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By S. H. Ash

THE MAGNITUDE of the anthracite industry's drainage problem in the Northern field of Pennsylvania is realized when it is known that, for the 8-year period 1944-51, all pumping plants in this region pumped an average volume of 112.5 billion gallons of water from the mines to the surface each year. This is over 214,000 gallons per minute pumped against an average hydrostatic head of 400 feet each year for that period (12).4 By comparison, Lake Wallenpaupack, the largest artificial body of water lying wholly in Pennsylvania, contains 71 billion gallons of water in its 24-square-mile area; the average volume of water pumped from the mines in the Northern field each year during the 8-year period was 58 percent more than the volume impounded in Lake Wallenpaupack. The natural configuration of the drainage area overlying the Northern field subdivides the total area into two major drainage areas-the Lackawanna River drainage area and the Susquehanna River drainage area overlying the Wyoming Basin. Although the 169-square-mile drainage area overlying the Wyoming Basin is slightly less than half that of the Lackawanna River drainage area (10), the total volume of water pumped to the surface from mines in the Wyoming Basin is 21 percent more than the total volume pumped to the surface from mines in the Lackawanna Basin. From this, it is apparent that the Susquehanna River and the pervious deposits in the buried valley over which it flows in its course across the coal measures of Wyoming Valley is the greatest single source of mine water affecting mines in this area. Because of its relatively flat terrain, the wide flood plain of Wyoming Valley does not facilitate rapid runoff; consequently, much of the surface water seeps directly into the buried-valley deposits and eventually into the mine workings.

Jan 1, 1953

By A. D. Mutch

IT has long been known that there are wide variations in the thermo-electric potential of pyrite. In the last few years a study of this variation and other properties of pyrite was carried out at the University of Toronto by F. G. Smith on specimens of pyrite from many loyalities. As a result of these studies the pyrite geothermometer was developed by Professor Smith. The calibration of the pyrite geothermometer is based on the assumption that "crystals of any one electronically conducting mineral species deposited at a high temperature have a more positive thermoelectric potential than crystals deposited at a low temperature, and the thermo-electric potential varies continuously between any given limits of the temperature of deposition." The cause of the variation was postulated to be crystal discontinuities, such as lineage boundaries. As yet this postulated relationship has not been established as fact. On theoretical grounds it is indicated that the thermo-electric potential of pyrite or any other partial conductor is dependent upon a number of factors as well as the temperature of formation. For this and other reasons there is ground for doubt as to the validity of the relationship postulated above. To date a large number of readings have been made with the pyrite geothermometer which have been recorded in terms of the calibration of the instrument in degrees centigrade. So far most of the pyrite tested by this technique has been in association with gold ore. The values for the temperature of formation obtained in these tests appear to be reasonable and, in relation to geological problems, to vary in the right sense. Determinations on some specimens not in association with gold ore have given readings that appear to be much too high, taking into account the probable maximum temperature of the host rock. To sum up, although many determinations made with the pyrite geothermometer appear to give reasonable values for the temperature of formation of the pyrite, there are at the same time other readings which seem anomalous. On the basis of an examination of available results of work with the pyrite geothermometer, two problems must be considered: 1—the validity of the calibration of the pyrite geothermometer; and 2— the nature of the distribution of the thermo-electric potentials of pyrite in relation to the specific problems that have been examined. In this paper the academic problem relating to the validity of the calibration of the pyrite geothermometer will not be discussed. Instead, the variations of thermo-electric potential of pyrite in association with gold veins will be discussed with regard to specific examinations. The first of these two examinations deals with the distribution of thermo-electric potentials of pyrite in association with a gold vein and was carried out in the McIntyre Porcupine Mine, Schumacher, Ont., in the summer of 1949 as part of a study with this technique. The second problem deals with variations of thermo-electric potential of pyrite in gold ore specimens from all over the world. The specimens used in this study were part of the private collection of Frank Ebbutt, geologist for Howe Sound Exploration Co. Results of Detailed and Reconnaissance Studies In discussion of the results of determinations made in these two studies the values of thermo-electric potential in millivolts will be used. It will be noted that in some of the diagrams the determinations are recorded in terms of pyrite geothermometer temperatures. Fig. 1 is a calibration chart relating pyrite geothermometer temperatures and thermoelectric potentials. A full discussion of the technique is given in the original paper by F. G. Smith.' Briefly, the determinations are made by placing two stainless steel probes, one hot and the other cold, against the surface of the pyrite crystal being tested. The thermoelectric potential that is developed is read with a null-point potentiometer that is calibrated in what

