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By W. L. Fink, L. A. Willey

DURING the war there was introduced a new higher strength aircraft alloy designated 75S.1,2.3 The properties of this alloy assure extensive applications in both military and commercial aircraft. It is therefore important to understand its limitations as well as advantages. The properties of 75S alloy in the heat-treated tempers, like those of many other aluminum alloys, are affected by the rate of quenching. In general, low quenching rates tend to cause low strengths and to adversely affect the resistance to corrosion. Commercial quenching procedures are usually sufficiently rapid to permit the development of maximum properties. However, in the center of heavy sections, such as large rolled and extruded shapes, the quenching rates may not be rapid enough to develop maximum strength or resistance to corrosion. The investigations of 75S alloy described herein reveal the most critical range of temperature and the effects of quenching sheet and extrusions at different rates through that temperature range, on the tensile properties and resistance to corrosion. PROCEDURE Preparation of Specimens Sheet specimens (3 in. by 9 in.) were prepared from a commercial lot of 75S "as rolled" sheet (0.064 in. thick). The composition° was as follows: Weight Percentage Cu Mn Mg Zn Cr Al with Normal Impurities 1.64 0.16 2.58 5.66 0.27 Remainder The specimens employed for the determination of the time-temperature relations during quenching of sheet were prepared by the following procedure: the hot junction of a 28-ga. iron-constantan thermoelement (asbestos insulated) was brazed to a thin strip of aluminum which was in turn brazed into the end of a 3/16 in. i.d. by ¼ -in. o.d. by 30 in. long aluminum protection tube. Before brazing, the tube was flattened to 0.064 in. thickness over the junction and adjacent lead wires for a distance of 1 ½ in. The flattened end of the tube was fitted into a slot cut from one edge to the center of the 3 in. by 9 in. by 0.064 in. sheet and brazed into place. The brazed joint was dressed to the thickness of the sheet and the entire specimen buffed to approximately the brightness of "as rolled" material. Because of the brazing operations required, these specimens were prepared using 3S alloy. For the investigation of quenching rates in heavy sections, there were used 75S extrusions which had compositions similar to that of the sheet. The specimens consisted of 14 in. lengths of ¾ in., 2 in., 3 in. and 4 in. diam cylindrical rods and a roughly rectangular extruded section which was approximately 4 in. by 7 ½ in. Thermocouples were peened into the bottoms of 1/8 in. diam wells drilled into one end and parallel to the axis to a depth of

Jan 1, 1947

By M. R. J. Wyllie, P. F. Southwick

The importance of the so-called "dirty sand" or "conductive solids" problem in electric log interpretation was first stressed in a paper presented in 1949. Since that time the problem has been generally recognized as a most serious one. Several research papers bearing on the theory of the effects of clay contaminants on reservoir rock resistivities have appeared. These papers, while contributing to the theory of the problem, have not offered any practical solution. In the present paper an experimental investigation has been made of the effects of ion-exchange materials on the electrical properties of natural and synthetic porous media. The method used to make synthetic dirty sands is entirely novel and has proved a valuable guide to a better understanding of the properties of dirty sands generally. The effects of ion-exchange materials on both the resistivity and self potential (S.P.) logs have been examined. From the data obtained it has been possible to formulate a simple, practical method whereby electrical logs of dirty sands can be qualitatively interpreted. The method is in all essentials identical to that presently in use for interpreting clean sands. New light has also been thrown on the significance of the term formation factor when it is applied to dirty sands. In 1949 a paper was presented1 which showed that the presence of so-called "conductive solids" introduced considerable complexities into the analysis of the resistivities of dirty sands, i.e., permeable formations containing clay. The reduction of the self potential (S.P.) resulting from the presence of interlaminated shale or interstitial clay in permeable formations has been discussed by Doll.2,3 Noteworthy papers which dilate further upon the effects of shale and clay on the resistivity of permeable formations are those of deWitte,4,5 Berg,6 Wyllie,7 and most recently, Winsauer and McCardell.8 The last authors have endeavored to elucidate the chemistry of the resistivity phenomena in dirty sands in terms of an adsorption hypothesis. Specifically, they attribute the electrolytic conductivity of shales and clays within a permeable formation to an ionic double-layer effect and, for this reason, regard the term "conductive solids" as a misleading one. Some consideration has been given to the effect of dirty sands on the S.P. by Wyllie7 and by McCardell, Winsauer and Williams." Published work to date has cast light only on certain theoretical aspects of the problems created by the presence of clays and shales within permeable formations. One object of this paper is to describe experiments which serve to elucidate further the theory of the dirty sand problem and particularly the significance of the term "formation factor" as applied to dirty

