Search Documents

By F. W. McQuiston

INTRODUCTION IDARADO Mining Company's mill and surface plant are at the portal of the Treasury tunnel at elevation 10,625 ft, 12 miles south of Ouray, Colo. In 1943 and 1944 this tunnel was extended in a westerly direction to tap the Black Bear vein, and, together with the recently completed 1100-ft inclined Treasury raise, provides access to the Black Bear mine. In 1945 a 250-ton mill was placed in operation to process development ores containing much needed copper, lead and zinc for war requirements, and to serve as a pilot testing unit for larger scale milling operations. In the years 1902 to 1927 some 329,000 tons of ore were produced from mine workings on the Black Bear vein that extended downward from elevation 12,325 ft at the Black Bear tunnel portal to elevation 11,618 ft, the lowest level of the mine. The ores were taken to the Cascade and Smuggler-Union mills near Telluride over two aerial tramways. Gold bullion, a copper-lead concentrate, and a zinc concentrate were produced. ORES The Black Bear is a compound fissure vein that has undergone several stages of mineralization. The first important stage is represented by complex ores of copper, lead and zinc in a quartz gangue. Precious metal content in this stage is low. The galena is argentiferous and varying amounts of tetrahedrite, freibergite and bornite tend to increase the normal copper content represented in chalcopyrite. The zinc occurs as a true sphalerite with little or no iron. Later re-openings of the fissure took place more or less co-extensively with the successive introduction of (1) abundant quartz gangue containing minor amounts of chalcopyrite, galena and sphalerite; (2) free gold in a fluoritic quartz gangue; and (3) barren, low-grade quartz with minor amounts of pyrite as the only important sulphide. The sulphides show practically no oxidation and little mineralogic intergrowth. Because of the common overlapping of these successive stages of mineralization within a given mining area, considerable dilution of the base-metal content takes place, thus lowering the average mill-head grade. PLANT PRACTICE Metallurgical testing was started shortly after the Black Bear vein was encountered on Treasury tunnel level in 1944. Laboratory tests showed good flotability of the minerals in the ore and indicated an economic separation could be made of the copper, lead and zinc minerals into their respective concentrates. The success of the separation is close reagent control to maintain a balance between promotion and depression of the sulphides. To maintain this balance reagent consumption for the three metal separation is considerably higher than in ordinary lead-zinc flotation.

Jan 1, 1947

By Charles W. Wright

At most mines where large tonnages are handled, "bulldozing" or secondary blasting is an important and costly operation. To reduce the large blocks from primary blasting operations or stoping so that they will be small enough to pass through the chutes into the cars at the haulage level, and not too large for the crushing plant, requires blasting. Often this is done by placing a few sticks of dynamite on top of a block with or without a capping of mud, but to consume less dynamite and to promote safety, most secondary blasting is now done by blockholing, or the drilling of holes 6 to 12 in. long in the blocks, using only a part of a stick of dynamite per hole. Regardless of the method of blasting, however, the term "bulldozing chamber" is applied to the room where this work is done. Bulldozing chambers permit secondary blasting at all times in a safe place without disturbance to the other mining operations. The chambers are usually high above the haulage level and well below the stope level or open-pit floor. In most instances the material is passed through a grizzly in the bulldozing chamber, but sometimes no grizzlies are used. One to four raises extend from the chamber to the stope floor and one or two from the haulage level to the chamber floor. Occasionally large slabs of ore or rock choke the raises above the bulldozing chamber, and these have to be blasted by attaching a bundle of dynamite sticks on the end of a long pole and placing them up in the raise between the pieces causing the choke. This is called "chute-blasting." To give a picture of the progressive developments in the use of the bulldozing chamber, a few typical mines that show the application of this method to both metal and limestone mines have been selected for description here. Limestone mines have been included because many metal miners do not realize to what extent the nonmetallic, or rock, miners' are now applying metal-mining methods successfully in their operations. The bulldozing chamber is the "neck of the bottle" for some mines.

