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By Enid C. Plante, K. L. Sutherland

Practical metallurgists are unanimous in stating that oxidation of mined sulphide ore adversely affects separation of the constituent minerals under standard conditions in a mill. Frequently, the need for different operating conditions in different plants is attributed either to the extent of oxidation of the mineral surfaces or to soluble oxidation products. The investigations reported in this paper study the effect of oxidation on the primary condition necessary for flotation, namely that of adhesion of an air bubble to the mineral. Oxidation Products from Sulphide Minerals Weinig and Carpenter1 state that the relative rates of oxidation of some sulphides are: FeAsS > FeS2 > CuFeS2 > ZnS > pbS > Cu2S tetrahedrite. They also show that oxidation is rapid at first, that sulphides of older geological formations are more stable than those of recent date and that mixtures oxidize more rapidly than any one mineral alone. The more rapid oxidation of mixtures is borne out by results of Gottschalk and Buehler2 who found that PbS, zns and cus oxidized 8 to 20 times faster when pyrite was present. Only the end products of oxidation, sulphate and the metal ion, were identified in these tests. Gaudin3 states that pyrite is difficult to oxidize in the laboratory. Winchell,4 using pyrite containing 99.98 pct FeS2, allowed water to percolate through a bed of this ground material. At the end of three months only a trace of Fe+++and So4- were found. Even after 10 months the quantity of Fe+++ was only 7.8 mg and SO4- 25.5 mg per liter of percolating solution. Car-michael5 confirmed Winchell's results on the slow oxidation of pyrite. Usually the oxidation of sulphide surfaces has been conducted in neutral or acid solutions, the acidity being caused by the oxidation products. Eliseev and Nagir-nyaka found that treatment of pure pyrite with lime gave only thiosulphate, but considered it possible that thiosulphate was obtained not by oxidation of the pyrite itself, but by oxidation of calcium disul-hide. Mitrofanov7 suggested that thiO~ulphate was formed by the following process: oxidation of sulphide to give free sulphur (this frequently happens with marcasite), followed by oxidation of the sulphur to sulphur dioxide and reaction of the sulphur dioxide with sulphur to give thiosulphate. Ferric and ferrous hydroxides, or similar compounds, were shown to be present. The Research Staff of the United Verde Copper Co.8 treated ore from the United verde mine with lime. Thiosulphate, sulphide and polysulphides were stated to be

Jan 1, 1949

By E. W. Davis

On the eastern end of the Mesabi Range, in Northern Minnesota, is a large formation of siliceous rock which contains bands and fine grains of magnetite. The magnetite comprises about 35 per cent. of the rock, the remainder being chiefly quartzite and iron silicates. The rock has a specific gravity of 3.4, a hardness of 7, and is extremely tough. This large deposit was located early in the history of the Minnesota iron-ore industry but has not been utilized because of its low percentage of iron as compared with the other Mesabi ores, and because of the difficulty and expense of any milling treatment that would concentrate the iron. An investigation, begun about 3 years ago, shows that the magnetit,e is finely disseminated throughout the entire formation and that there are bands or lenses of higher- and of lower-grade material, in which the magnetite and silicate are intimately mixed. As a result, the scheme of milling adopted must include a fine-crushing plant. As it is necessary to crush to 200 mesh in order to produce the desired grade of product, the fine crushing is one of the largest items of expense and for this reason has been given detailed study. It is the purpose of this paper to present some of the results of the work on fine crushing, as to both theory and practice. Previous to fine crushing the part of the rock that contains little or no magnetite can be discarded by magnetic concentrators after each reduction in size in the dry-crushing plant. This-makes it possible to fine-crush a minimum of rock and also establishes the feed to the ball-mill as below % in. The fine-crushing problem, then, consists simply in crushing the rock from 1/4 in. to 200 mesh at the minimum expense. Equipment of the Testing Plant In order to determine, among other things, the operating conditions of the ball-mill when working on this rock, a test mill of about 300 T. daily capacity was erected at Duluth, Minn. The fine-crushing plant contains a Hardinge 8-ft. by 22-in. (2.4-m. by 55.8-cm.) conical mill, a 6- by 27-ft. (1.8 by 8.2-m.) Dorr duplex bowl-type classifier, a 41/2-ft. (1.37-m.) standard Akins classifier, and the auxiliary machinery necessary to handle the products. Each machine is driven by an individual motor, each of which is provided with meters for measuring the power required. Over 150 tests have been made in the ball-mill, varying in

