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By Edgar Stansfield

ONE of the most striking features of the coal series passing from peat through brown coal, lignite, etc., up to anthracite is the gradual reduction of moisture content with the increased coalification of the original plant material. Thus drained peat from a bog may contain 90 per cent water, brown coal contain 50 per cent, lignite 30 per cent, while a bituminous coal may contain only 1 per cent moisture. Moisture, therefore, is one of the important factors to be considered in coal classification, especially with the lower rank coals. With bituminous and higher rank coals the moisture content is less satisfactory for classification; it may even pass a minimum value and then increase with increasing rank to anthracite and superanthracite. Coal in an undisturbed seam contains moisture which is an integral part of the coal, but it may also be wet with free, underground water percolating through the seam. Only the former must be considered in evaluating the moisture content of the coal for classification purposes; this will be called the "true moisture" of the coal. When the seam is mined and sampled the sample taken may show the true moisture; on the contrary, it may contain in addition free mine water or, especially in dry, well ventilated mines, it may contain less than the true moisture. Coal contains unstable organic compounds which may decompose, with the production of moisture, when the coal is exposed to air at ordinary temperatures, or is heated with or without exposure to air. The potential moisture of a coal therefore is higher than its actual moisture. The lower the rank of the coal, the greater its instability, as a rule, and the greater the care necessary to avoid oxidation or decomposition in any investigation of moisture content. The majority of coal workers have preferred, on account of the difficulty in evaluating the true moisture of a coal, and for other reasons, to classify coals by analyses calculated to the dry-coal basis. A number of workers familiar with lower rank coals have recently insisted that the classification of such coals can be satisfactory only if analyses on the moist-coal basis are employed. The moisture-holding capacity of coal is therefore intimately connected with coal classification, and in this paper a procedure is outlined for determining the true moisture of a coal.

Jan 1, 1932

By H. J. Gluiskoter

The chlorine content of the coals in the Illinois Basin ranges from 0.00% to more than 0.60%. The chlorine content of the Herrin (No. 6) Coal has been mapped on a regional scale and, in general, increases with the depth of the coal. The depth-chlorine correlation exists because the coal is in apparent equilibrium with the composition of the ground water associated with it, and the salinity of the ground water generally increases with depth. At least part of the chlorine can be easily removed from the coal in the laboratory. In a natural weathering experiment, chlorine values decreased markedly during an 8-week period. Results to date indicate that none of the coals studied has a sufficiently high chlorine content to make it unusable in high-temperature steam boilers, although special steps may be necessary in the preparation or utilization of some of the highest chlorine coals. Investigations into the occurrence and distribution of chlorine in Illinois coals have been in progress at the Illinois State Geological Survey for over 35 years. Since 1948, chlorine analyses of face channel samples and of drill core samples of coal have been made routinely. The increased interest in chlorine and alkalies in coal in the U.S. followed that in Europe, where power plants during World War II were called upon to produce at higher levels than previously and with less down time for maintenance. Higher steam temperatures were reached, resulting in increases in the amount of fouling of external heating surfaces and in corrosion of boiler tubes when high chlorine coals were used. Early studies of the problem showed that coals with high chlorine content were more likely than those low in chlorine to cause difficulties in installations fired with powdered fuel. Crossleyl reported that the first rule of thumb developed for British coals was that coals considered to be high in chlorine (more than 0.30%) caused the most trouble, those intermediate in chlorine content (0.15% to 0.30%) were less likely to cause difficulties and those low in chlorine (less than 0.15%) generally were not associated with alkali bonded deposits and corrosion. However, this relatively simple picture was not adequate to characterize the difficulties that could be expected during the utilization of a large number of coals and Crossley1 developed another scheme for assessing the chances of superheater corrosion. This scheme took into consideration the observation that coals high in sulfur as well as chlorine are more likely to cause corrosion and fouling than coals low in sulfur and high in chlorine. Crossley also considered the ash content. When two coals had the same chlorine and sulfur contents, the one with the greater amount of ash would be the less likely to cause difficulties. Knowing only the amount of chlorine in a coal obviously will not give all the answers. Indeed, the significance of the chlorine content has been much discussed and it has been suggested that perhaps the total alkalies are a better indicator of possible troubles. The observation that the deposits that form

