Search Documents

By Richard H. Olson

"Rarely in our technological society does the discovery of a new class of inorganic materials result in such a wide scientific interest and kaleidoscopic development of applications as has happened with the zeolite molecular sieves." That opening sentence in a landmark volume on zeolite molecular sieves by D. W. Breck (1974), is, if anything, an understatement. Zeolites were recognized as a new group of minerals in the 1750s, but it was not until 1930 that the first analysis of the crystal structure of a zeolite mineral was made. In the late 1940s research workers at Union Carbide Corp. began a program of zeolite synthesis and study which has resulted in one of the major research achievements of all time. Naturally, with the vast research and development efforts devoted to the synthetic molecular sieves, Union Carbide became concerned in the mid-1950s about its position should minable deposits of natural analogues be discovered. Zeolite minerals have diverse origins, and even a brief discussion of these is beyond the scope of this paper. The early work on zeolites was confined to igneous rock occurrences (e.g., amygdules and veins) which were formed by "space-filling;" these crystals tend to be euhedral, thereby rendering them appealing to both mineralogists and collectors. During the first year or so of Union Carbide's exploration (which began in mid-1957) attention was devoted solely to such igneous, occurrences. A landmark paper by Bramlette and Posnjak (1933) heralded the potential significance of the occurrence of zeolite minerals as alteration products of vitric ash and similar materials. In the summer of 1958, full attention was directed by Union Carbide to the search for deposits of this type in the western United States. Since then, such exploration has been continuous by both commercial firms and private parties. The future economic potential for natural zeolite deposits seems to be restricted to those of the "open-and-closed system" types as described by Sheppard (this chapter). Therefore, this and the following discussions will concentrate upon these types; the other types of zeolites in sedimentary rocks (e.g., deep-sea sediments, burial metamorphic, and hydrothermal) will be, for the most part, ignored. Despite the relative cheapness of natural zeolite deposits as compared with the cost of synthetic molecular sieves, there has been minimal development of zeolite mining in the US over the past 25 years or so. Mumpton (this chapter) discusses the present commercial utilization of natural zeolites and their future potential in detail, but perhaps the following will serve as useful background. In the early days of synthetic molecular sieve research and production, the efforts were concentrated largely upon such high-value applications as physical separation of components in a stream (based upon molecular size and geometry) and in catalysis. Due to a number of reasons (some of which are difficult for an outsider to understand), natural zeolite ores (beneficiated or not) have not made substantial inroads upon the use of the higher-priced synthetic molecular sieves for the foregoing applications, but this is not to say that such a condition will exist forever. Furthermore, in view of the many other uses which are now known, or which loom in the future, the competitive position of the natural zeolites vs. the more expensive

Jan 1, 1983

By P. W. Bennett, E. M. Elkin

A new technique for the recovery of palladium and platinum and sludge from go12 electrolyte eliminates many of the drawbacks of the zinc-dust cementation process. In the electrolytic refining of gold by the Wohwill method, the electrolyte contains about 100 gpl gold as AuCl, and 100 gpl free hydrochloric acid. Any palladium and platinum contained in impure gold dissolve and accumulate in the electrolyte. When their concentration approaches that of gold, it becomes desirable to discard the electrolyte and to recover the gold and the palladium and platinum. As practiced at Canadian Copper Refiners until recently, discarded electrolyte was treated with sulfur dioxide to precipitate the gold. 2AuCl3 + 6H2O + 3SO2 —2Au + 6HC1 + 3H2SO4 The gold precipitate was filtered off, washed with water, and melted with scrap anodes. The wash water was added to the gold-free filtrate and treated with zinc dust to cement the palladium and platinum. PdCl2 + Zn — Pd + ZnCl2 PtCl4 + 2Zn—Pt + 2ZnCl2 The precipitate was separated and sold as Pd-Pt concentrate, and the barren filtrate and wash water were discarded. The receipts of palladium and platinum at this company were too small to warrant their refining. The process suffered from a number of disadvantages. Handling the gold-free solution was disagreeable, as it was laden with sulfur dioxide even after blowing with air overnight. Subsequent treatment with zinc dust was also troublesome. A large excess of zinc dust was required. Spray, acid mist, and vigorous evolution of hydrogen accompanied the reaction. The Pd-Pt precipitate was grossly contaminated with occluded unreacted zinc and with yellow granules of sulfur, thought to be formed by the reduction of sulfur dioxide and its derivatives. Repeated boiling of the precipitate with hydrochloric acid and washing with water decreased somewhat, but did not eliminate, the zinc. After drying overnight, the precipitate hardened to a clinkerlike mass that was difficult to grind. Grinding, handling, and packing created heavy dusting. Even weighing in an analytical balance generated dust, indicating that the powder was easily charged with static electricity. The total palladium and platinum content of the powder varied from 56 to 72 pct, with an average of 65 pct. The powder dissolved in aqua regia with difficulty, leaving a small amount of insoluble residue. However, the main drawback of the process was the strongly hygroscopic Pd-Pt product. The powder showed a marked though erratic increase in weight and a corresponding decrease in assay on exposure to air, even during the course of laboratory analysis. Such changes were the source of disagreement between Canadian Copper Refiners and the buyers of concentrate. The cause of the change in weight is believed to be hydrogen, liberated by the action of zinc dust on hydrochloric acid. Some of this hydrogen was adsorbed so strongly by the precipitate that it could not be driven off during the drying. On exposure to air it oxidized catalytically, forming water. Experiments soon showed that the entire process of treatment of discarded electrolyte then in use would have to be changed. A small quantity of apparatus was moved into the gold room, and experimentation was held to a minimum compatible with the development of a new process. PALLADIUM AND PLATINUM PRECIPITATION It was thought that zinc could be replaced with a reagent other than a hydrogen-evolving metal. Semiquantitative experiments showed that platinum and palladium could be precipitated completely from the gold-free solutions with such well-known reagents as sodium formate, formic acid, formaldehyde, and paraformaldehyde. Sodium formate was the preferred reagent, since the other three are volatile and somewhat toxic. The gold-free solutions used were those saturated with sulfur dioxide, partly freed of sulfur dioxide by aerating overnight, completely freed by boiling, as well as strongly and weakly acidic, neutral, and alkaline solutions. The reactions are complex and can be represented by these over-all equations: PdC1, + HCOONa — Pd + NaCl + HC1 + Co2 PtCl4 + 2HCOONa — Pt + 2NaCl + 2HC1 + 2CCX, Strongly acidic solutions required as much as five times the theoretical amount of sodium formate as did solutions neutralized to pH 4.5. Increasing the pH decreased the consumption of