Jan 1, 1920

By R. M. Brick

Segregation can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-I2 per cent Si alloys. The phasial condition implicitly described above—solidification over a range of temperatures with a compositional difference between solid and liquid—is found in nearly all solid solutions or combinations of solid solutions and eutec-tics, Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually deter-minable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be described first because it is an essential part of the picture. Coring Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus I, 3, 7 and solidus 2, 5, 8, and where the vertical I, 4: 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. Ib) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1945

By Walter Knox, J. D. Doherty

IN 1939, at the request of The Koppers Coal Co., the Koppers Company Research Department established a Stoker Coal Research Laboratory for the purpose of investigating the performance characteristics of stoker coals in typical domestic stoker installations. Fig. I is a photograph of part of the laboratory. The material in this paper deals with the performance of one coal in a single installation. Presented are details of this installation, mechanical characteristics of the stoker, and the results of a series of burning tests in which adjustments were systematically varied. SUMMARY OF RESULTS Mechanical Features I. A large percentage of the total power consumed by a domestic stoker is used to operate the gear case and motor (Fig. 3). 2. The power consumption per ton goes down with an increase in rate of coal feed (Fig. 4). 3. The automatic air control in this stoker showed advantages over manual control (Fig. 5). 4. The air velocities through the retort tuyeres were uniform around the retort, but varied between the rows of tuyere rings (Fig. 6). 5. The crushing of coal with this stoker increased the minus 1/8-in. from 1 1.6 per cent to 19.2 per cent. There was a noticeable segregation of coal as it came from the retort and distribution was not uniform (Fig. 7). 6. Measurement of air entering over the fire showed that with some not uncommon adjustments this air may he a high percentage of the total air supply (Fig. 8 and Table I). Operating Performance I. The removal of clinker was shown to give a period of poor performance characterized by a high fuel-bed resistance and a high percentage of carbon monoxide in the flue gases (Fig. 10). 2. The fuel-bed resistance was found to decrease as the fuel bed built up in a normal response to heat demand after a prolonged hold-fire (Fig. II). 3. With intermittent operation the burning rate was almost always less than the feeding rate. The wide variations were found to be greatly dependent upon the length of the On period and the length of the intervals between On periods (Fig. 12). 4. The maintenance of a low furnace draft led to less fly ash, better clinker formation, and higher efficiencies (Fig. I3). 5. The maintenance of a minimum of excess air also resulted in less fly ash, better clinker formation, and higher efficiencies (Fig. 14). GUIDING PRINCIPLES In planning the investigations, the following principles were adopted: Selection of Healing Equipment.-Use only standard models of stokers and furnaces representative of those widely used.

