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By B. Lustman

IT has been known for a number of years that the addition of certain alkaline-earth and rare-earth metals to nickel-chromium base electric resistance alloys causes marked increase in their oxidation resistance as measured in an intermittent oxidation test similar to the ASTM—B 76-39 test. However, the mechanism whereby such additions confer protection is still unknown. On the basis of the experimental observation that the increase in life in intermittent tests of nickel-base alloys is proportional to the atomic radius of the added element, Hessen-bruchl has proposed that the added metal ions occupy holes in the oxide lattice which prevent diffusion of nickel ions in the oxide. Horn2 has postulated that the effect of such additions is to accelerate the rate of diffusion of chromium atoms in the metal and thus to favor the formation of Cr2O3 scales. Hickman and Gulbransen3 concluded from electron diffraction observation that the addition of the elements in question results in the formation of a barrier to the diffusion of nickel ions to the surface. In connection with some experiments conducted to develop a test for the resistance to oxidation of alloys in massive form under conditions of intermittent heating and cooling, some features of the oxidation of nickel-chromium base alloys were revealed which may serve to elucidate the mechanism of protection conferred by rare-earth and alkaline-earth elements. Specimens of cylindrical shape 0.360 in. diam x 0.37 in. long were placed in alumina thimbles and inserted into and withdrawn from a Globar-heated furnace operating at 2150°F at 7.5-min intervals. The weight of oxygen absorbed as well as the weight of oxide spalled were measured at intervals. With the particular experimental conditions used, the specimens in a 7.5-min cycle were at temperature for 2 min which corresponds to the heating time of the ASTM test. The weight changes of similar specimens under conditions of continuous heating in air at 2150°F were also measured. The specimens after oxidation were examined metal- lographically and samples of the spalled oxide collected for X-ray diffraction identification of the phases. The specimens used were from the same lot of material used by Hickman and Gulbransen3 and had the compositions shown in table 1. Included in table I are results of ASTM life tests on the materials in the form of wires. These materials, their composition and the ASTM life test data thereon were all supplied by F. E. Bash of the Driver-Harris Co. It may be noted that alloy 13246 of 80 pct nickel, 20 pct chromium nominal composition showed the shortest life in the ASTM test; alloy 12246 with the addition of small amounts of the elements zirconium, calcium, and aluminum, intermediate life; and alloy 12046 with the further addition of silicon, the longest life. In fig. 1 are shown the results of intermittent oxidation tests made on bulk specimens at 2150°F as well as continuous tests conducted at the same temperature. Duplicate tests were made on each specimen. The ordinate scale, inches of metal oxidized, was derived from the experimentally observed weight gain of oxygen by assuming the scale to be entirely Cr2O3. It may be noted that the metal-loss curves during intermittent oxidation show a constant or continuously increasing rate of weight

Jan 1, 1951

By G. F. Sager, B. J. Nelson

Magnesium alloy forgings offer higher and more uniform mechanical properties than heat treated magnesium alloy castings and are used principally for light weight parts that may be stressed in fatigue or subject to impact loads, or where space limitations do not permit the use of the necessarily bulkier magnesium alloy castings. Compositions and Properties of Magnesium Forging Alloys The nominal compositions and properties of the principal commercial magnesium forging alloys are given in Table 1. The two that are most commonly used are AMC58S and AM65S. The former has the highest strength and is, therefore, employed for heavy duty applications. However, the forging of this alloy and of AMC57S ordinarily requires the use of slow speed hydraulic presses. The forging alloy AM65S combines good, although somewhat lower, mechanical properties with excellent forging characteristics. This alloy can be forged on hammers, upsetters, rolls, and mechanical presses, as well as on hydraulic presses. These characteristics make it particularly useful for many applications. Manganese Segregation in AM65S The alloy AM65S contains 5 pct tin, 3 1/2 pct aluminum, and a small amount of manganese, the manganese being added to insure satisfactory resistance to corrosion. Some manganese segregation was occasionally encountered in this alloy. In many applications, such segregation is of no particular consequence, but when forgings are acid dipped prior to the application of various chemical coatings, the segregated particles of manganese constituent may stand in relief. The resultant surface roughening may impair appearance and is undesirable in forgings employed in the textile industry, where very smooth surfaces are essential to avoid the catching and breaking of fine threads. An effort was therefore made to determine the cause of manganese segregation in this alloy and find a method for its elimination. Radiographic examination of a series of cast ingot sections and extruded samples of the AM65S type having manganese contents ranging from zero to about 0.7 pct revealed no appreciable manganese segregation when the manganese was less than about 0.4 pct. A small amount was observed with a manganese content of 0.46 pct and considerable with manganese contents of 0.6 pct or higher. Attempts to eliminate the manganese segregation by variations in the melting and casting conditions were unsuccessful and it soon became apparent that the trouble was attributable to the fact that the manganese contents that caused segregation were in excess of the amounts that would remain in solution at temperatures encountered in the melting and/or casting operations prior to the complete solidification of the ingots. A knowledge of the amounts of manganese that would be soluble in molten alloys of the AM65S type at various temperatures was obviously desirable. The liquid solubilities of manganese in binary Mg-Mn alloys and in Mg-Al-Mn and Mg-Zn-Mn alloys have been determined by Tiner and others,* but no data on the solubility of manganese in molten magnesium alloys containing tin and aluminum are given in the literature. For this reason, an investigation to determine the solubility of manganese in a magnesium alloy containing 5 pct tin and 3.5 pct aluminum (AM65S type) was undertaken.

