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By Walter Showak

The published phase diagrams for the copper-zirconium system1,2 indicate that the solid solubility of zirconium in copper is not accurately known. Studies made on relatively impure alloys by Pogodin, Shumova, and Kugucheva3 yielded a maximum solubility value of 1 wt pct Zr at the eutectic temperature. Allibone and sykes5 reported that an as-cast 0.2 wt pct Zr alloy is single phase at room temperature. Limited results obtained by Raub and Enge14 indicated that zirconium solubility in copper is less than 0.13 wt pct Zr at 940°C. Tn 1960, on the basis of a microstructural examination of several copper-rich Cu-Zr alloys, saarivirta6 placed the maximum solubility of zirconium in copper at 0.15 wt pct at the eutectic temperature, 980°C. The present note describes results obtained during a re-investigation of the Cu-Zr system for the purpose of accurately establishing the solidus and solvus curves and the eutectic temperature in copper-rich alloys. High-purity copper (99.99 pet) and zirconium (99.64 pet) consolidated reactor grade sponge were used to prepare several alloys, containing up to 2 wt pct Zr, by induction melting in graphite crucibles in vacuum and chill casting into a split steel mold. The melting procedure consisted of first melting the copper charge and then adding the bulk zirconium wrapped in pure copper foil. Chemical analyses were made of both the cold-rolled alloy ingots after homogenization at 925°C for 450 hr in evacuated quartz capsules and of small specimens which had been used in the phase diagram studies. 'The carbon content of each alloy was also determined and was found to be less than 0.001 wt pct in every case. Metallographic and electrical resistivity measurements were used as the primary methods for this investigation, although some thermal analysis studies were also performed. Heat treatments of all the alloys were carried out with the specimens wrapped in molybdenum or alloy foil (of the same composition as the specimen) and sealed in quartz tubes either in vacuum or under a purified helium atmosphere. Following high-temperature anneals for long periods of time, slight depletion of zirconium from the specimen surface was observed. Therefore, careful preparation of samples for microscopic examination and chemical analysis of the samples themselves was necessary to check the composition of samples used in determining phase boundaries. Points on the solvus curve were determined on quenched specimens by both isothermal reaction after solution heat treatment at 950°C for 8 hr and by isothermal annealing of alloy specimens at successively higher temperatures for times ranging from 24 to 500 hr. Liquation studies for positioning of the solidus and eutectic temperatures were performed by holding a pre-

Jan 1, 1962

By Reuben B. Ellestad, Fremont F. Clarke

Lithium chemical plant extraction methods are discussed with reference to 1) base exchange with alkali sulphates; 2) processing based on roasting with lime; 3) miscellaneous methods; and 4) application of the Lithium Corp. process to extraction of lithium from run-of-mine, low grade spodumene ore, or concentrates. IN the early days of the lithium industry most of the production was from lepidolite, zinnwaldite, and amblygonite. Nearly all the early extraction processes described in the literature involve heating the finely ground mineral with sulphuric or hydrochloric acid. On subsequent water leaching most of the bases present in the mineral (especially aluminum) are dissolved as sulphates. As a result, the leach solution required extensive chemical purification before the lithium could be precipitated as carbonate. Following the remarkable growth of the lithium industry to its present size, zinnwaldite and amblygonite ores must be considered of minor importance only. Attention is now focused on spodumene, abundant enough in North America to be a major source of supply, and there are important supplies of lepidolite and petalite in Africa. The extraction processes described below all apply to spodumene, although several will also operate on other lithium minerals, such as petalite. Base Exchange with Alkali Sulphates: A distinct advance was made with the disclosures of Wadman and von Girsewalt. In these methods the finely ground silicate ore (spodumene or lepidolite) is intimately mixed with an excess of alkali sulphate (usually K2SO4) in at least a 1 to 1 proportion, and the mixture was heated to a relatively high temperature. Base exchange results, with the formation of lithium sulphate. A water leach dissolves the lithium sulphate, together with the excess potassium sulphate. Successful operation of this type of process requires very thorough grinding and mixing, as well as careful temperature control. The use of K2SO4 is objectionable from cost considerations since purification of lithium carbonate requires the use of potassium carbonate, if the K2SO4 is to be recovered and recycled. The lower solubility of K2SO4 as compared with Na2S04 is also objectionable, since it limits the concentration of the Li2SO4 solution to be precipitated by K2SO4. Early laboratory-scale investigation of this process by Lithium Corp. was not encouraging. Other related base exchange processes are those of Lindblad, Wallden, and Sivander3 and Sivander, Gard, Villestad, and Wallen4. The former covers the reaction of lithium silicate minerals with a sodium sulphate solution, at 100" to 300°C (under pressure), while the latter involves the extraction of silicate minerals with molten sodium sulphate. Both these processes would seem to be difficult and expensive to operate.

