Search Documents

By John W. Cabot

In the manufacture by the Bessemer process of soft steel suitable for rolling into fine sheets, tubes and 60 forth, a difficulty is sometimes met with, in the tendency of this kind of metal to rise violently and boil in the moulds while being cast; this results in hollow-topped ingots, and consequently in an undue amount of scrap in the subsequent rolling. It has been noticed that this peculiarity does not pertain to all pig-irons, some grades producing a blown metal which pours quietly, while others, in whatever way the blow may have been conducted, give a metal which rises in the moulds, accompanied by the evolution of large quantities of hydrogen and carbonic oxide gases, and requiring a long time to solidify. This difference in behavior has been some-

Jan 1, 1891

By T. M. Chatard, Cabell Whitehead

The Republic mine, situated forty miles from Marcus, a station on the Spokane Falls and Northern Railroad, in the northeastern part of the State of Washington, was located in 1896, but no development-work was dolie until the spring of 1897. While much of the ore mined since then has been rich enough for shipment to smelters, a method of locally treating the lower-grade ores soon became a matter of prime importance, because only about 40 per cent. of the values could be recovered by plain amalgamation, even with ores assaying 4 to 5 ounces of gold per ton. Experiments with cyanidation, in various ways, led to the adoption of the Pelatan-Clerici process and the erection on this system of a 10-ton experimental plant, which was later increased to a capacity of 35 tons per day. The extractions by this process showed much improvement over previous work, especially when the ore was crushed to

Jan 1, 1901

By J. W. Cunningham, W. A. Tiller, D. H. Lane

The effect of ultrasonic vibrations on ingot solidification has been considered both theoretically and experimentally. The theoretical section elucidates the mechanisms by which the ultrasonic vibrations might refine the ingot structure. The experimental section describes a very efficient means of introducing the ultrasonic vibrations to the freezing interface. The application of this technique to the consumable-electrode arc melting process shows that the columnar mode of freezing may be effectively suppressed yielding an ingot structure consisting predominantly of equiaxed grains. The results support the contention that the ultrasonic vibrations increase the nucleation frequency in the layer of liquid adjacent to the freezing interface. CERTAIN structural characteristics of as-cast ingots are undesirable since they create considerable difficulty for subsequent processing and often produce defects in the finished product. These structural defects are illustrated in Fig. 1(a), and are: 1) planes of weakness where columnar grains growing from the different mold faces meet, 2) strength anisotropy due to the preferred orientation of the columnar grains and 3) inhomogeneity due to segregation at dendrite boundaries within the columnar grains and at the columnar grain boundaries. The type of ingot structure that eliminates 1) and 2) and diminishes 3) is the fine-grained equiaxed structure illustrated in Fig. 1(c). Many attempts have been made to produce the desirable ingot structure illustrated in Fig. 1(c) by inoculating, casting with varying superheats, vibrating or stirring, or by irradiation with ultrasonic vibrations. These attempts have met with various degrees of success, the ingots generally having the structure illustrated in Fig. 1(b). All four methods have been the subject of numerous investigations,1"4 the latter producing the most erratic behavior and inconsistent success. The method of ultrasonic irradiation during ingot solidification has shown considerable promise on small-scale ingots (diam 2 in.) but has not yet been successfully adapted to large-scale operation. The present paper considers the application of ultrasonic radiation to ingot solidification both theoretically and experimentally. The purpose of the paper is to elucidate the mechanism by which ultrasonic energy refines the ingot structure and to describe a method for producing the desirable ingot structure in both laboratory scale experiments and in ingots of commercial size. THEORY Conventional Casting—Before discussing the possible effects of ultrasonic radiation upon ingot structure let us first briefly review the reasons for the breakdown of columnar crystallization to equiaxed crystallization during ingot solidification. The following is a slightly oversimplified description. In the conventional method of casting, the alloy having a certain degree of superheat, T, is poured to fill a cold mold which is at room temperature, Tc,. Due to conduction of heat through the mold wall the outer rim of liquid metal cools rapidly to the liquidus temperature and begins to supercool. At some degree of supercooling, nuclei of solid form at random in this supercooled layer at the mold surface. The grains in this chill layer begin to grow inwards producing a solute build-up, thus lowering the freezing temperature at the interface as illustrated in Fig. 2. As growth proceeds, the temperature gradient in the solid conducts away not only the latent heat of fusion evolved during growth but it also conducts away some of the superheat of the melt so that the temperature