Jan 1, 1950

By O. J. C. Runnalls, L. M. Pidgeon

Some observations on the kinetics of the iodide process are reported. The deposition rate is geometry-sensitive in a system containing a finely divided titanium charge. Further, results indicate that the iodine diffusion rate influences the velocity of the process. The nonvolatile iodide, Til,, forms in the hot filament zone, thus removing iodine from the cycle. TITANIUM metal of 99.9 pct purity may be prepared using a refining technique originated by Van Arkel and de Boer.' The purity of this metal, commonly called iodide titanium, exceeds that produced by any known process. In a recent application, the method was employed by Gonser et al.² to prepare titanium rods up to 2 to 3 cm in diam. In the Van Arkel-de Boer system, the relative influence of the fundamental mechanisms: l—production of titanium iodides, 2—gaseous countercurrent diffusion, and 3—decomposition, on the deposition rate have not been clearly established. Blocher and Campbell" have indicated that the controlling step in the process under practical conditions of operation may be the reaction rate of iodine with the crude metal. Fast' reported that crude titanium metal reacted with iodine rapidly, even at room temperature, in his apparatus. Little has been reported on the effect of gaseous diffusion or decomposition on the deposition rate. It is these aspects of the process about which this investigation is centered. An attempt has been made to separate these latter effects from those due to the formation of the iodides at the crude metal surface by a division of the experimental program. Reaction of Iodine with Titanium Apparatus: In the investigation of gas-metal reactions of this type, the chemical reactivity of the halogen and halide vapors dictates the use of all-glass apparatus. In such a system standard techniques for measuring reaction rates are difficult to employ. Here, a simple apparatus was devised (Fig. 1) so that some indication of the reactivity of titanium powder with iodine vapor could be obtained. A stream of iodine gas was evolved from a bulb of controlled temperature and passed over a sample of titanium powder heated in a horizontal tube furnace. The product of the reaction, TiI4, volatilized and was condensed outside the furnace in a series of four glass bulbs, each cooled to room temperature in turn. Preliminary experiments indicated that distillation was retarded in a sealed evacuated system due to a pressure build-up in the condensing end of the apparatus. Hence, the system was pumped continuously using a mechanical pump and two oil diffusion pumps in series, through a liquid air trap. The iodine bulb was made large and a capillary restriction was inserted between the titanium bulb and the condensers so that the iodine pressure over the metal would approach the equilibrium pressure over solid iodine crystals. The effect of this restriction on the evaporation rate of TiI4, was determined separately. The iodine bulb was heated in an oil bath controlled to ±2°C. The titanium bulb temperature was automatically controlled to ±5°C. Procedure: About 200 mg of —30 mesh titanium powder, weighed to 0.1 mg, was placed in the reaction bulb after part B had been joined to part A. The powder was tapped into a long (5 cm) shallow mass along the bottom of the tube. Two chromel-alumel thermocouples were inserted into the magnesium radiator which was clamped to the reaction

