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By L. R. Testardi, J. R. Wiese

OBSERVATIONS have been made that the substitution of antimony for bismuth in Bi2Te3 leads to anomalies in some of the electrical and magnetic properties of the Bi2Te3-5S2TeS alloy system at the composition ratios 2 Bi2Te3 : 1 Sb2Tes and 1 Bi2Te3 : 2 Sb2Te3. Airapetiants and Efimova1 have reported the peaking of the nondegenerate hole mobilities, at these compositions for sintered materials and ascribe the peaking to the formation of ordered alloys. From a study of these materials produced by the Bridgeman

Jan 1, 1962

By R. J. Wasilewski

OBSERVATIONS have been made that the substitution of antimony for bismuth in Bi2Te3 leads to anomalies in some of the electrical and magnetic properties of the Bi2Te3-5S2TeS alloy system at the composition ratios 2 Bi2Te3 : 1 Sb2Tes and 1 Bi2Te3 : 2 Sb2Te3. Airapetiants and Efimova1 have reported the peaking of the nondegenerate hole mobilities, at these compositions for sintered materials and ascribe the peaking to the formation of ordered alloys. From a study of these materials produced by the Bridgeman

Jan 1, 1962

By G. W. Toop

In a recent publication,31 Darken has derived an equation to describe thermodynamic behavior in ternary metallic solutions with compositions near pure component 1: Eq. [I] is understood to be a general equation, consistent with the ternary Gibbs-Duhem equation, which is proposed as a logical formalism in view of observed behavior in some binary metallic solutions31'32 rich In Eq. and am are constants obtainable from the 1-2 and 1-3 binaries. The parameter 023 may be determined from measurements on the ternary The purpose of this discussion is to compare Eq. [I) or [3] with other ternary formulations involving binary terms, within the regions of validity of Eqs. [I], [2], and [3]. First, the ternary point is considered to be at the intersection of two composition paths, one with constant N1 and another with constant N2/N3 as shown in Fig. 10. The terms in Eq. [3] may be related to the binary points shown by multiplying the first term on the right-hand side of Eq. [3] by N2 (1) /l -N1, the second term by the third term by and the fourth term by each multiplier being unity: It should be noted here that no suggestion has been made that either the binary or the ternary systems form regular solutions. However, Eq. [5] and hence Eq. [3] shows that the contribution made to the ternary excess free energy from the 1-2 and 1-3 binaries has the same form as for a regular ternary system.1 Before considering the term a23 for the above case, a second geometrical relationship is examined with the ternary point at the intersect ion of three composition paths with constant N1/N2, N2/N3, and Nl/N3, respectively, as shown in Fig. 11. For this geometry, ternary values of NZ and N3 in terms of the binary values shown may be substituted into Eq. [I]. Then by making use of identities of the form Eq. [6] contains terms that are similar to those in a ternary regular solution formulation34 based on the geometry shown in Fig. 11. Although at finite concentrations, unless the 1-2 and 1-3 binaries form

Jan 1, 1968

By N. A. Gokcen, M. Ohtani

Thermodynamic intevaction pararnetevs of elements E2(2), for dilute binary solutions of a component "2" in liquid iron, i.e., E(22) = 9 In f2/?N2 where f2 is the activity coefficient and N2 the mole fraction, and E(3) 2 = In f2/ N3 dilute ternary solutions of "2" and "3," and the carbon saturation parameter sc(3) (In f c/ N3) N c/N Fe for N3 - 0, are critically examined and correlated. It has been found that the interaction parameters and the atomic numbers of alloying elements follow regular periodic putterns. PHYSICO-chemical behavior of alloying elements in molten iron have become the subject of numerous investigations during the past 25 years. Consequently, the mutual effects of elements in the iron-rich solutions Fe-C-X, Fe-N-X, Fe-H-X, Fe-O-X, and Fe-S-X where X represents an alloying element, have gradually become better understood. These effects for a given temperature and pressure may be expressed by the interaction parameter of Wagner1, 2 derived briefly in the following manner. The complete differential of the Gibbs free-energy equation at constant temperature and pressure is dF = Fl dn, + F2 dn, + F3 dn3+ . . . [ 1] where F is the free energy; F 1, the partial molar free energy of "I"; and n,, the number of moles of "i." Cross-differentiation of this expression* *Cross-differentials are obtained as follows: Since the order of differentiation of F with n2 and n3 is immaterial, the left sides of the second differentials are equal, hence the derivation of Eq. [2] is obtained. For a dilute solution of components 2 and 3 in solvent 1, with the substitution of RT In f i = Fi xs for Fi where fi is the activity coefficient, and Fixs is the excess partial molar free energy, Eq. [2] becomes O) [3] where N2 and N, are the mole fractions. The interaction parameters are defined by

Jan 1, 1961

By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah' in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.' studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.' studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h'hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969