Jan 1, 1968

By Research Staff ? Verde Copper Mines

FLOTATION is now commonly practiced in alkaline ore pulps, yet little is known regarding the action of the alkaline solutions on the ore particles beyond the fact that films of oxidized material form. We wish to chronicle our discovery of the presence of soluble reducing agents in alkaline ore pulps of the United Verde, and present some data on lime consumption. During the grinding and flotation of a pyritic ore containing small amounts of ferrous sulfate and other soluble salts, an excess of lime was added to precipitate the salts, and filtered samples of the solution were titrated with standard permanganate solution. Even in pulps of high causticity an appreciable permanganate titration was always obtained, in spite of the fact that the solutions were shown to contain little iron. Investigation of the cause brought about the discovery of several previously unsuspected compounds in flotation pulps made from pyritic ore. Not only the reducing agents present had to be identified, but also the amount of dissolved oxygen, and a survey was finally made of the free oxygen content and reducing agents of the mill pulp in the concentrating mill at Clarkdale. A great many. compounds might form, caused by oxidation of pyrite or other metal sulfides or by reaction between a lime solution and pyrite. The most probable compounds considered were calcium sulfides, polysulfides, thiosulfates, and polythionates. Later it was discovered in the literature that in alkaline pulp polythionates do not exist and if introduced are decomposed into sulfites and thiosulfates.1 Any precipitated sulfur is changed by alkali into thiosulfate and polysulfide. Sulfites and sulfides react to form thiosulfate, so that in the end it is possible to have in an alkaline solution only thiosulfate and an excess either of sulfide or sulfite. Confirmatory tests were made and it was finally established that the alkaline mill pulps made from the United Verde ore contained

Jan 1, 1929

By Charles White Merrill, James W. Pennington

No metallurgical process developed in the 20th century compares with froth flotation in its effect on the mineral industry. Processes like gravity - concentration, amalgamation, and pyrometallurgical reduction are of ancient origin; others like cyanidation and electrolytic reduction were well established by 1900. Such metallurgical processes as heavy-media separation, ion-exchange, and solvent extraction belong to this century, but their influence is small compared with froth flotation. Data collected by the U. S. Bureau of Mines* in a canvass of 202 froth flotation plants reveal that, in 1960, 198- million tons of material was treated to recover 20-million tons of concentrates which contained approximately $1 billion in recoverable products. SIGNIFICANCE OF FLOTATION Froth flotation as described in this chapter refers to a wet process for separating properly ground mineral particles into two or more products. It involves the separation of mineral particles from each other in a liquid pulp by means of air bubbles. Finely crushed ore is agitated in water with the addition of air or other gases. Various chemicals and oils are added to cause the selected mineral particles to attach themselves to the air or gas bubbles. These bubbles, carrying the mineral particles, rise to the surface where they are removed in a froth, while the other particles remain suspended in the pulp. The earliest flotation divided the raw material into two products: a bulk concentrate that was removed as a froth and a tailing that remained in the flotation machine. The froth usually contained the valuable constituents. The successful application of such a process depended on the recovery of a single concentrate from which one or more valuable constituents could be recovered by a chemical or smelting process. With the advance of the art, however, the principle of selective flotation, by which two or more relatively pure products could be recovered from complex raw materials, was evolved. Other chapters in this volume describe the developments during the last 50