Jan 1, 1965

By Howard Scott

Manganese being perhaps the least expensive of the metallic alloying elements that can be advantageously added to iron in considerable quantities, the basic characteristics of its alloys with iron are properly receiving much attention at present. In the course of a dilatometric investigation of this system several years ago, the writer observed certain transformation phenomena not found in other iron-base alloys. The interpretation of those effects was not evident from the information then available, but recent X-ray studies clear up at least one anomaly and permit a more satisfactory description of the results than would have been possible otherwise. Aside from the new phenomena observed, the effect of manganese on the Arg transformation is of timely interest because of its bearing on the critical compositions of austenitic alloys, the applications of which are now being greatly extended. It is known that the properties of these alloys are unstable unless the As transformation occurs at a tem-pcrature considerably below atmospheric and that manganese is very effective in depressing the temperature of this transformation. The writer aims to establish a simple general relation which expresses the location of Ar3, quantitatively in terms of the content of the common alloying elements used in steel. A step in that direction is taken here. Early dilatometric investigations1 indicated that only one transformation other than the eutectoid A1 occurs in the high-iron alloys of the iron-manganese system. Dejean represents the Arg point as falling to 0" C. with a manganese content of 11 per cent and carbon content of between 0.30 and 0.40 per cent. Esser and Oberhoffer," sing alloys low in carbon (under 0.03 per cent), arrived by extrapolation at 14 per cent for the manganese content at which As is depressed to 0" C. Not until both low carbon contents and alloys having a manganese content

Jan 1, 1931

By John Wulff, Richard P. Seelig

The importance of the pressing operation in the forming of articles by powder metallurgy depends to a great extent on the type of product to be made. While in some few cases the pressing is merely a means of compacting loose powder particles into a solid mass preliminary to a sintering treatment, in most applications it constitutes a molding operation with the purpose of shaping the raw material in powder form into a certain predetermined, accurately defined part not altered in shape by subsequent sintering. In still other cases, no pressing at all but sintering in molds gives useful articles. A limited number of products are made by the simultaneous application of pressure and heat. The factors that control the product of the pressing operation are raw material, lubricant, type, size and shape of die and compact, magnitude and time of application of pressure, as well as temperature of pressing. All such factors need to be controlled; yet, depending on the function of the pressing operation, greater emphasis may be placed on processing factors other than the pressing operation. In any complete discussion of pressing, subsequent sintering cannot be disregarded. For the sake of brevity, the present paper has been limited to the mechanics of pressing and only occasionally refers to sintering. For the same reason, hot-pressing has been omitted as beyond the scope of this paper In any survey of the literature on the pressing of metal powders, the 1938 paper of Balshinl on the theory of the process of pressing deserves mention. The first attempts at an interpretation of pressing phenomena were made by Balshin' and RakovskL2 The experimental results of both are of great interest. Since the experimental results are not described, the work was repeated, using our own interpretation of the possible techniques, and is reported in the following pages. The basic theory of Balshin,' based on a hydro-dynamic analogy, however, leads to hut another way of plotting density and pres- , sure against height of a pressed compact. Since it does not give any new insight into the phenomena, nor account for the influence of side-wall friction, a discussion of the theory has been omitted from this paper. Density Gradients in Compacts The process of pressing metal powders in a die (disregarding for this consideration the powder filling and ejection operations) may be divided into three phases: (I) packing, (2) elastic and plastic deformation, (3) cold-working with or without fragmentation. It must be emphasized that these three steps do not follow each other in sequence; on the contrary, in practice