Jan 1, 1956

By M. T. Worley

This paper reports investigative work conducted to develop a method of estimating the groundwater influx from a homogeneous permeable formation into a vertical mine shaft during sinking. A method of analysis was developed using data obtained from pumping tests and a modification of the Theis non-equilibrium interpretation technique. Excess influx of groundwater into mine shafts has long been one of the more important problems encountered in the development of a mining property. Much work has been done on methods of preventing such influx and on pumping schemes to control inflow if preventive measures fail. The fundamental aspects of the problem, on the other hand, seem to have been neglected. The purpose of this paper is to review the fundamentals of groundwater flow and to propose a rapid method of analyzing hydrologic data in order to estimate influx from a homogeneous permeable formation into a mine shaft. Such an estimate of the quantity of water to be encountered is of value in planning grouting, pumping and other programs designed to control that influx. It is emphasized that the proposed method of analysis should be regarded only as a tool to be used in evaluating the problem before investing the capital necessary to begin development of a property. FUNDAMENTALS OF GROUNDWATER FLOW In order to effectively approach the problem of estimating influx into a mine shaft, a knowledge of the fundamentals of fluid flow through a porous medium is necessary. Darcy, in 1856, developed an empirical relationship to explain the flow of water through sand filters. This relationship V = k (dh/dl), is the basis for all other flow formulae. It has been shown that Darcy's relation is a solution of the Laplace equation and thus is analagous to other natural phenomena such as heat flow. Theis, using the analogy of heat flow by conduction, developed an expression for determining the transient or time-dependent groundwater flow through a homogeneous, isotropic medium. The resulting equation Was also derived by Jacob using hydrologic considerations alone.' The individual terms in the equation are described in Table I. It is important to understand the assumptions upon which this equation is based. 1) The medium through which the fluid flows is infinite in areal extent, homogeneous and isotropic. 2) The well into which the fluid discharges completely penetrates the medium. 3) The characteristics of the medium remain constant at all times. 4) The initial pressure surface is horizontal. 5) The confining media are impervious and horizontal. 6) Fluid is removed from storage instantaneously by a decline in pressure. 7) The diameter of the discharge well is infinitesimal with respect to the drainage radius of the medium.

Jan 1, 1962

By S. Beatty

RECENT experimental results' on the superconductive properties of vanadium indicate that the magnetic behavior of the metal is greatly affected by internal strains caused by mechanical work, and particularly by oxygen and nitrogen impurities. These result in an increase in the hardness of the metal such that metallurgists' have used hardness as a measure of the impurities. An increase in the impurities should also be reflected in a change of lattice parameter with increasing impurity content. The lattice parameter of vanadium prepared by the thermal decomposition of the iodide has been determined by two workers. Neuburger3 obtained a value of a, =3.0338 ± 0.0003A for the body-centered cubic lattice by means of the powder method. The work of Katelaar is referred to by van Arkel4 in which a value of a0 = 3.025 is given. Four samples were used for this investigation. Sample A, the vanadium of the highest purity in the group, was obtained by means of the thermal decomposition of vanadium diiodide and deposited on a 3 mil diam tungsten filament in the form of crystals. The second sample, labeled B, was obtained by the calcium reduction of the pentaoxide at a sufficiently high temperature to give a melt. A third sample, C, was obtained in the same manner as B but remelted in a pure argon atmosphere. The last sample, D, was prepared by the calcium reduction method and the fine powdered vanadium was then sintered by means of applied heat and pressure. Samples A, B, and C were thus essentially free of mechanical strain in their preparation. Sample D was annealed in a high vacuum at 800°C. The samples were prepared for X-ray diffraction analysis such that all additional strain by cold work or by contamination with oxygen and nitrogen was kept at a minimum. Powder obtained from filings was deemed unsuitable since this would require annealing to get rid of the cold work. A heat treatment up to 1000°C at 10-6 m pressure might still increase the impurity content by means of adsorbed oxygen from residual gas in the vacuum chamber. The most satisfactory samples were prepared for back-reflection film techniques. Samples were cut to size, etched with hydrobromic acid, and mounted in Bakelite. They were then lightly polished on 3-0 paper and lightly etched. Chemical and Hardness Analysis of Samples Spectrographic analyses were made of the four samples and indicated similar metallic impurities for the group. The major metallic impurity in each sample was iron, which was less than 0.01 pct. The sum of the other metallic impurities was approximately 0.1 pct. The carbon content was assumed low by virtue of the methods of sample preparation. The principal impurity difference between the samples was in the oxygen and nitrogen content.

Jan 1, 1953

By W. A. Mudge

ONE of the most prominent features of our present-day industrial development is the ever-increasing demand put upon materials of con-struction. Engineering ingenuity, within the past 25 years, has been unusually active, and in some fields at least engineers frankly say that engineering design has progressed as far as the limitations imposed by the properties of the present materials of construction will permit. Consequently, they are today demanding improvement in their working materials and seeking new ones, through the aid; of which the present limitations of design may be overcome. The activity of this search is evident in all fields, but it is particularly so in that of structural materials required to be resistant to corrosion. The corrosion resistance of metals and alloys is never absolute and all-inclusive; a particular alloy will withstand some corrosive conditions well and fail utterly tinder others. Furthermore; other properties, physical and mechanical, required in-conjunction with corrosion resistance vary considerably for different commercial applications. One wants a soft, ductile sheet metal resistant to atmospheric corrosion; another, a high-strength- alloy resistant to sulfuric acid. The last decade has witnessed active and definite progress in the development of high-strength, corrosion-resisting alloys. In June, 1924, a symposium by the American Society for Testing Materials, on Corro-sion-Resistant, Heat-resistant and Electrical-resistance Alloys, disclosed no less than 60 commercial alloys the properties of which were described as being suitable for industrial service where corrosion resistance

