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By J. Gordon Parr, D. H. Polonis

High purity alloys of titanium and iron, made by a technique of levitation melting, have been investigated with particular reference to martensite formation and decomposition in the hypoeutectoid range. A preliminary study has been made of the occurrence of the phase corresponding to the structure Ti2Fe. MANY of the previous investigations of Fe-Ti alloys have been made using Kroll sponge as a source of titanium; and the subsequent heat treatments to which alloys have been subjected has, on occasion, led to further contamination. Worrier,',' who suggested a part of the equilibrium diagram for the binary system, and Wallbaum and coworkers,3-5 who worked largely with iron-rich alloys, all used Kroll sponge. Van Thyne, Kessler, and Hansen,6 in their determination of the equilibrium diagram, used iodide titanium for alloys up to 30 pct Fe. Duwez,7 who measured the M. temperature of titanium binary alloys with many solute elements, used iodide titanium in all cases except in his work on Ti-Fe alloys for which he used Kroll sponge. The investigation of the supposed phase Ti2Fe by Rostoker8 nvolved the use of iodide titanium. A section of the constitutional diagram, after Van Thyne et al., is reproduced in Fig. 1. Frequently too much stress is placed on the effect of contaminants in equilibrium and nonequilibrium systems, but there is no doubt that titanium alloys are extremely susceptible to interstitial atoms. Consequently, the main purpose of the work to be described was to determine those features of phase transformations in pure Ti-Fe alloys that were considered of importance in commercial heat treatments. For, although commercial alloys may not be of high purity, the investigation of a system uncomplicated by traces of impurity is a desirable starting point. Another incidental feature, the occurrence of Ti2Fe, was also investigated. The entire study was carried out using powders obtained from alloy ingots, for diffusion reactions are often more rapid in small particles than in bulk specimens. The frequently adopted practice of ascertaining phase constitutions by X-ray analysis of powders, and relating these to the microstructures and mechanical properties of bulk specimens, is considered by the authors to be open to criticism. In the martensite reactions in the Fe-Mn system, for example, it has been shown- hat similar phase distributions in solid and powder may result in different hardness values and appearance under the microscope; and it is possible that similar anomalies might occur in the Ti-Fe system. Consequently, in order to

Jan 1, 1955

By Oliver C. Fursman

The Bureau of Mines undertook this investigation in order to determine the feasibility of producing commercially acceptable alumina and iron by application of the Pedersen process to high-silica, high-titania, ferruginous bauxites of the Pacific Northwest. Calcium aluminate slags were produced by smelting bauxite with coke and lime in an electric-arc furnace. Over 90 percent of the total alumina can be extracted by sodium carbonate solution from slags of properly controlled ternary-phase composition (CaO-Al203-SiO2) that are cooled slowly enough to permit adequate crystallization of the 2CaO-SiO2 and the calcium aluminate compounds. Most of the iron charged was recovered in the regulus; the slag contained about 2 percent iron (as iron oxide), regardless of smelting time.

Jan 1, 1968

By John Chipman

DESPITE the rapidity of chemical reactions at steelmaking temperatures, deoxidation reactions cannot be expected to reach equilibrium immediately after addition of a deoxidizing agent. A considerable period of time may be required merely to obtain complete mixing of the deoxidizing element throughout the volume of steel to which it is added. Evidence in the literature indicates that in some cases the time is long compared with that allowed for completion of the experiment or for teeming of the heat. The great turbulence observed during the filling of the ladle is no guarantee of complete dispersion on a fine scale throughout the heat. During the process there are initially certain volume elements which are high in deoxidizer and others which retain substantially their original oxygen content. Mixing consists of the subdivision and ultimate destruction of these liquid segregates through the process of shear and elimination of concentration gradients by diffusion. The shear process does not continue indefinitely and a quiescent state may be reached in the ladle before all volume elements of divergent deoxidizer and oxygen content are completely eliminated. In furnace deoxidation the time required for complete mixing may be very long unless continuous stirring is employed.' In Fig. 1, let the circle represent one small volume element of aluminum-rich metal surrounded by oxygen-rich steel in which no stirring movement remains. Further mixing requires inward diffusion of oxygen and outward diffusion of aluminum, resulting in precipitation of A12O3 in the diffusion zone. It is important to note that such a precipitate may itself interfere with the diffusion process. Moreover, if the precipitate forms as a film with even minimal mechanical strength, it may interfere not only with diffusion but with shear as well, thus stabilizing compositional differences in volume elements of greater than microscopic size. A film surrounding such a volume element would have little or no ability to rise or to sink unless it enclosed a liquid whose density differed from that of the ambient. Consider now the effect on the overall composition of the melt. Fig. 2 represents the A1-O equilibrium at the temperature of the bath. High-aluminum elements of composition X may exist alongside high-oxygen elements of composition Y in such proportions that the average composition 2 has a much higher A1-O product than that corresponding to equilibrium. The A1-O product supposedly corresponding to equilibrium at 1600 °C was found by Wentrup and Hieber2 to be 10-10, by Hilty and crafts3 to be 2 X 10-9 and by Gokcen and chipman4 to be 2 x 10-14. Only the last named investigators approached equilibrium by means