Jan 1, 1955

By G. K. Manning, A. R. Elsea, A. B. Westerman

A considerable number of high-tem-perature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. .4t the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in vitalliurn after various heat treatments. Howcver, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chro-mium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja and Guertler2 indicated that cobalt and chro-mium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to 85 pct chromium undergo a transformation at [zoo to 12 50 c More recently, Wever and Haschimoto,3 Wever andLange,4and Matsunaga5 carried Out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallogra~hic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Mat-SUnaRa. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these excep-tions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data arid the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitalhum by deter-mining the diagram for the cobalt-chro-mi~m system- Experimental Work For the convenience Of the reader, the diagram as determined by the present investigation is presented in Fig 3. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the melting point for pure chromium is the

Jan 1, 1949

By R. Al-Hussainy, H. J. Ramey

Previous gas well test analyses have been based mainly upon linearizations of ideal gas flow results, although a method for drawdown analysis based upon real gas flow results has been proposed. Linearizations based upon ideal gas flow require estimation of gas physical properties at Tome sort of average pressure, and implicitly involve the assumption that pressure gradients are small everywhere in the reservoir. A new real gas flow equation has been developed by means of a substitution which couples presTure, viscosity and gas law deviation factor. This sub-stitution has been called the real gas pseudo-pressure. Use of the real gas pseudo-pressure leads to simple equations describing real gas flow which do not contain pressure-dependent gas properties, and which do not require the assumption of small pressure gradients everywhere in the flow system. Equations required to determine flow capacity, well condition and static formation pressure from pressure drawdown and build-up tests with the real gas pseudo-pressure concept are presented. Also shown are applications of the real gas pseudo-pressure to back-pressure testing, the gas materials balance and rigorous determination of average gas properties for previous gas flow equations. Included are sample calculations for well test analyses. INTRODUCTION A recent study' of the flow of the transient flow of real gases in ideal radial systems showed that it is possible to consider gas physical property dependence upon pressure by means of a substitution called the real gas pseudo-pressure. The substitution has the advantage that it enables engineering solutions for steady and transient flow of real gases that are more accurate and general than those previously available. The solutions are particularly important for the case of gas flow in tight, high-pressure formations under large drawdowns. Even for more ideal flow conditions, the real gas pseudo-pressure concept leads to important rules for finding average gas physical properties pertinent for older well test analyses. Ref. I provides a detailed study of the theory behind the real gas flow correlations to be used in this paper. The purpose of this paper is to provide necessary engineering forms for use of the real gas flow results, and to illustrate applications. The following considers flow of real gases in an ideal radial flow system. It is assumed that: (1) formation thickness, porosity, water saturation, absolute permeability, temperature and gas composition are constant; (2) gas compressibility and density are functions of pressure as described by the gas law pv = znRT; (3) gas viscosrty is a function of pressure; (4) effective permeability to gas may be a function of pressure to account for liquid condensation; (5) condensate is immobile; and (6) the formation has no dip.

Jan 1, 1967

By Daniel R. Hull

IN 1026 Genders' reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan,3 and by Phillips and Brick,2 so that no resume is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. VAPOR SEGREGATION There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table I, which represents a [ ] cylindrical billet 7 in. in diameter by 5; in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. The lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps up a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By M. G. Driessen