By J. M. Vonfeld, V. D. Hanson, W. K. Heinlein

TWO overfeed drum-type separators using a suspension of magnetite in water as the separating medium have been installed in the Champion No. 1 preparation plant of the Pittsburgh Coal Co., Division of the Pittsburgh Consolidation Coal Company. A simplified flow diagram of the Champion No. 1 coarse coal circuit is shown in Fig. 1. A railroad car rotary dump, capable of handling 20 cars per hr, discharges the coal into a hopper. Coal is fed from the hopper of the rotary dump to a 60-in. belt conveyor by two reciprocating pan-type feeders. The belt conveyor feeds the run of mine coal onto the main raw coal screen. The first deck is fitted with 3 in. round hole perforated plate which removes the 3x0-in. coal. The second deck of the screen is equipped with 6-in. lip screens which separate the remaining coal into +6 in. and 6x3 in. The +6 in. coal is transferred to a shaking picking table and then discharged onto the loading boom. The 6x3-in. coal is fed to the No. 2 dense medium vessel for cleaning. The clean coal from this unit flows to a vibrating screen where the medium is removed and the coal sized into 6x4 in. and 4x3 in. The 6x4-in. coal is transferred to the loading booms and the 4x3-in. is conveyed to the clean coal classifying screens to remove degradation. The 3x0-in. raw coal is blended in a system composed of three storage bins having a total capacity of 400 tons. From these bins the coal is fed onto a 48-in. flight conveyor by three reciprocating feeders. This flight conveyor delivers the coal to the Rheo plant. The 3x0-in. coal is then cleaned in two 48-in. Rheolaveur launders each equipped with two Rheo boxes. The first set of boxes removes a primary refuse and the second set produces a middling product which is recirculated in the launders. The cleaned coal and water overflows from the primary launders to two sizing and dewatering shaker screens where the water and - 3/8-in. coal are removed for further cleaning in the Rheo fine coal plant. The 3x3/8-in. clean coal is combined with the 4x3-in. coal from the No. 2 vessel, sized into 4x2 in., 2x1 1/4 in., and 11/4x3/8 in., then sent to the loading booms. The 3x0-in. refuse from the primary launders is normally fed to the No. 1 dense medium circuit, but any portion or all of this material can, as an alternate, be processed in the Rheo rewash launder. The primary refuse when fed to the dense medium circuit is screened into 3/8x0 which is cleaned in the fine coal plant and 3x3/8 for cleaning in the No. 1 vessel. The clean coal from this vessel is passed over a vibrating drainage and rinse screen, then sluiced to the rewash sizing shaker where it is dewatered and sized for loading. The installation of a pilot plant separating vessel using a suspension of magnetite in water was pro-

Jan 1, 1952

By Anthony G. Reid

INTRODUCTION At the time of the death of Mao Tse-tung in 1976, China was a major oil producing country with a daily oil flow in the order of 1.735 million barrels. This position had been achieved with minimal assistance from the outside world. Further, only some fifteen years had elapsed since the country's daily oil production capacity had hovered at the barely significant level of one hundred thousand barrels. Why then did the new leaders of China, after this very creditable record of success, suddenly change the direction of the country's drive for future hydrocarbon production? First, by switching much of the emphasis of exploration from onshore to the offshore continental shelf basins, and further by apparently abandoning the philosophy of self reliance calling upon the world's oil industry to share in the task of locating and developing these potential offshore energy reserves. The answer is probably only partly understood by those of us outside China, However, a number of factors exerting an important influence on this decision can be identified. THE MOVE OFFSHORE The new leadership was anxious to rapidly move China into her rightful place amongst the powerful and technologically advanced nations of the world. Modernization became the slogan, specifically modernization on four fronts, agriculture, industry, technology and military with the goal to "catch the west by the year 2000". But how to generate the capital to finance this massive modernization program? The rapid escalation of the price of crude oil following the 1973 Oil Embargo and the continuing apparently insatiable world demand for this now extremely precious primary resource was very clear to all. China, as a major producer, could export crude to help finance the ambitious development programs of the government. To do this, however, would require a very significant in¬crease in present production capacity, as the domestic demand even for China with her relatively low per capita energy consumption, is essentially equal to the current production. Trying to rapidly move the new regime's programs into actions, one can only assume that the planners looked at the success of the petroleum industry over the preceding fifteen years and quickly concluded that this well established curve could be maintained and indeed steepened with an increase in effort. The rapid discovery of a few more Daqing's (China's premier oil field, producing one million barrels a day) would have the country's ambitious modernization goals within reach. Petroleum would At the time of the death of Mao Tse-tung in 1976, China was a major oil producing country with a daily oil flow in the order of 1.735 million barrels. This position had been achieved with minimal assistance from the outside world. Further, only some fifteen years had elapsed since the country's daily oil production capacity had hovered at the barely significant level of one hundred thousand barrels. Why then did the new leaders of China, after this very creditable record of success, suddenly change the direction of the country's drive for future hydrocarbon production? First, by switching much of the emphasis of exploration from onshore to the offshore continental shelf basins, and further by apparently abandoning the philosophy of self reliance calling upon the world's oil industry to share in the task of locating and developing these potential offshore energy reserves. The answer is probably only partly understood by those of us outside China, However, a number of factors exerting an important influence on this decision can be identified. THE MOVE OFFSHORE The new leadership was anxious to rapidly move China into her rightful place amongst the powerful and technologically advanced nations of the world. Modernization became the slogan, specifically modernization on four fronts, agriculture, industry, technology and military with the goal to "catch the west by the year 2000", But how to generate the capital to finance this massive modernization program? The rapid escalation of the price of crude oil following the 1973 Oil Embargo and the continuing apparently insatiable world demand for this now extremely precious primary resource was very clear to all. China, as a major producer, could export crude to help finance the ambitious development programs of the government. To do this, however, would require a very significant increase in present production capacity, as the domestic demand even for China with her relatively low per capita energy consumption, is essentially equal to the current production. Trying to rapidly move the new regime's programs into actions, one can only assume that the planners looked at the success of the petroleum industry over the preceding fifteen years and quickly concluded that this well established curve could be maintained and indeed steepened with an increase in effort. The rapid discovery of a few more Daqing's (China's premier oil field, producing one million barrels a day) would have the country's ambitious modernization goals within reach. Petroleum would be the principal bridge to the bright future. The next decision involved the question of where to look for these vast new reserves. Chinese exploration teams had already looked at most of the onshore sedimentary basins and, while they were the first to admit that there was much yet to do, it was fairly clear to them that the potential for large new accumulations was confined to two areas: the little explored, remote, inhospitable regions of western China, principally Xinkiang Province and the equally unexplored offshore basins of the continental shelf and slope. In both cases China faced a very serious problem. The inhospitable environments were severely straining her petroleum industry's current technological ability to cope, particularly as the government needed rapid results. Thus the pragmatic and, to the foreign oil industry, unexpected decision to invite cooperation with the outside world. The reasons for the initial emphasis on the exploration of the offshore basins with the cooperation of foreign oil companies are again supposition on my part, but probably involved considerations of technical merit, ease of development and delivery to markets together with more sensitive issues such as controling the influence of foreign philosophies and values on the Chinese population by containing most foreign activity to the offshore. So within three years of the death of the great helmsman, China had developed a plan to involve foreign oil companies, both state and private, in a grand plan to rapidly increase the nations oil production. In fact, by this time, the first round of talks had been concluded and the first phase begun, and what a beginning. Some forty eight companies from thirteen countries had signed documents to participate formally in this world scale event. It was far easier to list those companies which did not participate than to list those which did. FOREIGN COMPANY INTEREST Why the rush by the world's oil industry to be involved in China? What was China offering which made everyone so anxious to join in? Again the answer is complex in detail, but principally involved a combination of factors which together caused this virtual stampede. Timing was a major element. Oil Companies, despite an ever increasing take by governments, were beginning to benefit. from the' rapid escalation of crude prices induced by OPEC and were looking for suitable areas to reinvest these funds. Producers

