, but a different, small anomaly below 900°K. This is perhaps the same anomaly found in CrNi, which was once attributed to superlattice formation,' but is probably due to some other cause, such as antifer-

Jan 1, 1960

By Molly Gleiser

The standard free energies of formation of some gaseous metal oxides together with those of their condensed oxides have been plotted against temperature. The heats of formation of the gaseozcs oxides are tabulated. An explanation is given of the use of the data to predict the importance of the gaseous metal oxides at high tenzperatures. RECENT mass spectrometric work1 has resulted in the detection of several hitherto unknown gaseous oxides and the measurement of their free energies of formation. Of especial interest is the fact that several of the refractories in common use either as crucibles or furnace tubes, and metals used in Knudsen cells and in furnace windings, have been found to have one or more stable gaseous oxides. In view of the present emphasis on high-temperature techniques, the development of vacuum metallurgy.z heating by electron bombardment and plasma jets, and the resultant shift to ever higher temperatures, it is no longer possible to plan experiments without taking into consideration the significance of the presence of these gases in the system, the reactions they undergo. and their contribution to the vapor pressure. A good example of what went wrong in earlier work, when the existence of these gaseous molecules was not yet known, is presented by the work of Hoch, Nakata, and Johnston. Hoch and coworkers attempted to measure the vapor pressure of solid ZrO2 by letting the vapor in equilibrium with zir-conia effuse from a tantalum Knudsen cell. The free energies of formation of solid zirconia and tantala are such that a short calculation showed that the reaction

Jan 1, 1962