Jan 1, 1953

By F. R. Zacher

Unmined blocks in the Sewickley seam, surrounded by worked out areas, have been found to transmit overburden oads through the interval strata to the Pittsburgh seam workings 90 ft below. Operating experiences under these conditions are described in this paper. IT has always been understood, in northern West Virginia where both the Pittsburgh and Sewickley seams are mined, that pillaring or splitting in the lower Pittsburgh seam could break the interval strata and make mining in the overlying Sewickley difficult or impossible. In some instances, however, mining methods practiced in the overlying Sewickley have reversed the problem, resulting in a shifting of the intermediate layer and destroying valuable acreages of the Pittsburgh seam below. The Pittsburgh seam in this area is, on the average, 102 in. thick. About 18 in. of low-quality head coal are left for roof protection as it is mined. Immediately over the coal are two draw slates, two rider seams, and a good hard black shale, locally called black rock, which serves as a permanent roof where draw slates and riders are taken down on certain main haulroads. In most areas mined in this seam in the past the bottom has been satisfactory but soft. However, in areas now being mined by the Christopher Coal Co. in Monongalia County the bottom is very hard and unyielding. The Sewickley seam, lying 85 ft above the Pittsburgh, will average nearly 70 in. in thickness and is overlain by massive shales and sandstones. Much of the seam is mined only down to the "sheep skin," a hard band about 4 in. above the bottom, which is composed of relatively hard shale. Fig. 1 shows a typical cross-section through the Pittsburgh and Sewickley seams in the area being discussed. The thin Redstone seam is not deep-mined but is stripped in some locations where it outcrops. Most of the Sewickley seam in the Morgantown areas has been mined out from 10 to 30 years. There are at present only two large mines and five or six others of small production operating in that seam. Mining systems in the past were generally of the room and pillar type with some full pillar extraction. This seam in the Scott's Run area was operated by as many as thirty or forty different companies at one time, during an era beset with strikes, market failures, and depressions. Most of the barrier pillars along the many main haulroads were abandoned, and blocks of Sewickley coal that would be fully recovered with today's machinery were left unmined when conditions became anything less than favorable. Consequently the mined-out Sewickley is spotted throughout with solid blocks varying in size from 100x100 ft to 200x400 ft and larger. It is these unmined Sewickley blocks surrounded by worked-out portions that have caused transmissions of roof stresses to underlying Pittsburgh mining areas, see Fig. 2, resulting in untold difficulty. As the Christopher Coal Co. operates both the Pittsburgh and Sewickley seams, accurate maps of workings in both seams are readily available and are regularly consulted. The first Pittsburgh squeeze attributed to overlying Sewickley blocks occurred in the Arkwright mine, where a shuttle car crew was developing a section consisting of seven panel headings. These entries were being driven in solid coal 3400 ft from the nearest worked-out Pittsburgh area. As mining advanced it was noticed that certain ribs began to slough and certain areas to show signs

Jan 1, 1953

By Andrew Allan

[Research conducted by the Bureau of Mines hrinq the last 5 years on the uce of machines for 7!naer:rolmrl ?.eve loym~nt in pi.t,c hlng anthracite beds l~a~ provide? data ?howin? that ?:;panrt of thc roof an9 str?eg of thes? oTen - jnqs requires almst half of' the PRS? workin? time. The possibilitie~ of i!rinz a mvable,. te1.ee*co@. c tpr? 3f ?tee1 ~h-!.oltl at the face in~tetcrl of conventional wood a*ti~yorts w?r? si:~q~eteil by engineers engaqad on the~ work If ~uch a shi~l8 COLI.~,~. be ~sve~.~yad, it tnillil man that face workera w~uld be provi8ed with mulrnu.m prot?ct+on from falls of' roof and ribs mi! the en- tire ehift could he I~W? Lo ~lro,J.~:ce cocl. Fermanent tim3er coald be p'l.acnA behind the shielR independently of the 'face work as the face advanced.]