Jan 1, 1962

E. E. THUM,* Salt Lake City, Utah (written discussion?).-While the present paper is confined exclusively to the microstructure of fusion welds, it may be of interest to draw attention to certain appearances existing in resistance welds such as spot or butt-welded joints produced by the Thomson process. For instance, a butt weld between two pieces of carbon tool steel (carbon about 0.90 per cent.) will show concentric ellipsoids of the various materials from pearlite to martensite. The surfaces of demarcation are quite well defined, the center of the ellipsoid being at the intersection of the axis of the piece and the plane of the weld. Often these unannealed welds show a troostitic center; evidently this core was not quenched as rapidly as the surrounding shell. Such specimens are beautiful samples for instruction purposes. An annealed butt weld of this kind will show a very well defined central ellipsoid of decarburized, materials. It is interesting to consider the reason why this change takes place. It must be understood that the heat is on the metal for a very short time, possibly 30 sec. It is therefore evident that the decarburization, or migration, of the carbon takes place with extreme rapidity. Since no blowholes are evident in a well-made butt weld, the deoxidizing air and the products of combustion must migrate with the highest speed; second, the carbon might migrate back into the stock; or, last, a large proportion of the pearlite may be extruded with the hot metal, which forms a fin at the plane of weld. Examining these possibilities in detail, it is not probable that such deep-seated decarburization, extending with maximum effect to the very center of a 2-in. round bar, is done by reaction with the oxygen of the air. This would postulate entrance of oxygen and egress of carbon oxides in large quantity without leaving behind traces in the form of oxides or

Jan 5, 1919

By V. A. Josendal, J. W. Wilson, B. B. Sandiford

Two radioactive tracers have been tested as a means of determining core saturation in multiphase flow studies. Cesium chloride was tried as a water-phase tracer, but complications in its use in low permeability cores resulted from sorption of cesium by the core or water-wet pads. IodoI3'ben-zene proved very satisfactory as an oil-phase tracer. The synthesis of iodobenzene from the sodium iodide as received from Oak Ridge is simple and direct. The tracer is insoluble in water and there was no evidence of sorption by any of the core materials used. use of the method to determine saturation profiles during capillary and dynamic desaturations and relative permeability measurements on oil-water and oil-gas systems is described. Comparisons of the dynamic and capillary methods of relative permeability determination were made using the tracer to check core saturation and saturation distribution. Other experiments are also described in which mobility of the oil phase at various saturations was measured by displacing labeled oil by flowing inactive oil. Similar experiments were made using water labeled with cesium 134. INTRODUCTION To be fundamentally sound. any laboratory method of determining relative permeability must meet, among others, the following requirements: (1) the core saturation between the pressure taps must be uniform, and (2) there must be uniform pressure difference between the phases in the region between the pressure taps. In practice it may eventually be shown that appreciable departure from either or both of these conditions may be permitted without introducing sensible error. but the magnitude of such error remains to be established. There is need then for methods of saturation determina- tion which will determine the saturation profile in a core as well as the overall average saturation given by the gravimetric or material balance methods usually employed. Methods which have received consideration include resistivity, X-ray absorption, gamma ray absorption, neutron diffraction, and radioactive tracers. The resistivity method has use in the determination of profile, but needs checking by independent means.' The X-ray method has been used successfully, but requires elaborate equipment and calibration.23 4 At present gamma ray absorption is practical only for very large cores. The neutron methodo does not appear adaptable to measurement of saturation variations in short cores since it is a scattering method. Russell, Morgan and Muskat' employed radiovanadium in a study of the mobility of interstitial water. Coomber and Tiratsook used radioiodine as an oil-phase tracer and measured profiles in unconsolidated sand packs. ADVANTAGES OF RADIOACTIVITY METHOD A thorough discussion of the theory of radioactive tracers and the technique of using them to study the movement of fluids in sands is given by Coomber and Tiratsoos and need not be detailed here. The method requires less equipment than the X-ray method; the counting problem is similar, but the generation and regulation of the radiation, which is a major problem in the X-ray method, is not required in the radioactivity method. In the X-ray method it is customary to add up to 20 per cent of absorber, usually an iodine compound, to the phase to be labeled. while in the radioactivity method a mere trace is sufficient. A possible disadvantage of the radioactivity method is that a disproportionate amount of the activity comes from the portion of the core nearest the counter, whereas the X-ray gives a true average saturation in the region traversed by the beam. 011 the other hand, this characteristic of the radioactivity method renders it peculiarly adaptable to study of certain types of radial variations in saturation. As with the X-ray method, a tracer may be added to either the oil or water-phase. An oil-phase tracer is more generally useful. however. since it permits work on oil and gas in the

Jan 1, 1952

By Raymond L. Jones

With the inauguration of open-pit copper mining in Bagdad, Ariz., plans were formulated for a large scale leaching operation. Dump stockpiling was started almost immediately, but actual production was not initiated until spring 1961.