Jan 1, 1937

By T. R. Armstrong

Total crude oil production in Mexico in the year 1941 is estimated at approxi- mately 41,000,000 bbl.; a daily average of 112,700 bbl. and a decrease of about 5 per cent as compared with the daily average of 120,000 bbl. produced in the year 1940, and nearly 11 per cent decrease as com-

Jan 1, 1942

By T. R. Armstrong

Total crude oil production in Mexico in the year 1941 is estimated at approxi- mately 41,000,000 bbl.; a daily average of 112,700 bbl. and a decrease of about 5 per cent as compared with the daily average of 120,000 bbl. produced in the year 1940, and nearly 11 per cent decrease as com-

Jan 1, 1942

By Ian W. Wark, Keith L. Sutherland

IT has been shown' that in the absence of heavy metal salts, the nature of the alkali used to promote differential flotation-whether caustic soda, lime or sodium carbonate-is unimportant. The hydroxyl ion is the active depressant upon which differentiation depends, and the pH value determines whether a film of collector forms on any given mineral surface. Even when sodium cyanide is used in conjunction with alkalies, it is the pH value and not the nature of the alkali or its concentration that is important, for upon the pH value alone depends the fraction of the added sodium cyanide that is present as cyanide ion, which is the true depressant. When heavy metal salts become dissolved from partly oxidized ores, or are added intentionally as activators, conditions are different, and metallurgists have found that lime and sodium carbonate do not give identical results, even when added in amounts sufficient to produce the same pH value. In the few instances in which we had attempted to confirm this view, we had failed to do so, for, with nothing to guide us, we had inadvertently chosen solutions that gave contact curves of a "standard type," which correspond to conditions of ready floatability. Now, however, we find that, in the presence of copper salts, and within a restricted range of reagent concentrations, the nature of the anions present is important, and that sodium carbonate does influence the results, apart from the usual effect due to its influence on pH value. With the recognition of this anion effect, and with the control of temperature already introduced,2 it appears that the factors of major importance in connection with this set of reagents have been taken into consideration, and that the results obtained and the conclusions drawn from contact tests will be of more immediate value to the operator. It is not difficult to suggest an explanation for the influence of the carbonate ion in the presence of copper sulphate. The works of Picker-

Jan 1, 1939

By Walter Crafts

ALTHOUGH many elements reduce the tendency to porosity in steel castings, manganese, silicon, aluminum, calcium, titanium and zirconium appear to be most generally suitable for the purpose. The manganese and silicon contents are usually maintained in a fairly constant range. Sili-con-killed castings often are made to be sound with little or no addition of the stronger degasifiers. In many cases, however, it is more practical to utilize the stronger degasifying elements, aluminum, calcium, titanium and zirconium. Since they greatly modify the composition, shape, and distribution of the nonmetallic inclusions, and thereby the ductility, the strong deoxidizers must be used in such a way as to form the least harmful types of inclusions. As the reasons for failure always to obtain good results have not been obvious, an effort has been made to determine the mechanism of solidification of steels deoxidized to produce certain types of inclusions. Diagrams representing the mechanism of their formation have been constructed from the appearance of the nonmetallic con-stituents and have not only illustrated the limiting features of specific deoxidizing treatments with respect to inclusion formation and ductility, but have also indicated a relation between inclusions and resistance to hot tearing. Three different types of deoxidation treatment have been used for obtaining sound castings with relatively high ductility. The first method is to make and cast the steel under such conditions that deoxidation with silicon and a small addition of a strong deoxidizer assures soundness. The effective addition that will promote soundness without causing the formation of intergranular inclusions varies with the furnace practice and composition, but may be limited to about 0.025 per cent Al, Zr or Ti. Up to 0.10 per cent Ca and 0.15 per cent V are also used for this purpose. The inclusions in these steels are characteristically glassy silicates and round or irregular sulphides. As pointed out by Sims and Lillieqvist,1

Jan 1, 1940

By Edward L. Fidler, Thomas E. Finch

Thin seam coal mining in the western US nominally equates to recovery of stray seams associated with thicker, major seams. The thin or stray seams encountered are generally recovered, but not in all cases. The alternative to extraction is, of course, spoiling. The majority of thin seams are encountered somewhere in the overburden above the major seam or in the parting between thick seams. Although some are true strays and appear anywhere in the geologic sequence, others might be classified as thin "rider" seams immediately above or below a thick seam and separated by some equally thin parting. For the purpose of this discussion, stray or thin seams are defined as those which are less than 1.2 m thick or represent less than 10% of the expected extractable coal. [Figure 1] is a graphic representation of typical thin, stray, or rider seams which actually appear in a western operation. Operationally, stray seams create irritating scheduling problems and require special handling techniques which do not always lead to efficient equipment utilization. Additionally, coal recovery from a thin seam is considerably less than the 95% usually recovered from thick seams. Higher recovery in thin seams leads to dilution problems, which depreciates Btu quality, and most western coals are not in a position to lose heating value. Thin western seams also undulate and pinch or swell more than thick seams, and this leads to more difficult recovery. Often they are associated with equally dark carbonaceous shales and visual selectivity is difficult at best during daylight hours. Resource Recovery Regulations Thin seam recovery in western mines is encouraged by both federal and state regulations and by the mining industry's concern for total resource recovery. [Table 1] lists the western coal states and their recovery regulations. The federal regulations are found in the Surface Mining Control and Reclamation Act of 1977. They state, "General performance standards shall . . . require the operation as a minimum to … conduct the surface coal mining operations so as to maximize the utilization and conservation of the solid fuel resource being recovered." Economic stimulation for thin seam recovery appears to be marginal or at the least controversial. Scheduling and operational problems often outweigh the nebulous profits created by engineering analysis. The only alternative to extracting thin seams occurring above major production seams is to strip directly through them and lose the resource to the spoil pile. Although this is not palatable to environmental emotions or resource promoters, it is the most simple expedient to operations people.