Jan 1, 1961

By Richard H. Jahns

Gem materials, comprising those minerals and closely allied natural substances used for personal adornment, for the fashioning of ornamental objects, or for other decorative purposes, have been valued in human commerce for thousands of years. Amber, jet, natural glasses, and at least 15 mineral species were sought and used by primitive man, and most of the materials in common use today were known well before the time of Christ. Their variety is remarkably great, and the traceable relationships among their respective sources, modes of occurrence, properties, and histories of production, preparation, and valuation are extremely complex. Their uses have been affected by numerous shifts in fashion, and from time to time by superstition, by decrees of church and state, by personal interpretations of religious significance, and by various presumptions concerning medicinal value and influence on human behavior (Ball, 1935, 1950; Kunz, 1913; Pogue, 1915; Whitlock, 1946). Thanks to their durability, portability, and relative scarcity, some gem stones have been employed as media of exchange, and the investment value of the more precious stones has long been recognized and exploited, especially in Asiatic and European countries. Demands for gem materials have stimulated trade among various peoples for centuries, and they also were responsible for much early geographic exploration. During more recent times they have prompted numerous geological studies and a considerable amount of research on the growth and properties of crystals. Apart from decorative uses, some naturally occurring gem materials also are employed directly in numerous fields of industry. Substances that are manufactured for gem or industrial uses are termed synthetic gem materials; most of these correspond in composition and crystal structure to certain minerals found in nature. Imitation materials are those whose use is based upon their resemblance to substances of different composition and greater intrinsic value. Gem stone is a designation commonly restricted to those materials suitable for personal adornment, and the complementary term ornamental stone is applied to the remaining materials not used industrially. This distinction is arbitrary and somewhat inconsistent, owing to numerous geographic differences and historical shifts in end uses. Further, there is a complete gradation between the category of ornamental stones and that of dimension stone. Substances that lose their identity in use are excluded from the gem category; thus a transparent crystal of beryl would not be classified as a gem stone if it were processed as a source of beryllium metal. The adjectives precious and semiprecious have been employed as a means for distinguishing different gem materials on the basis of recognized value. Diamond, emerald, ruby, and sapphire consistently have been regarded as precious stones, and in cut form they commonly are referred to as the noble gems. Opal, pearl, turquoise, and chrysoberyl also have been classed as precious at various times. In recent years, however, it has been increasingly recognized that no satisfactory distinction can be based upon assessed value or any group of specific properties, and now all gem stones normally are referred to as precious. Indeed, the tendency is to extend this term to include many of the so-called ornamental stones, and the designation semiprecious has been essentially discontinued. Unlike most mineral commodities of economic value, gem materials are little altered in processing for end uses. Some stones are used in essentially their natural form, and most are reshaped and polished without significant changes in their fundamental properties. Thus the preparation of gem and ornamental stones is intended chiefly to emphasize or enhance

Jan 1, 1983

By Richard H. Jahns

Gem materials, comprising those minerals and closely allied natural substances used for personal adornment, for the fashioning of ornamental objects, or for other decorative purposes, have been valued in human commerce for thousands of years. Amber, jet, natural glasses, and at least 15 mineral species were sought and used by primitive man, and most of the materials in common use today were known well before the time of Christ. Their variety is remarkably great, and the traceable relationships among their respective sources, modes of occurrence, properties, and histories of production, preparation, and valuation are extremely complex. Their uses have been affected by numerous shifts in fashion, and from time to time by superstition, by decrees of church and state, by personal interpretations of religious significance, and by various presumptions concerning medicinal value and influence on human behavior (Ball, 1935, 1950; Kunz, 1913; Pogue, 1915, Whitlock, 1946). Thanks to their durability, portability, and relative scarcity, some gem stones have been employed as media of exchange, and the investment value of the more precious stones has long been recognized and exploited, especially in Asiatic and European countries. Demands for gem materials have stimulated trade among various peoples for centuries, and they also were responsible for much early geographic exploration. During more recent times they have prompted numerous geological studies and a considerable amount of research on the growth and properties of crystals. Apart from decorative uses, some naturally occurring gem materials also are employed directly in numerous fields of industry. Substances that are manufactured for gem or industrial uses are termed synthetic gem materials; most of these correspond in composition and crystal structure to certain minerals found in nature. Imitation materials are those whose use is based upon their resemblance to substances of different composition and greater intrinsic value. Gem stone is a designation commonly restricted to those materials suitable for personal adornment, and the complementary term ornamental stone is applied to the remaining materials not used industrially. This distinction is arbitrary and somewhat inconsistent, owing to numerous geographic differences and historical shifts in end uses. Further, there is a complete gradation between the category of ornamental stones and that of dimension stone. Substances that lose their identity in use are excluded from the gem category; thus a transparent crystal of beryl would not be classified as a gem stone if it were processed as a source of beryllium metal. The adjectives precious and semiprecious have been employed as a means for distinguishing different gem materials on the basis of recognized value. Diamond, emerald, ruby, and sapphire consistently have been regarded as precious stones, and in cut form they commonly are referred to as the noble gems. Opal, pearl, turquoise, and chrysoberyl also have been classed as precious at various times. In recent years, however, it has been increasingly recognized that no satisfactory distinction can be based upon assessed value or any group of specific properties, and now all gem stones normally are referred to as precious. Indeed, the tendency is to extend this term to include many of the so-called ornamental stones, and the designation semi- precious has been essentially discontinued. Unlike most mineral commodities of economic value, gem materials are little altered in processing for end uses. Some stones are used in essentially their natural form, and most are reshaped and polished without significant changes in their fundamental properties. Thus the preparation of gem and ornamental stones is intended chiefly to emphasize or enhance