Jan 9, 1977

By J. H. Brophy, A. L. Prill, H. W. Hayden

An error lzas been found in the conventional way of determining the time exponent of linear shrinkage for the solution-precipitation stage of liquid-phase sintering. Large amounts of shrinkage due to initial rearrangenzent result in erroneously low exponents and tni si dentification of the rate-controlling process. Two alternative, mathematically correct, methods of calculation are applied to existing data on Fe-Cu, WC-Co, and Tic-Ni-Mo. This results in reidentifi-cation of the rate-controlling process and somewhat better agreement with related data. In each case the solution-precipitation process is solution-controlled and not diffusion-controlled. THE liquid-phase sintering process has been the object of a considerable amount of research for many years. Linear shrinkage vs time data at various sintering temperatures have been used recently in an attempt to identify the prevailing mass-transport processes in a number of metallic and nonmetallic systems. There is an analytical error inherent in the methods previously used for handling data during the "solution-precipitation" stage of shrinkage which must be recognized before the correct rate-controlling processes can be determined. It is the purpose of this paper to show how the error has affected previous conclusions and to suggest corrections. A number of mechanisms have been proposed to explain experimental observations during sintering in the presence of a liquid phase. The earliest of these is due to Price, Smithells, and williamsl who attributed the observed growth of the solid phase to the simultaneous solution of smaller particles and growth of larger particles. From the work of Lenel et al.2,3 and Gurland and Norton4 has come the suggestion that the liquid-phase sintering process may be divided for analysis into three steps: 1) rearrangement upon formation of the liquid phase; 2) solution and reprecipitation of the solid phase in the liquid; and 3) "coalescence" or a final stage of sintering, characteristically slower than the solution-precipitation process. The sequence of steps is shown schematically in Fig. 1. Kingery5 presented a thermodynamic and kinetic analysis of the first two "stages" of the liquid-phase sintering process in which the functional dependence of lineal shrink- age on time at temperature was used to identify the rate-controlling mass-transport process. Table I summarizes the time dependences and processes considered by Kingery.5 This method of data presentation has been employed by Kingery and coworkers for Fe-CU,6 WC-Co, and a number of nonmetallic systems," and bv Whalen and Humenik for Tic-Ni-Mo and Fe-cu.8 In each of these studies, the rate-controlling step during the "solution-precipitation" stage was identified from the slope of the curve in that stage on a logarithmic plot such as Fig. 1. However, in all of the previous studies, at a certain composition, relatively large amounts of shrinkage due to rearrangement preceded the solution-precipitation stage. Under these conditions, the larger the amount of rearrangement shrinkage the

Jan 1, 1965

By Kenneth K. Humphreys, Joseph W. Leonard, Robert L. Llewellyn, William F. Lawrence

INTRODUCTION Cleaning fine coal sizes utilizing air currents in machines as the primary separating medium is called dry concentration or pneumatic cleaning. In 1947 approximately 18 million tons (16.38 million mt) of bituminous coal were cleaned by air machines; in 1965, 25.4 million tons (23.1 14 million mt); but in 1975, only 7 million tons (6.37 million mt). Table 11-1 shows the tonnages cleaned of bituminous coal and lignite in the United States by various types of equipment from 1938-1963. Table 11-2 shows only tonnages cleaned by pneumatic methods from 1964-1975. The decrease in tonnage to approximately 7 million tons (6.3 million mt) is due to a higher moisture content in the mined coal and the greater difficulty in cleaning the coal by air. There also was a definite trend to load raw coal at the mines, especially the slack which is the most expensive to clean due to the dewatering and drying requirements. While there have not been any applications of pneumatic cleaning in the anthracite field, its use has not been fully explored. The same is true for lignite and subbituminous coals.