For a number of years the cyclone, familiar to Americans as a dust collector, has been used as a thickener of suspensions at one of the coal-preparation plants of the Netherland State Mines in Limburg. The plant treats nut-size coal at 120 tons an hour in a heavy-medium washer. The diluted medium from the rinsing screens is thickened in cyclones. More recently the cyclone has been adapted to act as a coal cleaner. The principle of the cyclone thickener is the same as that of the cyclones used in industry for catching dust or fine particles suspended in the air or in gases. Generally the latter are more efficient in this respect—the smallest particles that can be caught with reasonable efficiency are considerably smaller than with the cyclone thickeners. The reason is obvious; the ratio of specific gravities between the dust particles in a gas and the gas itself is about 800 times larger than the ratio between, for instance, the specific gravities of shale particles and water. The ratio of the velocities of fall of shale particles (? = 2.5)† in air and in water is as follows: In the range of Stokes: ?air = 93?water In the range of Allen: Wair = 49Wwater In the range of Newton-Rittinger: ?air = 36.6?water The same ratios apply for the velocities in the centrifugal field, from which it follows that it is especially difficult to catch the very fine suspension particles in a liquid. The efficiency of a cyclone thickener depends mainly on the circumferential velocity of the liquid at its innermost radius, because here the centrifugal forces are the highest. However, these velocities cannot easily be calculated, as the flow is three-dimensional, and thus the axial components cannot be neglected .(p. 252, condition 3). We believe that at first a spiral tangential motion along the cyclone wall is created, which causes the inner vortex ascending from the apex of the cyclone (Fig I). At the same time the inner vortex is strengthened by the individual vortices in horizontal planes, and thus a part of the total flow can find another and perhaps quicker way to the outlet. In any case, the exact motion, not only of the fluid but especially of the suspended particles, is so difficult that we have to refer to the experiments to find the exact behavior of this kind of apparatus. Method of Judging PerforMance of Coal Washer Geologists, rather than mechanical en-gineers, would be able to describe the separating or stratifying effect in nature, but even a bather on the shore lying on the soft sand near the sea wonders why all the small sand grains have approximately the same size. A child playing on the border of the river could easily

Jan 1, 1949

By J. Doig, A. A. Bauer, F. A. Rough

AN investigation of the phase relationships between the 6 phases of the uranium-molybdenum and uranium-titanium systems was conducted by studying alloys ranging in composition from uranium-31.5 at. pct Mo to uranium-34 at. pct Ti. A ternary cut showing these phase relationships is presented upon the basis of thermal-analysis data obtained and upon the basis of metallographic and X-ray examination of heat-treated and quenched specimens. Isothermal ternary sections, inferred from phase relationships determined between the two 6 phases, are presented for the uranium-molybdenum-titanium system. In the compositional range investigated, a y-ura-nium solid solution exists at elevated temperatures. At about 900°C the 6-U2Ti phase, with limited molybdenum solubility, forms. Epsilon, a molybdenum-titanium-rich solid solution appears at the same temperature and appears in all phase regions that exist below this temperature except in the terminal 6-phase regions. The y phase is stable to approximately 660°C in titanium-rich alloys; the y and 6-U,Ti phases decompose at this temperature to a uranium in a peritectoid reaction. The y phase in molybdenum-rich alloys of the ternary cut studied decomposes in an apparent eutectoid reaction, at about 593°C, to the 6-uranium-molyb-denum and a-uranium phases. The e phase while present, presumably plays a negligible role in these reactions. Titanium was found to markedly decrease the stability of retained y in these alloys. Age-hardening characteristics developed in titanium-contain ing uranium-molybdenum alloys quenched from 900°C and aged at 500°C are ascribed to decomposition of Y to the a and E phases. INTRODUCTION Alloys of uranium with molybdenum, titanium, and zirconium, respectively, are of great interest because of their potential use as reactor fuels. As a result, this interest extends to the constitution of these alloys, particularly in view of their uniqueness of constitution. In these systems, alone, among known uranium-alloy systems, an intermediate phase forms by direct decomposition of the high-temperature y-uranium phase. As a prelude to possible future alloy development, an investigation has been undertaken of the phase relationships that occur between the intermediate phases of these systems. These phase relationships have already been reported for the intermediate 6 phases of the uranium-zirconium and uranium-titanium systems.' The results of an investigation of the phase relationships between the 6 phases of the uranium-molybdenum and uranium-titanium systems are reported here. The phase relationships that occur in the binary systems pertinent to this investigation are shown in Fig. 1. Phase nomenclature appearing throughout this report is as shown in these diagrams; the crystal structure of the phase is given in Table I. EXPERIMENTAL PROCEDURE Alloys were cast and fabricated to flat plate. Specimens were heat treated and examined metal-

