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By A. J. Shaler, H. Udin, J. Wulff

In the study of the sintering of meta powders, we have come to the conclusion in this laboratory that further progress requires a more basic understanding of the operating mechanisms. This is emphasized in detail by Shaler. He has shown that a knowledge of the exact value of the surface tension is imperative for a solution of the kinetics of sintering. This force plays a principal role in causing the density of compacts to increase.2 Furthermore, a knowledge of the surface tension of solids is also applicable to other aspects of physical metallurgy. C. S. Smith3 points out the relation between surface and interfacial tension and their function in determining the microstructure and resulting properties of polycrystal-line and polyphase alloys. This paper describes one group of results of an experimental program designed for the study of the surface tension in solid metals. As a by-product of this work, considerable information has been obtained on the rate and nature of the flow of a metal at temperatures approaching the melting point and under extremely low stresses, a field of mechanical behavior heretofore scarcely touched by metallurgists. The importance of this additional information to students of powder metallurgy need not be stressed. Theoretical Considerations Interfacial tension arises from the condition that an excess of energy exists at the interface between two phases. Gibbs proves that this energy is a partial function of the interfacial area; thus: ?F/?s = ? where ?F/?s is the rate of change of free energy of the system with changing surface area, at constant temperature, pressure and composition, and ? is the interfacial tension, or interfacial free energy per unit area. If one of the phases is the pure liquid or solid, and the other the vapor of the substance, ? may properly be termed "surface tension," and is a characteristic of the solid or liquid. The attempt of a body to lower its free energy by decreasing its surface gives rise to a force in the surface which is numerically equal in terms of unit length to the free energy per unit area of the surface. Thus ? may be expressed either in erg-cm-² or in dyne-cm-1. Similarly, surface tension may be determined either by a thermo-dynamic measurement of the surface energy or by a mechanical measurement of the surface force. We have chosen the latter approach. Tammann and Boehme4 determined the surface tension of gold by measuring the amount of shrinkage or extension of thin weighted foil at various temperatures and interpolating to zero strain. The method is of questionable accuracy because of the tendency of foil to form minute tears when heated under tension. Their assumption of F = 2W?, where W is the width of the foil, is unsound, as the foil can decrease its surface area by transverse as well as by longitudinal shrinkage. Although their experimentation was meticulous, the paper does not include details of the sample configuration required for recalculating ? on a correct basis, even if such a calculation were possible. In the experimental procedure chosen here, a series of small weights of increasing magnitude are suspended from a series of line copper wires of uniform cross-section. This array is brought to a temperature at which creep is appreciable under extremely small stress. If the weight overbalances the contracting force of surface tension, the wire stretches; otherwise, it shrinks. The magnitude of the strain is determined by the amount of unbalance, so a plot of strain vs. load should cross the zero strain axis at w = F?. If balance is visualized as a thermodynamic equilibrium, the critical load is readily calculated. At constant temperature, an infinitesimal change in surface energy should be equal to the work done on or by the weight: ds = wdl [A] For a cylinder, s = 2pr2 + 2prl [2] If the volume remains constant, r = vV/pl [31 s = 2vpl+2V/l [4] ds = vpv/l - 2V/l²) dl [5] Substituting [5] into [I] gives for the equilibrium load, w = ?(z/rV- 2V/12) [6] and, again expressing V in terms of r and l, w = pr?(1 - 2r/l [7] Here the end-effect term, 2r/l, is neglected for thin wires in subsequent work. Eq 7 can be confirmed by means of a stress analysis. If the x-axis is chosen along the wire, then the stress is 2pr? - w pr² pr2 [8] A cylinder of diameter dis equivalent to a sphere of radius r, insofar as radial surface tension effects are concerned.³ Thus xv = 2?/d = ?/r = sz [9] For the case of zero strain in the x direction, the strain will also be zero in the y and z directions. Since the wire is under hydrostatic stress, Eq 8 and 9 are

Jan 1, 1950

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.1-5 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 and 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.6 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.7 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: Coking index =[ a+b+c+d 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/1.3 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.8,9 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, 1952

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. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.' udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4'5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A'-B' develops at the other intersection. The angles A + B and A' + B' are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