Jan 1, 1979

By William P. Blake

The literature of the occurrence of quicksilver-ore in the United States does not contain, so far as the writer is aware, any mention of the locality herein described. In the preliminary report * upon the resources of the transPecos region of Texas, von Streerwitz gives a long list of minerals observed as occurring there, but cinnabar is not mentioned. In the second report upon the same region † mention is made of the reported existence of cinnabarite in one of the mountain ranges north of the Sierra Carrizo and the Bofecillos, but the author adds: " In spite of my careful examination of the float, I have not yet found any traces of this metal (quicksilver) up to the present time." Prof. Dumble, also, in * Geol. Surv. of Texas, E. T. Dumble, 1889, p. 225 (first report). † Geol. Surv. of Texas, E. T. Dumble, 1890, p. 713 (second report)

Jan 1, 1896

By C. W. Gennet

Announcement was made in the spring of 1926 that the Boston & Maine R. R. Co. had contracted with the well-known German steelmakers, Messrs. Fried Krupp, for the manufacture of 15,000 tons of basic open-hearth steel rails at the Rheinhausen Works, for delivery to Boston, Mass. The manufacture of rails in the United States has for many years been almost a national pride, and as this feeling is chiefly the result of a long-time liberal and consistent patronage of American rails by American railroads, it is not strange that this somewhat unusual announcement should arouse more than ordinary interest. Since the end of the World War, the importation of foreign rail has been fairly large, principally because the newly created economic conditions have rendered some American competition more difficult, but the tonnage imported, for the most part, has been made up of small orders for miscellaneous use; and the contract referred to constitutes the largest single importation of foreign rail in over ten years. In 1915, the Algoma Steel Co. of Sault Ste. Marie, Canada, supplied the Illinois Central R. R. with 30,000 tons of rails,' and various other American roads with smaller amounts. In 1902, 1903 and 1904, large tonnages of rail from abroad were purchased, the Louisville & Nashville R. R. alone obtaining 30,000 tons from German mills. It is the object of this paper to present, in what is believed to be a new and concise form, figures showing the production and consumption of rails in the United States, and to record some of the testing and inspection results of the recent Krupp rails; also, to direct attention to two quite unique departures from American practice that were regular features of the Krupp process and which are worthy, it is thought, of careful study. Production and Consumption of Rails in the United States Table 1 shows the tonnage of rail produced in the United States and the amount imported, exported, and consumed by years since 1849. That, evidently, was the first year of record, for the statistics of the American Iron and Steel Institute and its predecessor, the American Iron and

By E. C. W. Perryman

The recovery of X-ray line broadening, hardness, and electrical resistivity from cold worked AI-Mg alloys has been investigated. The results, together with those from density measurements, suggest that magnesium atoms freeze in the excess vacancies formed by cold working, and that this affects the climb of dislocations during the recovery process. PREVIOUS work1, " has shown that while 1 pct Mg increases the activation energy for recrystalliza-tion, it decreases the activation energy for the recovery of mechanical properties and decreases the subgrain size both after cold working and annealing. A similar result has been reported by Varley2 for an A1-2 pct Mg alloy. With plastic deformation at high temperatures, McLean and Farmer' and Rachinger have found that magnesium appears to retard the motion of dislocations and, furthermore, they find little or no effect of magnesium on the size of subgrains formed during high temperature deformation. In view of the apparent contradictions as to the effect of magnesium on subgrain size, the recovery process in Al-Mg alloys has been investigated more thoroughly by studying the annealing out of X-ray line broadening, hardness, and electrical resistivity from alloys cold worked at room temperature. Material Used—The chemical analyses of the alloys are given in Table I. Fabrication—The material used was cold rolled 20 pct at room temperature, the grain size prior to the last cold rolling operation being similar to that used in previous work; i.e., 230. The experimental procedure for annealing, determination of X-rav half-veak breadth. hardness measurement, electEica1 resistivity, and density and metallographic examination was exactly the same as previously described." Variation of X-Ray Half-Peak Breadth with Annealing Time—Isothermal annealing curves at 100°, 200°, and 250°C were obtained for material cold worked 20 pct. The half-peak breadth of the (333) Ka, line directly after cold working is shown as a function of magnesium content in Fig. 1. Only with the 2.87 pct Mg alloy was overlapping of the a, and n.. reflections observed to any appreciable extent. To separate these, Rachinger's method' was used. Typical isothermal annealing curves are shown in Figs. 2 and 3 for 100" and 200°C, respectively. These curves are similar to those obtained previously for super-purity aluminum except that the