Jan 1, 1975

By M. J. Spendlove, H. W. St. Clair

The problem frequently arises, particularly in refining metals or smelting scrap metals, of separating metals in the metallie state. Many metals may be separated by taking advantage of their difference in vapor pressure. Such separations can be made at atmospheric pressure, but the separations are much more selective and can be carried out at considerably lower temperatures if the distillation is done at pressures of a few millimeters or less in an evacuated enclosure. Until recently, this has not been considered feasible as a metallurgical operation, but the recent improvemcnts that have been made in vacuum technology have broadened the applicability of vacuum processes and have prompted re-examination of low-pressurc distillation of metals as a practicable process. The distillation of zinc from lead is one separation that has already been reduced to practice.l This paper is the first of a series of studies being made on separation of nonferrous metals by distillation at low pressures. Although these experiments were confined to the separation of zinc from aluminum, the significance of the results is by no means confined to these two metals. The purpose has been to investigate a metallurgical technique rather than merely to devise a means of separating specific metals. The experimental work on distillation of zinc from zine-aluminum alloys at reduced pressure grew out of earlier work on distillation at atmospheric pressure.2 The earlier work indicated that it would not be practicable to decrease the zinc in the alloy much below 10 pct owing to the high temperature required. Therefore attention was turned to distillation ah low pressures, at which lower temperatures are required. After preliminary tests were made in a small, evacuated tube furnace, a larger furnace having a capacity of 100 to 150 Ib of metal per charge was constructed. Distillation tests were first made on pure zinc and then on aluminum-zinc alloys of various composition. Particular attention was given to the limit to which zinc could be reduced in the residual metal. Data were also taken on the rate of evaporation, and heat balances were made for both the crucible and the condenser. Distillation Furnace The vacuum-distillation unit is illustrated schematically in Fig 1. The major components are the induction furnace, the condenser, the vacuum system, and the power-conversion unit. Power is supplied to the induction furnace from a 50-kw 3000-cycle motor-driven alternator. The pressure in the furnace is reduced by a vacuum pump having a nominal pumping speed of 10 liters per sec. When in operation, the metal vapors travel upward from the furnace to the water-cooled condenser where they are collected in amounts of 50 to 100 lb. The condenser is removed with aid of an electric hoist. When the system is under vacuum, the condenser is made self-sealing by a rubber gasket between the smooth-faced, water-cooled flanges at the top of the furnace and the bottom of the condenser. The pressure of the atmosphere is more than sufficient to insure sealing. At the conclusion of an experiment, the residual metal can be removed from the furnace by removing the condenser and tilting the furnace with the electric hoist. The metal was cast into the molds carried on a mold truck. A photograph of the furnace and auxiliary equipment is shown in Fig 2. The details of the vacuum furnace are illustrated in Fig 3. The furnace proper is made vacuum-tight with rubber gaskets placed at each end of a fused quartz cylinder. A clamping plate at the bottom and a ring at the top are made to squeeze the rubber between the metal and the end of the quartz tube. A large graphite crucible placed inside the quartz cylinder is thermally insulated and physically supported by refractory insulating bricks. A thermocouple in a quartz protection tube is located at the bottom of the crucible: the leads pass through a rubber seal in the bottom plate. The supporting structure for the furnace is an angle iron frame with transite board sides. The condenser is made in the form of a water jacketed cylinder with an opening to the vacuum line at the top. The bottom has a projecting skirt inside the machined flange to provide additional cooling for the rubber gasket. Condenser sleeves are made in the form of two semicylindrical pieces of sheet metal that fit snugly inside the cooling jacket. The split sleeve facilitates removal of the condensate. Measurement of Temperatare and Pressure The metal temperature was measured by a platinum-platinilm rhodium thermocouple inserted in a well extending up into the bottom of the graphite crucible. During rapid evaporation there is a wide difference in temperature between the surface and the main body of metal in the crucible because of the large amount of heat that must be conducted to the surface to supply the heat of evaporation. The heat of