Jan 1, 1946

By N. J. Grant, B. C. Giessen, R. Koch

The system Nh-Ir was investigated over the complete concentration range by metallography and X-my techniques, using forty one alloys. The solubility limits of terminal and intermediate phases and the solidus temperatures were determined. Five intermediate phases were found: a Nb3Ir, cubic, Cr3O type; tetragonal, ofecr thorhomhic, isostruc-turn1 with (ta-Rh); and a Nhlr3. cubic, AuCu, type. a Nb3lr and a Nbfr3 melt congruently; three eutectic and three pentectic reactions occur. The phase diagram of the Nb-Ir system had not been fully treated in the literature; only surveys of intermediate phases were found.1"5 In this study, the details of the phase boundaries were investigated as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS The experimental procedures such as arc melting of powder compacts, heat treatments, solidus measurements, X-ray, and metallographic observation were identical with those used in the work on the Nb-Rh phase diagram.&apos; They will therefore not be repeated here except where the conditions differed. The purity of the niobium powder was as stated in Ref. 6; the iridium powder of 99.9+ pct purity from J. Bishop and Co., Malvern, Penn., did not contain impurities exceeding 100 ppm, except rhodium (200 ppm). The melting points and vapor pressures of both elements are very similar. This fact contributed to a very small weight loss on melting and facilitated preparation of homogeneous alloys. As shown in Ref. 6 for Nb-Rh, no oxygen pick-up exceeding 200 ppm had to be considered; this was regarded as valid also for Nb-Ir. A total of forty one alloys were used in the determination of the phase diagram; their concentrations are shown in Fig. l, which presents the phase diagram. The concentration limits as determined by the weight-loss method averaged <0.2 at. pct, and never exceeded 0.5 at. pct. Heat treatments were carried out as described in Ref. 6. Depending on the concentration, only tantalum, tungsten, or iridium containers were employed, avoiding oxide crucibles altogether. Alloys from 0 to 25 and from 65 to 100 at. pct Ir were homogenized at 2095°C for 15 hr, intermediate compositions from 25 to 65 at. pct Ir for 65 hr at 1780°C. A typical annealing-time schedule is presented in Table I. Solidus points were measured as described in Ref. 6 with the modification that samples rich in niobium were held between pieces of tantalum foil and samples of high iridium concentrations were held between rhenium platelets or in iridium wire. After each run it was ascertained metallographically that no reaction with the holder had occurred. Rhenium was selected as holder material after it had been shown in separate tests that the melting points of Re-Ir alloys rise continuously from 2440°C. Metallographic examination was carried out as described in Ref. 6, and the same procedure and etchants were used successfully. While metallographic discrimination between a Nb3lr and o was easily possible, X-ray diffraction was necessary to separate al and ct2. X-ray powder patterns were taken and evaluated as for Nb-Rh6 yielding the error limits indicated in Table 111, to be introduced later. For the determination of the invariant reactions and phase boundaries, the same techniques as for Nb-Rh6 applied. The general accuracy of invariant concentrations is regarded as somewhat higher than for Nb-Rh due to the small slope of most solvus lines.

Jan 1, 1964

OF the many categories into which scientific knowledge has been arbitrarily divided, the one that has proved most applicable in our attempts to gain an insight into the details of steelmaking processes is physical chemistry. To the young metallurgist who has only recently survived a college course in this subject, the application of its principles to reactions in liquid steel should not be difficult. The many excellent textbooks of physical chemistry1 provide ample material on the principles of this subject for the student of steelmaking processes; yet with- out exception those texts draw the greater part of their illustrative material from room-temperature data. It is the purpose of this chapter to provide a concise review of the principles of physical chemistry that have proved useful in studies of steelmaking and at the same time to present some of the data that are essential to the application of physical chemistry to reactions at high temperatures. Certain parts of physical chemistry require rather formidable mathematics for their complete development but in the main those applications in which we are here interested can be ex- pressed in fairly simple terms. Many of the equations are logarithmic, and we shall use the symbols In X and log X to represent respectively the natural and the common logarithm of X. The two are related by In X = 2.303 log X. Logarithms may be read from a good slide rule with sufficient accuracy for our purposes. In a few spots a knowledge of the calculus will be, helpfu1. MATTER Innumerable forms of matter may be recognized, and these may be converted by chemical processes into others, as ore, coke, and air are converted into iron, slag, and gas. Whenever such a change occurs there is a corresponding change in