Jan 1, 1957

By P. T. Carter, A. B. Murad, H. B. Bell

N. A. Gokcen (Michigan College of Mining and Technology, Houghton, Mich.)—The activities of silica, represented in Fig. 5 for the systems MnO-SiO2 and CaO-SiO2, are in disagreement with the established binary phase diagrams. At Ns102 = 0.50 in MnO-SiO2, and at Ns102, = 0.65 in CaO-SiO2, each binary system is saturated with respect to silica at 1550°C, and therefore as102, is unity in each case. The curves for as102 (FeO-SiO2) and as102, (MnO-SiO,) should nearly co-

Jan 1, 1953

By F. T. Selleck, H. H. Reamer, B. H. Sage

An experimental investigation was made of the effect of temperature upon the three-phase pressure associated with the propane-water and propene-water systems when hydrates were present. In addition, the characteristics of the propane-propene-water system were established over a limited range of ternperatureo under conditions such that hydrate was formed. The hydrate phase for this system may he a solid solution and the distribution of propane and propene in it is similar to that found in the coexisting hvdrocarhon liquid phase. INTRODUCTION A knowledge of the characteristics of hydrates of the hydrocarborrs encountered in industrial practice is of importance in connection with the design of process equipment. Villardl.1,2 carried out early studies of hydrates, and de Forcrand1 con-sidered the more probable compositions of the hydrates of hydrocarbons. Hammerschnid1 presented information about the propane-water and the isobutane-water systems. Scheffer5 studied the hydrate of hydrogen sulfide in detail, and de For-crand reported on the hydrates of krypton, argon, and xenon.1 Roberts and co-workers1,2 determined the nature of the hydrates formed in the methane-water and ethane-water systems. Carson and Katz10 studied the methane-propane-water, methane-pentane-water, and the methane-hexane-water systems in the four-phase region. The results of this rather extensive investigation indicated that the paraffinic hydrates formed solid solutions. The experimental evidence now available does not Support the existence of hydrates of the pentanes-antl-heavier hydrocarhons but it cannot be stated with certainty that such hydrates are not formed. Stackelherg. 11,12,13 made extensive studies of the crystal structure of paraffinic hydrate; by means of x-ray techniques and found that hydrates poses; a definite structure and composition. The existence of such a Structure does not preclude the firmation of Solid solutions of hydrates in aqueous systems containing two or more hydro-carbon~. Wilcox, Carson and Katz" reviewrd the information on the hydrates of importance in the processing of natural gas and presented data concerning their formation from natural gas. Kobayashi and Katz1' made studies at high pressure of the Hydrate of methane. and Unruh and Katz"' investigated hy-drates in mixtures of carbon rlioxide and methane. Frost and Deaton contributed to the knowledge of the composition of the paraffinic hydrates The irregularities in the experimental results were several times the expected uncertainties. This experience confirms the behavior encountered by other investigators indicating that hydrates tend to occlude water during their formation, thus rendering difficult the direct measoremeut of their composition. Miller and Strong2 investigated a number. of paraffinic hydrates from the standpoint of their possible application to (, the industrial storage of gas. Powel1 studied the effect of solutes upon the decomposition temperature of paraffin hydrates. Marked lowering of the decomposition temperature at a given pressure may he obtained by the use of such additive agents as ethylene glycol, urea. and sodium chloride. APPARATUS AND METHODS Two method* were here employed to study the behavior of hydrates. The first involved a glass capillary within which the hydrocarbons and water were confined over mercury. The second made use of a double-ended weighing bomb technique." The glass capillary equipment has been described elsewhere.'" A schematic drawing of it is presented in Fig. 1, where the arrangement of the agitator and mercury reservoir is shown in some detail. The lower part of the glass capillary, D, was enlarged to afford space within which the fluids used in the investigation could he stored at low pressures after their introduction through the valve. G. The temperature of the capillary was controlled by the circulation of a hydrocarbon oil of low viscosity from the agitated bath, B, through the vacuum jacketed column. C. The pump, A, was employed for the circulation of this oil. A relatively clear view of the capillary tube, D, was obtained through the vacuum jacket. Mercury was introduced into the lower part of the vessel, E, from