Jan 1, 1942

By C. E. Mills

The Verde mining district is in Yavapai County, in north-central Arizona. Jerome, the principal town, has a population of 6000 and the two important mines of the district—the United Verde and the United Verde Extension—lie almost within its limits. Perched high on the southwest side of the Verde valley, at elevations of 4800 and 5500 ft. (1463 and 1676 m.) respectively, both mines have long tunnels from their lower levels through which the ore is hauled to the smelters. Clarkdale, the smelter town for the United Verde mines, lies in the Verde valley 4.1 miles (6.5 km.) distant in an air line from Jerome and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel and Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 miles long and has a compensated grade of 4 per cent. At Clarkdale it connects with the Verde valley branch of the Santa Fe railroad. Clemenceau, the smelter town for the United Verde Extension mine, lies 3.5 miles (5.8 km.) in a southeasterly direction from Clarkdale, at an elevation of 3420 ft. It is connected to the Verde Valley branch of the Santa Fe railroad at Clarkdale by the Arizona Extension R. R., a subsidiary of the United Verde Extension Mining Co. The portal of the haulage tunnel, at an elevation of 3757.5 ft., is also connected with the smelter town by 4 miles of standard-gage track belonging to the same company. In the vicinity of Jerome, the great southern escarpment of the Arizona plateau forms the northeast side of the Verde valley. The general level of this escarpment, or "rim" as it is called, is about 4000 ft. above the Verde River. A corresponding elevation is reached only by the highest peaks of the Black Hills, which bound the valley to the southwest. Two lava-capped mesas, known as "Mingus" and "Woodchute mountains," form the culmination of the Black Hills. That part of the Old Black Hills mining district which lies between their crests and the Verde River is now known as the Jerome, or Verde, mining district. If the smelter towns are not included, a strip about 7 miles long by 3 miles (11 by 5 km.) wide, embraces practically all of the properties belonging to the Jerome district. T-bis strip lies parallel to and along the side of the Verde valley from First View, 2 miles northwest from Jerome, to the

Jan 1, 1925

By Earl G. Alexander, W. R. Runyan

The nature of silicon growths which form on amorphous silicon dioxide during epitaxial deposition in unmasked areas was investigated. Octahedral silicon crystals nucleate and grow on the oxide at pinholes, adjacent to foreign matter, and probably at oxygen-deficient sites. Generation of these oxygen-deficient sites on the oxide surface is shown to be thermody-namically favorable under usual deposition conditions. The conditions which affect saturation (SiCl4 concentration, flow rate, temperature) determine the number of sites on which silicon will nucleate and grow. Reaction product HCl is likely responsible for suppressing silicon growths on the oxide near exposed areas of silicon. Evidence is given that the oxide-silicon interaction occurs in hydrogen only and involves water as a transport agent. SINCE shortly after the first epitaxial layers of silicon and germanium were grown over large areas, efforts have been underway to grow selectively on specified portions of the surface. Such selective growth should be particularly applicable to monolithic integrated circuits. Usually the approach has been to use a mask to delineate the desired area,'-7 but the VLS methoda can also be used, and direct programmed atomic beam deposition has been suggested.9 The masking techniques may embody two forms: in one the mask is a material which can later be removed along with any growths attached to it; in the other, attempts are made to prevent growth on the mask, so that over a whole slice the only deposition that will occur is in the unmasked regions. The present work is concerned with only the latter case, and specifically with silicon. Joyce and Baldrey1 suggested the use of thermally grown silicon dioxide as a mask material and showed that for the proper choice of operating conditions (total flow, SiCl4 concentration, total deposition time, and temperature) spurious growth could be minimized and that if the deposition times were not too large, and the criteria not too stringent, a usable process occurred. Later Schnable et al 4 observed that after extended deposition times, during which most of the silicon dioxide became covered with growth, there was always a band of oxide around the exposed silicon area that was quite free of spurious silicon crystallites. This latter observation is particularly intriguing since it extends the hope that with proper precautions masking can be much more versatile than it presently is. EXPERIMENTAL PROCEDURE Silicon substrates oriented to within 1.5 deg of a (111) plane were prepared by etch polishing lapped

Jan 1, 1967

By G. Gutzeit

METAL-ORGANIC INNER COMPLEXES AN inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity. 4,1-13 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime.) It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry,, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals.17 CHELATE-FORMING COMPOUNDS AS COLLECTORS In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxylamine (Cupferron) C6H5NO(=NONH4). Holman19 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-dioximes were generally selective collectors for nickel ores. Taurin NH2(CH2)2SO3H has been proposed for the concentration of oxidized lead ores.19 Diphenylthiocarbazone

Jan 1, 1946

By J. R. Long, T. R. Graham, R. S. Dean

ALTHOUGH considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to 11 pct aluminum, with some incidental information on the single-phase alpha solid solution alloys. Strauss1 gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper5 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50° temperature levels from 400° to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solubility of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 1300°F and higher,