Jan 1, 1953

By J. P. Morris

PREVIOUS investigations1,2 have shown that alloying elements in liquid iron influence the thermodynamic activity of sulphur and thereby affect the partition of sulphur between metal and slag in the desulphurization process. For example, the greater efficiency of desulphurization in the blast furnace as compared to the open hearth can be attributed in part to a higher level of sulphur activity in blast-furnace metal due to the higher concentration of carbon and silicon. In the present investigation, a short study was made of the influence of manganese on the activity of sulphur in liquid iron and iron-carbon alloys. In contrast to carbon and silicon, manganese was found to decrease the activity coefficient of sulphur; and in iron-carbon alloys it counteracts to some extent the influence of carbon. However, at manganese concentrations normally present in the blast furnace or open hearth, the effect of manganese is small. Since manganese sulphide has a limited solubility in iron, manganese can act, under certain conditions as a desulphurizing agent. Considerable data on the manganese-sulphur product in carbon-saturated melts were obtained in the investigation and have been included in this report. The experimental procedure was the same as that used in the earlier investigations on the effect of silicon' and carbon' on sulphur activity. Briefly, the method was as follows: The molten alloy, contained in a graphite or sintered alumina crucible, was brought to equilibrium at a constant temperature with a mixture of hydrogen and hydrogen sulphide of constant composition by bubbling the gas through the metal. Samples of' the melt were taken for analysis at regular intervals by suction through a 2 to 3 mm bore silica tube dipped into the metal. The experiments were run in a graphite spiral resistance furnace with melts weighing 50 to 60 g. The gas bubbling tubes were made of sintered alumina and were 5/16 in. OD, 1/16 in. ID, and 24 in. long. Equilibrium was assumed to have been attained when the sulphur content of the liquid metal reached a constant value. During an experiment there was a rapid loss of manganese from the melt by volatilization. To offset this loss, small additions of manganese were made periodically. The rate of manganese addition needed to maintain a constant manganese concentration was determined in preliminary tests. In all of the experiments, deposits of manganese sulphide formed above the melts in a cooler region of the furnace. Apparently, these deposits resulted from a reaction between manganese vapor and hydrogen sulphide in the gas. To prove that manganese sulphide did not volatilize from the melts to a measurable extent, an experiment was run in which helium was bubbled through liquid iron containing both manganese and sulphur. Although manganese volatilized rapidly in this test, there was no appreciable loss of sulphur. Volatilization of manganese sulphide from a melt would have led to an apparent equilibrium condition in which the sulphur content of the metal was lower than the true equilibrium value. The experimental results are shown in the first seven columns of Table I. The data in the last two columns were obtained from the previous work on the effect of carbon' and show what the results would have been in the absence of manganese but with temperature, gas composition, and carbon content of the metal remaining the same. Comparison of the last four columns show that, in the presence of manganese, the sulphur content of the metal increased at equilibrium and the activity coefficient of sulphur decreased. However, the results show that, for manganese concentrations below 3 pct, the effect of manganese is small. The values for activity coefficient of sulphur given in Table I were calculated from the following relations: S (in liquid metal) + H2 (gas) = H2S (gas) [l] K ph2s/?s X %S X phg = 0.00251 [2] where K is the equilibrium constant for the reaction, PH2S and ph2 are the partial pressures of hydrogen sulphide and hydrogen, respectively, and ?s is the activity coefficient of sulphur. The standard state for sulphur was taken to be a 1 pct solution of sulphur in pure iron. The numerical value for K at 1600°C was determined in the earlier work. For the purpose of showing graphically the results of the tests run at 1600°C, the activity coefficients of sulphur were recalculated so as to correspond to a manganese concentration in the metal of 2 pct in each case. In the calculation it was assumed that the increase in sulphur content of the metal at equilibrium caused by the presence of manganese

Jan 1, 1953

By S. R. B. Cooke, W. Philippoff, Donald E. Cadwell

THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle 8 is determined only by the reagent1 and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox&apos; showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0&apos; to the equilibrium value of 60". Further, Gaudin and Vincenta showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, 0 varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher&apos; were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by the difference of the free surface energies (surface tensions) of the respective phases 7j and yZ before contact and the interfacial free surface energy y, after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation of W from the surface tension of the liquid y and the contact angle 8: W = y (1 + COS0) [1] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are 8, and 8.. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: Wm = x-W2+ (l-x)-W, [2] in which W, is the work of adhesion of the composite surface. Eq 1 can be introduced into Wt and Wa, but in the case of W, some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle 8m calculated from W,, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that 0m would have a physical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically

Jan 1, 1953

By J. L. Wyatt

THE strain sensitivity, K, a property of metals defined as the unit change in electrical resistance per unit strain, was measured for commercial purity titanium wire to determine its usefulness as a strain gage material. A Kelvin double bridge, accurate to 0.000001 ohm, was used to make measurements from 0 to 1 pct total strain. A positive value of 0.17 for K was found. This compares with 2.15 for constantan and 3.5 for cold-worked invar, two of the more common strain gage materials. The effect of temperature also was determined. It was found that a change in temperature of 30°F caused the same resistance change as 1 pct strain. It is therefore concluded that titanium would have utility as a strain gage only if the thermal fluctuations in the specimen could be controlled to a high degree and in applications of very large total strain.