Jan 1, 1951

By M. Garfinkle, W. D. Klopp, W. R. Witzke

The tensile properties of binary W-Re alloys containing up to 33 at. pct Re were determined at temperatures from 78" to 3630°F. Elongations as high as 260 pct were observed in electron-beam-melted tungsten containing 23 at. pct Re when tensile-tested at 3630°F after a 1-hr anneal at 3090°F. All alloys tested under these conditions with rhenium contents between 20 and 28 at. pct exhibited elongations of at least 200 pct. These alloys also showed enhanced grain growth rates. The values of strain-rate sensitivity ranged between 0.2 and 0.3 for the alloys exhibiting high elongations. Houlezler, for swaged alloys tested just above the re-crystallization temperature, strain-rate sensitivities as high as 0.8 were observed. The high-temperature strengths of the high-rhenium-content alloys were also less than those of alloys with intermediate rhenium contents. ALLOYING with rhenium has two distinct effects on the mechanical properties of tungsten. One effect occurs in dilute solid solutions and is most clearly seen in the lowering of the hardness and of the ductile-brittle transition temperature at about 5 at. pct Re.1-3 The second effect occurs in the concentrated solid solution at about 25 at. pct Re, and is characterized by twinning and a larger decrease in the ductile-brittle transition temperature. An aspect of the high-rhenium-content alloy which has received little attention is the higher-than-usual tensile ductility at 3500°F.3 Anomalous high ductility has been observed in several other alloy systems. usually associated with a phase transformation or a solid-solubility limit.4&apos;5 The phenomenon is now commonly termed superplasticity. High-strain-rate sensitivities6 and grain boundary sliding7 have been reported for materials that undergo superplastic deformation. Also, it has been found that superplastic materials usually have a very fine grain structure (less than 10 pm).8 and it has been proposedg that such a structure alone is sufficient for superplasticity. The purpose of the present study was to further characterize the high-temperature tensile properties of W-Re alloys to determine the conditions under which they might be superplastic. Tensile and selected strain-rate sensitivity tests were conducted on alloys containing 0 to 33.3 at. pct Re at temperatures from 78" to 3630°F. Grain-growth rates were also determined on most alloys at 3630°F. Fig. 1 indicates the compositions evaluated and their locations relative to the solvus line in the tungsten-rich end of the W-Re phase diagram. Twelve binary W-Re alloys containing up to 33.3 at pct Re were double electron-beam-melted and subsequently fabricated to 0.3-in. rod by extrusion and swaging. The starting materials were commercial powders of tungsten and rhenium with impurity levels as listed in Table I. The various blended W-Re compositions were hydrostatically pressed at 70 ksi. The pressed bars were drip-melted into 1.5-in.-diam ingots and then remelted into 2-in.-diam ingots at a chamber pressure of 10~5 torr. The ingots were canned in molybdenum and extruded to round bar at a reduction ratio of 6:l. The alloy extrusions were swaged to about an 80 pct reduction at 2100" to 2900°F. Buttonhead tensile specimens with a reduced section diameter of 0.16 in. and a gage length of 1.0 in. were centerless-ground from the swaged bars

Jan 1, 1970

By L. L. Swift

.It the present time there are four base metals being used for automo-tive bearing alloys. Of course there are numerous variations in the amounts of alloying elements added to each base metal and nearly all of these alloys have the conventional, if not classical, duplex structure; that is, they are composed of a hard constituent embedded in a soft matrix. The well-known theory is that the former will wear well, while the latter will be plastic enough to allow the bearing to be broken in and conform to the contours of the shaft. The requirements of the modern bearing have been most aptly described by W. M. Corse: In order to meet the engineering demands of today a good bearing metal must be able to carry the weight of the shaft and stand up under steady or suddenly applied loads, or even blows ill sorne types of service. A certain amount of plasticity is desired to compensate for minute irregularities in the shaft or bearing surface, and to permit yielding, thereby avoiding dangerous stresses in bearing and shaft and pre-venting overheating and rapid wear of parts. Less plasticity is required in a bearing tuetal if the surfaces of bearings and journals are machined accurately, aligned, and kept in alignment. It is desirable, of course, that a bearing metal have a low coeffi-cicnt of friction. Under most operating conditions the friction depends on the unit, pressure of the bcaring, the speed, the temperature, and the properties of the lubricant. A good bearing metal must have a low rate of wear to reduce the necessity for frequent replacements, and adjustment of the bearings. It must wear more rapidly, however, than the journal or shaft running on it, because replacement of the journal or shaft is more difficult and costly than replacement of the bearing.&apos; The hardness of the bearing alloy is a property closely related to several of the foregoing. With a duplex microstructure, the measurement of hardness with any of the usual commercial devices means little. The Bierbaum method of measuring the hardness of the individual canstituents was developed to fill this need. MICROCHARACTER The Bierbaum MicroCharacter~,~ measures the scratch-hardness of a solid by pulling a weighted diamond point over the surface. The diamond point is ground so that it is the corner of a cube, and Mounted