Jan 1, 1953

By Nick Holonyak

Halogen vapor-transport synthesis of Ga(As,-,Px) and its preparation into laser junctions are described. Electrical and optical properties of Ga(As,-,PX) laser junctions are discussed. The present limitations in these properties are related to material proble?vzs and the very early state of development of Ga(As,-,PX), and are discussed in this context. Inhonzogeneity problems, fluctuation of As :P ratio, and problems with deep-level contaminants are described and related to Ga(As,-,PX) junction performance. Laser junctions are demonstrated which operate to wavelengths as short as 6470 A (77°K). The prospect that Ga(As,-,P,) will operate to wavelengths perhaps 100A shorter is mentioned. IN this paper we wish to describe some of the more important features of almost 1 year of experience in the preparation and properties of Ga(As,-,P,) p-n junction lasers. Because much data so far available are far from complete, some of the results still must be considered tentative and subject to correction and revision as work on Ga(As,-,P,) crystal problems progresses. Although the electrical, optical, and device properties of Ga(As,-,P,) junction lasers are understandably of considerable interest, the work to date points out that by far the most serious problems extant and those deserving first attention are problems involving the growth, doping, and perfection of Ga(As,-,P,) crystals. One of the most formidable of these is to grow Ga(As,-,P,) sufficiently free of deep levels, either due to contaminants or to structural imperfections, to allow fabrication of laser p-n junctions which can be cooled and not suffer from "freeze-out" of carriers on deep levels (and consequent double-injection behavior). In addition to the problems of growing crystals adequately free of deep levels and generally of the highest perfection, so that the best possible laser junctions can be realized, the further goal remains of increasing the phosphorus content well beyond 40 pct in an attempt to determine the practical lower wavelength limits of laser action in the Ga(As,-,P,) system. Even though the laser junctions prepared in Ga(As,-,P,) are of importance in their own right, we have considered them at this point mainly a means to study the growth and crystal problems of the material. It can be concluded that the laser junctions now available are almost completely limited by the purity and structural deficiencies of Ga(As,-,P,) crystals, and cannot be fairly compared with, for example, GaAs p-n junction lasers until Ga(As,-,P,) crystal growth has been more extensively developed. The basis for the statements above will become evident in the following sections which describe Ga(As,-,P,) crystal and junction preparation, and laser-junction properties. G(As,-,P,) CRYSTAL GROWTH As previously reported,2 we have found it convenient to employ the halogen vapor-transport process3 for synthesizing Ga(As,-,P,) crystals for use in laser junctions. Commercially available GaAs and Gap, separately prepared by halogen vapor tranport, are sealed in the desired ratio in a quartz vessel with a quantity of column-VI donor and a small quantity of metal halide which supplies the halogen for transport. The sealed ampoule, as shown in Fig. 1, is heated at a temperature in the range from 1025" to 1100°C at the position of the source GaAs and Gap. The GaAs and Gap are simultaneously vapor-transported and deposited as Ga(As,-,P,) at one end of the ampoule