By J. L. Kenty, J. P. Hirth

The concept of a critical super saturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, is discussed with reference to vapor-solid nucleation. The necessary and sufficient conditions deduced for observations of this type of behavior are: 1) the nucleation rate must exhibit a sharp dependence on super saturation, 2) the growth rate must be sufficiently large that nuclei become observable in the time period of the experiment, and 3) the number of highly preferred nucleation sites must be small. Experiments reveal that the nucleation of silver on sodium chloride is visually detectable at all experimentally accessible super saturations and does not exhibit critical nucleation behavior. Failure to observe a critical super saturation is attributed to the insensitivity of nucleation rate to supersaturation as a consequence of the particular values of the contact angle and the surface free energy for this system. THE concept of a critical supersaturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, arises naturally in homogeneous nucleation theory. Experimentally this type of behavior has been found by Volmer1 and others for water and other low surface tension liquids, as reviewed by several authors.2'3 The same type of behavior has been predicted and observed for heterogeneous nucleation of solids by Yang et al.4 and others,596 as also recently reviewed.2,7,8 In the work reported here on the heterogeneous nucleation of silver on NaC1, however, no critical super-saturation was found. Similar observations have been made recently for other systems.9-11 These results led to a reexamination of nucleation theory which revealed that there are conditions for which critical behavior is not predicted, either for homogeneous or heterogeneous nucleation. Although heterogeneous nucleation is of primary importance in this paper, some insight into critical behavior for such a case can be gained by considering homogeneous nucleation. Accordingly both types of nucleation theory are reviewed briefly. The requisite conditions for critical supersaturation behavior are then considered. The experimental results for the nucleation of silver on NaCl are presented and interpreted in terms of the theoretical presentation. REVIEW OF NUCLEATION THEORY There are essentially two approaches to nucleation theory, the so-called classical theory involving the concepts of bulk thermodynamics, and the statistical mechanical theory in which nuclei are regarded as macromolecules. The classical theory is based on the work of Volmer and Weber12,13 and Becker and. Doring14 and has been extended by Pound et al.15 The crucial assumption in the classical theory is that the small clusters or nuclei can be characterized by the same thermodynamic properties as those of the stable bulk phase. Thus, the nuclei are assumed to have a surface free energy, y, and a volume free energy of formation (relative to the vapor phase), ,, identical to that of the bulk. For deposition under low super-saturation conditions, the nuclei are large and this assumption is satisfactory. However, in many cases of interest, the nuclei contain only a few atoms and this assumption is highly questionable. The statistical mechanical models originated, for the specific case of a dimer as the critical nucleus, with the work of Frenkel16 and were extended later to larger sizes by Walton,17,18 Hirth19 and, more recently, Ht Zinsmeister. These models describe the nucleus in terms of a partition function, the estimation of which is tractable for clusters of 2 to 10 atoms, but extremely difficult for clusters larger than 10 atoms. Although the classical and statistical mechanical models are expected to apply for the limiting cases of large and small nuclei, both are uncertain for intermediate sizes. In this paper we shall treat only the classical model, recognizing that it is exact only for large nucleus sizes and regarding it as a phenom-enological description for small nucleus sizes. When analyses of experimental data using bulk properties show the nucleus size to be small, the resulting parameters should be regarded as largely empirical parameters describing the relative nucleation potency of the system. Considerable justification for the continued use of classical theory is provided by its general success in predicting nucleation behavior as a function of supersaturation and temperature. We emphasize that the qualitative features of the statistical mechanical models, particularly the critical super-saturation behavior that is central to the present work, are the same as those of the classical model. Of course, potential energy terms and surface partition functions replace the volume and surface energy terms of the latter model. The most recent versions of classical nucleation theory have been extensively reviewed.2,3,7 so that only the results are presented here. For homogeneous nucleation of a condensed phase from the vapor phase, the volume free energy change is ?Gv=vrT = =^ln£ [1] where v is the molecular volume of the condensing species. The supersaturation ratio,

Jan 1, 1970

By J. Kennedy

Rare Earths: Understanding The United States complete failure of status and relevance in Rare Earth Oxides, Elements and Alloys. Although rare earth oxides are strategic and critical in their own right, elements and alloys are even more important for the development of "Green Technologies" and advanced weapons systems. America does not have an active domestic source of rare earth oxides. America does not have any Heavy Rare Earth Elemental or Alloy capabilities. The magnitude of this failure continues to become more apparent as the manufacture of REO based electronics and magnetic components moves eastward towards China. China has succeeded in outmaneuvering The United States and the world in its quest to control the Rare Earth Oxides, Elements and Alloys, and the many industries dependent upon REO. What can be done?