Jan 1, 1947

By B. Post, F. W. Glaser

Three borides of zirconium have been reported: ZrB,l ZrB2,2,3 and ZrB12, 4 The phase relationships, ranges of stability, and some physical properties of these compounds are described. THE zirconium borides differ considerably from one another, particularly with respect to their relative stabilities at high temperatures in the presence of carbon.4,5 ZrB2 is extremelv stable at all temperatures (to the melting point) in contact with carbon. Both ZrB and ZrB12 tend to decompose at elevated temperatures when carbon is present in excess of about 0.5 pct. ZrB forms ZrB2 and ZrC, and ZrB12 decomposes to form ZrB2 and a boron-carbide phase. In the ZrB12 preparation, boron present in excess of that needed to form ZrB2 reacts with carbon, if present, to form carbides, in preference to forming the higher boride. Similar instability of borides, other than diborides of the transition metals of the 4th and 5th groups of the periodic table, has been reported.5,6 special precautions had, therefore, to be taken to minimize carbon contamination in the preparation of ZrB and ZrB12. Reactions below 1400°C were carried out by heating powdered mixtures of zirconium hydride and boron in quartz tubes in a hydrogen atmosphere. For temperatures above 1400°C, reactions were carried out in graphite molds. Carbon contamination from the molds was minimized by employing extremely rapid heating rates to reduce carbon diffusion into the body of the specimen, and by subsequent "shaving" of sample surfaces that had been in contact with the graphite dies. A heating rate of about 2000°C per min was obtained by heating the dies (by direct conduction), using a current of 40,000 amp. Although this type of heating cycle apparently allowed little time for "homogenization," close approximations to equilibrium conditions were usually obtained as a result of the very strongly exothermic reactions between zirconium hydride and boron at elevated temperatures. Reproducibility of results in repeated runs under varying conditions was taken as a reasonable indication that equilibrium conditions had been effectively achieved. Quenching was accomplished by rapidly immersing the entire die, containing the reaction products, in water. Specimens could also be cooled at controlled rates by adjustment of the rate of flow of water through the water-cooled copper electrodes in contact with the graphite dies.

Jan 1, 1954

By D. K. Crampton, H. I. Burghoff, J. T. Stacy

The effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail. Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys. Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions. The large number of alloys investigated made it impossible to study every one in the detail it may have merited. Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors. It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly. In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold--working tends to disorder the structure, resulting in very marked lowering of conductivity. The random state of atomic arrangement produces lower con- ductivity than the ordered state for the same composition.1 Previous Work Previous work in the authors' laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked. Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys. The increase of resistivity due to severe working w is less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher. In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21.7 per cent increase of resistance for an alloy contaiiiing 67.9 per cent Cu as severely worked. Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens. The resistance decreased again when the cold-worked crystals were subsequently annealed. Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working. The conductivity of 72-28