Jan 1, 1964

By S. S. Shen, M. J. Pool, P. J. Spencer, J. R. Guadagno

VERY few thermodynamic data are available for rare-earth alloys, partly because of the difficulties of obtaining the metals in sufficiently pure form and also because of their comparative scarcity up to the present time. The rare earths form a very interesting series in the periodic table in view of the progressive filling of their 4f subvalence electron shell and would be expected to provide useful information with regard to alloying characteristics of transition elements. It has been found in recent calorimetric investigations that the heats of solution of a number of the rare-earth metals in liquid tin are highly exothermic.1-4 Exceptionally strong bonding between rare-earth and tin atoms is clearly indicated in the liquid solutions. Continued thermodynamic studies of the behavior of rare earths in solution could thus contribute a great deal to present theoretical knowledge of alloying behavior and would yield an insight into bonding of a strength hitherto unencountered in liquid alloys. The determination of the heats of solution of the pure components in liquid tin is an essential preliminary to calorimetric work of this nature. Heats of solution of praseodymium, neodymium, and samarium in liquid tin at 750" ' and the heats of mixing of Pr-Nd solid solutions' have already been determined in this laboratory. The present investigations with lanthanum continue the study of rare-earth elements. Details of the construction and operation of the liquid metal solution calorimeter used in this work have been published previously by Pool and Peluso and no further description will be given here. The lanthanum used in heat of solution determinations was supplied by Lunex who quoted the purity as 99.9 pct. Their detailed analysis of the material is given in Table I. Samples of 0.0003 to 0.0005 g-atom were used for each run and great care was taken to remove all surface oxide prior to weighing. The samples were stored at all other times in a beaker of oil to prevent their otherwise rapid oxidation. The compounds LaSn (Cudu, L1P type structure) and La&, (structure not classified) were prepared from the appropriate quantities of the two pure components by arc melting under a purified argon atmosphere and once again great precautions were taken to avoid any subsequent oxidation of the specimens. Although no structural examination of the compounds was made, the consistency of thermodynarnic measurements carried out on twenty or so individual samples of each indicates that the compounds were in fact homogeneous, single phase alloys. Samples of the compounds consisting of 0.0003 to 0.002 moles were used in the calorimetric measurements. A solvent bath consisting of approximately 80 g of 99.9 pct pure Sn was used for each series of runs and its heat capacity was determined at regular intervals throughout the experiments using pure tin or tungsten calibration samples. Measurements were made of the heat of solution of lanthanum in liquid tin at 725", 750C, and 775°K and at compositions up to 2.21, 4.76, and 5.25 at. pct La at the three temperatures respectively. In every case, the heat of solution of lanthanum remained constant at its limiting value, within experimental limits, up to the highest lanthanum concentration investigated. Since no change in was observed, it was concluded that the liquid/liquid + LaSn, phase boundary had not been

Jan 1, 1969

By C. H. Mathewson

CONSIDERABLE progress has been made during the last few years in analyzing the action of plastic deformation in metallic crystals. This is due largely to the development of X-ray spectrographic methods for studying changes in the orientation of single crystals, or of conglomerates, as they occur during the process of plastic deformation, but partly to the widespread knowledge of suitable technique for preparing large (single or variously combined) crystals for direct crystallographic observation under stress or in various conditions of strain. These two methods of studying changes in the crystalline structure of metals may of course be used in conjunction with features of mutual support, but unfortunately the advantage of direct crystallographic observation is lost when we proceed to the study of severely cold-worked structures, owing to the occurrence of real or apparent crystalline discontinuities which become more and more complicated as the amount of plastic action increases. Furthermore, the X-ray methods do not appear to be adequate, at least in their present stage of development, to fix definitely the character of structural alteration in the parent crystal lattice by plastic deformation. The principal question at issue concerns the nature of the crystalline particles that remain after plastic deformation. These are generally known in our American metallurgical literature as crystalline fragments,1 and they seem, indeed, to diffract as individuals causing the Hull pattern of a, severely cold-worked metal to resemble the pattern of a fine powder,2 with certain features of preferred orientation among the particles determined by the manner and intensity of cold working.

Jan 1, 1927

By Thomas L. Watson

MY thanks are due to Mr. Frank Firmstone, Easton, Pa., who has called my attention to the statement in my papers that " Barite, fluorite and quartz, though not observed in the Tennessee area," . . . as possibly misleading to the reader, if construed to mean that such a discovery had never been made. Mr. Firmstone is correct in assuming that this statement referred only to the study of the worked areas of the metallic ores, especially zinc, made in the course of the survey upon which my paper was based. The occurrence of barite and fluorite with lead-ores in Tennessee was reported by Prof. Safford,2 in 1869, and by Safford and Killebrew,3 in 1887, with the further statement that about 1,000,000 lb. of barite were annually mined in Greene, Washington and Jefferson counties, Tenn., and that considerable deposits occur also in McMinn, Smith and other counties. It is also noted that the barite ".usually occurs in veins, associated with galena." The present worked areas of barite are, however, distinct barite propositions, without workable quantities of either lead or zinc, so far as mining operations have gone, and the areas are more or less removed from the present areas of zinc-ores. Mr. Firmstone informs me also that, in 1892, he observed, in the magnesian limestone at Watauga Point, in Carter county, on the left bank of the Watauga river, a little below the mouth of Buffalo creek, small quantities of galena and some fluorite.