Jan 1, 1953

By G. H. Tausch, T. A. Huber

Very encouraging progress has been made ill the develop-ment of the permanent-type well completion which decreases considerable the cost of completions and workovers and aid-in the acquisition of reliable reservoir information at low cost. Completion and remedial operations are performed with tool,; which pass through the well tubing. Perforating and plug-hack operations can be done with the tubing in place and do not require pipe-handling equipment. Because of the many advantages afforded by this method, development work is going forward in anticipation of ultimately being able 10 use it to perform all usual well completion and workover operations. Effort is also being directed to the development of a more permanent type of lift equipment suitable for use with the permanent-type well completion. INTRODUCTION The permanent-type well completion in one in which the tubing and well-head are set in place only once in the life of the well and the completion or remedial work is performed through the tubing with a tubing-type perforator. a retrievable tubing extension. and other wire-line tools. This new type completion has made possible the saving of one to two days&apos; rig time in the completion of each of several hundred wells During the last two years, and use of equipment developed for this type of completion has resulted in a 75 per cent reduction in cost. of certain types of workovers. In addition. the more reliable indication of the commercial value of a reservoir and the more accurate general reservoir information made Possible promise to be of even greater value in oil recovery than the reduction of costs for completions and workovers Recently. several well.. were worked over by using the retrievable tubing extension suspended on a swab line to plug back with cement and then perforating a higher producing interval with the tubing-type perforator, thus opening the way for complete through-the-tubing workovers which may be performed without pipe-handling equipment or mud. Those items attendant to the use of pipe-handling equipment and mud. such as hoard matting rig substructure. and pits. were also eliminated. There are indications that the elimination of drilling mud during completion and workover operations will frequently give increased well productivity, as plugging of the perforation. will not occur. It ii now possible to perforate selectively small sections of the producing interval and to test a well through these sections prior to perforating more interval. The perforating of additional interval will not entail the costly operations of killing the well and pulling tubing, nor will the old or the new perforations be plugged. The productivity of .mall sections of a reservoir and the actual gas-oil or oil-water contacts may now be determined economically under flowing condition.. Selective completions can be made in this manner to delay gas and water problems and bring about maximum oil recovery. At the present time, gas lift appears to offer the greatest potentialities for artificial lift in the permanent-type well com"letion since it can provide full-open tubing to accommodate the through-the-tubing tools and it may be ultimately developed into a fairly permanent type of lift. With precent-day pas-lift equipment. valve or mandrel failure necessitates occacio11al removal of the tubing. thereby reducing to some extent the permanence of the completion. New gas-lift valves are now

Jan 1, 1953

By A. Ignatieff

"Demonstrations of Automatic Coal Burning EquipmentAT THE 1951 and 1952 Annual Coal Research Conferences sponsored by the Dominion Coal Board and attended by delegates from the Dominion and Provincial governments as well as industry, the importance ,of encouraging the co-operative interest of Canadian coal and equipment industries in •promoting the use of equipment types best suited to burn given Canadian coals was emphasized. It. was suggested that this idea •be enlarged upon at forthcoming C.I.M. meetings that would be .attended largely by coal mining engineers.With this in view, a Domestic Heating Forum (1) was featured in the Coal Division programme at the 1951 Annual Western Meeting of the Institute in Calgary, and a much more ambitious programme, highlighted by live demonstrations, was •staged at the combined Annual Western Meeting and Fourth Meeting of District 4 held in Winnipeg in October 1952.With the excellent co-operation of a number of equipment manufacturers and coal companies, and with facilities kindly provided •by the University •of Manitoba authorities, burning demonstrations were• arranged in the Agricultural Engineering Building, on October l 7th. These demonstrations were a fitting sequel to the Coal Division sessions held in the Royal Alexandra Hotel on October 16th, at which the combustion of coal was specially featured in a series of papers by prominent Canadian and United States specialists.The primary purpose of the demonstrations was to •show that all coal, regardless •of rank, can be satisfactorily used provided that proper application is made with equipment suited to its purpose."

Jan 1, 1953

By T. E. Leontis

Data are presented in this paper to show that addition of zirconium to sand-cast Mg-Th alloys effects a marked decrease in the grain size of these alloys which is accompanied by a significant increase in the mechanical properties over the entire range of thorium content investigated. The beneficial effect of zirconium on the strength properties is maintained at elevated temperatures up to 700°F. In addition the alloys exhibit exceptionally high creep resistance at temperatures up to 600°F. Zirconium does not greatly improve the strength or creep characteristics of extruded Mg-&apos;Th alloys. Cerium is not a desirable addition to Mg-Th-Zr alloys. IN a previous paper,&apos; it was shown that addition of thorium to magnesium imparts exceptionally high resistance to creep at elevated temperatures both in the sand-cast and in the extruded states. The large grain size of the sand-cast alloys, however, renders them of questionable value as engineering materials. Sauerwald² showed that the grain size can be reduced effectively by the addition of zirconium. Results of a detailed study of the properties of Mg-Th-Zr alloys over a wide range of thorium content are presented in this paper. In accordance with the preliminary findings of Sauerwald,² it is shown here that Mg-Th-Zr alloys possess the unusual combination of fine grain size and a high level of strength and creep resistance at elevated temperatures. Some information on the effect of cerium on the properties of Mg-Th-Zr alloys is presented also. Effect of Th on Solubility of Zr in Molten Mg Sand-cast test bars and 3 in. diam extrusion billets of Mg-Th-Zr and Mg-Th-Ce-Zr alloys* were pre- pared according to the procedures described in the previous paper.&apos; The zirconium was added in the form of sponge metal as supplied by the Bureau of Mines.&apos; The maximum amount of zirconium that usually can be introduced into magnesium at the customary alloying temperature of 1350° F is about 0.7 pct. The analyses in Table I clearly show that thorium in- creases the solubility of zirconium in liquid magnesium. The tabulated zirconium contents are designated as "acid soluble;" this serves to distinguish these values from the small amount of zirconium that is not dissolved when the alloy is subjected to the action of a dilute acid solution. The "acid-insoluble" zirconium is believed to be ineffective as an alloying ingredient. The acid-insoluble zirconium contents ranged between 0.03 and 0.16 pct in the present alloys, the tendency was toward higher values in alloys with higher thorium content. In contrast to the effect of thorium, cerium decreases the solubility of zirconium in magnesium. This is shown by the three Mg-Th-Ce-Zr alloyst in- cluded in Table I and stands in agreement with the observations of Nelson and Stricter".&apos; on Mg-misch-metal-Zr alloys. Effect of Zr on Grain Size of Mg-Th Alloys The potent effect of zirconium as a grain refiner has been demonstrated for many types of magnesium alloys.3-8 Of greatest importance to date are Mg-Zn-Zr alloys5,6,8 and Mg-mischmetal-Zr alloys.3,4,7 Zirconium has also been found to exert a marked grain-refining action on Mg-Th alloys. All the Mg-Th-Zr alloys cast in the form of ½ in. diam test bars have an exceedingly fine grain size (Table I). Reference to the previous paper&apos; will show that binary Mg-Th alloys containing up to 6 pct Th are almost completely columnar even in the M in. diam reduced section of a test bar, and that 10 to 50 pct Th alloys have an equiaxed grain structure of 0.03 to 0.08 in. The data in Table I also show that addition of cerium to Mg-Th-Zr alloys has no effect on the grain size. In addition to increasing the strength properties, the fine grain size of Mg-Th-Zr alloys