Jan 1, 1959

By J. C. McCarthy, J. B. Stone

At Fresnillo a series of veins that has yielded very large quantities of silver and other metals has been developed over a length of 6500 ft. and to a depth of over 3000 ft. In the course of this work striking changes in the mineralogy and metal content of the principal veins have been disclosed and are well illustrated by assay data and ore reserve calculations. This paper describes those changes and suggests their bearing on theories of ore deposition. Location The Fresnillo mines and the adjacent city of Fresnillo are in the central part of the state of Zacatecas, 35 miles northwest of the capitol city of Zacatecas, once a great silver-mining center whose total production is said to place it fourth in. the world. Another famous old silver district, Sombre-rete, lies northwest of Fresnillo. Fresnillo is connected by a 5-mile branch with Fresnillo On on the Mexican National Railways line from Juarez to Mexico City. Lying near the southwestern edge of the central plateau of Mexico, Fresnillo is Surrounded by a semi-arid rolling plain from which rise widely scattered low hills. One of these is Proano hill, an inconspicuous elevation rising barely 300 ft. above the plain, but in and around Proano hill are the Fresnillo mines, and it is marked now by a great gash cut by glory-hole mining. According to an account written in 1834 by Francisco Garcia, then Governor of the state of Zacatecas, Fresnillo was discovered in 1554, and a presidio was established there in 1568 to protect travelers on the road between zacatecas and sombreretea Little is known of the earliest mining at Fresnillo, which seemingly began soon after its discovery, but by piecing together various accounts, it appears that mines there were working in 1717 and were notably active in 1751 under an administrator named Murguia, who left detailed notes describing them. In I757, however, the mines became inactive because of dificulties with creditors and no doubt also because of increasing water troubles, and they remained abandoned until 1830. In 1830 the mines at Fresnillo became the property of the State of Zacatecas because the interest of Governor Garcia had been aroused by the long disregarded notes of Murguia. Under Garcia's energetic leadership the mines were reopened, and silver production began in 1832 in spite of serious difliculties, including abnormal rains and an epidemic of cholera. In 1835 English capital was sought to allow installation of steam-driven is pumps at the two principal shafts and to build the great hacienda de beneficio (the present Proano hacienda). The company formed in 1835 (Cia. Zacatecano-Mexicana) operated successfully until 1872, when its career was brought to an end by the political and economic disturbances

Jan 1, 1949

By J. C. McCarthy, J. B. Stone

At Fresnillo a series of veins that has yielded very large quantities of silver and other metals has been developed over a length of 6500 ft. and to a depth of over 3000 ft. In the course of this work striking changes in the mineralogy and metal content of the principal veins have been disclosed and are well illustrated by assay data and ore reserve calculations. This paper describes those changes and suggests their bearing on theories of ore deposition. Location The Fresnillo mines and the adjacent city of Fresnillo are in the central part of the state of Zacatecas, 35 miles northwest of the capitol city of Zacatecas, once a great silver-mining center whose total production is said to place it fourth in. the world. Another famous old silver district, Sombre-rete, lies northwest of Fresnillo. Fresnillo is connected by a 5-mile branch with Fresnillo On on the Mexican National Railways line from Juarez to Mexico City. Lying near the southwestern edge of the central plateau of Mexico, Fresnillo is Surrounded by a semi-arid rolling plain from which rise widely scattered low hills. One of these is Proano hill, an inconspicuous elevation rising barely 300 ft. above the plain, but in and around Proano hill are the Fresnillo mines, and it is marked now by a great gash cut by glory-hole mining. According to an account written in 1834 by Francisco Garcia, then Governor of the state of Zacatecas, Fresnillo was discovered in 1554, and a presidio was established there in 1568 to protect travelers on the road between zacatecas and sombreretea Little is known of the earliest mining at Fresnillo, which seemingly began soon after its discovery, but by piecing together various accounts, it appears that mines there were working in 1717 and were notably active in 1751 under an administrator named Murguia, who left detailed notes describing them. In I757, however, the mines became inactive because of dificulties with creditors and no doubt also because of increasing water troubles, and they remained abandoned until 1830. In 1830 the mines at Fresnillo became the property of the State of Zacatecas because the interest of Governor Garcia had been aroused by the long disregarded notes of Murguia. Under Garcia's energetic leadership the mines were reopened, and silver production began in 1832 in spite of serious difliculties, including abnormal rains and an epidemic of cholera. In 1835 English capital was sought to allow installation of steam-driven is pumps at the two principal shafts and to build the great hacienda de beneficio (the present Proano hacienda). The company formed in 1835 (Cia. Zacatecano-Mexicana) operated successfully until 1872, when its career was brought to an end by the political and economic disturbances