Jan 1, 1952

By S. Senderoff, D. E. Couch

A PROCESS for the electrolytic preparation of molybdenum from molten salts has been described previously. This previous work centered on electrowinning and electroplating characteristics of the process. In this paper the properties of the process as a refining medium are discussed. In producing metals from ores, it frequently has proven most economical to obtain a comparatively impure metal by smelting, and to purify the product by electro refining. Direct electrowinning from molten salts is rather difficult when a porous diaphragm is required in the process, as in the case of molybdenum, since satisfactory refractory materials for such a diaphragm in molten salts have not yet been developed. In electrorefining, however, a soluble anode is used. By suitable control of anode and cathode current densities, the lower-valent molybdenum compound used in the electrolyte is not oxidized, and a diaphragm is not needed, thus avoiding difficulties which are encountered with other electrowinning processes. Electrorefining may result from two different processes in the cell: Dissolution of the molybdenum and the less noble impurities with a separation of the more noble impurities as an anode sludge; the electrodeposition of molybdenum and the more noble metals at the cathode, leaving the less noble metals in the electrolyte. The amount of separation which occurs in each process is determined by the potential of the operating electrode and the relative concentration of the various species at (or in) that electrode. Since molybdenum has a comparatively noble position in the EMF series in molten alkali halides,2 most refining would be expected to occur at the cathode. In this work only the cathodic process was studied. The objective was to determine to what extent various metallic ions, if they dissolve from the anode or are otherwise introduced, were concentrated in the electrolyte. The necessary conditions for the separation of each and the limiting concentration which may be tolerated in the electrolyte for effective refining were studied. The deposits were chipped from the cathode and analyzed spectrochemically for metallic impurities. Besides determining the major contaminant, a general qualitative analysis was obtained to be sure that other metallic ions were kept at a very low level during each series of runs and to be sure that the baths were not being contaminated accidentally. Samples of the bath, for analysis, were taken at the temperature of operation so there was no chance of selective crystallization during cooling. In this way the ratio of molybdenum in the bath to the other metal could be determined readily. These data permitted a check on the anode efficiency and any volatilization that took place during the electrolysis. Experimental Apparatus—The apparatus as shown in Fig. 1 was used to determine the effect of the various foreign ions upon electrodeposited molybdenum. The entry chamber A allowed the cathodes to be removed without cooling the bath and without allowing oxygen or moisture to enter." The cathodes were made Prom 0.25-in. tungsten rods and were rotated during the electrolysis. The balloon in the lower arm B was inflated with helium after the cathode was drawn up into the upper section for removal. A new cathode was then placed into the entrance chamber A after which the chamber was flushed

Jan 1, 1959

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of' nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150' C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-'' of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami's slution' and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, 'Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By John A. Meech, J. G. Paterson

Activated carbon is a strong adsorbent for amyl xanthate, capable of removing from solution up to a quarter of its own weight in xanthate. In selective flotation system where depression is unstable, separation efficiency increases with activated carbon additions. The improvements observed are brought about by two mechanisms. First, by removing stripped and residual collector ions from solution, competition between depressant and xanthate is reduced and depression is stabilized. In addition, the texture of the froth phase at high pine oil concentrations is modified by activated carbon such that better drainage between the air bubbles takes place, alleviating the mechanical entrapment of depressed mineral particles. In treating a bulk copper/lead concentrate produced from GECO ore, selectively between galena and chalcopyrite is increased when activated carbon is used. Although the rate of flotation of galena is marginally lowered by activated carbon, a small extension in the duration of flotation allows the lead recovery to increase by 19% at the same recovery of copper. An addition rate of 0.75 kg/ton (1.5 lb/st) of bulk concentrate is suggested as optimum from this testwork. However, the actual level used in the mill is dependent upon the residual concentrations of collector and frother in the bulk concentrate pulp.