Jan 1, 1935

By H. E. Stauss

THE time-to-fracture test has been applied to pure platinum and to two alloys of platinum under the special conditions of small cross-sectional area of the specimens and of a test temperature above the annealing temperature. While the results are similar in character to those secured with large specimens of steel at temperatures below the annealing temperatures, two differences are noted: (I) an upward inflection in the curves for log stress vs. log time for the alloys, and (2) a sharp break in the curve for log stress vs. log time for pure platinum when single crystals filled the wire. The experiments showed that: (I) platinum and 10 per cent rhodium-platinum maintained their strengths at 1100°C. better than did 10 per cent iridium- platinum, and (2) the rhodium-platinum after a time exceeded the iridium-platinum in strength at 1100°C. Platinum alloys in their service at high temperatures encounter conditions some- what similar to those that exist in the usual form of the time-to-fracture "l test with steel. This paper is intended primarily to present results obtained by a "time-to- fracture" test under conditions approximating actual service for platinum (at the temperature 1100°C. under oxidizing conditions) with three materials, pure platinum (99.99 per cent), a platinum alloy with lo per cent iridium, and a platinum alloy with 10 per cent rhodium. The experimental procedure differed from that previously used in this type of measurement in that the samples were of small diameter (0.010 in.), were fully annealed, and were tested at a temperature definitely above their annealing points (600°C., 1000°C. and 1050°C., respectively, for 60 per cent cold reduction and 15 min. heating time2,3). The experimental arrangement was similar to that previously described,4 using as heating unit a small, horizontal, platinum- wound furnace, ½ by 12 in., maintained at constant temperature by an automatic controller. The samples were 0.010-in. wires, which had been annealed at 1200°C. by drawing them slowly through the furnace. The time-to-fracture was measured electrically. Elongation was not determined because of the difficulties inherent in the experimental arrangement. Life-that is, the time-to-fracture-was considered the important property in these first tests. No attempt was made to measure the reduction in area, but the types of fracture were noted qualitatively; in the text they are referred to as (I) the normal, plastic, or necked fracture, (2) the knife-edge fracture, and (3) the brittle or intercrystalline fracture with small reduction of area. Results for different constant applied stresses are plotted in Fig. I. In all cases at least two trials were made for each stress, although they cannot always be indicated separately on the curves. The breaking stresses drop very rapidly to a small frac-

Jan 1, 1943

By A. W. Schlechten, A. H. Larson

Equilibrium H2S/H2 ratios were determined as functions of temperature (500o to 900°C) and composition in a hydrogen-circulation apparatus. Within the composition range studied there exists a two-phase region of "Zr3S4" and "ZrS2". The upper composition limit of this two-phase region is hounded by a disulfide phase and is practically constant over the temperature range investigated. The lower composition limit of this two-phase region is bounded a "Zr3S4 " phase and varies appreciably with tem- perature. The upper composition limit of the homogeneous region of the disulfide phase is not definitely determined, but it appears to he bounded by the stoichiometric composition of ZrS2. The lower composition limit of the homogeneous region of the Zr3S4 phase could not he determined due to the extremely low values of the equilibrium H2S/H2 ratios. Various thermodynamic quantities are evaluated from the data. PUBLISHED free-energy data for the Zr-S system are practically nonexistent. Strotzer, Biltz, and Meisel1 measured the sulfur pressures for the reaction 2ZrS2(s) + S2(g) = ZrS3(s) in the temperature range 783" to 874°C. The average heat of reaction calculated from the temperature dependence of the sulfur pressure is -47 keal. It should be noted, however, that according to these investigators, the two-phase region as determined by sulfur pressure constancy under isothermal conditions extended from approximately ZrS2, 3 to ZrS2.7. From consideration of X-ray data they concluded that the homogeneous regions of the disulfide and trisulfide phases are ZrS1.8-2.0 and ZrS2.8-3.2, respectively. Hahn and coworkers2 have made a structure study of the zirconium sulfide phases. They summarized the zirconium sulfide phases as follows: the compounds ZrS3 and ZrS2 with narrow homogeneous regions, a "Zr3S4" phase with a homogeneous region roughly within the limits of ZrSl.5 and ZrSo.9, the compounds ZrS and Zr4S3, and a "Zr3S2" phase with a homogeneous region within the limits ZrSo.8 and ZrSo.5. It is noted that the compounds ZrS and Zr4S3 are only formed in the gaseous state through sublimation of a phase which has the approximate composition of the compound. This paper describes the determination of the stability of the zirconium sulfide phases by a hydrogen-reduction method in which hydrogen is circulated over the heated sulfide until equilibrium is attained. The resulting H2S-H2 mixture is then analyzed. Partial molar free energies, enthalpies,