Jan 1, 1939

By L. L. Swift

.It the present time there are four base metals being used for automo-tive bearing alloys. Of course there are numerous variations in the amounts of alloying elements added to each base metal and nearly all of these alloys have the conventional, if not classical, duplex structure; that is, they are composed of a hard constituent embedded in a soft matrix. The well-known theory is that the former will wear well, while the latter will be plastic enough to allow the bearing to be broken in and conform to the contours of the shaft. The requirements of the modern bearing have been most aptly described by W. M. Corse: In order to meet the engineering demands of today a good bearing metal must be able to carry the weight of the shaft and stand up under steady or suddenly applied loads, or even blows ill sorne types of service. A certain amount of plasticity is desired to compensate for minute irregularities in the shaft or bearing surface, and to permit yielding, thereby avoiding dangerous stresses in bearing and shaft and pre-venting overheating and rapid wear of parts. Less plasticity is required in a bearing tuetal if the surfaces of bearings and journals are machined accurately, aligned, and kept in alignment. It is desirable, of course, that a bearing metal have a low coeffi-cicnt of friction. Under most operating conditions the friction depends on the unit, pressure of the bcaring, the speed, the temperature, and the properties of the lubricant. A good bearing metal must have a low rate of wear to reduce the necessity for frequent replacements, and adjustment of the bearings. It must wear more rapidly, however, than the journal or shaft running on it, because replacement of the journal or shaft is more difficult and costly than replacement of the bearing.&apos; The hardness of the bearing alloy is a property closely related to several of the foregoing. With a duplex microstructure, the measurement of hardness with any of the usual commercial devices means little. The Bierbaum method of measuring the hardness of the individual canstituents was developed to fill this need. MICROCHARACTER The Bierbaum MicroCharacter~,~ measures the scratch-hardness of a solid by pulling a weighted diamond point over the surface. The diamond point is ground so that it is the corner of a cube, and Mounted

Jan 1, 1939

By R. B. Yerxa, C. F. Green, H. O. Hofman

MASSACHUSETTS INSTITUTE OF TECHNOLOGY, In refining copper, the metal is melted down in a reverbera tory furnace in a more or less oxidizing atmosphere and then further subjected to an oxidizing smelting in order to eliminate the common impurities, most of which have a stronger affinity for oxygen than has copper. In these operations some of the copper is oxidized to cuprous oxide and dissolved by the metal bath. When the quantity of dissolved cuprous oxide has reached about 6 per cent, the metal is said to have been brought to " set-copper." A button-sample will show a depressed surface and, when broken, a single bubble at the apex of the depression; the fracture will be brick-red and dull. It is essential to carry the oxidation to this point in order to know that the impurities have been oxidized as far as it is possible under the given working-conditions. Nearly all the cuprous oxide of the set-copper is now reduced to the metallic state by poling, when "tough-pitch" copper will be obtained. A button-sample will show a flat surface. Upon breaking, it will be found that the former bubble has disappeared and that the fracture has become rose-colored and shows a silky luster. The quantity of cuprous oxide allowed to remain in the copper will vary with the impurities still present in the metal and with the degree of pitch that it is desired to reach. It is essential for the general physical and the mechanical properties of the resulting copper that such impurities as arsenic, antimony, bismuth, lead shall be present in the oxidized state, as they are

Jan 1, 1904

By W. A. Backofen, D. Lee

The deformation of textured sheet of titanium and several of its all-a (hcp) alloys was investigated with two kinds of experiments: tension testing along different directions in the plane of the sheet, and combined-stress loading along the principal axes of anisotropy (the rolling and transverse directions). Texture and plastic anisotropy were evaluated with pole figures and by measurement, as a function of orientation, of the tensile transverse-strain ratio, or R parameter. The results as a whole can be rationalized qualitatively with the present understanding of deformation mechanisms in titanium. Quantitative agreement between the orientation dependence of tensile yield strength and the Predictions of continuum ANISOTROPY in the properties of engineering materials is more the rule than the exception because anisotropy in structure is so common, and the one generally follows the other. Two broad categories of structural anisotropy are represented by mechanical fibering and crystallographic texture. The former is important in many aspects of fracture.&apos; The latter has more significance for yielding and plastic deformation, theory, using the R measurements, was relatively poor. However, in tension-tension quadrants of the yield-locus diagrams, the difference between theory and experiment was hardly more than 10 pct. The maximum texture-hardening effect was found in a 4Al-1/4O2 alloy to be nearly 50 pct. In the compression-compression quadrant, {1012} deformation twinning prevented the locus from expanding much beyond the Position predicted for isotropic material. With increasing temperature the trend in R was downwards, approaching unity (isotropy) near the a-transus temperature; an accompanying development was large amounts of neck-free extension. which are of special concern in this paper. The tendency has been to view crystallographic texture more as a liability or curio than as an asset. The prominent exception is found in silicon-ferrite sheet for power-transformer cores, which is processed to develop a new optimum texture for high electrical efficiency. Yet it should be possible to find other examples, involving other kinds of properties. More specifically, there is good analytical reason to expect improved combined-stress yielding resistance in suitably textured material,2,3 and it has now been shown by experiment that texture hardening or softening is a potentially useful phenomenon in certain engineering devices and processes.&apos;-I To date, work has included measurements of the transverse (width to thickness) strain ratios in the

Jan 1, 1967

By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.&apos; Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.&apos; STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

By C. L. Bulow

In this discussion of stress-corrosion cracking of widely used copper-base alloys, no attempt has been made to prepare an extensive review or bibliography since this has been quite ably covered by other investigators. An excellent bibliography was published by H. P. croft(1)2 in connection with his studies of stress-corrosion cracking in mercurous nitrate solutions and his analyses of the magnitude and distribution of stresses in brass parts. We are reporting on a few of the results which have been obtained to date in connection with an ammonia vapor test and an alternate immersion test. These are accelerated corrosion tests for determining the susceptibility of materials to failure from season or stress-corrosion cracking due to the presence of moist ammonia and oxygen so prevalent in nature. Our experiences with the ammonia test seem to indicate that it is a more searching test, than the mercurous nitrate test.