Jan 1, 2010

By Jeffrey R. Taylor

The distribution of low concentrations of Cr, Mn, Rh, Co, Ni, Ag and Fe between copper matte and bullion phases has been measured at 1200oC. These results. together with values for nine other elements, have been used to develop a simple model to describe the distributions in terms of known thermodynamic properties?. The Temkin model for ionic melts was assumed to apply to the sulphide species in the Cu-S matte? phase and it is shown that the choice of sulphide species is particularly important for successful representation of the experimental .results?. In general, the lowest sulphlde (minimum sulphur :. metal ratio)? formed by the. metal is most suitable, although Ni, Co, Rh and Pd appear to associate with more sulphur in the melt than suggested by the? composition of their lowest sulphide. A correlation between the composition of the metal sulphide species formed in the ternary system and the? position of the minimum in the free energy of mixing curve in the metal-sulphur binary -system is? proposed.

Jan 1, 1983

By W. S. Landers

This bulletin is a detailed study of low-temperature, entrained-bed carbonization of a Texas lignite. The lignite studied was from the Sandow strip mine and is representative of the Rockdale formation of the Wilcox formational group. Carbonization was conducted in a continuous entrained-bed reactor at several temperatures in the 8801 to 1,52°C F range, and at air-coal ratios it the 0 to 10.30 scf/lb range (moisture- and ash-free basis). Carbonization rates ranged from 97.1 to 410.0 lb/hr (as-received basis), At the higher air-to-coal ratios employed, all or most of the carbonization heat was provided by internal combustion with air in the reactor. At the lower air-to-coal ratios, parts of the heat for carbonization was supplied externally. It was demonstrated that the entrained-bed carbonization of lignite is a complex reaction and that several variables, of which carbonization temperature, air-to-lignite ratio, and the average size of lignite are important, act together to influence both the carbonization yields and the properties of the resultant products, Process variables established by pant tests were used to design the industrial scale carbonizer operated at Rockdale, Texas, by the Texas Power & Light Company as agents for the Aluminum Company of America. Properties of the carbonization product obtained from the industrial scale reactor were essentially the same as those obtained from the pilot plant reactor operated under the same conditions.

Jan 1, 1968

By Jakub Szary

Excavation and shoring adjacent to the above-grade Gilmore train station and elevated guideway was undertaken in 2019. A perimeter secant pile cut-off wall was constructed to a depth 37 m (121 ft) below ground surface consisting of 1.0 m (3.3 ft) diameter drilled piles spaced 750 mm (2.5 ft) on-center, tied back with soil anchors, and reinforced with W610 steel sections every 4th pile. A bracing/jacking system was also constructed to support 3 free-standing guideway caissons within the excavation. An automated instrumentation program was installed to monitor movements of shoring walls and train infrastructure in real time and consisted of a robotic total station, inclinometers, tiltmeters, strain gauges, extensometers, and anchor load cells. Baseline monitoring was able to establish diurnal and seasonal movements within the structure, strongly correlated with temperature. The system actively monitored various shoring elements and train infrastructure in real time and alerted the project team when values exceeded predetermined threshold values. Remote reconfiguration of the automated system allowed for more frequent monitoring during jacking of Pier 29 in March 2022. Monitoring data was in agreeance with on-site manual surveying results and jacking dial gauges, and proved to be a reliable monitoring system for construction applications.

Sep 1, 2022

By Amalia Giannakou

When designing structures in seismically active areas, foundations of critical structures are typically located away from known faults. Indeed many seismic codes prohibit construction in the immediate vicinity of seismically active faults establishing minimum setbacks from the faults. However, for long structures such as bridges, tunnels and pipelines, a fault maybe unavoidable, and fault rupture risk impossible to preclude. This paper presents a case study of a bridge foundation design that incorporates the consequences of fault deformations passing through the foundation. A series of site surveys were conducted to characterize the fault environment, and fault displacement hazard analyses were conducted to develop design displacement demands. Subsequently, numerical analyses were performed to evaluate the fault rupture-induced demands on a pier foundation in terms of displacements and rotations. Initially, analyses were performed that model the free field fault rupture propagation to the ground surface of the fault to ensure that the basic site characteristics are captured. Subsequently, the foundation elements were introduced in the model and the fault rupture is simulated again. The interaction and influence of the foundation on the fault rupture propagation is calculated, and the consequent demands and distortions of the foundation block provide a basis for structural engineers to design the bridge.