Jan 1, 1964

By Jose A. Ruiz

INTRODUCTION For heterogeneous non-catalytic solid-gas reactions carried out in fluidized bed reactors, nominal bed temperature is an average value between gas and solid. For highly exothermic reactions, actual particle temperature can be up to hundred degrees above termocouple temperature, since heat dissipate at slower rate than heat generation during some steps of transformation. These micro instabilities at particle level can displace thermodynamic equilibrium from the desired phase to others. This effect is important when relatively narrow range of phase stability exists, like in sulphation roasting of sulphides, where bed discharge contains, in addition to the desired sulphate others metastable phases such as basic sulphate and ferrite. For example, for copper-iron sulphide concentration roasted below 680°C, no cupric ferrite is formed, as shown by Jakob et al., therefore the separate Kellogg's stability phase diagrams Cu-S-O represent the roasting (Fig.l). At temperature above this one, like 760°C for example, phase stability changes from CuSO4 to the basic sulphate Cu0•CuSO4. Solid state reaction between Cu0•CuSO4 and Fe203 also occurs to form cupric ferrite, Cu0•Fe2O3, therefore the Cu-Fe-S-O Kellogg's phase diagram of Fig. 1 (continuous line) represents this condition of roasting. Although both Cu0•CuSO4 and Cu0•Fe2O3 are metastable phases under normal operating conditions of sulphation roasting(1-10% SO2, 1-10% 02 and 680°C, points A and B,Fig. 1) sulphation of these species and particularly ferrite are slow and limited due to diffusional control. This explain why reactors discharge contains several phases: CuSO4, Cu0•CuSO4, CuO•Fe203 plus small amounts of CuS and FeS due to the baclonixed conditions of fluidized bed reactors. The presence of cuprous ferrite due to reducing conditions inside individual particles also occurs, but in very limited extent at the reaction interface, as it is demonstrated by the low soluble iron levels of calcines. On the other hand, the presence of cupric ferrites can be explained only due to the higher temperature achieved by particles, since below 680°C cupric ferrite formation does not take place. [ ] This phenomena also occurs for others non-ferrous metal sulphides concentrates roasted under sulphation conditions, such as 7n, Co and Ni. Therefore the prediction of discharge composition of fluidized beds is not possible based only on kinetics and mechanistics models alone or purely thermodynamical considerations, since all factors should be integrated to describe the overall phenomena. SINGLE PARTICLE TRANSFORMATION Assuming a first order reaction with respect to the gas and zero for solid, such as

Jan 1, 1984

By Donald M. Liddell

From a commercial standpoint, the only beryllium mineral warranting attention is beryl, 3Be.Al2O3.6SiO2, which is of fairly widespread occurrence. The chief deposits are in Brazil, Argentina, India, Canada and Portugal. When pure this contains about 14 per cent of beryllium oxide. The mineral richest in beryllium is phenacite, (BeO)2SiO2, or beryllium orth-osilicate, which contains 45.55 per cent beryllium oxide when pure, and if anyone is ever fortunate enough to discover a large deposit of it, it will revolutionize beryllium metallurgy. Gadoljnite, zBe0.Fe0.2Yz0~.zSi0~, is also often referred to as a beryllium mineral, though the occurrences are comparatively scant and it is of more interest as a source of yttrium than it is of beryllium. There has been a good deal of talk recently regarding some occurrences of helvite in the United States. Helvite is a complex manganese-iron beryllium silicate and, apart from difficulties that would arise in its treatment because of its compo-sition, the beryllium content of the known deposits is not high. Early Metallurgy The elemcnt beryllium was first isolated by L. N. Vauquelin in 1797.~ He crushed and heated beryl, having the idea that this heating made it more readily amenable to attack by chemicals, and then mixed the mineral with three times its weight of caustic potash and fused the mixture. The melt after cooling was dissolved in hydrochloric acid: dehydrated, and again taken up with hydrochloric acid and filtered to separate the silica. The filtrate was treated with an excess of potassium carbonate and the precipitate after draining was leached with a solution of caustic potash, which dissolved the alumina. The undissolved material was, in Vauquelin's own words, "une terre nouvelle." He dissolved the precipitate with nitric acid and evaporated it to dryness, took up with hydrochloric acid and threw the iron out with potassium hydrosulphide, though he found that to make a complete separation of the iron involved a second treatment. The solution, after throwing out of the iron, had a pronounced sweet taste, and though Vauquelin always speaks of working on "terre du beril" he suggests that the new element should be known as "glucine" (glucinum) from the Greek word for sweet, because of this outstanding property. Vauquelin did considerable work on the comparison of aluminum and beryllium, working out a separation of most of the aluminum based on its precipitation as alum. His work is reviewed at some length, since ordinarily his procedure is incorrectly stated. It will also be recognized by those who have studied beryllium metallurgy that a good many technicians have followed his ideas since, including preheating the beryl before treatment. The fusion with