Jan 1, 1950

By R. C. Himes, K. Zanio, J. B. Wagner, J. W. Moody, J. F. Miller, W. Johnson

The recent research with which this paper deals has been concerned with the preparation of pure PbTe crystals suitable for control of radiative processes and othe.v electronic applications. The research has been directed toward the developrnent of methods for the preparation of puve, homogeneous, loul-ca,wier-density PbTe crystals suitable for use in the fabrication of optically pumped and electrically pumped diode lasers. Steps in the preparation of the crystals include 1) purification of the starting materials, 2) synthesis and purification of the PbTe, 3) growoth of PbTe crystals, and 4) adjustt~zertt of composition of the crystals This Paper describes the general preparation procedure employed and discusses some investigntiotzs of purification processes. THE as-received lead and tellurium are nominally 99.999 to 99.9999 pct pure. Assays furnished by the suppliers, obtained by emission spectrographic analysis, show only the presence of about 2 ppm Mg in the tellurium. Such analyses are not very informative, however, since they give no information on the concentrations of normally gaseous impurity elements such as oxygen. Both the lead and the tellurium in the as-received state usually contain appreciable concentrations of oxygen—primarily in the form of oxides on the surfaces of the material. To reduce the oxygen content, the lead is held in the molten state in hydrogen at -700°C for several hours. For this treatment, the lead is contained in a graphite boat which is rf-heated, and the hydrogen is passed through a liquid-nitrogen trap prior to use. Tellurium is subjected to multiple distillation in hydrogen to remove oxygen and other foreign impurities. If, in conducting the distillation, approximately the last 10 pct of the charge at each "stage" is left as the discard cut, purification of the tellurium proceeds as indicated in Fig. 1.l Tellurium used in this work has been distilled two or three times to reduce carrier concentration to about 10" per cu cm. The PbTe is prepared from the purified elements by reacting them in the molten state in sealed, evacuated, or hydrogen-filled silica ampoules. The charge is usually held above the melting point of PbTe (923°C) at 1000 C for 24 hr to ensure that it has been homogenized. Two methods have been employed for the growth of the required single crystals of PbTe: growth from the melt, which will be discussed first, and growth from the vapor phase. Large single crystals of p-type PbTe can be grown readily from the melt by the Bridgman method. For this method of crystal growth, the PbTe is synthesized in situ from proper proportions of the purified elements. Growth (dropping) rates in the range 1.3 to 6.5 mm per hr are employed. Material near the maximum melting composition (about 50.012 at. pct Te) is utilized to avoid composition change on freezing, and thus to obtain crystals of nearly uniform composition. Crystals prepared by use of procedures described up to this point were sufficiently pure and perfect that they could be used for the preparation of laser crystals in studies at Lincoln Laboratory.2-5 ADJUSTMENT OF COMPOSITION Good n-type crystals of PbTe cannot readily be grown from the melt. Further, growth from the melt of crystals of any compositions (n or p type) other than those near the maximum melting composition is difficult because of the large composition changes that must occur on freezing.'" However, melt-grown crystals can rapidly be brought to other desired compositions by isothermal equilibration through the vapor phase with a two-phase Pb-Te stock material, essentially as described by Brebrick and Allgaier.1 The work to be discussed has been concerned with the preparation of n-type crystals; thus, the two-phase stock which was employed contained excess lead, and all ensuing discussion is of the preparation and properties of n-type crystals. The equilibration was designed to the shift composition to the lead-rich limit of stability at the selected temperature. Initial treatment of the crystals at high temperature was employed to minimize the total time required for the equilibration. Final adjustments of the composition and state of the crystals were made by use of low-temperature heat treatment at temperatures in the range 200" to

Jan 1, 1968

By V. Jares

DESPITE the fact that a combination of metals-aluminum-zinc-tin, and sometimes aluminum-zinc-cadmium-is extensively used for aluminum solders, as well as for die-castings, the constitution of these alloys has not yet been made clear. I. BINARY SYSTEMS The system aluminum-zinc is the basis of the ternary alloys under consideration. Their composition was made sufficiently clear by the investigations of Rosenhain and Archbutt,1 Bauer and Vogel,2 Sander and Meissner,3 Hanson and Gayler4 and Isihara.5 Only the temperature of decomposition of the crystals 0 seems still to be doubtful, whether it is considered as a compound of Al2Zn3 (according to Bauer and Vogel) or as an intermediate phase of variant composition (according to Hanson and Gayler). This temperature is given by most of the authors as in the neighborhood of 256° C., only Isihara giving 280° C. As its accurate determination is of special importance in the study of the ternary alloys under consideration it was experimentally controlled in the following manner: An alloy corresponding in composition to the formula Al2Zn3 was made, in which the temperature effect was found to be the greatest. This was drilled and a silver-constantan thermoelement inserted into the cavity so as to be in direct contact with the alloy. The whole was then very slowly heated and the heating and cooling curves determined. The transition temperature from the heating curve was found to be 281° C., whereas from the cooling curve it was 252° C.