Jan 1, 1981

By F. W. McQuiston

Idarado Mining Company's mill and surface plant are at the portal of the Treasury tunnel at elevation 10,625 ft, 12 miles south of Ouray, Colo. In 1943 and 1944 this tunnel was extended in a westerly direction to tap the Black Bear vein, and, together with the recently completed 1100-ft inclined Treasury raise, provides access to the Black Bear mine. In 1945 a 250-ton mill was placed in operation to process development ores containing much needed copper, lead and zinc for war requirements, and to serve as a pilot testing unit for larger scale milling operations. In the years 1902 to 1927 some 329,000 tons of ore were produced from mine workings on the Black Bear vein that extended downward from elevation I2,325 ft at the Black Bear tunnel portal to elevation 11,618 ft, the lowest level of the mine. The ores were taken to the Cascade and Smuggler-Union mills near Telluride over two aerial tramways. Gold bullion, a copper-lead concentrate, and a zinc concentrate were produced. Ores The Black Bear is a compound fissure vein that has undergone several stages of mineralization. The first important stage is represented by complex ores of copper. lead and zinc in a quartz gangue. Precious metal content in this stage is low. The galenn is argentiferous and varying amounts of tetrahedrite, freibergite and bornite tend to increase the normal copper content represented in chalcopyrite. The zinc occurs as a true sphalerite with little or no iron. Later re-openings of the fissure took place more or less co-extensively with the successive introduction of (I) abundant quartz gangue containing minor amounts of chalcopyrite, galena and sphalerite; (2) free gold in a fluoritic quartz gangue; and (3) barren, low-grade quartz with minor amounts of pyrite as the only important sulphide. The sulphides show practically no oxidation and little mineralogic inter-growth. Because of the common overlapping of these successive stages of mineralization within a given mining area, considerable dilution of the base-metal content takes place, thus lowering the average mill-head grade. Plant Practice Metallurgical testing was started shortly after the Black Bear vein was encountered on Treasury tunnel level in 1944. Laboratory tests showed good flotability of the minerals in the ore and indicated an economic separation could be made of the copper, lead and zinc minerals into their respective concentrates. The success of the separation is close reagent control to maintain a balance between promotion and depression of the sulphides. To maintain this balance reagent consumption for the three metal separation is considerably higher than in ordinary lead-zinc flotation.

Jan 1, 1949

By A. E. Wells

In this paper are described various comparative tests made on cracked and straight run gasolines. The results of these tests may be briefly summarized as follows: Samples of 54 to 55° Bé. gravity cracked gasolines, with end point of about 442° F., and with a somewhat larger proportion of the less volatile fractions than conformable to government specifications, were used in a single cylinder variable compression engine under the same conditions as were samples of straight run gasoline of 58 to 59° Bé. gravity, and of which one had a greater proportion of the more volatile fractions than called for in government specifications. The cracked gasolines showed decidedly less tendency to knock, hence could be used at higher compression ratios and thereby developed from 10 to 20 per cent. more power than did the straight run gasolines. These figures may be taken as one measure of the superiority of the cracked gasolines under test with the straight run gasolines. It is not claimed that all cracked gasolines are superior to all straight run gasolines to the extent indicated by the above tests; cracked gasolines vary as do the straight run products. Cross's work and that of others have indicated that certain cracked products may have a much greater superiority over straight run than that determined above. From various sources and by different methods of testing data are being obtained to show the definite and generally quite considerable superiority, as an anti-Cetonating fuel of cracked gasolines over straight run gasolines. It is now becoming generally recognized that by increasing the production of cracked gasoline motor fuel from those heavier petroleum fractions, which otherwise would be used for burning purposes, the petroleum industry is not only working in the interest of the conservation of the world's supply of petroleum, but is at the same time making available to the gasoline-consuming public a product distinctly superior to the straight run gasolines.

