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By AIME

Rapid exhaustion of iron ore in Minnesota's Mesabi range has led the Jones & Laughlin Steel Corp. to develop the world's largest open quarry mine for magnetite iron ore, at Star Lake, N. Y. Already contributing more than one eighth of the total iron ore used by the Corporation, the expanding Benson mines are destined to become Jones & Laughlin's important source of ore within the next ten years. In 1947 over 650,000 long tons of high-grade ore was produced. Output this year is expected to reach 800,000 long tons and studies are under way to increase production further. The future of the Benson mines is assured as present indications show large reserves of ore. The property, briefly described in M & M for November 1943, then under

Jan 1, 1948

By H. A. Wilhelm, P. Chiotti, G. A. Tracy

A summary of analytical, X-ray, thermal, and metallographic data obtained in the study of the Mg-U system is presented. No intermetallic compounds are formed by these two elements, and their mutual solubility is limited at temperatures up to 1255°C. The compositions of the liquids which coexist at 1135°C under a pressure of 3 atm are 0.14*0.05 wt pet U in magnesium, and 0.004 wt pet Mg in uranium. The solubility of uranium in magnesium decreases to 0.0510.03 wt pet at 675OC, and to about 0.0005 wt pet at 650°C. Due to the reactivity of both uranium and magnesium toward crucible materials, the choice of a suitable crucible presented a problem. Crucibles made from high purity magnesia to which 10 wt pet MgF2 was added to reduce porosity proved to be satisfactory. Some observations made with the use of other crucibles are given. THIS investigation was made to establish the phase diagram for the Mg-U system. Ahmann,' formerly of the Ames Laboratory, did some work on the system. He used several methods in an attempt to prepare Mg-U alloys. One of the methods involved the reduction of UF, with a large excess of magnesium. In these experiments, the magnesium wet the surface of the uranium, but there was no evidence for compound formation. The maximum solubility of magnesium in uranium was indicated to be 0.01 wt pet. In another set of experiments, uranium chips as well as uranium powder were heated in contact with molten magnesium in a graphite crucible for periods of time up to 48 hr. A reaction layer was found at the Mg-U interface in several instances. X-ray analysis of the layer material showed the presence of UC and some additional unidentified lines which were interpreted as indicating the possibility of an intermetallic compound of uranium and magnesium. These studies indicated the maximum content of magnesium in uranium to be 0.043 wt pet. One sample of magnesium which had been heated at 1025°C in contact with excess uranium was found by chemical analysis to contain 0.275 wt pet U. Rules, based on empirical or semi theoretical considerations, which attempt to predict the alloying behavior of metals have been presented in the literature. Although these rules are not infallible, they nevertheless serve as useful guides. Using them, several generalizations can be made concerning the Mg-U system. According to Hume-Rothery's' atomic

Jan 1, 1957

By D. E. Peacock, B. Harris

Thermal-expansion and electrical-resistivity measurements have been carried out below 400°K on niobium and two niobium alloys containing tungsten. For anonaly in the expansion us temperature curve below aboct 300°K. This reslt is consistent with an earlier obsercation that Young's modilus joy Cb-132 lms an unusiully strong -tenperati-e dependence below roon temperature. No anonulous behavior was observed in the resistiuity vs temperature curve for either alloy or in the magnetic susceptibility us tenperature curve for Cb-132. These results are disclssed in terms of various electronic and bonding theories of the transition metals and their alloys, but it has not been possible to reach any definite conclusion as to the cause of the results obtained. ALONG with investigations of the low-temperature mechanical behavior of niobium and its alloys, some of the physical properties of these materials have also been studied. In the work described here, thermal expansion and electrical resistivity were measured below 400°K for niobium and two of its alloys, Cb-132 and D-43. In addition, the magnetic susceptibility of Cb-132 was measured over the same temperature range. The alloys are representative of two distinct tion-hardened alloy such as might find service as a turbine blade, while D-43 (Nb, 5.3 at. pct W, 1.1 at. pct Zr. and 0.08 at. pct C) is a solution- and dispersion-hardened alloy, of considerably lower strength than Cb-132. which is a potential vane material. Their significant common feature is the presence of tungsten as the principal source of solution hardening. EXPERIMENTAL TECHNIQUES Thermal-expansion measurements were made with a quartz-tube dilatometer using baths of liquid nitrogen, liquid bromoethane, and a liquid polyalkylene glycol derivative to cover the range 80 to 400 K. Results are recorded as expansion relative to that of quartz, and the probable maximum error in any value of relative expansion. All, is about il pct. The metallurgical condition of the specimens, which were in rod form. will be discussed in the section dealing with experimental results. Resistivity was measured on recrystallized wires 0.030 in. in diam using a potentiometric technique. The same baths were used for temperatures between 80' and 400°K as were used for the expansion measurements. and in addition the resistance of D-43 and Cb-132 was measured at 4.2 K by immersion in liquid helium. The maximum expected experimental error in any resistivity value is about 3 pct and that in any change in resistivity about i0.05 pct. Temperatures in both sets of experiments were measured with liquid-in-glass thermometers with an accuracy usually better than 1°K. EXPERIMENTAL RESULTS 1) Thermal Expansion. In Fig. 1 is shown the relative linear expansion of recrystallized niobium. D-43. and Cb-132. The curve for Cb-132 is composed of results from several runs on three different samples. Two of the samples were annealed for an hour at 1500°C to cause recrystallization and the third was annealed for an hour at 2000'C to remove some mi-crosegregation of tungsten which was known to be present in the wrought alloy received from the manu-