Jan 1, 1941

By S. J. Aresco, George E. Keller, J. Visman

INTRODUCTION The accurate sampling of coal, as with most minerals, is a difficult task. Coal is a very heterogeneous material made up of different types of coal and varying amounts of mineral matter. The product as mined may contain all of the layers of coal and impurities found in the seam as well as portions of the strata above and below the coal seam. The preparation plant is the device to size, crush and/or remove impurities so that the coal may be shipped as a saleable product. Sampling may be needed at many stages in the preparation process. Although this chapter is mainly concerned with sampling in connection with preparation processes, the principles will apply to all coal sampling. The main reasons for sampling in connection with coal preparation are: 1. To determine the washability characteristics of the raw coal by means of float and sink tests. These may be used for the design of a preparation plant, prediction of results to be obtained or for monitoring raw coal delivered to the plant. 2. To check the performance of various operating units in the plant, either by float and sink tests or chemical analyses. 3. To determine the analytical characteristics of the products produced, such as moisture, ash, Btu, sulfur, etc. HISTORY The earliest accepted methods of sampling coal in the United States were given in U. S. Bureau of Mines publications by J. A. Holmes,1 G. S. Pope2 and A. C. Fieldner.3 The American Society for Testing and Materials more or less adopted the methods proposed by the U.S. Bureau of Mines in their Standard D-21-1916, and it remained a standard for many years. Briefly, the standard called for a 500 pound sample for coals less than. 3/4 -in. in size and a 1,000 pound sample for all coals over ?4 -in. in size. No mention was made of increments but there was an instruction that the sample should spread over the coal to be sampled. Sample preparation was by hand crushing with the alternate shovel method for reduction to 250 pounds followed by coning and quartering below 250 pounds. Obviously, with the amount of work involved, this method of sample preparation was rarely followed. This method of preparation resulted in samples that were practically air dried because of long exposure while crushing, shoveling and quartering. In the late nineteen twenties and early nineteen thirties, studies for more practical methods were begun. Dr. E. S. Grummell4, Imperial Chemical Industries, Ltd, London, summarized the work to date at the

Jan 1, 1968

By D. K. Crampton, H. I. Burghoff, J. T. Stacy

The effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail. Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys. Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions. The large number of alloys investigated made it impossible to study every one in the detail it may have merited. Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors. It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly. In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold--working tends to disorder the structure, resulting in very marked lowering of conductivity. The random state of atomic arrangement produces lower con- ductivity than the ordered state for the same composition.1 Previous Work Previous work in the authors' laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked. Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys. The increase of resistivity due to severe working w is less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher. In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21.7 per cent increase of resistance for an alloy contaiiiing 67.9 per cent Cu as severely worked. Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens. The resistance decreased again when the cold-worked crystals were subsequently annealed. Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working. The conductivity of 72-28

Jan 1, 1941

By John B. Mertie

More than 200 minerals are known that contain the rare-earths and thorium. Monazite and bastnaesite, however, are the principal commercial sources of the rare-earths, and monazite is the principal source of thorium. Monazite was in demand in earlier years mainly for its content of thorium, which was used in the manufacture of Welsbach gas mantles; but beginning in the latter part of the nineteenth century, the rare-earths became progressively more important than thorium. Recently, however, the tenor of thorium in monazite has again become a matter of commercial interest. Rare-Earths and Thorium The rare-earths proper are defined by spectroscopists as the oxides of 14 elements with atomic numbers ranging from 58 to 71; but more commonly lanthanum, with an atomic number of 57, is also included, in which case these 15 elements are often designated as the lanthanides. Chemists also include scandium and yttrium as elements of the rare-earths. A second group of elements, beginning with actinium and including thorium, protactinium, uranium, and all the transuranium elements so far produced, with atomic numbers ranging from 89 upward, are chemically and structurally related to the lanthanides, and are known as the higher rare-earths or actinides. Berzelius discovered that the lanthanides could be separated roughly into three groups, based upon the solubility of their double salts, R2(SO4)3-K2SO4-2H2O, in excess of K2SO4. This separation, with the substitution of sodium for potassium, is still used commercially. The double salts of the cerium earths were found to be almost insoluble; the terbium earths, partly soluble; and the yttrium earths, completely soluble. Based upon the degree of solubility, scandium belongs with the cerium earths; and yttrium belongs with, and gives its name to, the yttrium earths. These three groups with their atomic numbers are shown below. [ ] The prevailing state of oxidation for the rare-earths is R2O3, but cerium may readily be oxidized to the tetravalent state, in which condition it may be separated chemically from the other cerium earths. Praseodymium and terbium may also exist with the valence IV, and samarium, europium, and ytterbium may have the valence II. Most of the elements of the rare-earths, however, are very difficult to separate, and their initial isolation required the work of many chemists over a period of 150 years.20 Fractional crystallization, fractional precipitation, and ion exchange are the principal methods so far used, and fractional precipitation is now employed commercially on a large scale. Ion exchange columns are