Jan 1, 1907

IN NOVEMBER 1933 I had the pleasure of receiving an autographed copy of a small brochure entitled "Birth of the Porphyry Coppers." The author, James Colquhoun, a distinguished British mining engineer, had been the dominant figure in the Arizona Copper Company, Limited, which, until its acquisition by the Phelps Dodge Corporation in 1921, had been the principal producer of copper in the Morenci district. In addition to the highly productive Humboldt and Longfellow mines it owned the Clay property, which, of course, has now become Arizona's No. 1 copper mine. Except for Utah Copper it is the premier Porphyry copper enterprise in the United States. Mr. Colquhoun's little volume was inspired by THE PORPHYRY COPPERS which had appeared early that year. In a most courteous and friendly way he adduces data to show that "we (Arizona Copper Company Limited) were successfully treating low-grade porphyry ores in quantity for at least four years (1901 to 19W) before the Utah Copper Company did anything at all." This last remark is based on the figures in THE PORPHYRY COPPERS showing that Utah's first production came from the Copperton pilot plant in 1905. Mr. Colquhoun traces the story of Morenci beginning in 1883 when he first arrived there. He tells how the rich self-fluxing ores (containing lime- stone, silica, and iron in proportion to permit direct smelting to produce black copper) were gradually exhausted. High-grade siliceous ore could be mixed in limited quantity with the self-fluxing ores; and oxidized ores were leached to contribute substantially to the production of the district. But

Jan 1, 1957

By Harold W. Aldrich, Walter G. Scott

The leaching process of the Inspiration Consolidated Copper Co. is based upon the solubility of oxidized copper in sulfuric acid and the solubility of sulfide copper, largely in the form of chalcocite, in ferric sulfate solution. This necessitates the carrying of a rather large amount of iron in solution. The ferric sulfate is regenerated from ferrous sulfate by the oxygen given off at the anode during electrolytic precipitation of the copper. In September, 1924, excavation was started at Inspiration, Arizona, for the construction of a plant to treat 7500 tons of ore per day. When the plant was begun, the fact developed that by a minor change in the height of the overflow on the leaching tanks, 9000 tons could be charged into each tank and treated satisfactorily. This determined the maximum capacity of the plant as 9000 tons per day. The first ore was charged in October, 1926, and there are now available the records of five complete years of operation; namely, 1927 to 1931, inclusive. The original estimate of copper content of the ore to be mined for this plant was 1.19 per cent, of which 0.77 per cent was as oxide and 0.42 per cent as sulfide. From the metallurgical results obtained at the 35-ton pilot plant, it was estimated that a 90.0 per cent extraction of the oxide copper and a 75.0 per cent extraction of the sulfide copper could be made. It was estimated that the tailing would carry 0.182 per cent total copper, resulting in a

Jan 1, 1934

By E. A. H. Tays, F. A. Schiertz

In 1893 the Anglo-Mexican Mining Company, Limited, purchased the Guadalupe and adjoining mines, and, after opening up the Guadalupe, constructed a 20-stamp mill, which was started in August, 1894. Although the results were extremely profitable (the ore being very rich and carrying much free gold) they were not satisfactory, because the tailings were found to average about $20 per ton in gold. Early in 1895 the late Mr. James E. Mills made for the company a very thorough study of the subject, and decided that the tailings could be treated most advantageously by the cyanide process. In view of this opinion, Mr. Henry R. Batcheller, of Boston, was sent down in the winter of 1895-96 to experiment on a working scale. Mr. Batcheller was successful; and, during 1896-97, built a cyanide-plant with a capacity for treating 1500 tons per month. This was run until May, 1899, when all the sands suitable for the process had been treated. The mill was stopped about the same time for lack of ore; but no tailings from the mill had gone to the dump since October, 1897, as the values they contained after that date were far too low to warrant further treatment. When the cyanide-plant was stopped there still remained on the dump about 16,000 tons of slimes, consisting of about 75 per cent. of clay-slimes and 25 of sand-slimes. The successful treatment of this very unfavorable material is the theme of this paper. Fig. 1 is a view of the hacienda, taken in 1897.