Jan 1, 1945

By L. S. Darken

A quadratic formalism is developed lor the representation of the excess free energy, and of the activity coefficients of each component of a ternary system in the vicinity of a single component selected as solvent. This formalism, in contrast to the e formalism, is thermodynamically consistent at .finite concentrations. Numerous specific systems are used as illustrations, with cross checks where possible; these systems are Fe-C-X systems in the vicinity of 1600°C and include practically all those for which reliable data are available. It is shown that this formalism is usually quite adequate to rebresent available data up to a solute concentration of 20 to 30 at. pet. It is hoped that the formalism here presented may prove useful for the treatment and tabulation of data on ternary and multi-component solutions. SINCE, as discussed in a prior paper,&apos; we do not as yet have an adequate basic understanding of the nature of binary metallic solutions, we cannot hope to be in better position for ternary and multicomponent systems. However, the accumulation of thermodynamic data on ternary and multicomponent metallic solutions has led to an urgent need for a rational formalism for the presentation and use of such data. Notable attempts to represent the isothermal isobaric thermodynamics of ternary solutions were made by Benedict et 01.&apos; and by Wohl.3 These attempts were directed toward developing an analytic expression adequate to encompass the entire ternary triangle, primarily for organic systems; they generally involve the power-series approach, which has been shown&apos; to be inappropriate, in general, even for binary metallic systems. On the other hand, interest in the thermodynamics of ternary and multicomponent metallic solutions has tended to focus either on general thermodynamic relations4-10 over wide compositional ranges, or on cases where one or more components have been at rather low concentration. This latter approach has been followed by Wagner,= by chipman,11 and by Alcock and Richardson,12 and more recently in many publications by the same and other authors. It has already been shown&apos; that the thermodynamic behavior of binary metallic systems is, in general, relatively simple only in the terminal regions. Hence, it would appear that any approach, at this time, to a simple formalism for ternary and multicomponent systems must, a fortiori, be limited to the vicinity of the major component or solvent. The present treatment is aimed to be useful for a given solvent with moderate solute concentrations ranging up to 20 or 25 at. pet and in exceptional cases to considerably higher concentrations. In order to achieve even this modest objective, it is necessary that any appropriate formalism have built into it 1) a thermodynamic consistency (at least within the desired degree of approximation), and 2) an approach at infinite dilution to Raoult&apos;s law for the solvent and to Henry&apos;s law for each solute. Let us first formulate the condition of thermodynamic consistency for a ternary system. Under isothermal isobaric conditions, we may write for the molal value G of any extensive function dG - C1 dN1 + G2 dN2 + G3 dN3 [l] where the G&apos;s are the corresponding partial molal quantities and the N&apos;s are the atom fractions. Taking component 1 as the solvent, this relation may be rewritten in terms of the independent variables N2 and N3

Jan 1, 1968

By P. W. Bakarian, C. H. Mathewson

THE greater part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation, in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)1 by geometrical analysis identified the {102} ? plane in magnesium as the twinning plane, Schiebold and Siebel (1931)2 confirmed this twinning plane, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also reported twin formation in a secondary role on the {101} plane. Schmid (1931)3 summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-i.e., the critical resolved shear stress-were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C., at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the original specimens of circular section had been

Jan 1, 1943

By J. H. Craig

As a result of information that the Navy Department was questioning the advisability of raising the maximum allowable exposure temperature for zinc-coated steel parts from 500 to 750 F., it was decided to make a series of high temperature tension tests on several types of uncoated and zinc-coated steels. The objective was to determine at what temperature intergranular penetration of galvanized steel by zinc might take place under conditions of rapidly applied stress and temperature. Tests were conducted in the range from room temperature to 1400 F. In this range, low-carbon and high-carbon steels did not suffer any adverse effects due to zinc coatings. In fact, at 1400 F. the zinc coatings appeared to have a beneficial effect. In stainless steel, the coating had no effect up to 1000 F. Above this temperature, the zinc coating appeared to cause a marked loss in ductility and a less pronounced loss in strength. There was no visible evidence of zinc penetration of the stainless steel structure, but it was assumed that this was the cause of the adverse effect.