Jan 1, 1927

By J. Szekely, P. Tarassoff, N. J. Themelis

In a copper converter air enters the bath in the form of turbulent jets. The interaction of these jets with the molten matte is fundamental to the converting process. In the present study, an equation is derived to describe the trajectory of a gas jet in a liquid. Calculated and experimental results for air jets injected into water are in good agreement. The trajectories of air jets in copper matte are predicted. THE air injected through the tuyeres of a Peirce-Smith copper converter emerges into the bath of molten matte in the form of a highly turbulent jet. The air jets affect a number of chemical and physical processes occurring in the converter: i) Converting Rate. It is generally recognized that the production capacity of a converter is limited by the flow of air which can be injected through the tuyeres and by the oxygen efficiency. In turn, the air flow is limited by pressure drop considerations or by the amount of splashing within the converter. ii) Oxygen Efficiency. This depends on the dispersion of the air jet in the liquid bath, and its trajectory through the bath. iii) Mixing. The jets act as mixing devices by transferring momentum energy to the bath; in this way the heat generated by the converting reactions occurring in the jets is distributed through the bath. iv) Refractory Wear. The proximity of the jets, which are centers of heat generation, to the refractories in the tuyere zone may have an important effect on refractory life. Mixing conditions in the bath will also influence refractory erosion. v) Splashing, and Accretion Build-Up. The energy of the jets is not dissipated entirely in mixing the bath. particles of liquid are carried out kith the gas above the surface of the bath in the form of liquid spouts and droplets. These result in the undesirable build-up of accretions on the converter mouth, and dust losses in the flue gas. Despite the importance of the interaction of the air jets and the matte in a converter, very few studies of the fluid dynamics of converting have been reported in the literature. Metallurgists in the USSR appear to have been more concerned with the subject than their Western counterparts. Deev et al.1 studied the interaction of an air jet with aqueous solutions in a converter model and qualitatively determined the tuyere air velocity and tuyere inclination which produced the most favorable results with respect to good mixing in the bath, and minimum splashing. Shalygin and Meyer-ovich2 also examined the air-matte physical interaction both in models and in industrial converters; they concluded that in conventional converting practice, there was no significant penetration of the air jets into the matte layer, and consequently the converting reactions occurred mainly in a zone adjacent to the tuyeres. The behavior of air jets in a converter bath, and the aerodynamic characteristics of tuyeres are discussed at length in a monograph on converting by Shalygin.3 However, the description of the phenomena occurring in the converter bath is largely qualitative. The side-blown Bessemer converter for steelmak-ing is very similar to the Peirce-Smith copper converter. Among the few investigations of the behavior of air jets in the bath of a Bessemer converter are those of Kootz and Gille4 who studied splashing in the course of an investigation on the effect of blowing conditions and converter shape on nitrogen pick-up in Bessemer steel. They found that during blowing standing waves were formed on the surface of the bath; the amplitude of the waves increased with the depth and angle of tuyere immersion until the whole bath moved backwards and forwards causing heavy splashing. Kazanstev5 used a model of a Bessemer converter to obtain correlations between the axial velocity of a gas jet and distance from the tuyere orifice and the Froude number of the jet. shalygin3 used these results to calculate the horizontal penetration of an air jet in a copper converter; the penetration was defined as the distance in which the axial jet velocity decreased to 10 pct of its initial value. However, the rising trajectory of the jet was not taken into account. In the absence of quantitative information on the fluid dynamics of converting, the design of copper converters has been based mainly on operating experience. Such experience tends to vary widely from smelter to smelter., This is reflected in Table I which is based on data compiled by Lathe and Hodnett.6 Aside from a rough, and perhaps obvious correlation between the total air flow and converter volume, Fig. 1, no pattern emerges from the data. For example, tuyere throat air velocities vary from 215 to 465 ft per sec in converters of the same size, for little apparent reason. The air jet energy input per cubic foot of converter volume, which may be taken as a measure of the amount of mixing in the converter bath, also varies greatly. A recent analysis of converter data by Milliken and Hofinger7 has also revealed unexplained variations in operating parameters. It is believed that by gaining a better understanding of the fluid dynamics of converting a more rational basis may be provided for the design of converters. In particular, it is proposed that if one takes into account the desirable criteria of a high converting rate, high oxygen efficiency and long refractory life, there should be an optimum configuration of tuyere air flow for a converter of a given diameter. The present investigation is concerned with the form and trajectory of an air jet in a converter bath. The general theory of turbulent jets has been expounded by Schlichting8 and Abramovich.9 However, most experi-