By R. E. Sundell, S. M. Correa

"A mathematical model is developed for the fluid flow in tungsten-inert gas weld pools. The fluid is taken to be incompressible, viscous, electrically conducting, and confined within a pool of specified shape. The flow is driven by surface-tension gradient (thermocapillary), electromagnetic, and buoyancy forces generally in this order of importance. Analysis indicates that the electromagnetic field may be calculated a priori and so decoupled from the nonlinear fluid mechanics and heat-transfer problem. The resulting set of equations is solved numerically by a line relaxation process. Computational errors caused by truncation in finite-difference schemes and by inadequate grid distributions are considered. The model is used to study several cases of differing heat and current input to the pool with and without surfactant-induced thermocapillary forces. The principal conclusions are that the thermocapillary flow, when present, is dominant with surface velocities on the order of 1 m/s. The heat transfer, as deduced from isotherms within the pool, is crucially dependent on the flow. Also, flow velocities and weld-pool surface temperatures were measuredand agree well with the model.2. IntroductionThe requirements of improved control and of automation in the TIG (tungsten-inert gas) welding process have led to the development of mathematical models for the heat transfer to the workpiece. It is now widely recognized that the fluid flow in weld pools sufficiently distorts the conduction heat transfer pattern to warrant inclusion in a process model. The experiments of Woods and Milner (1), among others, demonstrated that TIG weld pools could be driven by the electromagnetic J x B body forces present, J being the current distribution and B the induced magnetic field. Atthey (2) calculated that in typical pools the buoyancy force was about an order of magnitude less important - despite the large temperature gradients present - and neglected it in a computational study of the magnetohydrodynamic (MHD) flow. This work also reviewed many earlier studies of MHD flow caused by a source of current at a fluid surface, including analytical studies by Shercliffe (3), Sozou (4), and Sozou and Pickering (5), and a numerical study by Andrews and Craine (6). These works establish the importance of the electromagnetic force in the weld-pool flow."

Jan 1, 1986

By Tanai Marin

Modelling of pyrometallurgical processes can become extremely challenging when the process involves complex chemical reactions, phase change, multiphase flows, heat and mass transfer and fluid flow. Traditionally modelling involving complex thermodynamic equilibrium and thermochemistry are treated separately from problems in which transport phenomena are dominant, such as CFD and heat transfer studies. The separation is also necessary due to the lack of modelling tools that can effectively couple both solution thermodynamic and transport phenomena or even multiphysics problems. However, there are, quite often, problems in high temperature process metallurgy in which it is not possible to simplify this two modelling approaches. Typical cases of this are for example, the modelling of slag freezing on furnace walls (electric or flash furnaces) to create a protective layer in front of the refractories hot wall, the formation of build up from the matte or metal phases at the hearth of the furnace, calcine smelting from charging piles into slag phase, etc. The problem is even more challenging in nonferrous pyrometallurgy as most, if not all, of the condense phases are highly non ideal solutions involving several components and exhibiting complex crystallization paths and miscibility gaps, such as the Fe-Ni-Cu-S matte, FeO-Fe2O3-SiO2, FeO-MgO-SiO2 slags, etc. In this paper, an approach to model coupled problems involving multiphysics and solution thermodynamic is presented. The approach consists in developing in-house a library containing the Gibbs energy minimization routines and using the local equilibrium concept for process modelling from a multiphysics commercial software (COMSOL). Simple test cases, such as building a non-ideal binary phase diagram on a CFD package is presented, the limitations and of other classic approaches such as equilibrium or Scheil cooling are discussed and compared to this model.