Jan 1, 1945

BASIC open-hearth slags have no obviously unique features when compared with slags from other metallurgical operations. Open-hearth slags form and exist at temperatures ranging from 2500 to 3100 F (1370 to 1700 C). In the course of an open-hearth heat, the liquid slag changes slowly and continuously in chemical analysis-the changes reflecting changes in temperature, changes in metal analysis, solution of charged materials, solution of feed additions, and solution of refractories. Through- out the process, the slag performs specific primary functions that are responsible for a large measure of the technical and economic importance of basic open-hearth steelmaking. It is intended in this chapter to present the chemical reactions by which the primary functions of basic open-hearth slags are carried out, to describe the physical and chemical principles governing the extent to which these reactions proceed and can be regulated, and finally to indicate the limitations imposed on other features of the process by the fulfillment of the primary functions. Basic open-hearth slags perform three primary functions. First and foremost, the slag provides a means of removing phosphorus from the liquid metal. The ability to remove phosphorus is largely responsible for the widespread use of the basic open- hearth process. Second, the slag serves as a controlling factor in transferring the oxygen required for the other oxidizing reactions. Third, the slag provides a means of eliminating some sulfur from the open-hearth bath. While the extent of sulfur removal is not comparable to that of phosphorus, the ability to remove some sulfur contributes much to the value of the process. The effectiveness with which the slag fulfills its functions varies with temperature and composition. Since operating temperatures are fixed largely by the specified nature of the product and the equipment, the speed and extent to which the functions of the slag are carried out depend largely on its composition. The necessity for regulating slag composition to accomplish the re-

Jan 1, 1951

By W. L. Fink, R. S. Archer

THIS paper describes results obtained on aluminum-beryllium alloys and aluminum-beryllium-copper alloys in the preparation of which aluminum of 99.95 per cent. purity was used. The constitution and structure of the high purity binary alloys are given. The aluminum-beryllium eutectic occurs at 0.87 per cent. beryllium and 645° C. The solid solubility of beryllium in aluminum at 631° C. is 0.05 per cent. beryllium, and at room temperature is less than 0.013 per cent. beryllium. The densities of the alloys are substantially the same as the values calculated on the assumption that the densities of the elements are not changed by alloying. All of the alloys age-harden at room temperature after a solution heat treatment, and the chill cast aluminum-beryllium-copper alloys age-harden at room temperature without a prior solution heat treatment. Hardness and tensile properties are given. Salt spray corrosion tests on sheet specimens are described. It is shown that beryllium does not lower the corrosion resistance of aluminum to salt spray provided the alloy has received a solution heat treatment. COMMERCIAL POSSIBILITIES OF BERYLLIUM ALLOYS Beryllium has certain properties such as low density, high hardness, good corrosion resistance, low thermal expansion and fairly good electrical conductivity, which would indicate that it is worthy of consideration as an ingredient of light alloys. It was not until recently, however, that beryllium could be produced with sufficient ease to encourage research along this line. The production of beryllium by electrolysis from a fluoride bath has now developed to the stage where it could be used commercially if there were sufficient demand for the element. Claims made in certain newspapers and technical articles in regard to the strength and corrosion resistance of the aluminum-beryllium alloys are not justified by experimental results. Moreover, beryllium is an expensive metal ($200 a pound at the time this work was done) and, on account of the nature of its ore and the consequent difficulty of its extraction, it will in all probability continue to be a relatively expensive metal, although the cost would undoubtedly be a great deal less than $200 a