Jan 1, 1953

By R. C. Buehl

[Improvements in refractories for high-temperature service have made possible the use of higher temperature in many processes. Consequently, it sometimes is desirable to use gases heated above 1,600° F., and for moderate rates of gas flow, there gases can be heaters best with pebble heaters. Pebble heaters of the stationary-bed type in which the chanber was lined with mullite brick and pebbles of pure alumina served as the heat-exchange medium have been used recently to heat the air blown into an experimental blast furnace4/ These pebble heaters worked well and made it possible to use air temperature up to 2,500° F. at the tuyere of the furnace. Since little has been published on this type of gas heater, a review of the construction on employed and operating data should assist in selecting applications and designing units.]

Jan 1, 1953

By R. W. Balluffi, B. H. Alexander

RELATIVE diffusion rates of copper and zinc in a brass have been measured in a vapor-solid type of couple with which the amounts of copper and zinc diffusing past inert Kirkendall markers can be obtained by means of a few simple experimental measurements. If inert markers are placed on the surface of copper which is then exposed to zinc vapor from a brass chips, the particles become buried due to outward diffusion of the copper, as shown in Fig. 1. A schematic diagram of such a couple after diffusion is shown in Fig. 2. Consideration of the diffusion flow of copper and zinc shows that the entire hatched area, including the cross-hatched area, is proportional to the amount of zinc diffused inward past the markers and that the smaller cross-hatched area is proportional to the amount of copper diffused outward past the markers. These areas are completely determined by the expansion of the couple, the depth of the buried particles below the surface, and the chemical composition at the specimen surface. As Darken1 has shown, the ratio of diffusivities of copper and zinc is then given by the ratio of these two areas. Polycrystalline copper and two copper single-crystals made by the Bridgman method were prepared in the form of 1.5 cm diam disks approximately 0.5 cm thick with faces plane and parallel. Tungsten particles approximately 0.001 cm in diam were bonded to the surface of each disk by heating 5 hr at 1060°C in vacuo. Each specimen was next

Jan 1, 1953

By C. E. Lesher

THE Disco* process for the production of low temperature coke and its immediate predecessor, the Wisner or Carbocite process have been described in the voluminous literature of low temperature carbonization.1 This paper will describe the development of the process from the first attempt at commercial operation by the American Gas and Electric Co. at Philo, Ohio, Yn the 1920&apos;s to the successful operation in 1949 by the Disco Co., a division of the Pittsburgh Consolidation Coal Co., of the 1000-ton per day Disco plant near Pittsburgh, see Figs. 1-2. In the 1924 coal industry depression following the hectic post World War I expansion, the northern Appalachian, unionized bituminous coal fields were affected first and foremost, and Western Pennsylvania as hard as any. Competitive market pressure was heaviest on the lower grades of steam coals, notably the from the Panhandle district where ash and sulphur are inherently higher than in the same Pittsburgh coal bed to the east along the rivers. The firm structure of Panhandle coal while favoring the prepared sizes, depressed the usefulness and value of the finer sizes. Panhandle slack and nut slack were marketed with difficulty at consistent, and at times considerable, loss. Many solutions were suggested, and the Pittsburgh Coal Co. investigated all. Lower delivered prices through lower mine costs and more advantageous freight rates were obvious goals, but equally obvious were the difficulties of self attainment of either in any substantial measure. Selling Btu&apos;s in pipes was abandoned as an idea after a thorough study of the economics of distribution of what was then, and is even now, the only developed continuous process of complete gasification of bituminous coal-producer gas. Although the coal company purchased huge blocks of electric power, it sold not a car of coal to the central power stations. Public utilities controlled the markets for electric current, and it was found that no matter at how low a cost current might be put on the bus bars by the coal company, distribution to its widely scattered coal mines made such an enterprise practically impossible. Consolidation of underground operations and a huge modernization program of mining operations in the 1920&apos;s were but preparation for the introduction of mechanical cleaning of the coal for market, particularly the smaller sizes of steam, gas, and by-