Jan 1, 1970

By R. W. Raymond

Since the foregoing paper (see p. 387) was printed, I have received the decision of Judge William E. Church, of the first District Court of Dakotah, in the case of Michael Duggan et al. v. John H. and Frank J. Dnvey (Silva Terra—Sitting Bull case), published in full in the Black Hills Weekly Pioneer of August 9th, 1584. The journal mentioned gives also several interlocutory decisions rendered in earlier stages of the case; but I shall quote here only so much of the final decision as bears upon the .construction of the Revised Statutes concerning the apex, the end-lines, and the extra-lateral mining right, together with a sufficient statement of the facts of the case to explain the scope of the decision. " This is an action in equity, brought in the first instance to restrain a threatened trespass by the defendants upon certain mining property in the possession of the plaintiffs, known as the ' Silver Terra' claim ; the allegation being that the defendants were about to enter, through underground workings, the ground of the plaintiffs, and remove therefrom valuable bodies of silver ore. " The answer of the defendants, admitting the acts constituting the alleged threatened trespass, further averred that they had, in fact, at the time complained of, reached and passed, in their underground workings, throngh and beyond the vertical side-line of the Silver Terra claim, and therenpon justified the acts complained of, and claimed the right to pursue their workings into and through the Silver Terra ground, by virtue of their alleged proprietorship of a vein, lode, or ledge of rock in place, hearing silver, having its top or apex within the lines of a certain other mining claim called the ' Sitting Bull,' of which they claim to be the owners, which vein, lode, or ledge extended in a continnons body of mineral-bearing rock from such top or apex to the ground in controversy, and constituted the body of ore in dispute; and that it was in the pursuit of this vein, lode, or ledge in its downward course that they had passed beyond the vertical side-lines of the Sitting Bull claim, and for some hundreds of feet beyond, into the ,ground in controversy " Subsequently, a supplemental complaint was filed, setting up the entry into plaintiffs' ground by the defendants, and their claim of right to do so, and asking fnrther relief by a decree restraining the assertion of such claim, and quieting the title of plaintiffs. "The case was tried before the court without a jnry..... " Custer hill, upon which these claims are located, is situated in the village of Galena, in Bare Butte mining district, in this county. The village lies at the base of the western slope of the hill, which presents a lateral face from south to north

Jan 1, 1884

By John B. Myers

Vermiculite is the commercial name used to describe a micaceous mineral that expands appreciably when heated. This process, called exfoliation, results in a light weight material. The light weight material is also called vermiculite, or more exactly, expanded vermiculite. Practically all uses of vermiculite are for the expanded material. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit and a perfect basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. The hardness varies from 1.5 to 2 or more, depending on the composition. The specific gravity varies from 2.2 to 2.7; specific heat 0.2; fusion temperature 2,000° to 2,500°F; luster pearly to greasy; color amber, bronze, brown, dark green, and black. Feel is like talc and sometimes soapy when wet. When heated quickly at elevated temperatures, vermiculite exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin vermiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted to steam. The increase in bulk volume of commercially prepared material is 8 to 12 times, but individual flakes may expand as much as 30 times. There is no expansion parallel to the cleavage. Vermiculite may also be expanded by several chemical processes such as soaking in hydrogen peroxide, weak acids and other electrolytes. The color changes during expansion. Heat-treated material changes to a light golden bronze or cream color depending on composition. The conditions of heating affect color. Heating in an oxidizing atmosphere produces reddish colors and heating in a reducing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. Vermiculite is hydrated magnesium-aluminum silicate. Although there has been much research on the chemical and structural composition, there is not yet complete agreement on the exact formula and composition. This is to be expected since vermiculite is not a mineral of fixed composition and different workers have examined different varieties. It has been proposed that vermiculite is not a single species but a family of related minerals. This has also resulted in many names for the particular vermiculite found in a certain deposit. All of this difficulty arises from the very nature of its crystal chemistry. Unlike most minerals, certain crystal structure properties and the chemical composition can be changed by the ordinary forces of nature or in the laboratory. This would suggest that vermiculite be thought of more as a variable mineral rather than a group of related species. It was stated on page 261 of this volume in the chapter on Clay Minerals by H. H. Murray of the Georgia Clay Co., that vermiculite is an equidimensional, expandable clay mineral. Gruner (ref. 14, Chap. 12) showed that the structure consists of a layer made up of two silica tetrahedral sheets with a central magnesium, iron octahedral sheet separated by two layers of water molecules and adsorbed magnesium and calcium ions. Mathieson and Walker,2a in a recent publication, agree that vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation ex-

Jan 1, 1960

By O. W. Ellis

IN VIEW of the extensive use of the brasses and bronzes in engineering practice it is indeed surprising that so little scientific work has been done on the oxides in these alloys. Recognition of the ill effects of these compounds is universally accorded, both in foundry procedure and in such specifications as cover the melting of these useful mixtures. In the latter, limits, for example, are placed on the proportions of scrap metal in the charge, and clauses governing the use of fluxes are included, the addition of fluxes to the charge being made with the object of avoiding oxidation during the process of melting and of subducing and separating non-metallic matter from the melt.1 In the manufacture of brass it occasionally, though rarely, occurs that the virgin metals, copper and zinc, alone are used. In the event of virgin metals being employed, that of the higher melting point is always melted first. If it is melted under suitable conditions, little or no oxidation will occur. Whether oxidation has occurred or not, however, can best be determined by microscopic examination of a sample taken from the melt.