Jan 1, 1960

The following additional notes about prices of coal in the early days were collected from the sources shown. Several data about canal tolls and labor conditions are also included. 1796, November: "The inhabitants lay it (coal) in at about 3;d. (83¢) sterling per bushel." (Ref. 73: p. 147.) 1804, March: "In March, 1804, I sent a person accustomed to mining to open the vein of coal, and to load the ark, which was accomplished, and early in the month of April the ark, with the first cargo of bituminous coal passed safely the Conewago falls, and landed her coal at Columbia, Lancaster County. The coal was sold at 31¢ per bushel at Columbia." ($7.75 per ton). This was the first coal from Clearfield County near the town of that name. (Letter from William Boyd: Pa. Senate Jour., 1833-1834, vol. 2, p. 561.) 1807: The following notice appeared in the Bedford Gazette: "Huntingdon, June 4. "Stone Coal.-Such of the farmers as wish to make experiment with stone coal as a substitute for plaster, in manuring their Indian corn, may be supplied with coal gratis upon application to Peter Hughes, at Mr. Riddle's mines, on the Raystown Branch. The proprietor of the mines offers not only to refund the carriage, but to pay the expenses of applying the coal, if upon a fair experiment it is found to be inferior to plaster, which now sells at two dollars per bushel." (Ref. 735: p. 708.) 1809: Coal was delivered in Pittsburgh at 5¢ per bushel or $1.25 per net ton. (Ref. 444: p. 50.) Coal was delivered in Connellsville at 4¢ per bushel or $1.00 per net ton. (Ibid.: p. 185.) 1810: Pittsburgh.-"Coal may be obtained of a good quality, ready delivered at 5¢ a bushel." ($1.25 per net ton.) (Ref. 315: vol. 2.) 1811: "It (coal) costs 6¢ a bushel at your door." ($1.50 per net ton.) (In Pittsburgh.) (Ref. 277: 1811, p. 68.) 1814: At Columbia, now part of Donors, Washington County, Pa., an original sale of lots in 1814 gave the purchaser of each lot the right to mine stone coal gratis from a bank on the property. (Ref. 410: vol. 1, p. 547.) "A laborer is able to dig upwards of 100 bushels per day." (4 tons.) (Ref. 277: 1814, p. 109.) A paper about the early newspapers in West Virginia says: "Collier Wanting. From 10 to 20 steady and industrious men, who understand digging coal, may obtain high wages in Kenhawa for that business, if immediate application is

Jan 1, 1942

By W. R. Opie

The object of this paper is to show the manner in which typical electrodeposits of hexagonal-close-packed metals—zinc, titanium, and zirconium—tend to form. The conditions of electrodeposi-tion markedly affect the nature of the deposits in regard to crystal size, orientation, and appearance. No attempt is made to correlate cell conditions with deposit quality but, rather, characteristic types of deposits were selected and a study made to show the relationship between outward appearance and crystal structure. The zinc deposits were made in aqueous electrolytes and the titanium and zirconium deposited from fused salt baths. ZINC deposits studied were made in the American Smelting and Refining Co.'s Central Research Laboratories. They were representative of bright, shiny, smooth deposits, which can be obtained by using proper current densities and electrolyte addition agents, and of deposits which are dull and tend to be nodular. Four deposits were selected which ranged from smooth and bright to very nodular and dull, and their classifications are shown in Table I. These were examined microscopically and were found to differ quite markedly in outward surface structure and in microstructure. The outward surface variation is illustrated in Figs. 1 to 4. At X50 the texture could be seen to progress from granular to platelike to smooth. The microstructures of the deposits' cross sections from starting sheet to outer surface are shown in Figs. 5 through 8. The dull nodular deposits (sample Nos. 1 and 2) show some tendency for acicular growth. The platelike sample (No. 3) shows tendency for columnar growth development and the smooth deposit (No. 4) has a well developed columnar structure. Back-reflection X-ray patterns of the deposit surfaces revealed some interesting information. The crystal orientation was random in all deposits except the smooth deposit. Fig. 9 is a typical back-reflection pattern of a nodular deposit. All planes are reflecting in the proper relative intensity. The pattern of the smooth deposit is shown in Fig. 10. The only planes which reflect are the (10.4). This series of planes is in the right position, with the FeKa radiation used, to satisfy the Bragg equation if the basal planes {00.1) are at right angles to the X-ray beam. The results were interpreted to mean that in the bright smooth deposit preferred orientation has occurred with the basal hexagonal planes oriented in the plane of the sheet but with all other planes randomly oriented around the c-axis.