Jan 1, 1953

By M. B. Bever, J. E. Reynolds

IN several alloys of iron, copper, and lithium as well as in some pure metals, martensite formed on cooling reverts to the parent phase upon heating to a temperature below the equilibrium temperature at which the parent phase becomes stable.&apos; These martensitic transformations, therefore, are thermally reversible, although appreciable hysteresis may be involved. The martensitic reaction has long been

Jan 1, 1953

By Reginald S. Dean

THE commercial availability of electrolytic manganese has greatly changed the position of manganese as a nonferrous alloying metal. Manganese metal commercially available up to about ten years ago was reduced with either silicon or aluminum and contained substantial amounts of the oxides of these metals and other impurities. Manganese was accordingly not available as an alloy base and its addition to copper-base and nickel-base alloys was generally limited to a manganese content of a few per cent. Several special alloys like manganin contained up to 12 pct of manganese. A method for the production of electrolytic manganese was developed by the Bureau of Mines in 1936 and commercial production was begun in 1938. At the present time (June 1951), production is about 12 tons per day but appears likely to be substantially increased. Electrolytic manganese is deposited from an aqueous electrolyte containing manganese and ammonium sulphates and is marketed as cathode fragments about 1/8 in. thick. The impurities in its composition are as follows: iron, 0.0015 pct; copper, 0.001; arsenic, 0.0005; cobalt, 0.0025; lead, 0.0025; molybdenum, 0.001; sulfide sulfur, 0.017; sulfate sulfur, 0.014; insoluble, 0.002; carbon, 0.002; hydrogen, 0.015. These figures are from Bulletin 463, U. S. Bureau of Mines. From an alloying standpoint, the most important impurity is hydrogen. This can be removed by heating; 95 pct of the hydrogen can be removed in this way without introducing significant amounts of oxygen or nitrogen. Much of the commercial electrolytic manganese used in alloys is dehydrogenited by the producer, since the amount

Jan 1, 1953

By E. S. Machlin

RECENTLY, there has been much activity in the field of nucleation of martensitic transformations.&apos;- One of the problems in this field is the calculation of the rate of nucleation (number of plates nucleated per unit untransformed volume per unit time) in terms of observable parameters. Two such observable parameters are the fraction of the length of a straight line which corresponds to the portion of the total length of the line that lies in the martensitic phase and the number of plates intersected by this straight line per unit length of line. Because of the necessity of a valid answer to this problem, the following investigation was undertaken. Although this problem has been treated in the past, a derivation of the relation between the volume and linear fractions of martensite will be described to illustrate the method used in the succeeding analyses. It is assumed that the martensitic plates are in the form of a right circular cylinder having a small height relative to the radius of the base. The volume fraction of martensite is then: fr = lXNl,hjAl [1] where f, is the volume fraction of martensite, and Nij is the number of plates per unit total volume having the area Ai and the height hi. The linear fraction of martensite is obtained as follows. For the plates having the particular area A, and height h,, the fraction sin 0 dB* will have their cylinder axes between the angles 0 and 0 + d0 to the straight line along which the linear fraction of mar-

Jan 1, 1953

By F. S. Buffington, Morris Cohen

THERE is little quantitative information available concerning the effect of applied stress, in both the elastic and plastic ranges, on diffusion kinetics. Accordingly, a program has been undertaken to determine the rate of self-diffusion in high purity iron, with the specimens subjected to stress during the course of diffusion. Results are reported here for body-centered cubic iron at a diffusion temperature of 890°C. The iron used was 99.97 pct Fe, the principal impurities being 0.002 pct C, 0.008 pct 0, and 0.02 pct Si. The surface-decrease method of self-diffusion analysis was employed, and Fe55 Mn x-radiation, 2.9 years half-life) was the tracer element. Details of specimen preparation and equipment are given elsewhere.&apos; Disks of the high purity iron, % in. diam x 1/4 in. thick, were annealed at 890°C for 18 hr in dry hydrogen to produce large grains of a ferrite. The faces of the disks were then surface ground, and possible grinding stresses were relieved by annealing at 890 °C for 45 min in vacuum. A layer of radioactive iron 0.00186 cm thick was electroplated on one face of each disk. The self-diffusion coefficient was calculated from the ratio of the radiation intensities emanating from each of these faces, as measured before and after diffusion.&apos; The heating was carried out in a vacuum furnace (10-5 mm Hg) controlled to ±1.5°C. The specimens were loaded in compression between two quartz disks during the diffusion runs by means of a lever system operating through a vacuum seal. Thus one quartz disk was pressed directly against the radioactive face of the specimen, minimizing the vapor loss of radioactive iron. Steady-state creep occurred in all instances where permanent deformation could be detected, but the specimens did not exhibit appreciable transverse barreling until natural strains of 0.2 to 0.3 were attained. Essentially, the diffusion took place under uniaxial stress. The plastic strain in each case was obtained at the diffusion zone by measuring the diameter d there before and after the run: e = 2 In — do Let Du equal the self-diffusion coefficient which would have prevailed at the given temperature if no stress had been applied. This was calculated from the temperature-dependence equation which had been previously determined: —59,800 D, = 6.2 exp ( I sq cm per sec* [I]