Jan 1, 1982

By ERNEST A. HERSAY

ACCURATE ore-sizing with screens is drawing attention to certain details that now, more than ever before, require attention. There are many tests that must be preceded by careful sizing. The assayer often could profit by a more careful selection of screens. In milling, more attention is given the slimes produced. Cement-manufacturers are pulverizing and screening finer than they formerly did, and others are reducing materials to fine sizes at high cost, with screens used to govern the fine¬ness of the pulverized product. Fine screens are expensive, easily injured by mis-use, are carried in stock sparingly by most dealers, and are handled often by those who know little about them except their designated number. More attention, on the whole, needs be given the actual size of the mesh-openings, and less emphasis placed upon any custom or conventionality in numbering. An effort to classify wire screens, in this respect, leads at once into computations, where one is confronted with details of sizes and standards, of different wires, different gauges, and different customs. There is always uncertainty about the exact working-size of a screen until one gives the matter special attention, and devotes more time to it than its simplicity seems to demand. To know only the number is not sufficient for all uses. Often, in sets, superfluous sizes are used; and sizes are omitted that are of critical importance. In wire screens, the use of different standard sizes of wire makes important differences in dimensions that must be taken into account. The dealer usually grades screens by the number of openings per linear dimensions, regardless of the size of the openings or of the wire. Certain 100-mesh screens in use are found, by measurement, to he actually coarser than others of 90-mesh, a result which is due, of course, to the use of larger

May 1, 1906

By E. J. Fasiska, L. Zwell

PREVIOUS investigations 1,2 of Fe3P described by pearson3 and schubert4 show that Fe3P has a bct unit cell having four Fe3P tetrahedra centered around each lattice point. The space group is 14, No. 82, and all atoms occupy general positions 8(g). The cell dimensions3 are: a = 9.090, c = 4.446 kX, with an axial ratio of c/o = 0.4891. We have measured the lattice parameters of Fe3P, using a Fe as an internal temperature standard, at 23°, 414°, and 678°C and computed the thermal expansion over this temperature range. The Fe,P was prepared by melting under vacuum (after flushing with argon) a commercially pure iron and "ferrophosphor" in a high-frequency induction furnace. Part of the ingot was crushed for X-ray examination and for chemical analysis. X-ray diffraction and light microscopy indicated iron phosphide (Fe3P) present as the major constituent and a small amount (about 5 pct) of a Fe. Chemical analysis showed 0.05 wt pct Si, 0.008 wt pct N, 0.018 wt pet C, and less than 0.02 wt pct each of other metallic elements. X-ray diffraction powder patterns were obtained from a mixture of iron and Fe3P sealed in an evacuated quartz capsule using a Unicam high-temperature

Jan 1, 1968

By W. C. Winegard, C. J. Beinjessner

PREVIOUS investigations 1,2 of Fe3P described by pearson3 and schubert4 show that Fe3P has a bct unit cell having four Fe3P tetrahedra centered around each lattice point. The space group is 14, No. 82, and all atoms occupy general positions 8(g). The cell dimensions3 are: a = 9.090, c = 4.446 kX, with an axial ratio of c/o = 0.4891. We have measured the lattice parameters of Fe3P, using a Fe as an internal temperature standard, at 23°, 414°, and 678°C and computed the thermal expansion over this temperature range. The Fe,P was prepared by melting under vacuum (after flushing with argon) a commercially pure iron and "ferrophosphor" in a high-frequency induction furnace. Part of the ingot was crushed for X-ray examination and for chemical analysis. X-ray diffraction and light microscopy indicated iron phosphide (Fe3P) present as the major constituent and a small amount (about 5 pct) of a Fe. Chemical analysis showed 0.05 wt pct Si, 0.008 wt pct N, 0.018 wt pet C, and less than 0.02 wt pct each of other metallic elements. X-ray diffraction powder patterns were obtained from a mixture of iron and Fe3P sealed in an evacuated quartz capsule using a Unicam high-temperature