Jan 1, 1930

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

By J. G. LECKIE

During the first ten months of 1943 copper was produced at a higher rate than in 1947. However, on Oct. 24 one of the large mines was shut down due to a strike. As of Dec. 31 the strike was still in effect and had already resulted in a loss of production of 50,000 tons of copper. The demand for copper was considerably greater throughout the year than the supply. The price of electrolytic copper delivered at the Atlantic Seaboard refineries advanced from 21.20 to 23.20 cents per lb during the year. This sustained demand for copper, together with the increase in price, has had the natural effect of spurring interest in uncovering new deposits, and in re-examination of known low-grade deposits and old tailing clumps. This is in addition to the usual reevaluation activities which normally result from the constant improvements in efficiency of ore concentration.

Jan 1, 1949

By J. A. Solomon, H. E. Shafer

As a result of the great demand for metallic aluminum and the scarcity of domestic bauxite, numerous processes have been proposed and developed to extract the oxide of this metal (Al2o3) from clays, shales, and other low-grade raw materials.1-4 An exploratory study was made to extract alumina with sulfuric acid from relatively impure coal-associated draw-slate and to establish an optimum calcination temperature for maximum recovery. Draw-slate is the term used to describe the hard, slaty material directly overlying many coal seams and may range from a few inches to a few feet in thickness. Alumina content of these draw-slates may range from as low as 15% to over 35%. Although the following results are limited in scope, some of the data should prove beneficial for further work. Coal-associated clay, shale, and gob heretofore have been considered nuisance products; any successful alumina extraction process would greatly enhance the worth of these almost limitless resources. This research demonstrated that an optimum calcination temperature for alumina extraction could be established for a coal-associated draw-slate and that this temperature was lower than those suggested in previous work with unspecified clay types. It should be noted that slightly higher acid concentrations and somewhat finer particle sizes were used in this series of tests as compared to previous work. EXPERIMENTAL WORK Essentially, alumina extraction proceeded in four steps: 1) grinding, 2) calcining, 3) acid leaching, and 4) precipitating of aluminum sulfate. An initial series of reference tests to determine the optimum temperature of solubility for alumina was run using relatively pure kaolin. Kaolin forming clays are hydrous aluminum silicates of the approximate composition 2H2O A12O3 2SiO and kaolinite is the mineral that predominates in most kaolins. 5 The kaolin was ground to -30 mesh and subsequently calcined at temperatures ranging from 100°C to 700°C. Each sample was calcined for 1 hr in a muffle furnace and in turn subjected to sulfuric-acid leaching (H2SO4, 9 molar) for a 2-hr period. The filtrates were analyzed for the amount of dissolved alumina recovered.637 Also, each sample of leached or barren residue was

Jan 1, 1968

By A. Kenneth Schellinger, O. Cutler Shepard

INTRODUCTION OVERGRINDING, or the breaking of ore particles into sizes smaller than required for liberation, is a first-magnitude problem in grinding for concentration processes. The conventional ball mill-classifier circuit used in commercial grinding produces mineral particles that are all ground to pass an upper size limit, while the proportion of very fine sizes, or slimes, is uncontrolled. Calculations based on measurements made in commercial plants which were grinding ore for flotation concentration indicate that about 90 pct of the energy used in grinding is consumed in useless overgrinding.1 In addition to accounting for the consumption of a large amount of energy, overgrinding is detrimental to the flotation process. Overground slime coats larger particles and inhibits selective action by the flotation reagents on particles which by themselves could be separated very well. A further difficulty is that extremely finely ground minerals do not respond satisfactorily to flotation-collecting reagents, and both selection and recovery decrease markedly with particles finer than 5 to 10 microns.2 Conventional classifier-ball mill circuits inherently tend to overgrind the valuable minerals more than the gangue minerals because most valuable minerals are of higher density and are softer and more friable than the gangue minerals. The remedy to this situation would seem to be a separating mechanism which would separate free valuable mineral particles regardless of size and density considerations and a mechanism which would operate in the grinding mill so that valuable mineral grains would be removed from the grinding machine as soon as they are freed. A consideration of these ideas led the authors to the conception of a simultaneous grinding and flotation mechanism. So far as the authors are aware, such a machine has never been tried, even on a laboratory scale. DEVELOPMENT OF APPARATUS AND EXPERIMENTAL METHOD Apparatus development went through several stages before a really workable machine was devised. Work was started with a large cast-iron mortar 7 ½ in. in diameter and 8 in. deep. A cast-iron disk was mounted on the end of a vertical shaft so that it fitted loosely into the bottom of the mortar. On top of the disk four radial cleats ¼ in. high were bolted to agitate the ball charge as the disk, or impeller, rotated. The vertical shaft was driven at 100 rpm by a mechanism improvised from an old coffeemill type of grinder. A hole was drilled into the bottom of the mortar through which compressed air was introduced for frothing. In operation, weighed charges of ore which had been crushed to pass an 8-mesh screen were placed in the bowl along with water and suitable reagents. The impeller was then started and the compressed air turned on so that the ore was ground while being exposed to air bubbles. Mineralized froth was