Jan 1, 1928

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-A1 alloys has been measured up to the solubility limit for formation of aluminum nitride using the Sieverts method. The activity coefficient of nitrogen decreases slightly with increasing aluminum content in the range of 0 to 4 wt pct Al. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from fhe elements dissolved in liquid iron has been determined to be: ?F" = -59,250 + 25.55 T in the range from 1600º to 1750ºC. The solubility of nitrogen in liquid iron alloys and the interaction of nitrogen with dissolved alloying elements in liquid iron have been the subject of a number of research investigations.&apos; Most of this work, however, has been reported for concentrations well below those necessary for the formation of the alloy nitride phase. Data in the concentration region near the solubility limit of the alloy nitride, particularly for systems exhibiting stable nitrides, are important in evaluating the denitrifying power of various alloying elements. They are also useful in determining the stability of a given nitride if it is to be used as a refractory to contain liquid iron alloys. In view of the importance of aluminum as a deoxidizing agent in commercial steelmaking and the fact that its nitride, AIN, is a highly stable compound and has merited some consideration as an industrial refractory, the following investigation was undertaken. The use of the Sieverts technique provided a measurement of the equilibrium nitrogen solubility in liquid Fe-A1 alloys as a function of nitrogen gas pressure up to 3.85 wt pct A1 in the temperature range of 1600º to 1750°C. The values obtained by the Sieverts method were checked by means of a quenching method in which liquid iron was equilibrated with an A1N crucible under a known partial pressure of nitrogen gas, and the solubility of A1N in liquid iron determined by chemical analysis. EXPERIMENTAL PROCEDURE The theoretical considerations involved in determining the solubility product of a solid alloy nitride phase in liquid iron by measuring the point of departure of the nitrogen gas solubility from Sieverts law have been discussed by Rao and par lee.&apos; The principal problem is to determine the variation of nitrogen solubility in an alloy as a function of the pressure of nitrogen gas over it with sufficient precision to establish the break point in the curve at the solubility limit of the alloy nitride phase. A fairly large number of data points are required to do this. A second problem is the determination of the composition of the precipitated solid nitride phase. This is necessary in order to define completely the thermodynamic relationships. The Sieverts apparatus used to make the nitrogen solubility measurements in this investigation is of essentially the same design as that described by Pehlke and E1liott.l The charge materials were Ferrovac-E high purity iron supplied by Crucible Steel Co. and 99.99+ pct pure aluminum. Recrystal-lized alumina crucibles were used, and were not attacked by the liquid alloys. The hot volume of the system which was measured for each melt ranged from 46 to 50 standard cu cm and was found to decrease linearly with decreasing pressure and with increasing temperature. The temperature coefficient of the hot volume at 1 atm pressure of argon gas was essentially constant for all experiments at a value of -6 X 10-3 cu cm per "C. The melt temperature was measured with a Leeds and Northrup disappearing filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature scale was calibrated against the observed melting point of pure iron taken as 1536°C. The emissivity of all melts was assumed to be that of pure iron, taken as 0.43. The charge weights ranged from 110 to 140 g and the range of aluminum contents covered was from 0 to 3.85 wt pct. Aluminum additions were made as 12 to 15 wt pct A1-Fe master alloys previously prepared in the system under purified argon. The compositions of the master alloys were checked by chemical analysis and found to be in agreement with the charge analyses. Vertical cross sections of the master-alloy ingots were used as charge material for the equilibrations in order to minimize the effect of any segregation which might have occurred during solidification of the master alloys. Determinations of the solubility product of

Jan 1, 1964

By Z. F. Oszter

This paper discusses the materials handling problems encountered in cement plants in the areas of raw and finished product grinding and cement storage. It illustrates by examples taken from actual installations, how optimum feed rate is maintained in grinding circuits with properly applied bin dischargers (vibrating hoppers, Mexican feed boxes and aerated bin bottoms) for materials with high moisture content and/or difficult handling characteristics. Initial operating problems with the equipment will be discussed and maintenance requirements will be indicated for comparison purposes. In a modern cement plant, properly functioning bins and feeders are as essential as process control, for no process control system, however sophisticated, can perform efficiently if raw materials do not flow into the plant processing facilities at the required time and rate. Most materials used in the manufacture of portland cement - such as silica sand, iron ore fines, crushed limestone, gypsum, clinker or cement itself-have difficult handling characteristics under specific conditions. High moisture content or even dampness due to condensation may create bin hang-ups, arching and ratholing, all of which result in improper functioning of the feeders or proportioning equipment. The occurrence of these problems in existing cement plants spurred a search for the corrective devices discussed in this article. The equipment investigated included bin dischargers in the form of vibrating hoppers for moist raw materials, Mexican feed boxes for clinker and aerated bin bottoms for cement. Operating experience with different types of bin dischargers showed that the actual performance of some did not come up to the expected level under prevailing operating conditions. The aim of this paper is to record the results of this experience and there- by aid designers and/or operators in selecting the most suitable equipment for their requirements. BIN DISCHARGERS (GENERAL) A discharger is a device that causes stored solids to flow out of a hopper without metering the rate of flow as a feeder does. The investigation discussed here encompasses the following types of bin dischargers used in a cement plant: (1) vibrating hoppers (horizontal motion), (2) whirlpool hoppers (horizontal and vertical motion), (3) aerated bin bottoms (air fluidization), and (4) Mexican feed boxes. Most of the bins used in the cement industry are of the plug flow type. Raw materials with difficult handling characteristics such as high moisture content may cause flow problems when fed through small openings (12 x 18 in.), even if two walls of the bin are vertical.&apos; The most appropriate solution to these flow problems would be the installation of separate mass flow bins for the different materials such as silica sand, iron ore fines, crushed limestone and gypsum, with each bin correctly designed from test data obtained by measuring the flow properties of representative samples. However, limited storage capacity and plant space usually preclude this approach. Quantitative design of bins for flow based on measured flow properties of representative samples of the bulk solid to be handled is no longer an "engineering art," thanks to the basic research done on the flow of bulk solids in bins during the last decade.2, Where space limitations exist, however, or where improvements are being sought for equipment already installed, bin dischargers offer a satisfactory solution to flow problems. They can be applied effectively under flat-bottom bins or mounted to existing plug-flow bins with very little modification to these facilities. In both the foregoing cases, plug flow will be maintained, but the flow channel will be considerably increased so that it is larger than the discharger&apos;s bin-side diameter, and material flow can be sustained if the discharger is correctly selected. The main purpose of a bin discharger is to draw the bulk solids across the whole area of the bin outlet, to make the opening fully effective. As long as the bin-side opening of the discharger is large enough

Jan 1, 1969