Jan 1, 1953

By C. W. Sherman, John Chipman

IN the mathematical statement of the law of mass action, the activity of each substance consumed or produced in a reaction is used to obtain a numerical constant which is characteristic of the equilibrium of that reaction at the given temperature. The activity in many cases is equal to, or proportional to, the concentration. If this is the case, any units denoting concentrations, such as weight percentage or mol fraction, may be substituted in the equilibrium expression. It is even permissible to use mixed units provided only that each unit is that used in defining the activity of the corresponding substance. The indiscriminate use of concentration units in writing equilibrium constants sometimes leads to very erroneous results. On the other hand, what appear to be contradictory results from similar investigations often might be resolved if the activity is the quantity that is used to determine the equilibrium constant for the reaction in question. De-sulphurization serves as an important illustration. Sulphur in lron and Steel The control of the sulphur content of the finished product is one of the oldest and broadest problems in the metallurgy of iron and steel. In general, this control must be exercised through the action of a slag, and for this reason experimental studies of the distribution of sulphur between slag and metal have assumed considerable importance. Under slags of the type found in the basic open-hearth furnace the ratio (% S)/[% S] does not in general exceed about 8. Under blast-furnace conditions, however, de-sulphurization ratios of 50 to 100 are readily obtained, and under laboratory conditions using similar slags, the ratio may be as high as 400. The fact that blast-furnace metal is much more readily desulphurized than is molten steel rests upon two distinct phenomena. The first of these is connected with the slag reaction. In the open-hearth furnace, the equilibrium in the following reaction places a definite limit on the sulphur content of the slag: S + 0-- = 0 + S- - where the symbols underlined indicate elements dissolved in the liquid metal, while slag constituents are represented as ions. The high oxygen content of the open-hearth bath prevents this reaction from proceeding far enough to effect good desul-phurization. In the blast-furnace process, however, the oxygen activity is limited by the presence of carbon in the metal and in the coke bed and the controlling reaction becomes: S_+O- + C_=S- + CO(gas) [2] The second phenomenon which contributes to the easier desulphurization of blast-furnace metal is the effect of high concentrations of other elements. These elements, notably carbon, silicon, and phosphorus, increase the thermodynamic activity of sulphur several fold. As a result of this increase, the escaping tendency of sulphur from the metal phase is increased and its removal facilitated. Previous Studies It becomes, therefore, a matter of importance to determine the effects of various elements upon the activity of sulphur in the melt. The experimental approach to this problem has been made through the equilibrium between sulphur in the melt and gaseous atmospheres containing hydrogen and hydrogen sulphide. The reaction and its equilibrium constant are written as follows: S + H2(gas) =H2S(gas);K1 = -- [3] Pn2 • as where the symbol a, represents the activity of the sulphur in solution in the metal. The understanding of the chemical behavior of sulphur in steel and pig iron rests on a firm knowledge of the binary system Fe-S. A number of studies of the equilibrium have given closely agreeing results from which the activity and free energy of the dissolved sulphur may be found. The recent paper by Sherman, Elvander, and Chipman1 includes a discussion and quantitative comparison of the results of several of the significant researchesr-" on dilute solutions of sulphur in iron. The results of this study indicate that the relationship between the ratio Ph,s/p+ and the percentage of sulphur in solution is not a linear one. This