Jan 1, 1962

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

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 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 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 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

Corrosion is a chemical or electro-chemical attack on a metal by the surrounding medium, and it can be stated in general terms that a non-corrodible metal possesses that property either because there is no chemical action between it and the medium, or because the medium reacts quickly with the metal to produce a thin protective coating.When iron or steel is attacked by dilute mineral acids, for example, the products of the reaction are soluble and the formation of a protective film cannot take place; on the other hand, rusting produces a porous film which flakes away and offers little protection to the underlying metal. However, when chromium is alloyed with iron, its resistance to corrosion is improved because the films produced on such alloys become more adherent and tenacious as the proportion of chromium is increased. Chromium is thus an essestial constituent of the corrosion- and heat-resisting steels.During the 40 years which have elapsed since their initial development, these alloys have made an important place for themselves in in<lustry and commerce, and it is the object of this paper to 'describe typical examples of the many types which are available; also, to give some indication of their particular properties, and applications in the mining industry.NOMENCLATUREVery few of the alloys which are about to be described can strictly be considered stainless, and most are not steels in the sense that they can he hardened by quenching from...

Jan 1, 1951

By Emma Smith, R. W. Guard

INVESTIGATION of the nickel-rich end of the Ni-Zr system has been prompted by an interest in the effect of small amounts of zirconium in high temperature alloys. Hansenl presents a hypothetical diagram based on the work of Allibone and Sykes,2 who investigated the system up to 44 atomic pct (55 wt pct) Zr by metallographic means. Since the alloys they used were melted in Alundum crucibles they were probably contaminated with appreciable amounts of aluminum. They found two compounds which they called Ni3Zr and Ni4Zr. Hayes, Roberson, and Paasche3 identified a compound NiZr (50 atomic pct Zr) with a melting point of 1470°C. Such a high melting compound is not compatible with the observation of Allibone and Sykes2 hat a eutectic is formed near 50 atomic pct. The alloys containing up to 60 atomic pct Zr were melted in an inert atmosphere in a noncon-sumable electrode arc furnace. Analysis of most of the alloys indicated negligible loss of zirconium. The alloys were examined in the as-cast condition and also after annealing for 6 hr at 1175°C (or 1000°C for the alloys between 25 atomic pct and 45 atomic pct). Metallographic specimens were etched using mixtures of HF-HNO3-H2O or acetic acid- HN0,-H,O. The specimens for the solidus determinations were wrapped in molybdenum foil and sealed in evacuated quartz tubes. Specimens to be heated above 1300°C were enclosed in zirconia tubes inside the quartz to prevent reaction with molybdenum. The solidus determinations were carried out by heating the specimens at various temperatures for a few minutes and then examining the interior structure metallographically to determine at what temperature melting began. The 150 mesh powders for X-ray analysis were annealed in an evacuated quartz tube for 2 hr at 540 °C to remove cold work. Alloys with 22.5 atomic pct Zr and 44.4 atomic pct Zr required annealing at 700 °C for complete recovery. The grains of both of these alloys were soft and rather ductile. Both Debye-Scherrer film patterns and spectrometer traces were made for each alloy using filtered copper radiation. Results and Discussion The presence of a substantial amount of second phase in an alloy with 1.1 atomic pct Zr indicated that the solid solubility of zirconium in nickel is somewhat less than 1 atomic pct. The a0 value for the face-centered-cubic matrix in the same alloy was equal to that of pure nickel, so that the solubility must be very small. This observation is as expected from the large atom size difference. Annealed specimens of alloys with 15.0, 16.7, 22.5, 28.6, 44.4, and 59.4 atomic pct Zr showed. micro-structures that were essentially single phase. When

Jan 1, 1958