Jan 1, 1902

By Harold C. Price

One year ago, that is in January, 1923, there had not been constructed a single oil-storage tank of 55,000-bbl. or more capacity with a completely electric welded roof and bottom. Today, there are at least fifty 80,000-bbl. storage tanks completed, or nearing completion, on which both the roofs and the bottoms are electric welded. It is the purpose of this paper to describe, in a general way, the construction of these welded roofs and bottoms, and to give their advantages over riveted construction. All of the following data and conclusions were obtained from observations made during the welding of tanks by the Welding Engineering Co. at Texas City, Tex., and Tonkawa and Burbank, Okla. As far as can be determined, the first electric welding on large tankage was completed in May, 1922. At that time the Empire Companies of Bartlesville, Okla., discovered a badly leaking bottom in a 55,000-bbl. tank at El Dorado, Kans. They had considered concreting this bottom, but because of the much smaller cost, decided to try electric welding; so a contract was given the Welding Engineering Co. of Bartlesville, Okla. In this instance, no new sheets were added, the bottom being repaired by electric welding of all seams and rivets, Fig. 1. In some places where the original rivets were missing, the holes were filled by welding; patch plates were also added at certain badly worn spots. This tank has since been used for over a year and a half, but no other

Jan 1, 1924

By W. C. Schroeder, A. A. Berk

Practical experience has shown that at elevated temperatures solutions containing sodium hydroxide may attack stressed steel in a manner that cannot be explained in terms of ordinary corrosion. Because the ductility of the metal has been greatly reduced during the reaction, the entire phenomenon is usually called "embrittlement." Thus, after several years of operation caustic evaporators have been so badly embrittled that rivets could be cracked off with the blow of a hammer. Since fine intergranular cracks are almost always present in the zone of fracture, it has often been assumed that a process of selective corrosion in grain boundaries was responsible for the failure, although this has not been clearly proved experimentally. Concentrations of sodium hydroxide below those necessary for the uniform, rapid attack of the steel surface are reported to be most effective in producing embrittlement2, 3. In the operation of steam boilers a similar type of failure has been found, mainly in riveted seams or other capillary spaces where the solution may concentrate and where high stresses may also exist. It is believed that in such localized areas the dissolved solids may reach a value many times the few hundred parts per million prevalent in the body of the boiler. While this type of boiler failure has been the subject of investigation for a period of 20 years1, an understanding of its mechanism and a rational basis for complete protection have not yet been secured. To procure this information the present investigation was

Jan 1, 1936

By A. A. Berk, W. C. Schroeder

Practical experience has shown that at elevated temperatures solutions containing sodium hydroxide may attack stressed steel in a manner that cannot be explained in terms of ordinary corrosion. Because the ductility of the metal has been greatly reduced during the reaction, the entire phenomenon is usually called "embrittlement." Thus, after several years of operation caustic evaporators have been so badly embrittled that rivets could be cracked off with the blow of a hammer. Since fine intergranular cracks are almost always present in the zone of fracture, it has often been assumed that a process of selective corrosion in grain boundaries was responsible for the failure, although this has not been clearly proved experimentally. Concentrations of sodium hydroxide below those necessary for the uniform, rapid attack of the steel surface are reported to be most effective in producing embrittlement2, 3. In the operation of steam boilers a similar type of failure has been found, mainly in riveted seams or other capillary spaces where the solution may concentrate and where high stresses may also exist. It is believed that in such localized areas the dissolved solids may reach a value many times the few hundred parts per million prevalent in the body of the boiler. While this type of boiler failure has been the subject of investigation for a period of 20 years1, an understanding of its mechanism and a rational basis for complete protection have not yet been secured. To procure this information the present investigation was

Jan 1, 1936

By E. P. Mathewson

The early development of the reverberatory furnace for smelting copper-ores was the work of the Welsh smelters, particularly those of Swansea. The first record of a reverberatory furnace is made by Jars, who states that in 1755 copper-smelting was effected .in reverberatory furnaces at Middleton-Tyas, in Yorkshire, England. The first patent, of any importance, for improvements in reverberatory furnaces was granted to Thomas Williams in 1778 for the granulation of the regulus. The next was that of William Evetts, in Sheffield, in 1812, for the cooling of the fire-bridge by the admission of air. Charge-hoppers above the furnaces were in common use in 1848. The size of the hearth of the furnaces about the beginning of the 19th century was commonly 11 by 8 feet. No material development was made until the Welsh process mas brought to Colorado, where Richard Pearce, as manager of the Argo works, near Denver, developed the furnace to meet the requirements of a custom plant, under keen competition with lead-silver smelting-plants, using blast-furnaces. His improvements are outlined in Fig. 1, elaborated by permission from E. D. Peters's excellent work,' to which the reader is referred for further details. This figure shows that the furiiaces were in 1878, 9 ft. 8 in. by 15 ft. in hearth; and in 1894, 16 by 35 ft., while the capacity of the furnace had been increased from 12 tons per 24 hr. to 50 tons in the same period.