Jan 1, 1927

By B. S. Tani, R. V. Schablaske, M. G. Chasanov

MEASUREMENTS of the solubility of scandium in liquid cadmium from 349" to 606°C by Chasanov, Hunt, Johnson, and eder' led to the isolation and characterization of the intermetallic compound ScCQ. The solid phase found in equilibrium with a saturated solution of scandium in liquid cadmium above 422°C is ScCQ. The equilibrium solid phase below this temperature has not as yet been characterized. Hexagonal needles of ScCG were isolated from a 5 wt pct Sc alloy which had been ice-quenched from 500°C. Free cadmium was leached away from the intermetallic with saturated ammonium nitrate solution. The concentration of cadmium in successive leaches was followed polarographically and the leaching process was terminated when the rate of cadmium dissolution decreased markedly. Chemical analysis of the intermetallic thus isolated is as follows: 11.5 wt pct Sc and 88.3 wt pct Cd. The composition of ScCQ is 11.8 wt pct Sc and 88.2 wt pct Cd. X-ray diffraction powder photographs of ScCds taken in a 114.6-mm Debye-Scherrer camera with CuKa, radiation can be indexed on the basis of a hexagonal nit cell. Lattice coonstants are a. = 6.330 ± 0.001A to 6.324 i 0.001A and co = 4.853 i 0.001A. The a0 has a slight range with the lower value seemingly associated with the cadmium-rich terminus of the phase. With eight atoms in the unit cell the calculated intermetallic density is 7.54 g per cu cm; the density as determined by a liquid-displacement method is 7.7 g per cu cm. Powder-diffraction data for ScCQ are recorded in Table I. Stoichiometry, symmetry, unit-cell dimensions, and the number of atoms per unit cell indicate the MgsCd (D019) type structure for ScCQ; space group is D,&-P6,/mmc. Atomic coordinates are:

Jan 1, 1964

By E. A. Anderson

In another paper' the writer has shown that the low permissible maximum fiber stress in a loaded zinc sheet demands a much closer support spacing than is used for steel. The limiting fiber stress in 13-gage (0.032 in.) sheets having a 1-in. depth of corrugation was found to be about 5000 lb. per sq. in. on a 37-in. span under a load of 40 Ib. per sq. ft. Corrugated steel sheets are commonly laid with spans varying from 48 to 60 in. In order to increase the span in 13-gage zinc to 54 in. (a common spacing) the metal must be capable of withstanding, under long-continued loading, a maximum fiber stress of about 10,000 lb. per sq. in. This is known to be impossible with unalloyed zinc. In this paper the writer describes a series of experiments leading up to the development of an alloy capable of safely sustaining this fiber stress. The effect of alloying on the slow creep of zinc was studied by means of static tensile tests, accurate determinations of apparent elastic limits and finally by means of loading tests on full-size roof sections. Two industrial buildings roofed with alloyed zinc sheets on spans involving fiber stresses in excess of 10,000 lb. per sq. in. have been under observation for over two years without signs of sagging. Experimental Work Two methods of increasing the maximum permissible fiber stress in zinc were considered. Cold rolling, which' increases the stiffness and tensile strength, was found to decrease the resistance to slow flow. Alloying, therefore, provided the only feasible means of obtaining the desired result, It was recognized that the improvement secured by the solid solution of natural impurities was insufficient. A series of alloys was outlined, therefore, in which a number of metals were added separately and together. The sheets rolled from these alloys were tested under

Jan 1, 1930

By GEORGE D. RAMSAY

ABOUT three miles west of Fontana San Bernardino County, California, and fifty miles east of Los Angeles, the Kaiser Co., Inc., has built an integrated steel plant. By integrated, I mean that from its wholly owned iron ore and coal supply, the Kaiser Co. is producing in its own mills iron and steel products. Pig iron to meet the West Coast needs has been produced at Fontana since Jan. 1, 1943; steel ingots were first poured there May 14, 1943; and steel plate for ships was first rolled Aug. 15, just sixteen months after ground was broken. Briefly, the plant consists of: (I) Two batteries of by-product coke ovens, totalling ninety ovens, carbonizing about 1740 tons of coal per day at capacity; with by-product facilities for the production of tar, ammonia, and ammonium suIphate, light oil distillates, and tar distillates. (2) One blast furnace producing at