Jan 1, 2015

By W. R. McClelland

GOLD-BEARING ores, representing many types, are found widely distributed through the Province of British Columbia. They range from those which by their nature may be considered as complex, to those whose mineral characteristics are simple. Those in which the gold is associated with metallic sulphides provide particular milling and metallurgical problems, the solution of which involves not only detailed laboratory investigation but also a careful consideration of economic factors. The location of an ore-body may have a deciding influence on the adoption of a method for the metallurgical treatment. Whether the ore should be treated with the object of recovering the gold as bullion or as a shipping concentrate is often dependent on such topographical considerations as the position of the mine at or near tidewater or within a reasonable overland distance of a smelter. British Columbia is fortunate in having the Trail smelter situated in the southern part of the Province, and the smelter at Tacoma, Washington, is accessible for coastwise traffic. Both of these provide a ready market for most types of gold-bearing concentrate. In order that the results obtained by laboratory tests may give a fair indication of what should follow in mill operation, it is essential that the test sample should represent as closely as possible in mineralogical character and in grade the ore that eventually will constitute the feed to the mill. In the early stages of mine development this consideration is sometimes overlooked and samples of a much higher grade than would be representative of run-of-mine ore are submitted. Flotation tests on such a sample of ore high in sulphides may show a low ratio of concentration, bu.t if the actual run-of-mine ore is lower in sulphides the mill operation will reveal a much higher ratio. The recommendations for treatment based on the results of laboratory tests may have been against concentration, when in actual operation this would be the most suitable method of treatment. Recommendations based on laboratory tests are necessarily from the results of work carried out on the sample submitted, modified only by such other economic or topographical information as may be known to the investigator. This paper deals with a few of the gold ores found in the six mining districts of British Columbia and is based on investigations made in the Ore Dressing and Metallurgical Laboratories of the Mines Branch, Department of Mines, Ottawa.

Jan 1, 1937

By Oliver Bowles

Under a cooperative agreement between the Bureau of Mines, the United States Geological Survey, and the United States Bureau of Standards, a study of the stone-quarrying industries of the country was begun in 1914. The results of investigations made have been published from time to time.1 During the World War the Bureau of Mines centered its attention on problems relating to national defense, and detailed studies of stone-quarry problems were not undertaken except for an investigation of labor saving at limestone quarries, reported in Technical Paper 203, which related to a question of military importance. Since the return of peace, the high cost of materials and labor has made more imperative than in prewar times the conduct of investigations for aiding the quarrying industries in every way possible to adopt more economical methods and to utilize the most efficient labor-saving equipment. The publications already issued have had a wide demand, and in the interest of the quarry industries the bureau proposes to issue additions to the series as rapidly as funds are available. In an endeavor to promote economy and the reduction of waste in the slate industry, a study of slate quarrying was begun in 1920 and covered a period of about two years. Sixty-five active quarries were visited, and a detailed study made of all problems bearing on their successful operation. Field study was supplemented by a study of all information available in books or published articles on slate quarrying.

Jan 1, 1922

By B. W. Naugle

A small-scale laboratory coke oven similar to those described by Swiniarski, Cryan, and Altieri and Fuchs, Sandhoff, Taylor, and Gauger was built by the Bureau of Mines in 1943. Tests made since that time have indicated that such a small oven is of questionable value in predicting the coking pressures to be expected in commercial coke ovens. This summary of the work done has been prepared at the suggestion of the Advisory Committee to the Bureau of Mines-American Gas Association Survey of Carbonizing Prop¬erties of American Coals.

Jan 1, 1948

By M. D. Amirova

Cyanide-free technology of complex copper-lead ores flotation may be improved through enlarged range of pH values, enhanced copper recovery into copper concentrates due to additional recovery of secondary copper sulfides, as well as through enhanced efficiency of lead sulfides depression in process of new flotation modifiers-based selective separation. Study of the effects of flotation modifier (of metal nature) on minerals surface conditions proved that the xanthate is practically not adsorbed on the galenite surfaces due to minerals hydrophilization. Joint effects of sodium sulfite and modifier enhance process conditions for intensive galenite depression and at the same time for effective chalcopyrite and chalcosine flotation within a large pH values range (from pH=8 to pH=10). Identified mechanisms carry inference that proposed chemical reagent treating method is very promising for selective copper-lead concentrates separation. Potential use of carbon-containing materials as zinc flotation modifier to enhancing zinc recovery in processes of lead-zinc ores treatment has been studied. In our flotation tests we used Shalkiya (South Kazakhstan) lead-zinc ores containing such impurities as carbon shales, which presence impedes the process of saleable concentrates production and gives rise to excessive consumption of flotation agents due to the xanthate adsorption on the carbon. Lead and zinc concentrates were produced by process stages as follows: ores milled to 95% Cl. -0.074 +0; lead and zinc roughing flotation and further recleaner and testing operations. Test flotation in open process cycle resulted in enhancing zinc recovery into zinc concentrates by 21.1% and increasing zinc content in zinc concentrates by 3.96% that evidences promising potentialities for use of carbon-containing products as additional zinc flotation modifier. Works were carried out under National Program 2003~2005 of fundamental researches ?Physical and Chemical Mechanisms of Interactions in Multicomponent Solid and Liquid Systems Specific for Integrated Processing of Complex Metal-Containing Minerals and Technogenic Raw Materials? and contractual Agreement 2005 Optimization of Production and Technology of Shalkiya Lead-Zinc Ores Processing at Kentau Dressing Works.