Jan 1, 1944

By Sylvan Z. Beer

The factors that determine the yield and crystal size in the two-temperature synthesis of A lp were examined. Low yields and small crystals were associated with low temperatures and pressure. Attempts to grow large crystals in the critical and supercritical region of phosphorus were unsuccessful. Crystal size increases markedly at elevated temperatures. Crystals grown at temperatures as high as 1450° C fluo-resced, under uv excitation, at energies close to the estimated band gap of about 2.4 ev, while crystals grown at lower temperatures tended to fluoresce in the red region of the spectrum. Those grown in the supercritical region showed no ALP fluorescence. Heating the high-temperature-grown ALP under vacuum greatly increased its fluorescence efficiency and moved the emission peak to higher energies. I HE III-V compounds, with few exceptions, have been prepared by the two-temperature method. In its classic form this technique is applicable to closed systems where at least one of the components, in this case the column V element, is a liquid or a solid with a high vapor pressure. One advantage of this method over flow systems is in its simplicity. In addition, because it is a closed system, it can, under the circumstances to be described later, be run at higher pressures of the volatile species than in flow systems. In instances where the III-V compound is soluble in the parent III metal to about 1 mol pct or higher, solution growth can be made to take place by slow cooling. This, for instance, is one way in which single-crystal GaP1 and Inp2 have been grown. Initial attempts to synthesize and grow A1P by this technique were not too successful; the yield was low and the crystals obtained were exceedingly small. The conditions required for improving the yield and growth by this technique were, therefore, sought. Two obvious conditions which could be controlling were examined. These were the temperature of the aluminum and the pressure of the phosphorus. The range of temperatures studied extended from about the melting point of aluminum, 660° to about 1450°C. The latter is dictated by the vapor pressure of aluminum which reaches about 1 Torr at that temperature and the limitations of the materials of construction as described in the next section. The pressure range of interest covers from below 1 atm to above the critical pressure of phosphorus, 82.2 atm. EXPERIMENTAL The Temperature of Aluminum as a Variable. A series of experiments were run in the conventional two-temperature manner. All refractories and quartz were dried by heating at 800° to 900° for a minimum of 24 hr, and usually much longer, before use. The aluminum

Jan 1, 1969

US 4,135,913-Extraction of nickel values from iron-containing nickel sulfide ore, particularly pentlandite or nickeliferous pyrrhotite A mixture of raw ore, roasted ore, or iron powder, and coal as a reductant is heated to a temperature of 800- 1000° C in a nonoxidizing atmosphere to convert the bulk of the iron content to metallic iron while diffusing into the iron the bulk of the nickel, the mixture cooled, and the cool material separated into a magnetic fraction containing most of the nickel and a non-magnetic gangue fraction A Illis arid L S Renzoni, assigned to International Nickel Co, Inc Jan 23, 1979 7 pp (75-21) Filed 10-10-75 (621,343) Priority Canada, 10-27-72 (155,032) Same Canadian 981,910, dated Jan 20, 1976 Same British 1,389,145, dated Apr 3, 1975 US 4,135,917-In the recovery of gallium from a solution obtained by the digestion of bauxite or nepheline in an alkali solution for the production of alumina, the digestion solution is neutralized, the neutralized solution evaporated to an op¬timum caustic alkali concentration and adjusted to a ratio of alkali metal oxide to alumina of above 2, the corrected solu¬tion contacted with a gallium-aluminum alloy, arid high-purity gallium recovered from the solution by electrolysis or cemen¬tation K A Badaliants, et al Jan 23, 1979 6 pp (75-109) Filed 12-19-77 (862,201) Priority USSR, 12-22-76 (2,428,¬006) US 4,135,918-Extraction of copper from copper sulfide ore containing also one or more of the metals iron, nickel, arid cobalt Ore is roasted at a temperature of 750-800° C to expel sulfur, the sulfur-free calcine slurried in water containing a sufficient amount of sulfuric acid to supplement any sulfuric acid formed in situ, the slurry heated at 150-165° C in the presence of a reducing gas to form soluble sulfates of metals other than copper while reducing copper to elemental form, arid the slurry filtered to recover copper solids Any precious metals present in the ore will report with the copper solids V A Ettel, A P Devuyst, R Sridhar, arid C. E O'Neill, as¬signed to International Nickel Co, Inc Jan 23, 1979 5 pp (75-117) Filed 3-2-78 (882,610) Priority Canada, 5-13-77 (278,360)

Jan 1, 1980

By J. H. Fletcher, S. M. Cassidy

Air has been cooled, heated, washed, humidified and dehumidified for many purposes and in many industries. At a number of metal mines air is conditioned to reduce the high humidity and unbearable heat found in deep workings, and at some mines air is washed to allay siliceous dust. Steam is introduced into the intake air at many coal mines, particularly in winter, for the purpose of keeping loose coal dust so moistened that the hazard of an explosion is lessened. This paper will describe a further successful application of air conditioning in a coal mine, where, for over three years, all intake air has been cooled to a constant temperature for the sole purpose of preventing roof falls. Effect of Warm Weather on Mine Roof It is generally known by mining men that some, if not all, coal mines have more trouble from bad roof during the warm summer months than in winter. Also, it has been observed that roof on intake airways is usually worse than on the return entries, after the air has circulated through the mine. Some mines and some coal seams are much more affected than others. In the Clinton district of Indiana, the No. IV coal seam has a good, firm, gray shale roof except during the summer months, when it deteriorates badly and falls in small slabs 1 to 6 in. thick. Timbering is not very efficacious during this period because in time the roof will shear around the supporting prop or crossbar and either dislodge the timber or leave it supporting only a few inches of crumbly shale (Fig. 1). This action is renewed each summer, choking airways with fallen slate, tearing down trolley wires, hampering haulage, endangering men and adding considerably to the deadwork cost. Only when mines have been worked for a period of years and have been advanced a long distance from the shaft do the active workings become comparatively free of this trouble, and even then the intake entries are still a source of much deadwork. Such was the annoying situation at the mine of the Saxton Coal Mining Co. operated in the No. IV coal just north of Terre Haute, Ind. During the months of warm weather it was possible to stand at any quiet spot in the mine and within 10 min. hear at least two or three falls,