Jan 1, 1968

By John J. Cioston

THE steadily rising flood of gold production from all parts of the world has created an avalanche of rumors regarding the stability of the present price of this metal. Markets have been unsettled from Johannesburg to London from New York and Toronto to Melbourne, despite repeated denials from, American and British authorities of any immediate intention to alter the price. Various economists and financial writers have blossomed forth with predictions that the price would be set at the old level of $20.67 per oz.; some have even been so brash as to state That a price of $15 would be necessary to bring production within control. These effusions, based entirely upon monetary theories and with no regard to production costs, serve to confuse rather than clarify the situation.

Jan 1, 1937

By J. D. MacKenzie

THE world production of copper for the first eight months of 1927 shows an increase of 3 per cent over the same period in 1926. Since February of this year, however, production has been considerably curtailed. The United States reduction in the last four months has been offset by the increased South Ameri-can and Belgian Congo production. The United States is now producing 58 per cent of the world production, Chile and Peru 17.3 per cent, Belgian Congo 5 per cent. In 1926 the United States produced 54 per cent, Chile and Peru 16.3 per cent, Belgian Congo 6.3 per cent. Production, Tons 1917-largest war year 1,580,000 1925 1,581,000 1926-increase 3 per cent 1,628,000 1927-increase 3 per cent 1,670,000 Copper Producing Countries, 8 mo., 1927: Tons Per Cent United States 644,000 58.0 Chile and Peru 192,000 17.3 Europe 90,000 8.1 Belgian Congo 56,000 5.0 Japan 46,000 4.1 Mexico 30,000 2.7 Canada 23,000 2.1 Figures are not available for Spain and Portugal, which would probably precede Mexico.

Jan 12, 1927

By D. A. Koss, R. O. Gordon

Changes in the ultrasonic attenuation in steel specimens have been observed during tensile tests. Samples of AISI 1020, 1045, and 1095 steel quenched and tempered to a spheroidized condition have been used. Both attenuation and microstrain measurements fail to reveal preyield dislocation motion in the as-tempered specimens. Upon reapplication of the load to samples in the strain-aged condition there is a large preyield attenuation increase but no observable micvostrain up to 90 pct of the flow stress. These and other observed changes can be related to changes in the free disloca-tion density and the average dislocation segment length. The results show that the increase inflow stress in the strain-aged condition is caused by increased fric-tional stresses rather than by dislocation pinning. Strain aging is found to proceed through three distinct stages. The second of these follows the t2,3 law and is characterized by an activation energy of 20 kcal per mole. RECENT years have seen substantial progress in the understanding of the sharp yield-point phenomenon in metals; the influence of solute atom pinning of dislocations, of dislocation multiplication, and of the stress dependence of dislocation velocity on the stress-strain curve has been investigated. Evaluation of the relative importance of these factors in the various metals and alloys is not complete, however, because observation of the stress-strain curve alone is not sufficient to determine the yield mechanism. In the experimental study of the sharp yield point it would be desirable to be able to directly observe the dislocations in a bulk specimen. Ideally, the observations should be made during deformation because of the rapidity of recovery processes in lightly strained metals. While direct observation of dislocations under these conditions is not possible, certain physical properties sensitive to the dislocation structure can be observed while a test specimen is undergoing deformation. Of these properties, one of the most useful is the ultrasonic attenuation. The total observed attenuation, a, is due to a number of causes: acoustic diffraction, scattering by inhomogeneities in the structure, heat flow, magnetostriction, and dislocation damping. Satisfactory measurements of the absolute a are difficult to make because all of these factors cannot be evaluated in any given specimen, but changes in a due to changes in the dislocation contribution alone can be reliably observed by appropriate technique. Because dislocation damping is sensitive to small concentrations of long, free dislocation segments, observation of acoustic attenuation due to dislocations is particularly useful in the study of the early stages of plastic deformation. In the experiments to be described, acoustic-attenuation measurements have been made on steel samples as these were pulled through their yield in tension. While many details of dislocation-damping phenomena in the bee metals remain obscure, the main characteristics of this type of internal friction are established. At low strain amplitudes and at frequencies well below that of dislocation resonance (the conditions of these experiments) the dislocation contribution to a is given by1 where A is the density of freely oscillating dislocation segments, L is the average segment length, B is the damping constant for a moving dislocation, w is the frequency, O is an orientation factor, C is the dislocation line tension, and t is a numerical factor relating average segment length to the distribution of lengths. Because of its fourth-power dependence on L, a is highly sensitive to changes in dislocation free segment length such as might arise from unpinning, recovery, jog formation, or dislocation intersection. The above equation is not valid near the resonant frequency of dislocations, but the segment length in steel is believed to be much too short to cause over-damped resonance near 10 Mc; this will be discussed later. In the present experiments plastic-strain measurements with a sensitivity of 2 x 10-5 were also made during the early stages of loading in order to detect preyield strain. The general plan of the experiments is to observe