Jan 1, 1944

By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

By Klaus Schwerdtfeger

The rules of solution of oxygen from H2O-H2-He gas and of nitrogen from N2-H2 gas in shallow melts of liquid iron were measured at 1610o and 1600o C, respectiuely. Concentration profiles were detemined in the liquid iron. Tire rate data indicate that the solution process is controlled by diffusion in the iron melt. The diffusivities for oxygen and nitrogen in liquid iron, as calculated from the present data, are DFe-o = (12 ± 3) < 10-5 sq cm per sec and DFe-N = 11 ± 2) X 10-5 sq cm per sec at the temperatures employed. AN attempt was made by Shurygin and Kryukl to measure the diffusivity of oxygen in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was measured. Assuming that the rate of dissolution of silica is controlled by diffusion of oxygen in the iron, the oxygen diffusivity was computed from the rate data giving Dfe-0 = 6.1 X 5 sq cm per sec at 1600°C. Although this value seems to be of the right order of magnitude, there is no proof of the correctness of the assumptions involved in the interpretation of these rate data. The oxygen concentration in the iron at the iron-iron silicate interface was taken to be that in equilibrium with the silica-saturated silicate melt. That is, it was assumed that no concentration gradient existed in the liquid silicate. This is a questionable assumption, unless it is proved that the thickness of the silicate layer is very much smaller than that of the diffusion boundary layer in the iron. Furthermore, Shurygin et al.1 used the Levich equation2 to interpret their rate data. This equation was derived for mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s derivations. In the present work the diffusivities of oxygen and nitrogen in liquid iron were measured at 1610" and 1600oC, respectively. EXPERIMENTAL METHOD Iron melts contained in high-purity gas-tight alumina crucibles were reacted with H2O-H2-He gas for the determination of the oxygen diffusivity and with N2-H2 gas for the determination of nitrogen diffusivity. At the end of the reaction period, the samples were quenched in a cold H2-He gas stream at the top of the furnace. Oxygen or nitrogen contents in the iron were determined by chemical analysis. Two different types of diffusion experiments were perforxed. To determine concentration profiles, a few rate measurements were made using 4-cm-deep melts. The solidified samples were sliced into discs and each disc was analyzed for oxygen or nitrogen. In another series of experiments, oxygen or nitrogen was diffused into shallow melts (about 0.5 to 1 cm in depth) and the total sample was analyzed to obtain an average concentration of the diffusate. In most experiments, 4- to 5-mm-ID alumina crucibles were used. Some experiments were also made in smaller (3 mm) and larger (7 mm) diam crucibles. This variation in diameter caused no difference in the reaction rate, within the limits of experimental uncertainty. To promote the establishment of a stable density profile in the melt, all the samples were suspended in the lower end of the hot zone so that the top of the melt was hotter by a few degrees. Molybdenum wire resistance heating was used. The reaction tube of the furnace was a gas-tight recrystal-lized alumina tube. In most experiments the furnace was heated by an ac power supply. To check the possibility of inductive stirring, some experiments were carried out in a dc operated furnace, with essentially the same results. The temperature of the furnace was controlled automatically in the usual manner. The temperature was measured with a Pt/Pt-10 pet Rh thermocouple and is estimated to be accurate within ±5°C. The iron used was prepared by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zir-conia crucible. The main impurities are: Si 0.004 pct P, S <0.002 pct Cr 0.005 pct N 0.001 pct Zr 0.002 pct O 0.003 pct Mn 0.004 pct C 0.002 pct The gas composition was controlled by constant pressure head capillary flowmeters. Oxygen was removed from the gas mixture by passing it through columns of platinized asbestos (450°C) and anhydrone. Selected H2O contents were obtained by passing the purified gas through oxalic acid dihydrate-anhydrous oxalic acid mixtures held at constant temperature in a water bath. Water vapor pressure data for the oxalic acid dihydrate-anhydrous oxalic acid equilibrium were taken from the 1iterature.3 The flow rate used was about 1.5 liters per min. The whole system was checked for tightness at regular intervals.