Jan 1, 1913

By Frank G. Snyder

INTRODUCTION Numerous deposits of lead and zinc sulfides, often accompanied by barite and fluorite, occur in carbonate host rocks throughout central and eastern United States. So similar are the deposits in broad general characteristics that they long have been classified as Mississippi Valley type. They differ widely, however, in details such as metal ratios, age of host rock, type of ore-bearing structure, and probable time of mineralization. The theories developed to explain the source and transport of the metals are many and are known to all. The deposits have been termed telethermal on the basis of their presumably shallow occurrence and the attempt to relate the metals to the classic hydro- thermal sequence. 1t is now recognized that deposits of this type can occur at any depth; the only depth limitation is thickness of the sedimentary section. Ideas on the source of the metals also have changed, A rapidly growing body of evidence suggests that the metals were brought by concentrated brines from nearby sedimentary basins. The hypothesis preferred today by many geologists postulates that the metals were deposited during the course of normal sedimentation in depositional basins of miogeosynclinal or orthogeosynclinal type. At some time after deposition of the sediments, the metals were carried out of the basins by migrating brines; the brines moved laterally and upward into structurally high areas; they entered any reservoir-like structure, either primary or secondary in origin, that happened to be available; in this reservoir, possibly in a sulfur-rich environment, the metals were precipitated as ore minerals.

Jan 1, 1970

By R. C. Allen

ABOUT four years ago the writer proposed a revision of the correlation of the Huronian formations in Michigan, and noted the bearing of the question on the correlations of the Huronian rocks in Wisconsin and Minnesota.1 Dr. C. K. Leith opposed this revision and argued for the retention of the correlations of the United States Geological Survey, published in 1911,2 for which he and Dr. Van Hise were mainly responsible. As late as June, 1917, Harder and Johnson, following Leith, thought it "premature to change radically a correlation based on years of careful field work."3 The work of Wolff on the Mesabi and Cuyuna Ranges, of Hotchkiss on the Gogebic Range (unpublished), and of the writer and assistants on the Michigan ranges, together with data developed by exploratory and mining operations, has introduced so many pew facts not recognized in the scheme of the U. S. Geological Survey that the correlations of 1911 must be considered, in some important respects, obsolete. Indeed new data are accumulating so rapidly that any classification, which for the moment may seem best to explain the facts, is almost immediately modified or refined by further observations. The problem of Huronian correlations is difficult, but interesting and important. With the aid of fossils, stratigraphers of the post-Algonkian formations have been able to show that slight disconformities may separate strata of vastly different ages, and that within physically conformable strata may be concealed a hiatus of great magnitude. In the non-fossiliferous Huronian group, minor physical breaks in the strata are

Jan 9, 1919

By James Norman

SPODUMENE is a lithium-bearing pyroxene, and is an important source of lithium compounds. Because of its high alumina and lithia content it might be a desirable constituent of glass batches. The use of spodu-mene in ceramics will undoubtedly increase, as it has been shown that a mixture of the proper proportions of this mineral with soda feldspar and potash feldspar has a much lower maturing temperature upon firing than has any one of the three components.1 The mineral spodumene seldom occurs as pure mineral, but ordinarily with feldspars, mica and quartz. All spodumene-bearing rocks tested contained these minerals as gangue. Small amounts of iron and manga-nese oxides also were present, usually as stains on the silicate grains. Mica associated with the spodumene carried a considerable amount of lithia. This was discovered in flotation tailings, which, although virtually free of spodumene grains when examined microscopically, showed 0.4 to 0.5 per cent Li20 on chemical analysis. The lithia content of micas picked from the North Carolina spodumene rock was variable. Some samples contained little lithia, others more than 3 per cent. In 1938, under the supervision of Oliver C. Ralston, ? the Bureau of Mines, in cooperation with the Tennessee Mineral Products Corporation, undertook to study the beneficiation of North Carolina spodumene by froth flotation. The Bureau had previously published investigations on the beneficiation of spodumene.2,3 The methods described in the second publication' did not give good results with badly weathered spodumene rock, so that more thorough investigation of the subject was warranted.