Jan 1, 2014

By Henry Kreisinger, F. K. Ovrrz, C. E. Augustine

The Bureau of Mines is conducting investigations to determine how fuels belonging to or for the use of the United States Govern- ment can be utilized with greater efficiency. As a result of these investigations a number of reports have been published, each report treating of one phase of fuel utilization. A list of these publications is given at the end of this bulletin. The efficient utilization of coal depends on the correct design of furnaces and on their proper operation. To attain both of these conditions a knowledge of the fundamental principles of combus- tion is necessary. Therefore, the study of the combustion of coal in industrial furnaces has been made a part of the bureau's fuel in- vestigations. The desirability of investigating the fundamental principles of combustion was suggested by the study of a large number of steam- ing tests made by the fuel-testing division on coals from all of the more important fields in the United States. The results of these tests have been published in Bulletin 325 of the United States Geological Survey and in Bulletin 23 of the Bureau of Mines. As a result of that study a plan to investigate the combustion of coal in a special apparatus in which all conditions could be controlled was presented to the National Advisory Board for Fuels and Struc- tural Materials at its meeting of April 10 and 11, 1906. The plan received the approval of the board, and since the establishment of the experiment station of the Bureau of Mines at Pittsburgh the investigation of the combustion of coal has been carried on intermit- tently. The history of these investigations is given in Technical Paper 63.

Jan 1, 1917

By Gerald A. Muson, Fremont F. Clarke

"INTRODUCTION The use of scrap mica as an industrial raw material has grown rapidly during the past two decades. Demands by various industries for ground mica for use in the roofing, paint, rubber, plastics, and wallpaper trades as well as for less extensive uses in insulation, oil-well drilling, welding, pipeline enamel, decorative material, and for other purposes exceed present (1947) supplies.A small proportion of the raw material used comes from the Black Hills of South Dakota, where casual recovery has been practiced in the exploitation of pegnatite deposits for more valuable minerals. The annual production of scrap mica in the Black Hills for the years 1939 to 1946 is shown in figure 19. 4/Although small, this production of scrap mica materially augments the incomes of numerous operators.Volume production of mica would offer attractive opportunities for obtaining steady and more economical supplies of the rare minerals as byproducts. Appreciable supplies of beryl, lithia minerals, sheet mica, tantalite-columbite, and cassiterite could accrue. Furthermore, a stable scrap-mica production would complement the production of quality feldspar, for which the Black Hills pegmatites are noted, and would help balance the economy of pegmatite mineral production.Mechanical methods of separation are requisite to production of enough scrap mica to be generally profitable. Various phases of the characteristics end treatment of mica have been investigated by the Bureau of Mines. A bibliography of these reports is appended.In 1945 the Bureau of Mines conducted pilot-plant tests to recover scrap mica by selective screening of crushed pegmatite. More recently the problem has boon studied in the Pegmatite Research Laboratory to aid in developing technological methods by which scrap mica may be separated from crushed pegmatite."

Feb 1, 1949

By John B. Goodman

A LOW-TEMPERATURE carbonization assay test is described, and factual data derived from this test are presented. The test procedure outlined in this report incorporates a mild-steel retort of improved design, an accurately controlled method of heating, and a complete collection and condensation system for the solid, liquid, and gaseous products of carbonization. The test described establishes, under closely controlled conditions, the relationship of temperature to yields of products on carbonization. Noncoking or weakly coking coals and other carbonaceous material are particularly amenable to testing by the assay. Mass balances of 100 percent± 0.3 are obtainable by this test. It is believed that the efficiency of the test and the accuracy of the type data obtained have been materially increased.

Jan 1, 1953