Jan 1, 1967

By G. Townsend Harley

STOPING methods in which shoveling plays an important part are gradually being replaced by other and cheaper methods. But there will always be considerable shoveling done underground in stopes as well as in drifts, tunnels, urinzes, and shafts. At the mines of the PhelpsDodge Corporation at Tyrone, N. M., the cost of shoveling in all stopes in 1917 amounted to 24c. per T. In the top-slice stopes for the same period, it cost 27 c. per T. or 16 per cent, of the total cost of these stopes. The tonnage for shovelers from all stoping was 9.3 T. per man, and for topslicing 8.2 T. per man. These stopes were not unduly hot, and there was not more than the usual amount of timber to interfere with the work of the men. The tonnages obtained per shoveler were considered low; first, because of a poor grade of Mexican labor, many of the men having come in from railroad grading camps; and second, because of a poor spacing of raises, especially in the top-slice stopes, where, in general, they were spaced 25 ft. by 66 ft. (7.6 by 20.1 m.) centers. The average wage per laborer shift was $2.67 during the year. It was thought, however, that even under these conditions the men were not producing the tonnage that they should, so, with the consent of the management, the writer undertook to determine how the general efficiency of the underground shoveling could be improved. No predetermined plan for conducting these experiments was arranged because we had no definite ideas as to the scope of the work or the number of elements into which the investigation would resolve itself, before all of its phases could be determined. We were sure, however, that any work that would thoroughly cover the ground would have to be in the nature of a systematic time study, combined with a course of instruction in correct shoveling methods and adequate and intelligent supervision of the work. Two or three companies in the Southwest have done some work to determine the proper shovel to be used undcrground, but so far as is known the work has been limited to equipping certain parts of their mines with a particular type and size of shovel and thereafter watching the cost and efficiency records. In each case it seems to have been the shovel that held the 21-lb. (9.5-kg.) load that gave the bcst results. Excepting personal communications from these companies, the only data available on scientific shoveling are contained in F. W. Taylor's book, "The Principles of Scientific Management," and D. J. Haucr's article, in The Contractor for March 29, 1918, "A Hundred Hints for Shovelers." This paper discusses and draws conclusions from several thousand time-study readings, taken both on the surface and in the mines for nearly a year. A sufficient number of readings were taken on each factor in the problem for the plotting of curves of the performances and to obtain accurate indices of the work to be expected from this class of labor. The work is not as complete in all of its details as we would like to havc it, because we were forced to stop the work temporarily, owing to the numbcr of men going into the National service and our inability to get others who could make time studies. The results obtained so far, however, have been of such a startling nature that we have decided to submit them at this time, subject to future modification. It is hoped, also, that a free discussion of this paper will lead to a disclosure of any errors that may have becn embodied and offer some valuable suggestions for the conduct of future work.

Jan 1, 1920

By John F. Elliott, Robert D. Pehlke

The rate of reaction of nitrogen with liquid iron and with binary alloys of iron and Al, Cb, Cr, Ni, O, S, Si, and W were measured. The surface active elements, oxygen and sulfur, decrease the rate markedly. The other alloying elements have very little effect on the rate except when they function as deoxidizers, The rates of absorption and de-sorption were found to be equal. Several possible reaction mechanisms which may control the rate are considered. In order to describe completely the behavior of nitrogen in steelmaking processes, the mechanisms of mass transfer between the gaseous and liquid phases, nitrogen and iron, respectively, must be understood. A kinetic study to determine the nature of these mass transfer processes was undertaken, and the results of that investigation are presented in this paper. Specifically, the study was directed toward determining the influence of alloying elements on the rates at which pure nitrogen gas at constant pressure is absorbed and desorbed by liquid iron solutions: A previous paper1 reported measurements of the equilibrium solubility of nitrogen in liquid binary iron alloys. The experimental data are presented and discussed first and then several possible rate limiting mechanisms are considered. PREVIOUS RESEARCH The results of several investigations on the rate of absorption of nitrogen by liquid iron and iron alloys have been reported.2-14 There is little agreement on the rate coefficients among these studies because of the influence of geometry on the experimental system and of the purity of the liquid iron. The rate was found to be influenced by alloying content for the binary liquid iron systems: Fe-Al,2 Fe-C,4,6 Fe-Cr,4,5,8 Fe-Mn,5 Fe-Ni,5,8 Fe-O,9,10 Fe-O,9,10 and Fe-Si.2,6,7,11 Several investigators12"15 have reported that the rate of nitrogen absorption is increased in a reducing gas mixture and decreased in an oxidizing atmosphere. A mechanism for the retardation by oxygen of the absorption of nitrogen has been described by Naeser18 as the formation of an iron oxide film at the gas-metal interface. The film slows the absorption rate until it disolves in the metal, thus permitting nitrogen to enter the liquid iron. Karwat17 discussed the influence of oxygen in terms of the formation of gaseous molecules of nitrous oxide which represent a higher energy form than the nitrogen and oxygen or the oxidizing gas and consequently constitute an energy barrier for the process. Fischer and Hoffmann10 showed that the oxygen markedly reduces the rate of absorption of nitrogen, the rate constant being one order of magnitude smaller in liquid iron containing 0.15 to 0.24 pct 0 as compared to that in melts containing 0.001 to 0.02 pct 0. Although Chipman and Murphy2 reported that the rate of absorption of nitrogen in liquid iron was essentially independent of temperature, Eklund3 found that the rate increases strongly with increasing temperature as did Kootz4 and Saito.5,6 Karnaukhov and Morozov7 also reported a large temperature coefficient, but related it to increased stirring at higher power inputs in an inductively heated system. All of the authors above have treated their results assuming that the reaction is diffusion controlled, that the surface reaction is in equilibrium with nitrogen gas, and that a "first order" reaction takes place. Karnaukhov and Morozov7 and Humbert; who studied the rate of absorption in a closed system by observing pressure changes in the system as a function of time, concluded that their results best fit a diffusion-type analysis. This was further verified by von Bogdandy, Dick, and stranski18 and Fischer and Hoffmann10 who found the initial rate of