Jan 1, 1949

By George H. Cunningham, Allen C. Jephson

The plant for production of electrolytic zinc recently erected by the American Smelting and Rcfining Co. is situated along Nueces Bay, on the Gulf Coast, some 5 miles west by rail and highway from the city and port of Corpus Christi. A ship channel from the port now approaches to within 2 miles of the site. It is expected that this will be extended at some future date and so provide direct water shipment from the plant. In addition to Gulf shipping, an intercoastal waterway connects Corpus Christi with Houston and New Orleans. Factors leading to the establishment oi this plant in the area were: ample supplies of natural gas for the generation of electric power, advantageous shipping lanes, favorable market for acid, adequate supply of labor, and moderate climate. General Description The plant was erected primarily to assist with the production of high-grade zinc much needed for war purposes. Production started during October 1942. The purity of the slab-zinc output meets the American Society for Testing Materials' special high-grade spccifications. Other products of the plant are electrolytic cadmium and sulphuric acid. Residues containing lead, copper and silvcr are sent for treatment to the Company's smelter at El Paso, Texas. The design of the plant includes the use of Trail suspension roasting equipment, contact acid equipment, also batch leaching in mechanically agitated tanks, pressure filtering and washing of leach pulp, batch purification in mechanically agitated tanks followed by clarification in filter presses and cooling of purified solution by evaporation. Electrolysis is performed in cells using Tainton alloy anodes and aluminum cathodes. Cathode current density is 60 amp. per square foot. Except for the portion returned to the leaching division, the cell solution is continuously flowing in closed circuit through the cells to cooling towers, which hold cell temperatures within desired limits. Direct current for electrolysis, is supplied by generators driven by steam turbines. The cathode zinc is melted in a gas-fired furnace and cast in the usual way into slabs for shipment. The plant divides into five major divisions: Concentrates Storage, Roasting and Acid, Leaching, Electrolysis, Melting and Casting. No attempt is made to give many tabulated data in this paper; it is mainly a general description of the divisions and methods employed for operation. A plan is shown in Fig. I and a general flowsheet in Fig. 3. Concentrates Storage The original plan for inward shipments was to receive zinc concentrates by steamer at the port of Corpus Christi, there to unload into open railroad cars and move into the plant by rail. Up to the present, however, concentrates have been received mainly in box cars from mines in Mexico.

Jan 1, 1944

By F. L. Robertson, C. H. Bacon, J. W. Till

A description is given of the development of a process for making low sulphur steel on furnaces fired with 2 1/2 pet sulphur oil. Slag and metal are analyzed at melt. Slag weight is estimated. A simple method for calculating necessary lime additions for making 0.025 and 0.035 pct sulphur steel is given. DURING the last 15 years John Summers & Sons have been confronted increasingly by the problem of producing a low sulphur steel from high sulphur materials. The principles adopted, the processes used, the data collected on a furnace specially set aside to study this problem, and speculation on future developments are dealt with in this paper. This study is limited to two melting shops which make sheet steel only, of the following analysis: C, 0.06 pct; Mn, 0.33; S, 0.04, 0.035, 0.03, and 0.025; and P, 0.02 and 0.015. All the processes described have reference to the manufacturing of this steel and are not necessarily applicable, without modification, to other steels. The raw materials used are given in Table I. Development of Process About 1934, Schenck's work on phosphorus was applied to frame quantitative rules for the removal of phosphorus, with great success. We could however, neither in our own work nor in the voluminous literature, find any assistance to frame quantitative furnace rules to remove sulphur. Perhaps, we should have persevered with Schenck's outstanding chapter on sulphur in The Physical Chemistry of Steelmaking, but we missed the importance of one (Ss) sentence on p. 478. "Evidently this ratio -------- is [S] the important quantity to be considered from the point of view of chemical reaction; it is clear that the sulphur content of the steel alone, as frequently given in the literature cannot suffice for judging the success of the reaction unless special details are given regarding the sulphur charge and the amount of slag."' We were not however very successful in getting values for Schenck's "n" that agreed with (S) arrived at by our direct analysis. [S] In addition to Schenck's work much attention was given to V value. The formula selected for V was: (SCaO) — 1.57 (2 P2O5) (S SiO2) After plotting many charges a curve was obtained, based upon the relationship between the percentage sulphur in the finished steel and V value, Fig. 1. For a long time this was used as standard with about a 60 to 70 pct success on producer-gas fired furnaces, if all uprising scrap was used and no bought scrap used. An inspection of this curve shows clearly that it is not a quantitative manufacturing process, and that it was not sure enough to go to the trouble and expense of doing stage analysis for P,O,,