Jan 1, 1931

By M. Schussler, J. S. Brunhouse

Arc-melted and electron-beam melted tantalum in the cold-worked and the recrystallized conditions showed high strength, good tensile ductility, and excellent notch toughness down to 321°F. Arc-melted material, containing moderate amounts of interstitials, possessed better short-time strength than higher purity electron-beam melted material up to 2000°F. Cold-working substantially strengthened arc-melted tantalum, whereas electron-beam melted material exhibited a low work-hardening rate and possessed better formability characteristics. With identical compositions and microstructures, the mechanical properties of melted tantalum and uacuum-sintered tantalum should be similar. TANTALUM metal usage is increasing rapidly in a number of applications. The outstanding chemical corrosion resistance of tantalum accounts for its applications in chemical processing equipment for severe service conditions and for surgical uses in the medical field. The largest present requirements for tantalum are in the electronics industry, where its special properties are useful in capacitors. The high melting point (5425°F) and inherent ductility of tantalum also suggest that tantalum and tantalum-base alloys might offer an excellent combination of high strength at very high temperatures and good fabri-cability. Pure tantalum has been used in significant amounts in parts requiring high-temperature strength, such as heating elements, reflectors, and heat shields in high-vacuum high-temperature furnaces and in electronic tubes. A few very promising tantalum-base alloys have been developed and are being investigated extensively. The possibilities for tantalum as a high-temperature structural material, either unalloyed or alloyed, will become better defined when more extensive mechanical property data are known. pughl measured the tensile properties of vacuum-sintered tantalum in sheet form for the temperature range of 78" to 1500°K (-321' to 2240°F), and Bechtold reported data obtained at low temperatures.' Drennen3 determined creep and stress-rupture properties of both vacuum-sintered and arc-melted tantalum sheet at 1200 °F. Some additional data on the mechanical properties of tantalum at temperatures up to 5000 °F have been summarized elsewhere.4'5 It is probable that large structural shapes of tantalum, either unalloyed or alloyed, can most readily be produced from ingots prepared by melting. Consequently, the present investigation was undertaken to determine more extensive short-time mechanical properties of tantalum metal consolidated by melting. EXPERIMENTAL PROCEDURE Melting and Fabrication—Two tantalum ingots were utilized in this study to obtain information on the effect of interstitial elements on mechanical properties. Both ingots were melted from Union Carbide Metals Co. tantalum dendrites.

Jan 1, 1961

By -Ing. Alexander Dohmen, -Ing. Gunter Hagen

In order to improve the thermal environment in deep coal mines, two principles can be applied: firstly, the reduction of heat flow into the air stream, and secondly, cooling of the air current. First of all one should try to minimize the heat-flow rate into the air stream underground by the mining method itself. German coal mines prefer the caving system of advance longwall mining simultaneously on several levels with ascensional ventilation. The effects of descensional ventilation and different face ventilation layouts on the thermal environment are discussed, besides the effects of pneumatic and hydraulic stowing. Application of all mentioned possibilities together instead of today's common mining method would reduce the Basis Effective Temperature considerably. In the future, hydraulic haulage of the raw coal underground substituting belt conveying may be a mean to improve the thermal environment further on. If the working depth of a coal mine exceeds about 1 000 m, cooling of the air stream under-ground will be necessary in addition to the above- mentioned measures. Generally, in German coal mines different types of indirect-contact air coolers located nearby the face are used. Besides such so-called cooling coils, large-capacity spray coolers are used because they work more efficiently if a great cooling duty is demanded. Common designs of both air cooler types and their possible utilizations are demonstrated. Deep coal mines in the Federal Republic of Germany need up to 30 MW of total cooling capacity. Mostly, the needed chilled water is cooled by large-capacity refrigeration plants placed on surface, underground or in combination of the above locations nearby the shaft. Due to the increasing underground cooling demand, the distribution of the chilled water and the control of the air coolers become more important. The conception of a control system is discussed, which is based on the control of the single air coolers. All air coolers of a mine are controlled so as to optimize the supply water-flow rate with regard to the demanded cooling duty of the coolers. On the next upper level of the control system the whole chilled water network and finally the refrigeration plant is regulated. Present research work deals with the use of ice for cooling mines. There are some unsolved problems in this new cooling concept. Some aspects of making, transporting and storing ice are described. The use of ice may probably reduce the cooling costs of German collieries, which are at present approximately 4 DM per ton of saleable coal.