Jan 1, 1963

By U. Andres

U. Andres (The Technion, Haifa, Israel)-The authors are to be congratulated on their research, new and interesting, in a field which, however, the present writer and his assistants have been trying since 1962 to bring to the attention of the scientific and technical world, by means of publications covering several different aspects of this many-sided problem. We announced, in these publications, the results of magneto-hydrostatic (MHD) separation of magnetic and nonmagnetic minerals which we made in magnetic fluids (in paramagnetic solutions and suspensions of magnetic particles) which interact with permanent" and impermanent" inhomogeneous magnetic fields. There is no doubt that the authors have succeeded in creating ferrimagnetic colloids made by dispergation of 10-30 wt % of magnetite in kerosene in the presence of 7-10 vl % oleic acid. It may be judged by [Figs. 3 and 4] that the suspensions represent great stability systems and also "hysteresisless" fluids [(Fig. 5)] which bear witness to the existence of superparamagnetic suspensions. If the viscosity of these colloids is not so high, and the cost of preparing them can be covered, the fluids which have here been received can possibly be of interest to the technology of mineral separation. The potential possibility and technological perspective of similar media is demonstrated in our joint work with G. Bunin18 in 1965. The research carried out on the pushing out of cylinders and spheres from magnetic fluid is impressive; it would, however, have been interesting if the authors had compared their results with those on the pushing out of bodies from magnetic fluids adduced from our work." In my books" there happens to be described an experiment on the pushing out of a sphere in magnetic wedge field, in which the pushing out force of suspension with 5 vl % of magnetite reached 125 g per cc. This testifies to interesting possibilities of these media. Our works' shows also, on the basis of Laplace's equation the receiving of an interesting distribution of pushing out forces by selection of corresponding configurations of magnetic poles. Objection must be made to the authors' introduction of the term "antigravity force." The direction of this force does not depend on the direction of the gravity force and their opposition, i.e., antigravity is only one particular case. I am in full agreement with the authors' statement that magnetic pushing out forces "can be utilized to separate nonmagnetic objects according to variations in their densities." It is, however, necessary to make only one important addition, which can be found in our research on MHS at the Technion in Haifa, namely, that magnetic fluids in magnetic fields can be utilized in the separation of minerals according to variations in their magnetic susceptibility. The authors' conclusion is especially important considering the fact that in our publications" (including one in English") some designs of MHS separators and some technological results received on MHS-separators have already been described. S. E. Khalafalla and G. W. Reimers (Authors' Reply)We were aware (mostly through Chemical Abstracts of the American Chemical Society) of the use of solutions of paramagnetic salts such as manganous sulfate in agnetohydrodynamic separations by the Russian school headed by G. Bunin."n Professor Andres' contributions to this school are also evident in his application of the ponderomotive forces in an electrolyte placed in electric and magnetic cross-fields to separate coal and other useful minerals." It must be realized, however, that the foregoing research by Bunin et al." involved the use of magnetic fields and field gradients of very large magnitudes, i.e., such that H • grad H - 101 Oe2 per cm. The magnetization of paramagnetic salt solutions range from 0.1 to 0.5 gauss (at fields of a few thousand Oersteds) and never reach saturation. The magnetization of our superparamagnetic ferrofluids ranges from 100 to 500 gauss and reach saturation at fields of a few hundred Oersteds. Hence, to effect the same separation, the quantity "H