Jan 1, 1952

By C. H. Mahoney, P. E. LeGrand, A. L. Tarr

MAGNESIUM, it is now generally realized, differs in some important aspects from most other structural metals, not excepting even its close neighbors, the aluminum-base alloys. This is particularly true with respect to the effects of elevated temperatures on the two light metals when in the molten state. Aluminum, on the one hand, should not be raised above its melting point any higher than is absolutely necessary if one is to avoid danger of gas absorption and a tendency toward grain growth in the resultant casting.1 Magnesium alloys, in sharp contrast, actually benefit by being heated to temperatures considerably above their melting point. It is a commonly accepted practice to establish the desired fine grain in the industrial magnesium alloys of the aluminum-bearing group by raising the temperature of the melt after the refining treatment to some 25e C (482°F.) above the melting range. To recall briefly the typical practice for magnesium alloys, the molten metal is refined by fluxing at about 730° C. (1350 F.), and after the melt has been covered with a suitable flux, the temperature is raised to between 870°C. (1600°F.) and 930°C. (I700°F.). It is then cooled as quickly as possible to the casting temperature. This superheating, as it is called, results in a fine-grained cast metal structure which has superior mechanical properties, enhanced amenability to solution heat-treatment, and better machinability than cast metal that has not been superheated. The minimum temperature of superheating varies to some extent with the composition of the alloys to be treated and usually increases with the percentage of magnesium in alloys containing the same constituent metals.2 It should be noted that the grain-refining effect of superheating is markedly apparent only in connection with the alloys containing aluminum as an alloying constituent-the binary alloy containing r.5 per cent manganese, for example, is not refined in grain to any noticeable extent by a superheating effort. While the phenomenon of superheating is well known in the magnesium industry, the mechanism of the process has remained a mystery. During the superheating cycle something occurs that forces a fine grain upon the solidifying metal. The process has been controlled in an empirical manner, and occasionally, especially on large-scale melts, and for no apparent cause, no grain refinement is obtained from a superheating treatment. Only a few papers of importance have been published on the subject. Of these, one of the most helpful is the paper by Achenbach, Nipper and Piwowarski,3 which gives considerable data concerning the effect of superheating on various properties such as fluidity, shrinkage and hot crack formation, as well as grain size, and a discussion without any definite conclusions on the theoretical aspects of superheating. A short article by Murphy, Wells and

Jan 1, 1945

By Walter E. Duncan

THE ores treated at the concentrating plant largely come from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately intergrown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four concentrates: (I) lead concentrates, (2) zinc concentrates, (3) acid-grade fluorspar concentrates and (4) metallurgical-grade fluorspar concentrates.2,3 Although fluorspar had been floated in Canada in 1921 4 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Mines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; such as, for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1946

By Harlowe Hardinge

[Crushing Tests by Pressure and Impact (T.P. 1895, by F. C. BOND,, Min. Tech. Jan. 1946). Discussion by H. HARDINGE and the author 1 Pumping Sands, Slurries and Slimes and Installation and Performance of Sand Pumps (T.P. 2013, by W. B. STEPHENSON, Min. Tech., May 1946 and T.P. 1978, by C. G. SOUTHMAYD, Min. Tech., March 1946). Discussion by OSCAR LEE, G. J. HOLT, L. D. ANDERSON, and the author 2 Rapid Polarographic Method for Determination of Copper, Zinc and Lead in Flotation Tailings (T.P. 2010, by G. A. CROWE and W. T. BISHOP, Min. Tech., March 1946). Discussion by E. H. ROSE and the authors 4 Ball Wear and Functioning of the Ball Load in a Fine-grinding Ball Mill (T.P. 1984, by W. I. GARMS and J. L. STEVENS, Min. Tech., March 1946). Discussion by J. F. MYERS, E. W. DAVIS, F. M. JARDINE, H. HARDINGE, F. C. BOND and the authors 5 Correlation between Mineral Behavior in Cataphoresis and Flotation (T.P. 2005, by A. M. GAUDIN and S. C. SuN, Min. Tech., May 1946). Discussion by 0. C. RALSTON, G. L. SIMARD and D. J. SALLEY 7 Accident Experience in Milling (T.P. 1981, by J. F. MYERS and S. E. SHARP, Min. Tech., May 1946). Discussion by C. E. MCKNIGHT, C. H. BENEDICT, T. S. WILSON and S. POWER WARREN9 Mill Design for Labor Economy (T.P. 1997, by NORMAN WEISS, Min. Tech., May 1946). Discussion by R. S. HANDY and the author13] Crushing Tests by Pressure and Impact (0.C. Ralston presiding) HARLOWE HARDINGE.*-Has the impact method described in the paper been used to compare the resistance to reduction in size of various materials with actual operation results of mills in the field? Is this impact method a better index of the true resistance to grinding under actual field conditions than other methods the author has reported in the TRANSACTIONS? F. C. BOND (author's reply).-The impact crushing device was designed to measure relative resistance to crushing, or what may be called the crushability, and is not used for comparing the resistance to grinding, or grindability. The correlation between crushability and grindability of different materials is not at all close, since fractures, zones of weakness, and structural features of rock have a much greater effect upon the crushability than upon the grindability. We still depend upon our standard grindability tests for measuring resistance to grinding, and use the impact crushing tests only in relation to crusher installations. The impact crushing device has several advantages over the measurement of crushing strength in pounds per square inch as an index of crushing resistance.