Jan 1, 1940

By Raimo Matikainen

Sublevel stoping has been used in Finland since the 1930's and today more than ten under- ground mines have adopted it as their main stoping method (Fig. I). Approximately 80% of the total underground tonnage is mined by sub- level stoping (Table 1) The first mines to introduce the sublevel stoping method in Finland were limestone mines. The development of sublevel stoping was very slow up to the mid 1960's when the switch to trackless mining started and the increase of mechanization lead to higher capacity and productivity. The method itself has been almost the same since the 1950's when long hole drilling was introduced. According to a future prognosis sublevel caving will give way to sub- level stoping; on the other hand, open pit mining will at the same time grow rapidly with some new mineral orebodies, which will he brought into production. Most Finnish orebodies are, however, only marginal ores and they could not support mining with more expensive methods than open pit mining or sublevel stoping. The future of sublevel stoping seems relatively bright. GEOLOGICAL AND ROCK MECHANICAL BACKGROUND The rock mechanical conditions in Finland are in general relatively good and the rocks firm. The compressive strength is normally 40 - 150 Mpa and modulus of elasticity 40 - 200 Gpa. Low values are common in altered and fractured rocks and near the ore contact Rock stress measurements have been carried out already for 20 years for mine design and monitoring purposes. The results of these measurements show that relatively high horizontal stresses seem to be common (Fig. 2).

Jan 1, 1981

By Carl Floe

THE possibility of separating the various constituents of mixed ores or metalliferous products by differentially producing their soluble sulfates has not received the consideration that it deserves. The production of the soluble sulfate may be accomplished by baking the ore with sulfuric acid or by treating it with gases containing oxides of sulfur. This paper is primarily concerned with the first method. The procedure used was to mix the material with a solution containing a definite weight of sulfuric acid, baking the mixture at various tempera-tures and then leaching out the soluble sulfate with water. The amount of acid used was calculated to produce certain desired soluble sulfates. The temperature of baking depended on the decomposition points of the sulfates involved. The object was to prevent the formation of or to decompose certain sulfates while leaving a maximum quantity of another sulfate in a water-soluble form. This procedure has two possible advantages over the ordinary method of leaching with an aqueous solution of sulfuric acid. First, a more selective leach may be obtained, and second, the higher temperatures and stronger acid concentrations involved will permit a better recovery of materials that are difficultly soluble in relatively dilute aqueous sulfuric acid solutions. The method of sulfuric acid baking followed by water leaching is not new, as it has been applied in the treatment of various metalliferous materials such as the recovery of cadmium from flue dust1, the re-treat-ment of zinc leach residues2 and the working up of electrolytic slimes3.

Jan 1, 1936

By Harry Seltz

INTERMETALLIC compounds are formed in many binary metal systems. Some compounds are stable to their melting points, and others decompose at lower transition temperatures. Even those of the first class are dis-sociated in the liquid state, as indicated by the continuous for in of their solubility curves at their melting points1. While the lattice structures of some of these compounds have been determined, their thermodynamic properties have not been investigated. In this paper is described the determination of the free energy and heat of formation of the compound CdSb, which is of the first class mentioned above, melting congruently at 455° C. This compound shows a rhombic structure, and the lengths of the edges of the elementary cell containing four molecules are: a =6.52, b = 8.60, c = 4.16 A.2 There are three possible methods of determining the free energy of formation of a compound of this type. The first method, applying the third law of thermodynamics, requires the measurement of its heat capacity preferably to liquid hydrogen temperatures, and a calorimetric determination of its heat of formation. The second method involves the study of the equilibrium of the compound in some gas reaction, such as: CdSb + CO2 = CdO + CO + Sb From the known free energies of formation of CdO, CO2 and CO the free energy of formation of CdSb could be calculated. The third method measures the electromotive force of a galvanic cell in which the cell

Jan 1, 1935