Jan 1, 1974

By G. Derge, R. E. Grace

Diffusivity of bismuth in liquid Pb-Bi alloys has been measured by the capillary reservoir method as a function of temperature and composition. Fair agreement between theory and experiment is found for the measured diffusion coefficients and activation energies of diffusivity and viscosity in dilute lead alloys. The measured diffusion coefficients in the high bismuth alloys describe mass transport in special concentration gradients. THE study of diffusion in liquid metals has been restricted largely to the amalgams over small ranges of temperature and composition. In contrast to this, diffusion and transport of ions and molecules in aqueous and organic solvents have been studied extensively for the past 50 years. The general difficulty of measuring diffusion coefficients in both gases and liquids at high temperatures has been that of eliminating convection currents. Measuring techniques based on freezing and sectioning after the diffusion period1 are not particularly satisfactory because of the volume changes and segregation which occur during freezing. The most promising technique which is currently being developed for liquid metals is the capillary reservoir method. This eliminates convection currents from the diffusion zone and requires measurements only of the length and initial and final compositions of the alloy within the capillary. Anderson and Saddington' have measured the diffusion coefficient of tungstate anions in aqueous Na,W04; Wane4' and Hoffman- ave studied structure and self-diffusion in water and self-diffusion in mercury, respectively, by similar techniques. Selection of the Pb-Bi system for initial study was made for several reasons: I—It afforded a low temperature system for development of techniques which would be suitable for high temperature measurements in liquid iron. This research on diffusion in liquid iron is now in progress as a part of a general program on the rates and mechanisms of slag-metal reactions. 2—Activity data on liquid Pb-Bi alloys of all compositions are available from the emf meas- urements of Strickler and Seltz.9 3—Some data are available on the diffusion of bismuth into solid lead. The measurements on solid alloys were made by von Hevesy and Seith7 for the concentration range of 0 to 2 pct Bi. An appropriate solution to Fick's law (unsteady state) for the capillary reservoir has been found by considering the mass flow which passes through a unit area of surface on a slab of infinite thickness as a function of time. This is the first application of this solution to diffusion measurements, although a similar solution is available for identical boundary conditions.' By analogy with heat conduction, the problem reduces to a perfectly insulated infinite slab at temperature C,, one surface of which is quenched to C, for all times, t. Heat is permitted to flow from quenched surface of the slab to an infinite supply of coolant at C.' (see Appendix). For the corresponding solution for diffusion in liquids, these terms become Where Cu is the initial concentration of component A" in entire capillary at t - 0, C, is the final con- In this case. component A is bismuth, and C, = 0. centration of component A in entire capillary at t = t, C, is the concentration of component A in bath for all t, 1 is the length of the capillary in centimeters, t is the time of diffusion period in seconds, and D is the diffusion coefficient in square centimeters per second. By comparison with solutions to Fick's law used in the solid state, this solution for liquids is similar to the Grube solution for solids, where the change in D with chemical composition is not taken into consideration. Difficulty is to be expected if large concentration gradients are employed and if the concentration gradients extend over an appreciable length of the capillary.

Jan 1, 1956

By U. N. Bhrany, N. Arbiter

F. C. Bond (Consulting Engineer, Processing Machin-Dept., AllisChalmers Manufacturing Co., Milwaukee) This is a very comprehensive paper. It deals with 1) size distribution functions, 2) energy-particle size relationships, and 3) criteria for grinding efficiency. The method of analysis used consists of tracing the increase and decrease of successive Tyler scale screen fractions as grinding progresses. The treatment is based upon the assumption that the work done in grinding is concentrated entirely upon the coarse size fractions in the mill. It is postulated that when a feed consisting entirely of particles of one size fraction is batch ground that finer fractions increase at a constant rate as grinding progresses, until finally each in turn begins to be ground and to decrease in amount. It is shown that under these conditions the empirical Gates-Gaudin-Schuhmann log-log size distribution plot can be logically explained. It is difficult to imagine any condition of ball mill operation, or any probability analysis, which would result in no grinding contacts on the finer particles present. However, the authors' postulate must be accepted if their conclusions are to be sustained. They conclude that the equation expressing the for mation rate of each size fraction can be resolved into the G.-G.-S. size distribution equation, and that the curvilinear portion of the log-logsize distribution line represents the only particle sizes which are being ground as well as produced. The author's statement that the G.-G.-S. Eq. 4 applies only to the finer portion of the size distribution while the Rosin-Rammler Eq. 6 applies over the whole size distribution range certainly supports the view that an exponential equation of the Rosin-Rammler type corresponds more closely to actual size distribution than does the power law G.-G.-S. equation. However, the G.-G.-S. equation is used to derive Eq. 8 and Eq. 9, which state that the energy required to grind a ton through a particular mesh varies inversely as the particle size to the exponent -a , whic h is the slope of the extended G.-G.-S straight line. This is stated to apply to both batch and continuous grinding. The G.-G.-S. slope exponent thus becomes very important in all crushing and grinding analyses by this method. The authors include some data which can be used to test their conclusions, as described below: We will consider grinding a feed composed of 14 mesh (1190u) to -200 mesh (74u). The average of 17 Allis-Chalmers grindability tests on quartz gives a work index (Wi) of 12.77. The -200 mesh product should have 80 pct passing 41.6u or P = 41.6. The equivalent 80 pct passing size of the 14 mesh feed particles is considered to be the particle diameter, as is true for spherical particles. Thus F is 1190u. In the work index equation 10 wi 10 wi 127.7 127.7 P f 41.6 1190 = 16.1 kw-hrperton. In Table I the ball mill exponent for quartz is 1.0 and from Eqs. 9 and 10: w=kw-hr/ton =Constan/(do/di) = 16.1 ton so that (1190) Constant/ Constant and the Constant equals 259. The tons per horsepower-hour value is 0.0464, in agreement with Table IV. The exponents for other minerals are listed in Tabl e 11. In Table IIA, the kilowatt hours per ton required to grind these minerals between the same sizes as the quartz, both by the authors' method and the work index equation, are listed. According to the authors kw-hrperton = 259/(16.1)".