Jan 1, 1947

By E. A. Elevatorski

Wollastonite, named after William H. Wollaston, an English chemist, is a calcium metasilicate, CaSiO3. It has a short history as an industrial mineral. The earliest production of wollastonite is reported to be from a deposit near Code Siding, located north of Randsburg, Calif. At this locality small tonnages of wollastonite were quarried during 1933-34 and 1938-41, and processed into mineral wool. This operation was largely experimental and virtually no United States production was again reported until the 1950s when a large deposit near Willsboro, N.Y., was developed by the Cabot Corp. A processing plant was placed on-stream in 1953, with nearly continuous production to date, and it is currently operated by Interpace Corp. Since 1958, wollastonite deposits in the Little and Big Maria Mountains of Riverside County, and in the Panamint Range of Inyo County, both in California, have operated intermittently for production of both ornamental and commercial wollastonite. During 1973, the United States was the major producing country, furnishing about 75% of the world's output. Recent production also has come from Finland, Mexico, and Kenya. Small amounts have been shipped intermittently from India, USSR, New Zealand, Republic of the Sudan, Republic of South Africa, and South-West Africa. The principal use of wollastonite is in the manufacture of ceramics, especially wall and floor tiles. Other uses are for paints, fillers, adhesives, reinforcing agents, plastics, fluxes, and glazes. Mineralogy Pure wollastonite, CaSiO3, has the composi¬tion of 48.3 % CaO and 51.7 % SiO,. However, it is seldom found in the pure state due to the ease with which it takes into solution the metasilicates of manganese, magnesium, iron, and strontium. Predominantly, wollastonite occurs as a contact metamorphic deposit forming between limestones and igneous rocks. Commonly associated minerals are garnet, diopside, epidote, calcite, and quartz. It has a specific gravity of 2.8 to 3.0, and hardness of 4.5 to 5 on Mobs' scale. When pure, it has a brilliant white color, but with impurities it may be grayish or brownish. Luster is vitreous to pearly. Melting point of wollastonite is about 1540° C. Wollastonite occurs in coarse-bladed masses, rarely showing good crystal form. It is usually acicular or fibrous, even in the smallest of particles. The most unique property of crushed and ground wollastonite is its cleavage. Fragments of crushed wollastonite tend to be needle-shaped, imparting a high strength, and this property is the basis for many of its uses. The fiber lengths are commonly in the ratio of 7 or 8 to 1, length to diameter. Some crystals of wollastonite fluoresce under short-wave or longwave ultraviolet light, or both; colors ranging from yellow-orange to pink-orange. Specimens may also show phosphorescence. The brightness of wollastonite is a property of considerable importance to the paint industry. Material, 99% pure, with a size of -325 mesh, has a General Electric reflectance rating of 92 to 96%. Chemically, wollastonite is inert and this property makes it useful as a filler and reinforcing agent. There are two polymorphs of calcium silicates: wollastonite, a low temperature form, and pseudowollastonite, a high temperature form. Inversion of wollastonite to pseudowollastonite occurs at about 1120° C, resulting in an increase in the coefficient of expansion and a color change. Pure white wollastonite, on inversion, may change to a cream tint, or various shades of red or brown. The color change is thought to be due to the presence of iron and strontium.

Jan 1, 1975

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By W. E. STOKES

COMPANIES operating airplanes have had a relatively prosperous year, permitting them gradually to re- place old types of equipment. The pre-eminence of American-made planes, engines, and accessories has been challenged, either by foreign designs or by domestic patterns that have, for one reason or another. been licensed for manufacture abroad.

Jan 1, 1938

By JOHN S. HEARDING

ON the Minnesota Ranges, 600 million tons of material have been moved in the past three years to produce 172 million tons of direct-shipping iron ore. Increasing wage rates and cost of equipment and supplies, coupled with the larger amount of waste material to be moved in comparison with the quantity of ore make it imperative that tile industry adopt all practices and methods which will enable it to move earth at progressively lower costs. Drilling. Prior to and during the war practically all blastholes drilled were 6-in. in diameter and put down by drills using strings of tools weighing from 2000 to 3000 lb. Present trends indicate that heavier drilling equipment making 9-in. holes wit11 3000 to 6000 lb tools will be more economical. Holes up to 12 in. diameter will be made with this equipment. Forging and hardening practices for bits to increase footage is receiving attention. One manufacturer expects to market 9-in. bits having sintered carbide inserts in the reaming and cutting edges. Oxygen and oil to burn holes in the rock are being tested for making blastholes at a considerably greater speed than can be obtained with a blasthole drill on the same size hole. To dale, however, the cost has been prohibitive.

Jan 1, 1949