Jan 1, 1968

By A. B. Cox, L. W. Wark

In the paper on the development of the flotation process at Broken Hill (Australia) prepared by the Broken Hill Branch of the Australasian Institute of Mining and Metallurgy and published in its Proceedings for 1930 (N. S. 80), it is stated that the concentration of ores by flotation has been established on a commercial basis in Australia since 1904 and that differential flotation was practised at Broken Hill in 1912. Since then, progress in flotation practice throughout the world has been rapid, and during recent years the knowledge of the reactions between comparatively modern so-called chemical promoters or collecting agents and the mineral surfaces has been broadened by the published accounts of many investigators, particularly those working in American universities. Because of the benefits the Australian mining industry has derived from the flotation process, it was felt that the industry should take some part in the efforts that are being made to extend the knowledge of the principles on which the flotation process is based. Accordingly, early in 1930, three Broken Hill mining companies—the Broken Hill South, the North Broken Hill, and the Zinc Corporation—together with the Electrolytic Zinc Co. of Australasia, Ltd., and the Mount Lyell Mining & Railway Co., established a laboratory in the chemistry department of the University of Melbourne for the purpose of investigating the principles underlying flotation. Subsequently, the Burma Corporation, Ltd., expressed a desire to cooperate. The two authors are directly employed and controlled by these six organizations, and the cost of the investigation is divided equally among them. The research has been carried out under the general direction and in close cooperation with Harry Hey, chief metallurgist for the Electrolytic Zinc Co. of Australasia, Ltd., and the authors desire to place on record their indebtedness to him for his ever willing help and constructive criticism. After an extensive search of the literature, it was decided to determine in a preliminary investigation whether the effect of chemical collectors could be evaluated quantitatively by the "contact-angle" method. This preliminary investigation showed that with the bubble machine of

Jan 1, 1935

By G. K. Manning, A. R. Elsea, A. B. Westerman

INTRODUCTION A CONSIDERABLE number of high-temperature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. At the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in Vitallium after various heat treatments. However, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases- might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chromium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja1 and Guertler2 indicated that cobalt and chromium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to &apos;85 pct chromium undergo a transformation at 1200 to 1250°C. More recently, Wever and Haschimoto,3 Wever and Lange,4 and Matsunaga5 carried out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallographic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Matsunaga. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these exceptions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data and the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitallium by determining the diagram for the cobalt-chromium system. EXPERIMENTAL WORK For the convenience of the reader, the diagram as determined by the present investigation is presented in Fig g. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the, melting point for pure chromium is the

Jan 1, 1948

By T. R. A. Gokcen

THE possibilities of separating and purifying metals by high vacuum distillation were examined by Kroll.1 He suggested vacuum treatment for the removal of zinc from the lead produced after Parkes desilverizing. The St. Joseph Lead Co. developed the first commercial vacuum dezincing process at their Herculaneum refinery, as described by Isbell.² The Broken Hill Associated Smelters at Port Pirie, Australia, has, after several years of pilot plant operations and fundamental investigations, developed a continuous process, which will be described briefly in a forthcoming publication." As the full-scale continuous vacuum dezincing plant at Port Pirie is still experimental, publication of full practical details of the plant will be deferred until the unit is operating as a normal part of the continuous refinery. This paper deals only with theoretical aspects of vacuum distillation processes, with particular reference to vacuum dezincing. The method of mathematical analysis is of general interest as it may be applicable to other metallurgical separations which have been investigated recently.4-6 Evaporation Processes At about atmospheric pressure, or higher, most liquids possess a boiling point—a temperature at which any heat put into the liquid is absorbed only as latent heat, not as specific heat. If a steady heat input is supplied, the liquid&apos;s temperature rises to this value, then remains constant while bubbles of vapor form beneath the surface. The rate of evaporation is determined solely by the rate of heat transfer to the liquid; the temperature of boiling is determined by the partial pressures of the volatile constituents in the liquid, and the total pressure above the surface. If the rate of heat transfer to the liquid is increased, the temperature remains constant, and the rate of boiling increases. When evaporating metals under vacuum, however, the partial pressures concerned are generally so small that boiling does not occur, because at even a fraction of a millimeter below the surface the hydrostatic pressure is usually too great to permit the formation of a pocket of vapor. In addition, the high thermal conductivity of metals tends to prevent the local superheating which is necessary for bubble formation.&apos; Although this effect is doubtless also exerted when boiling metals at higher pressures, the magnitude will be less because the degree of superheat required to form bubbles is very much less at the higher temperatures involved. Under vacuum, therefore, evaporation of volatile constituents takes place only from the exposed surface, and the rate of evaporation depends upon the surface area, the surface concentration of volatile constituents, the surface temperature, and the partial pressures of volatile constituents immediately above the surface. If the heat input is raised above a certain level, the effect is not to increase the evaporation rate at constant temperature, but to raise the temperature of the liquid until at some higher level an increased rate of evaporation (and thus of latent heat absorption) again balances the heat input rate.? Many substances (including metals) have a very large intrinsic evaporation rate at quite low temperatures—far below their normal boiling points. However, at atmospheric pressure, the large numbers of atoms evaporated are almost completely deflected back into the liquid (or solid) surface by air molecules. Thus the back condensation rate is practically equal to the gross evaporation rate, and the net evaporation rate is practically zero. It can therefore be seen that an overall distillation rate depends not only upon the intrinsic evaporation rate, but also upon the ability of the volatile atoms to move away from the evaporating surface. This movement is facilitated by the provision of a condensing surface close by. Vacuum Distillation: The function of the vacuum above the evaporating surface is to remove foreign molecules, so that the chances of deflection of an evaporated atom back into its source are reduced. When the residual gas pressure is reduced so far that the evaporated atoms have a high probability of reaching a nearby condensing surface without suffering collision with a foreign molecule, the state of affairs is termed "molecular distillation." This process is practiced commercially today for the purification of numerous organic chemical products of high unit value, but not, to the writer&apos;s knowledge, for any metallurgical separation. When the degree of vacuum produced in a still is not sufficient to promote molecular distillation, then the evaporated molecules must diffuse through the