Jan 1, 1946

By Benjamin Lustman, Robert F. Mehl

The study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation—i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from 0 to 1000-2000 ?ngstroms—has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difierence may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations.3'4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 Experimental Procedure Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and repro-ducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900° to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal. After this treatment, the specimens were cooled in hydrogen to room temperature and placed in the oxidation furnace, where

Jan 1, 1941

By Benjamin Lustman, Robert F. Mehl

The study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation—i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from 0 to 1000-2000 ?ngstroms—has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difierence may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations.3'4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 Experimental Procedure Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and repro-ducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900° to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal. After this treatment, the specimens were cooled in hydrogen to room temperature and placed in the oxidation furnace, where

Jan 1, 1941

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962

By T. J. Bosworth

The effect of hydrogen pretreatment of alumina, magnesia, and zirconia crucibles on reduced oxygen levels in iron charges has been studied. Hydrogen treatment of commercial high-purity magnesia crucibles was observed to produce as high as 70 pct reduction in oxygen content in iron melts. Hydrogen treatment of the commercial high-purity grade zirconia crucibles produced a 25 pct reduction in oxygen levels in iron melts. An average reduction of Knoop hardness of 47 pct was recorded on the iron charges melted in hydrogen-treated crucibles. On the basis of the experiments and the free-energy diagram, it appears that the major source of reducible oxygen to the iron charge is the suboxides and impurity oxides rather than the major oxide of the crucible. Suitable pretreatment of the crucibles to reduce and remove these oxides yields low oxygen levels in iron melted in the crucibles. DURING the last decade, attempts to produce more pure and uniform alloyed metals have brought about the development of many new melting techniques. Notable among these are vacuum-induction melting, inert and consumable-electrode melting, the cold-mold technique, and numerous techniques for removal of impurities by chemical reaction. However great the achievements in this field, metals must still be melted in contact with media of varying reactivity; i.e., gas, ceramic, and slag. Studies have been made to attain an understanding of the reactions that take place during melting, including slag-metal reactions and equilibria, equilibrium of hydrogen and water vapor, and carbon dioxide and carbon monoxide with oxygen in molten iron. These reactions have been treated quite thoroughly. There is one condition, however, that has been widely overlooked, and, to the author&apos;s knowledge, only cursive investigation has been made of it. This is the reaction between the ceramic crucible material and the iron charge. In recent years, Hadley and Bianchi&apos; made a series of studies on hydrogen deoxidation of iron in magnesia crucibles. Bianchi2 studied crucible-FeO equilibria in the temperature range 1525°to 1650°C in high vacuum with, however, inconsistent results. Richardson and Jeffes3 in their series of articles on thermodynamic reactions in the making of iron and steel refer to Wentrup and Hieber&apos;s4 work on iron and aluminum deoxidation. Their pork included melting iron in alumina crucibles and measuring the aluminum and oxygen content in the iron. Because of the low values obtained, question has arisen of their analytical accuracy.3 Dastur and chipman5 obtained values on hydrogen-oxygen equilibrium in molten iron contained in alumina crucibles similar to those obtained in experiments in the present program. Hochmann6 studied removal of impurities in chromium irons in high vacuum. His results with respect to oxygen level in chromium-iron melted in magnesia crucibles are consistent with results we have obtained.