Jan 1, 1979

By P. D. I. Honeyman, P. A. Faust

At the Miami plant of the International Smelting Co., Inspiration, Ariz., there are four reverberatory furnaces, all 120 ft. long. At present only one of these furnaces is in operation. It is operated as a wet-charge furnace, the charge being distributed for about 65 ft. down the furnace length. Usually this charge contains about 12 per cent moisture and runs 25 per cent sulfur, of which there is eliminated in the furnace from 25 to 30 per cent. The furnace is oil-fired, the fuel being burned in a battery of Cananea-type, low-pressure burners. The flame is kept short and conditions so adjusted as to obtain complete combustion within the furnace. The average furnace draft, taken through the verb arch, amounts to only 0.02 in. of H2O. Draft is purposely kept low to cut down infiltration through the flues and boiler settings, and control dampers are regulated to maintain this uniform condition throughout the charging as well as the smelting period. Hot gases discharge from the furnace uptake through a common header flue to the waste-heat boilers. The general layout and dimensions of the plant are shown in Fig. 1. Four Stirling boilers, two of class M-26 (713 hp.) and two class M-31 (850 hp.), serve the furnace. Three usually are sufficient to take care of normal operation, the fourth boiler being used as a spare when necessary. The distribution of hot gases to the various boilers is regulated by the dampers in the boiler exit flues. Normally the boilers closest to the furnace uptake would evaporate more water than do those farther away, but dampers are regulated so as to distribute fairly well the load between the several boilers. Steam from the waste-heat plant is delivered to the adjoining power house of the Inspiration company, where it is used both in the Nordberg blowing engines and for electrical generation. Steam pressures and temperatures recorded are those in the main power-plant header and are thus inclusive of all losses in about 500 ft. of 10-in. line. Steam for smelter heating and auxiliary use is taken from the main waste-heat header, is reduced to 125 lb. and distributed through separate lines. Boiler feed water is supplied by the power plant and consists of returned condensate, augmented to a large extent by make-up water

Jan 1, 1934

By A. S. Callen

These iron mines of Spain are located on the mountain ridge forming the boundary between the Teruel and Guadalajara provinces, called Sierra Menera. They form a property of 25 mines extending over an area of 1,677 hectares (4,140 acres) situated at a height varying from 1,200 m. (3,940 ft.) to 1,500 m. (4,920 ft.) above sea level. The deposit follows the direction north to south; huge masses of ore are being found both on the slopes and at the summit of the Sierra. The ore occurs among quartzites and magnesite limestone, in some places overlaid by quartzite 15 m. (50 ft.) thick; in some others (and this is more general) the ore is overlaid by earth and boulders of quartzite origin; this layer is about 8 m. (26 ft.) thick. The ore beds occupy the geological horizon of the Superior Trias or Muschelkask, which are here in direct contact with the Silurian quartzites. The lime-stones have been more or less transformed. There is ample evidence to show that these mines were worked in very ancient times—objects and tools employed in mining by the ancient Romans and Arabs are to be found plentifully in old workinigs which extend down into the deposits. It has been estimated that more than 10,000,000 tons of ore were mined in the old days in this district and carried to the primitive forges in the vicinity where iron of much renown in Spain was extracted. Remains of more than 20 of these forges are found in the neighborhood of Sierra Menera and are usually situated near waterfalls and forests. Much investigation has been carried on for the purpose of determining the quantity of ore to be found in these mines, but no exact calculations can be made at present. When the investigation is completed it will surely be found that the deposit contains a much larger quantity than the 100,000,000 tons indicated by the present workings. The mines are now worked as open quarries and this method can and will be followed for a long time, probably until the deposit is worked out. Figs. 1 and 2 give some idea of the quarries in operation and the reserves, the iron-ore stocks, screening installation and general arrangement. From these quarries 1,000,000 tons can be mined annually (987,000

Jan 1, 1916

By Paul Wilkinson

From the earliest times, the principal component of mallplaster has been ordinary lime. Plaster-of-Paris has also been known from early times, but never used to any extent in the actual base-work of plastering-materials; it is generally used for finishing over the brown coat and for ornamental work. As an illustration of the antiquity of the use of gypsum-plaster for mortar, I find that the analysis of the exterior covering of the pyramid of Cheops, as made by Dr. Wallace, is almost identical

Jan 1, 1898