Jan 1, 1954

By Sidney G. Parker, Jack E. Pinnell

Cubic ZnSe crystals have been grown with HCl, HBr, and I, as chemical transport reagents. The growth of large, well faceted crystals is in the order HCl < HBr < I, with some produced by I, transport being 1 cm on an edge. ZnSe:I crystals showed no strain in cross polarized light and were homogeneous as determined by electron microprobe. These ZnSe:I crystals had a mobility at 25°C of about 300 sq cm per v-sec and contained 103 dislocations per sq cm; further, these crystals were pure cubic and showed both photolumi-nescence and photo conductance. Doping was attempted during crystal growth. ZnS and Zn (S,Se) crystals were also grown by I, transport. ZnSe crystals have been grown by most of the common techniques.1"6 Of these, chemical vapor transport as developed by Kaldis2 showed promise of producing high perfection, cubic ZnSe. With chemical transport, crystals can be grown far below the transition temperature for conversion of cubic to hexagonal structure. A small temperature gradient between source and growth region tends to allow near equilibrium growth, which should lead to good crystalline perfection. Because it is necessary to form volatile compounds, halogens or their compounds are extensively used as transport agents. HCl, HBr, and I, were compared as transport agents for growth of ZnSe crystals. Doping during crystal growth was attempted. ZnS and ZnSxSe1-x crystals were also grown by chemical transport. Electrical and optical properties of the crystals were examined. EXPERIMENTAL Fig. 1 is a sketch of the growth apparatus, which was a modification of Kaldis&apos;. A quartz rod which butted against the seed crystal served as a heat sink to promote growth only on the seed. Initially, crystal growth was attempted with ZnSe prepared by wet chemical methods. Because such a material contained oxides and selenates, HC1 reacted with these oxygen compounds to form H2O and no ZnSe transport occurred. Further, this ZnSe contained about 10 ppm Cu plus other impurities. High purity ZnSe, containing small amounts or no oxygen compounds, was prepared by reaction of H2Se with zinc vapors at 600° to 800°C in an atmosphere of palladium diffused H2.7 The ZnSe thus produced was usually copper free and contained only 1 ppm by weight of magnesium as determined by emission spectrographic analysis. G.E.&apos;s electronic grade ZnS, which had about 10 ppm metallic impurities, was used without further treatment. ZnS-ZnSe charges were prepared by mixing the two compounds together, then sintering 24 hr at 1100°C in an H2S ambient. The gases, HBr and HC1, were commercial grade, of 99.9 pct purity, while the I2 was 99.999 pct pure. The single crystal seeds with (111) faces for growth were mechanically held in place by sealing the outer quartz tube to the growth tube. After the charge was introduced, the system was outgassed at l0-5 torr while heated to 500°C. The desired quantities of transport reagents were then sealed off in the system, which had been cooled to 25°C. The growth tubes were inserted into a furnace with the desired temperature and thermal gradient. The system was allowed to cool for 1 to 12 hr from growth temperatures of about 850" to 25°C. The tubes remained stationary during crystal growth. HCl CHEMICAL TRANSPORT GROWTH Preliminary runs with HC1 had a temperature gradient of 100° to 200°C and no seed or heat sink. Only small crystals were obtained in these experiments as