Jan 1, 1961

By A. Schild

The effect of heating a producing well on the rate of oil recovery has been analyzed in the simple case of a well producing oil by a radial drive and in the steady state. Differences of production rates with and without borehole heating have been calculated and plotted; these measure some of the benefits of the thermal recovery process. A striking feature is that the production increase tends rapidly to a constant value for large production rates. Some concrete examples, including a rough comparison with field data. are discussed. Heating requirements have been calculated and plotted on the assumption that the heaters used are 100 per cent efficient. Heating has been thought of as applying only to low volume wells producing heavy oils. However, the calculations suggest that the thermal process considered might be profitable even for some wells producing large quantities of light oil, especially in unconsolidated formations where fracturing is not possible. In the case of wells producing other fluids with the oil or of wells producing partly or wholly by gravity drainage, the theory developed does not apply in detail. It can be expected, however, that any general qualitative be-havior will remain valid. Under normal temperature conditions, high viscosity emulsions sometimes form around the wellbore, lowering the permeability in the vicinity of the well and impeding the production of oil. Borehole heating often prevents such emulsification. This important effect is not easily amenable to mathematical analysis and has not been included in the theory presented here. It should therefore be kept in mind that the benefits due to borehole heating may in fact exceed the values given by the following calculations. INTRODUCTION The recovery of viscous, low gravity oils can often be stimulated by applying heat to the production zone. The higher temperature lowers the viscosity of the oil, increasing its mobility, and therefore its rate of production. One thermal method of recovery 1,2,3,4. consists in operating a heater inside a producing well and, at the same time, producing oil from the well. In this paper a simple theoretical model is analyzed to study the effect of such heating on the recovery of oil. The reservoir mechanics of the process is the only aspect of the problem which is considered here. The details of the heating system are ignored, and it is simply assumed that the heater raises the temperature in the immediate vicinity of the producing well to a pre-assigned temperature T w. Although heating requirements are calculated, these refer only to the heat supplied to the formation and to the oil being produced; they do not include heat losses due to the inefficiency of the heater. A short outline of the theory follows: The heat supplied to the producing well flows out into the formation by means of thermal conduction. At the same time, the flow of oil carries heat by convection from the formation towards the producing well. After sufficient time has elapsed, a steady-state is reached where the temperature, the velocity of the oil, etc., no longer vary with time but are functions of position only. In the steady state the temperature decays like an inverse power from the high value Tw at the wellbore to the original reservoir temperature T. at some distance away from the well. The effect of the high temperature and low oil viscosity near the producing well is the same as if the oil were produced at reservoir temperature To but through a producing well of a larger radius. From this point of view, the energy and money being expended to provide heat

Jan 1, 1958

By A. G. Guy

In a special type of electrodiffusion experiment the entire specimen is at constant temperature. The vacancies are then created at one end of the specimen and flow to the other end where they are destroyed. The energy required to operate the corresponding sources and sinks results in a super saturation of vacancies at one end of the specimen and an under -saturation at the other end. This gradient in vacancy concentration produces a chemical-diffusion flux, J(D), of vacancies in addition to the flux, J(E), caused by the electric current. Using the experimental data of Ch. Herzig,5 it is shown that a super saturation of 1 pct can cause J(D) to be about 25 pct of J(E), and thus account for the anomalous behavior of short specimens. THERE are advantages in a phenomenological treatment as contrasted to an atomistic one. For example, there are many reactions involving the element copper that are quantitatively and usefully understood from a phenomenological viewpoint, even though electron theory is not yet able to predict whether copper should be fcc or cph.' Similarly, the lack of a complete atomic theory of vacancies need not prevent the development of a treatment based on thermodynamics and chemical kinetics. In the following discussion, models will be used for the vacancies and for the mechanisms by which they move or are created or destroyed, but the phenomenological treatments are not dependent on the details of these models. The important product of a phenomenological analysis is an equation that describes the relation among the measurable quantities determining the behavior of the system. Based on such an equation, experiments can be performed to study these quantities in detail. Eventually atomic theory will supply an adequate theoretical base for the phenomena in question. A chemical species whose chemical potential was invariant during reactions in binary and ternary systems of varying composition would indeed be an anomaly. Yet this is the role that has frequently been assigned to the vacancies in pure metals, in dilute solutions, and even in ordinary alloys. The weight of available evidence supports the view that supersatu-rations of vacancies are on the order of 1 pct in usual diffusion processes.' Although it may seem strange that such a small deviation from equilibrium could significantly affect the thermodynamic properties of the vacancies, it is well known that the driving force for an ordinary chemical reaction is the departure of the components from their equilibrium state. Similarly, the reaction of vacancies that results in the formation of pores in various types of diffusion3 can reasonably be attributed to the supersaturation of vacancies. In the present paper, it will be shown that small degrees of supersaturation can significantly affect the kinetics of the diffusion process itself. ISOTHERMAL ELECTRODIFFUSION Two different experimental techniques are convenient for studying the behavior of vacancies in a pure metal in the presence of an electric field. Gilder and Lazarus4 studied self-electrodiffusion in a gold specimen in which only the central portion was at high temperatures. In this case the significant vacancy sources operate inside the specimen in the presence of a temperature gradient. In the laboratory of Th. Heumann a method has been devised for studying self-electrodiffusion at constant temperature.5 In principle, there is then no effect of thermodiffusion. It will now be shown why in this case the significant ATungsten disks \^^ ^^ ^Gold disks^^ ^^"T>.... "TTZA ? Up Iy'7 markers ///// ////// initial plane p I y/y/y of joining \I 7//// V7//A_________I_________V//// -I 0 +I Distance from center of specimen (a) -— Direction of flow of electrons —Direction of flw of vacancies %yy} Matano I z~irkendall /%W, vy/A inlerfacej "interface ///// -} HfiK- +/ 0 Distance from center of specimen (6) Fig. 1—-Schematic illustration of the essential features of isothermal self-electrodiffusion. (a) Initial condition of specimen. (b) Condition of specimen after electrodiffusion.

Jan 1, 1970