Jan 1, 1957

By Lucien Eaton

IN anticipation of a shortage of labor for hand-tram-ming at the Cliffs shaft mine of the Cleveland-Cliffs Iron Co. at Ishpeming, Mich., early in 1923 three 4-ton Goodman storage-battery locomotives, equipped with Edison batteries, were purchased. Storage-battery locomotives were chosen for this work because the expense and time required to put up trolley-wire and to bond the rails of the complicated system of tracks on the levels, where the locomotives were to be used, would not have been warranted by the amount of ,ore to be handled. The only changes in the tracks necessary for storage-battery locomotives were new switches and extra ties and braces on curves. The tracks were 24-in. gage, and were laid with 20-lb. rail. Edison batteries were chosen, because it was desired to charge the batteries from the trolley circuit already, in the mine, and this would have been impracticable with lead batteries. Each locomotive is equipped with 126 A-4 Edison cells, which are charged in series from the 240-volt trolley circuit while the trolley locomotives are running; and are discharged in parallel in two banks of 63 cells each. These locomotives were so successful that later 5 smaller locomotives, weighing 11/2 tons each, were pur-chased for use e with cars that are filled by hand and on levels where the amount of ore handled is small. These locomotives, built by the Geo. D. Whitcomb Co. of Rochelle, Ill., are equipped with batteries of 40 A-4 Edison cells each, the cells being the same as those, on the larger locomotives. They are charged from mer-curial-are rectifiers. These locomotives are operated by the trammers themselves, and have not special oper-ators like the larger machines. The trammers are all young men of American birth, and take quickly to the operation of machinery, and the simplicity of the con-trol on these locomotives has made special training unnecessary. A survey of the results was made by the A. C. Nielsen So., an excerpt from which follows: Eight Edison-equipped battery locomotives are now in use at an Ishpeming mine of the Cleveland-. Cliffs Iron Co. This equipment was installed to take the place of men who formerly pushed loaded cars by hand. Results have been very satisfactory and the de-pendable, trouble-free operation of the Edison batteries is considered to have been an important factor in the effectiveness of the new hauling method.

Jan 3, 1927

By T. R. Graham, R. S. Dean. J. R. Long

Although considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to II pet aluminum, with some incidental information on the single-phase alpha solid solution alloys. Straussl gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper6 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50" temperature levels from 400' to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solub%ty of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 13oo'F and higher,

Jan 1, 1947

By G. Gutzeit

An inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity.4,7-l3 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime') It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals." Chelate-forming Compounds as Collectors In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxyl-amine (Cupferron) C6H5NO(=NONH4). Holmanl9 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-diox-imes were generally selective collectors for nickel ores. Taurin NH2(CH2)2S03H has been proposed for the concentration Of Oxidized lead ores.19 Diphenylthio-carbazone

Jan 1, 1947

By R. S. Dean. J. R. Long, T. R. Graham

Although considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to II pet aluminum, with some incidental information on the single-phase alpha solid solution alloys. Straussl gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper6 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50" temperature levels from 400' to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solub%ty of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 13oo'F and higher,

Jan 1, 1947

By G. Gutzeit

An inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity.4,7-l3 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime') It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals." Chelate-forming Compounds as Collectors In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxyl-amine (Cupferron) C6H5NO(=NONH4). Holmanl9 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-diox-imes were generally selective collectors for nickel ores. Taurin NH2(CH2)2S03H has been proposed for the concentration Of Oxidized lead ores.19 Diphenylthio-carbazone

Jan 1, 1947