Jan 1, 1970

By G. S. Cole, H. Biloni, G. F. Bolling

An experimental investigation of sovlze low .melting point alloys sJtows that a substvucture of isolated depressions can be the first manvestation of constitutional supercooling on solid-liquid interjaces veuealed by decanting. Electron-tni cvop vobe and wletallo gvaplic esanzinations, in tlze bulk belzind the interjace, oj the segregation associated with these isolated areas substantiate tlzei&apos;v depressed nature, since a solute of ko < 1 is enriched, and a solute of ko > 1 depleted. In contrast, the pox structuve, a set of projections often veported in the literature, leaves no trace oj. segvegation. These obserl;atims, accovlrpanied by a brief review of recent literature, point to inconsistencies between experirrental obsevvation and the idea that the fornzation of a projection is a causal step in the development of a cellular substructure. An argument is presented to show instead how it is plausible for substantial depvessiom to form in the pvesence of constitutional supercooling at dislocations threading the solid-liquid interjace. THE development of constitutional supercooling during growth from the melt leads to the formation of the cellular solidification substructure. This well-founded association between structure and instability has been basic in understanding cellular substructure and micro segregation; however, the initial formation of structure seems unclear. Rutter and Chalmers,&apos; in definitive experiments and theory, noted that in the presence of constitutional a planar interface might break down: "resulting in the formation of a small projection on an initially plane or uniformly curved interface." That is, the breakdown from a planar to a cellular interface was implied to be initiated via a projection into the unstable liquid. Later, Walton et (11. found that a structure of isolated projections, termed "pox", appeared at solid-liquid interfaces decanted under growth conditions near the onset of constitutional supercooling; the pox were taken as the indication of the instability promoted by the supercooling. Tiller and Rutter4 in their extensive work studied the shape transitions at decanted interfaces which were generally observed to proceed as— pox, "irregular cells", elongated cells, regular (hexagonal) cells, and so forth. The pox varied in size from lo-&apos; to 1CT4 cm, and tended to disappear as cells increased in number and regularity, but as noted,4 the first real array of cells did not seem to be a development from the pox. In fact these authors implied a lack of connection because they stated that the pox are denser on "irregular cells", and as cell boundaries increase in number (i.e., the cells become smaller) there is less need for the pox which do dis- appear. Thereafter, most authors dealing with either experiment or theory have accepted the reality of pox and have used them as a criterion for the onset of constitutional supercooling. In contrast, Spittle, Hunt, and smiths have now suggested that pox are irrelevant artifacts comprised of such things as entrapped oxide. This proposal invokes the observations of weinberg6 and chadwick7 each of whom have shown that the act of decanting leaves a residual liquid on a decanted interface; the remnant solid layer of the order 10 p may thus contain particles that might have been transported from the external surfaces, or elsewhere, during decanting. With the incentive of this suggestion,= some further experiments and a reexamination of the literature have been conducted, in order to question the validity of pox as evidence of an instability and to examine the initial development of the cellular substructure. 1) EXPERIMENTS Single crystals of zone-refined tin (-99.9999 pct) were grown from the melt in a controlled fashion with various, small concentration additions of lead and antimony, for which ko < 1 and > 1, respectively. The crystals were decanted at conditions near the onset of constitutional supercooling and were thus appropriate for observation of slight perturbations. It was possible to observe two types of small departure from smooth or "planar" interfaces in both cases of lead or antimony additions. Some were projections and others, if in regular array of any type, were depressions. The crystals were etched with suitable reagents progressively dissolving the decanted interface surface; projections left no record, but depressions were continuously associated with spotlike areas contrasting with the rest of the interface. Traverses were made with the beam of an electron microprobe across the regions of contrast; with lead addition the persistent spots were lead-rich, and with antimony addition the persistent spots were antimony-poor. This is consistent only with a dominant role for depressions, because if the projections had left spots but were incorrectly catalogued, a reversed observation should have been made; that is, the Pb(ko < 1) should have been depleted and the Sb(ko > 1) enriched. In the work of Cole and inegard, and elewhere, regular arrays of structure associated with the initial stage of instability have been shown, in photographs and represented as pox or projections. We believe this to be erroneous, by inference, since whenever a regular array was observed, in the present examination, it consisted of depressions, regardless of the nature of the solute, ko 1. Fig. 1 is reproduced8 as an ideal example of the possible optical illusion involved; the observer can satisfy himself from the distribution of illuminated areas that the markings are depressions. Fig. 2 from the present investigation is an interference photograph of an interface similar to that in Fig.

Jan 1, 1967