Jan 1, 1989

By Harry M. Mikami

Refractories are heat-resistant, generally nonmetallic materials used as the linings of furnaces or high temperature vessels in the steel, iron, nonferrous metals, glass, cement, lime, ceramic, chemical, petroleum, paper, and power and heat generation industries. Refractories must have structural strength at high temperatures but also, in many applications, must simultaneously resist chemical-physical corrosion-erosion from stags, metals, granular solids, or gases. Among the major uses are the pyrometallurgical processes for producing iron, steel, copper, aluminum, nickel, lead, zinc, etc. Rotary cement kilns, glass tanks, refineries, utility boilers, chemical and ceramic (including refractories) plants, and a myriad of other smaller scale users employ refractories in the high temperature parts of their operations. Thermal, chemical, and structural conditions under which refractories are used differ widely so there is a great variety of refractories to fill the various needs. Two major classifications are the "basic" and "acid" types. Basic refractories include magnesia and chromite, singly and in combinations, dolomite, and forsterite (olivine). The acid category includes aluminosilicates, alumina, and silica. There are a number of other specialized types such as carbon, graphite, silicon carbide, zircon, and zirconia that have important applications but are used in much smaller amounts than the major categories. Physically, refractories can be divided into bricks and shaped products on the one hand and unshaped or monolithic products (also termed specialties) on the other. There are many further subclassifications and divisions, a discussion of which is beyond the scope of this chapter; see Refs. 2 and 9. Raw materials for the principal basic refractories are magnesia and chrome ore. Magnesia, generally termed magnesite or periclase, is obtained mainly from seawater or saline brines extraction, but substantial amounts are produced from mined magnesite (MgCO3). Dolomite (CaCO3•MgCO3), another important basic refractory, is obtained entirely from mined sources. Acid refractory raw materials are: fire clays, flint clays, kaolin, and other natural clay minerals; aluminosilicate minerals such as kyanite, andalusite, sillimanite, pyrophyllite, bauxitic clays; calcined refractory grade bauxite, alumina from the Bayer process for the alumina group; and quartzitic rocks for silica refractories. The total value of all refractories shipped in the United States in 1974 was $989 million, a record to that date. Of this amount, about 73% represents bricks and shaped products and 27% is in nonshaped or monolithic products which comprise mortars, cements, castables, plastics, and ramming and gunning mixes. Fig. 15.4E.1 shows the rising value of all U.S. refractory shipments in the period 1948-1974. Values of brick and shapes paralleled

Jan 1, 1976

By Gordon G. Bentle, W. P. Fishel

GREINER, Marsh, and Stoughton1 have reviewed the literature in a monograph on the iron-silicon system. The lack of agreement among the various studies may be due to the difference in the purity of materials in some cases. The results of the X-ray method indicate only a general rather than a specific limit of the y loop. The iron-titanium system was investigated by Roe and Fishel,' whose results are used in determining the iron-silicon-titanium y loop. The literature indicates that no study has been made thus far of the iron-silicon-titanium system in the y loop region. Experimental Procedure The alloys were made from Armco iron, 99.86 pct Si, and 98.5 pct Ti. The titanium contains 1.07 pct Fe. The Armco iron contains 0.01 pct C, 0.005 pct Si, 0.02 pct Mn, 0.006 pct P, 0.01 pct S, and 0.04 pct Cu. A dilatation sample of Armco iron was prepared in the same manner as were the other samples. Several dilatation runs indicated that Ac3 begins at 905°C and ends at 910°C, which compares favorably with the study of Wells, Ackley, and Mehl' employing specially purified iron. All alloys were melted in an induction furnace in Alundum crucibles and were top poured into baked core sand molds. The ingots weighed about 600 g as cast. Dilatation samples of 4 in. by % in. diam were taken from the bottom end of the ingot, from which turnings for analysis were taken. Turnings from each end of two of the samples indicated that the alloys possessed uniform silicon content. A hole was drilled halfway through each end of a 4 in, dilatation sample. A chromel-alumel thermocouple was inserted in each hole and the surrounding metal peened in to hold the thermocouple in place. Fig. 1 represents the dilatation apparatus. The heating unit is an Alundum tube wound with resistance wire; the dilatation tube is a McDanel combustion tube; the push rod is zircon; the dial gage is graduated in 0.0001 in. and was vibrated to prevent sticking. A blank run over the temperature range of interest gave no significant dilatation. The thermocouples were attached to a multiple recording micromax which indicated the temperature at each end of the sample at 35 sec intervals. A Lindberg control unit governed the rate of heating of the furnace, and lowering or raising the

Jan 1, 1957

By Elmars Ence, Harold Margolin

The partial isothermal section of the Ti-Cu-Zr system at 750°C has been studied. The crystal structure of Ti2Cu has been detevnlined as tetragonal and when expressed as face-centered tetragonal, a = 4.164, c = 3.611 A, and c/a = 0.867. TITANIUM systems in which ß-titanium decomposes eutectoidally into a and a compound rather readily are known as active eutectoid systems. Recently in active eutectoid alloys based on the Ti-Cu system, and containing additionally A1 and Zr, it has been found that zirconium may produce both moderate weakening and marked strengthening at elevated temperatures.' In order to obtain some insight into the behavior of zirconium, an attempt was made to determine whether compounds of the type Tix Zr and TixZryCu exist. Only results of the Ti-Zr-Cu studies are reported here since data on Ti-Zr alloys will be presented in a separate publication. EXPERIMENTAL PROCEDURE Alloys were nonconsumably arc melted in argon atmosphere as 15-g buttons, prepared from materials of the following purities: Bureau of Mines electrolytic Ti — Bhn 63 OFHC copper Reactor Grade Zirconium Bhn .C 150 Prior to alloy preparation the electrolytic titanium was premelted to avoid excessive spattering of the charges during melting. The weight losses during melting did not exceed 1 pct of the total weight of the charge. The alloys prepared are listed in Table I together with analyzed compositions. in cases where they were determined. Specimens for heat treatment were wrapped in molybdenum sheet, annealed in argon-filled quartz capsules, and quenched by breaking the capsules under iced brine. About 1 to 2 sec are required to remove the capsule from the furnace, drop it into the iced brine and break it. Because of the insulation effect of the quartz, this delay in quenching should not produce a large drop in temperature. In many instances, no difference or little difference has been detected between the same specimen quartz capsule quenched or directly quenched in vacuum by an impinging stream of water.' Ti-Cu-Zr alloys were homogenized for 48 hr at 825°C prior to annealing at 750°C. Annealing for 5 days at 750°C produced the same results as 11 days at temperature and it was therefore assumed that 5 days was sufficient to establish equilibrium. Titanium-copper alloys were homogenized for 40 hr at 900°C prior to heat treatment for 6 days at 750°C. Specimens for metallographic examination were electropolished and etched with the following solution:

Jan 1, 1962

By S. Y. Ogawa

The effects of sulfur (up to 0.1 pet) on the deformation and fracture characteristics of iron, in cast form, were studied at strain rates up to 100 pct pcr sec and at temperatures of 1600o to -3300 oF. The effects of oxygen and manganese additions on the behavior of Fe-S alloys were studied under comparable test conditions. Brittle fracture characteristics, evident at all strain rates, resulted from the presence of the liquid iron sulfide phase at grain boundaries. Ductility could be restored in three ways: solution of the sulfide in solid y iron at higher temperatures, spheroid-zzation of the liquid sulfide, and increase. in the melting point ot the sulfide. THE literature shows that most previous studies of deformation and fracture at hot working temperatures have been based on measurements of energy absorption, reduction of height in forging upset tests, torsion tests of bar or wire samples, and so forth,' but that relatively few tension tests have been used at high temperatures and strain rates. The present work was initiated to study the ef- fects of temperature, strain rate, composition, and structure on the deformation and fracture characteristics of iron, utilizing cast specimens tested in tension. As in a previous study,' strain rates up to 100 pct per sec were chosen for the temperature range 1600° to 2400° to provide data which might be useful in the interpretation of the deformation and fracture behavior of steels under hot working conditions. The previous work was with Fe-P solid solution al10ys;2 this work is concerned with Fe-S alloys, and with the effects of oxygen and manganese additions. MATERIALS AND PROCEDURE Cast tes! specimens were employed throughout, since most of the difficulty during hot working occurs in the initial breakdown of the ingot. Alloy Systems. Ten 25 lb. heats containing sulphur were prepared. Of these, three had manganese additions, and two had oxygen additions. The sulfur content varied from 0.023 to 0.10 pct. Manganese contents were intended to be ten to twenty times the sulfur content of the particular alloy. Oxygen, being more difficult to control in small melts, was varied by the amount of solid deoxidizer added, but poor control of the oxygen content was experienced in most instances. Table I shows the chemical analyses of the heats. Melting and Casting. Electrolytic-iron chips were melted by high frequency induction in a prefired, clay-graphite crucible lined with rammed magnesite.

Jan 1, 1962

By Thomas H. Dubaniewicz

The National Institute for Occupational Safety and Health, Pittsburgh Research Laboratory conducted a study of laser safety in potentially flammable environments. Researchers measured threshold igniting powers as a function of beam diameter for butane and propane-air mixtures by laser-heating targets placed on optical fiber tips using a 1064 nm laser. The minimum igniting powers for propane-air and butane-air were about 250 and 300 mW, respectively. Threshold igniting powers for propane-air were approximately proportional to beam diameter for beam diameters from 0.1 to 2.0 mm. Results suggest that relatively powerful beams may be used in these atmospheres without causing ignition, provided the beam diameter is controlled. Threshold ignition delay times using 91125 and 62.51 125 pm fibers were approximately proportional to the inverse square of the laser power. Ignition delays were about 45 ms or longer for laser powers up to 800 mW. Preproduction samples of a commercial optical fuse prevented ignitions under selected test conditions. A self-healing effect was observed for one sample. Comparisons are made with the results of other researchers. O 2006 Laser Institute of America. Key words: propane ignition, butane ignition, laser ignition, nonbeam hazards, fiber optic fuse

May 3, 2006

By Roberto Parra

The operational control in a Flash Smelting Furnace is based on the mass and energy balance of the chemical and mineralogical composition of the concentrates. It is well known that many troubles in the dust formation and slag quality occur without a clear correlation to a specific process parameter such as the matte grade or heat balance. This paper outlines two new considerations that could both help improve the entire quality of the process: blend characterization and versatile slag composition control. Related to the blend control, laboratory scale study has shown that the magnetite and dust formation don't have a linear behavior with the weight proportion of the blend and some optimal blends of2 or 3 types of concentrates can be identified. Related to the control of stag composition, the quantification of the slag liquidus temperatures and viscosity could be an effective operational tool for both for ferrite and fayalite slag that can also directly help deciding the blending parameters. From these viewpoints the benefits of the combination of these two approaches for high temperature operation is discussed. Keywords: Optimization, Copper concentrates, Flash combustion, Blends, Slag composition

Jan 1, 2003