Jan 1, 1953

By F. W. Glaser

Metal-carbon-boron powder mixtures were hot pressed and the resulting specimens were studied by X-ray diffraction. It was found that regardless of the starting combination of the metal, carbon, or boron powders, a metal boride phase was always the major component in these samples. In the absence of carbon the boride phase formed on hot pressing depended only on the amount of boron present. Two new phases of the system Ti-B were found. They are Ti2B and Ti2B5. The existence of a controversial face-centered cubic phase of formula TiB was confirmed. Electrical resistivities were measured for various boride phases. It was found that the diborides are generally better conductors than the monoborides of the same metal. THE carbides and borides of the transition elements have very high melting points, in the range 2500° to 4000°C, and are therefore of interest as high temperature materials. The literature on the stability or chemical reactivity of these carbides and borides is very scarce. Various investigators&apos;-" have demonstrated a relative instability of certain carbide phases in the presence of boron or boron-containing substances. In a recent publication, Glaserl demonstrated the stability of zirconium-boride (ZrB,) in the presence of carbon at temperatures in excess of approximately 2900°C, while during a preliminary investigation of boride phases, Steinitz&apos; concluded that the diborides are stable in the presence of carbon while the monoborides of the fourth and fifth group are not, forming diborides plus carbides instead. Nelson, Willmore, and Womeldorph" have elaborated on the reaction B,C + 2TiC = 2TiB, + 3C, which was known to occur because of a relative instability of B,C and the great tendency towards TiB, formation at relatively low temperatures (approximately 1200°C). A similar study, involving as starting materials TiO, and B,C and resulting in TiB,, was recently described by Honak4, who observed the beginning of an exothermic reaction of a Ti0,-B,C powder mixture, which, when preheated in a hydrogen atmosphere to approximately 950°C, was carried to about 1600 °C by the heat of reaction. To shed more light on reactions of this type (Metal-C-B), the final product apparently always resulting in a boride phase at the expense of a carbide phase," a systematic investigation was started * Boride phases of various metals, as reported to date, are listed in Table I. and the following is an account of some of the results that were obtained. Materials, Preparation of Samples, Testing Methods The raw materials employed for this work consisted of various carbide, boride, and metal powders. as well as of boron and graphite powders. In cases where commercial grades of carbides were considered unsuitable because of low purity or excessive amounts of graphitic carbon, such carbide powders were prepared by this laboratory. The procedure for the preparation of carbide powders (zirconium carbide, titanium carbide, tantalum carbide, and niobium carbide) consisted of mixing graphite and the respective metal hydride powders in stoichio-metric proportions and subsequent heating of such mixtures in a hydrogen atmosphere in carbon crucibles. The heating was by high frequency to temperatures ranging between 1700" and 2100°C. The resulting carbide was then comminuted and screened to the desired particle size. ZrB, and TiB, powders were produced by the electrolysis of fused salt baths, according to the method described by Andriex.. The borides of niobium, vanadium, tantalum, molybdenum, chro-ium, and iron were obtained by mixing the respective metal and boron powders in the desired proportions. Such metal-boron mixtures were heated in a high frequency furnace to form boride powders. For each metal-carbon-boron group (Tables I1 through XI) a metal, its hydride, carbide or boride were mixed with carbon, boron or boron carbide powders. The additions of carbon, boron or boron carbide powders to any of these metals or metal compounds were calculated to satisfy a particular carbide or boride phase that according to the literature (Table I) had definitely been established by X-ray diffraction work. Samples of powder mixtures were hot pressed in graphite molds that were heated by direct conduction. The specimen dimensions were approximately 2.5X1X1 cm. Hot pressing temperatures were measured optically and maintained for approximately 30 sec under a constant pressure of about 1.3 ton per sq in. Wherever possible, an attempt to obtain maximum specimen density was made by temperature variation. Electrical resistivity testing was done by measuring potentiometrically the voltage drop over a length of 1.5 cm for a current of 10 amp, at room temperature. To obtain electrical resistivities for specific carbide or boride phases, values were plotted as a function of the respective sample densities

Jan 1, 1953

By C. J. Mains

The gas -flow oil-shale retort is a continuous, crass flow, gas -to -broken solid heat-exchange system in which heat is transferred by convection from the gas to the solide.2/ This type of heat transfer presents a problem of analysis that cannot be solved by methods in common use. Solution of this problem is necessary for design, operation analysis, and predict ion wherever that type of heat exchanger is used. This report embodies a method for calculation of heat transfer coefficient and temperature histories of gas and solid in the gas- flow retort operating at equilibrium conditions. Detailed calculations are presented to show the application of the method explained in this report to conditions of an actual run made in the gas-flow retort. Although used here for a specific case, the method is applicable to all heat exchangers that are characterized by continuous, crossflow, gas -to-broken solid heat transfer. INTRODUCTION In any direct, gas -to -broken solid heat -transfer system, it is difficult to measure the temperatures of the gas and solid inside the heat exchanger. The driving force for heat transfer between the two media in the bed there- fore usually is unknown. The major resistance to heat transfer is in the gas film surrounding the solid particles, and the thickness of this gas film is neither uniform nor can it be determined readily. It is well to point out also that determination of the surface area of the particles is of poor accuracy. Since the driving force, the major resistance, and the surface area in the heat-transfer system are such uncertain quantities, It is not feasible to calculate the heat transfer by usual methods. All of the fore- going statements are true of the gas-flow retort; as a result, efforts were made to determine apparent heat-transfer coefficients and temperature histories of gas and solid in the heat -exchange bed by calculation using those data that were available. The heat -transfer coefficient calculated has the following dimensions: B .t .u. per second, °F., cubic foot of bed volume, where heat - transfer coefficients normally have the units; B .t .u . per hour, square foot, °F. Only the Schumann-Furnas formulas may be used to determine the heat- transfer coefficient and temperature histories in this type of heat exchanger.

Jan 1, 1953