Jan 1, 1959

By George F. Weaton, Carleton C. Long, H. I. Najarian

Partial descriptions of the operation of the St. Joseph Lead Company&apos;s Joseph-town smelter have been published. In, 1936 the electrothermic production of zinc oxide was described;&apos; in 1939 appeared a description2 of the electrothermic method of producing zinc metal. Inasmuch as the plant capacity has more than doubled, and in view of the fact that operating practices have improved greatly since these publications, it seems worth while to prepare a fresh description of the present-day elec-trothermic zinc plant and practice. Josephtown smelter is situated on the south side of the Ohio River about 3 miles below its confluence with the Beaver River. In addition to river barge, the smelter is served by Pennsylvania state highway No. 18 and by a spur line of the Pittsburgh and Lake Erie Railroad (N.Y.C.). A recent extension of this spur line connects with the Pennsylvania Railroad. As originally contemplated the plant was to handle only the product of the com-pany&apos;s own mines in St. Lawrence County, New york, but owing to the incessant demand for zinc and zinc oxide, it has been necessary to supplement New York concentrates with foreign ores (principally from Quebcc and the Argentine). The general operational procedure followed comprises roasting the sulphide con-centrates, converting the sulphur dioxide into sulphuric acid, preparation of a strong-structure sinter from the calcine, crushing &lid sizing of coke, reduction of coke-sinter mixture by electrothermic means, condensation of the evolved zinc vapor to make zinc metal or burning of the zinc vapor to make zinc oxide, collection and packing of the zinc oxide. Dusts recovered by the roaster and sinter Cottrells are treated in the leach plant for separation of lead sulphate, cadmium metal and zinc sulphate. The general flowsheet is shown in Fig. I. Principal Items OF Equipment Roaster Plant Concentrate drier, 6-ft. &apos;ia. by 4O ft. 5 in., countercurrent, direct gas-fired. 3500-~on concentrate storage in three vertical steel tanks. Five modified Nichols-Herreshoff twelve-hearth roasters, 21 ft. 6 in. in diameter. Four fans for shaft-cooling air. One threedrum Stirling water-tube waste-heat boiler, 4&apos;8 hp., 200 1b. Per sq. in., with connections to upper and lower balloon flues. Direct gas-fired countercurrent rotary-kiln roaster for Cottrell dust. Necessary conveying equipment, described below. Instrumentation consists of: draft indicators, (3d hearth); various manometers; pyrometer served by thermocouples in each hearth, entrance and exit of waste-heat Joseph. entrance and exit of each hot Cottrell; roaster draft recorder and shaft air-pressure controller; temperature recorder and controller (10th and 12th hearths); SO* recorder (waste-heat boiler n

Jan 1, 1944

By S. Floreen, H. W. Hayden

The effects of additions of iridium, rhodium, ruthenium, and platinum on the mechanical properties of Fe-C alloys were determined. Each alloying element significantly improved the toughness. The results support the general correlation that substitutional alloying elements that stabilize austenite are beneficial to toughness, but the reason for this improvement is not obvious at this time. The effects of substitutional alloying elements on the toughness of steel has long been a subject of both practical and theoretical interest. Despite the obvious importance of this subject, there has been little progress toward understanding the mechanisms by which alloying elements influence the fracture behavior. In some cases the deleterious effects of alloying elements have been shown to be due to mechanisms such as embrit-tlement of prior austenite grain boundaries or inhibition of cross slip in the ferrite lattice. In other cases, however, the reasons for the change in properties are not clear. This is particularly true for elements, such as nickel, that improve the resistance to brittle fracture. Several investigators&apos;-3 have pointed out that there is a correlation between an alloying element&apos;s phase diagram with iron and its effect on toughness. Those substitutional alloying elements that stabilize austenite generally are beneficial to toughness, while ferrite-stabilizing elements generally are detrimental to toughness. The word "generally" should be emphasized, because exceptions to this rule can be found. Nevertheless, this correlation does offer a starting point at which to try to understand the effects of alloying elements on toughness. Thus far only two austenite-stabilizing elements, manganese and nickel, have been considered. In order to test the validity of this correlation several other austenite-stabilizing elements were evaluated. The noble metals, iridium, rhodium, ruthenium, and platinum, have binary phase diagrams with iron similar to the Fe-Ni and Fe-Mn diagrams. That is, each element expands the austenite field, and also higher concentrations of each element produce martensitic transformations at low temperatures. Presumably then, each of these elements should improve the toughness of steel. The present study was conducted to determine if this were so. EXPERIMENTAL PROCEDURE The alloys were made as l-lb air-induction melts using electrolytic iron and commercially pure noble metals. Each heat was initially deoxidized by a carbon boil, and further carbon was added to attempt to produce a 0.05 wt pct C content in each alloy. Before pouring, a final refining addition of 0.2 wt pct A1 and 0.1 wt pct Ti was made to each heat. The alloys were cast in a copper mold to produce ingots approximately 1 in. in diam and 5 in. long. The chemical compositions of the alloys tested are given in Table I. The residual nitrogen, aluminum, and titanium contents were all relatively constant at 0.003, 0.03, and 0.02 pct, respectively. The carbon

Jan 1, 1968