Jan 1, 1967

By Arthur G. Levy, Henry M. How

The purpose of the investigation on which this paper is based is to determine whether the structural change which occurs in the slow cooling of steel below the transformation range has an important effect on its engineering properties. We recognize two distinct things which occur in steel when it is brought from above to below the transformation range, first, the transformation proper, that is, the breaking up of the austenite or solid solution of the cementite in the remainder of the iron, and the liberation of its components as undissolved cementite and as ferrite or alpha iron; and second, a structural change consisting in the gradual coalescence of the ferrite and cementite respectively into larger and larger separate masses. Let us distinguish these from each other by speaking of them as " the transformation " and " the structural change " respectively. If the cooling is at all rapid the unevenness of contraction induces severe stress; so that in a sense a slow cooling has a third influence, the prevention of such stress. This transformation from austenite to ferrite plus cementite can complete itself only below the transformation range; and, because this structural change is a change in the structural arrangement of the products of that transformation, it too can complete itself only at temperatures below that range, say below 725°; and of these temperatures it is only those between 600° and 725° that give the metal sufficient mobility to permit this structural rearrangement to progress with ally rapidity. The transformation is now known to be rapid, but the structural change is relatively slow. The transformation, the liberation of the dissolved cementite from the state of solution in the austenite to a free state, leaves the steel structurally in the

Jan 1, 1913

American Zinc Institute, 60 East 42nd St , New York, N Y. Julian D. Conover, Secretary The monthly Journal of the American Zinc Institute contains papers on zinc deposits, mining and metallurgy of zinc, as well as affairs of the Institute, statistics, and many papers on phases of the utilization of zinc It has the title "Zn " The numbers for each year are collected as volumes for that year, the first volume was issued in 1918, and the latest complete volume available is Vol 12 (1929) Copies of Indexes to the volumes will be sent upon request Back numbers of the Journal are not generally available for distribution but may be seen in most libraries For further information regarding papers, back numbers of the Journal, or volumes, address the Secretary

Jan 1, 1933

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By C. H. Mathewson

THIS paper was prepared upon request as a contribution to a symposium covering the manufacture, properties, and uses of the important non-ferrous metals. In approaching a subject as broad as this, there is a natural desire to build up a comprehensive and finished production which shall constitute a dependable source of information on all questions properly belonging to this branch of metal technology. There are, however, a number of circumstances, apart from the mere routine of labor and thought involved, which operate rather effectively against the possibility of completing such an ambitious program at the present time. First of all, as far as any public record of results is concerned, the commercial rolling, drawing, and forming of zinc with relation to changes of structure and properties-and this we consider to constitute the elements of metal technology-might as well be an unpractised art. We have never seen a published photomicrograph showing the structural characteristics of either hard or soft sheet or strip, although the structure of castings has been frequently described, and other coarse-grained structures resulting from hard-hammering and annealing have been reproduced. Thus, an author in this field must proceed to his task without much assistance from the literature, and the outcome can represent only a personal estimate of principles, facts, or findings, and not a summary

Jan 9, 1919

By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.' udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4'5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A'-B' develops at the other intersection. The angles A + B and A' + B' are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

By Thomas L. Watson

A part of the field-seasons of 1900, 1901 and 1902 mas devoted by the writer to a study of the manganese ore-deposits of Georgia. A report embodying the results of this study is rapidly nearing completion, and when finished it will be published as a bulletin of the Geological Survey of Georgia. I believe, however, the importance of these deposits warrants a separate and earlier publication than that made possible by the Survey, in which the more important results of the study are briefly set forth. It is principally for this reason that the present paper has been prepared. Previous Work.—Some of the more important deposits of manganese occurring in the Paleozoic area of Georgia were studied to some extent previous to 1890 by Dr. Penrose;t and again in the early nineties by former State Geologist, J. W. Spencer. In a recent paper published in the Transactions, on the " Geological Relations of the Iron-Ores in the Cartersville District, Georgia," Dr. Hayes briefly mentions the manganeseores of the same district. Distribution of the Manganese-Ores.—Georgia is divisible into three geologically-distinct areas which, named in order from southeast to northwest, are (a), the Coastal Plain; (b), the Crys-

Jan 1, 1904

THE CHAIRMAN (EDWIN LUDLOW, Lansford; Pa.).-Mr. Wang's paper reminded me that some years ago I was asked if I would not go into the Tien Tsin district and take charge of Americanizing a Chinese mine. They said the trouble was that, while wages were only 9 c. a day, the coke cost $2 a ton delivered to the cars. Reading Mr: Wang's paper would indicate the need of a little Americanization in the Manchurian field. Wages are only 40 c: a day, yet the cost is $3.60 a ton. An efficiency engineer would have an excellent opportunity in that field. T. T. READ, New York, N. Y.-It is always true that low-priced labor is inefficient, wherever we find it; for example, in Japan, where wages are low, but not so low as in Manchuria, working costs are not relatively much lower than ours. Mr. Padshah, describing his experience in India, once told me that, while wages were only about one-fifth as high

Jan 4, 1918

By Rudolph G. Wuerker

With stepped-up work in rock mechanics, more and more data on strength and elastic properties of rocks has become available. Results of measurements of tensile strength, in addition to determinations of compressive strength, allow us to deter- mine, even if only in an approximate way, the third property influencing failure of a brittle material: shear strength. It is fairly generally agreed upon in rock mechanics, in drilling and blasting research, that Mohr's theory provides an acceptable method for explaining the failure of a brittle material. Mohr states that a material may fail either 1) through plastic slip when shearing stress Y in the planes of slips has reached a limiting value (which in general depends on the normal stress, X, acting normal to the surface), or 2) when the largest normal tensile stress has reached a limiting value. The mode of failure depends upon which of the two stresses is the smaller.

Jan 10, 1959

By Patrick M. Hurley

The relationships between mineral deposits and various plate margin mechanisms are examined under the constraints of radiogenic isotopes and other geochemical indicators. It seems like1 y that: (1) deposits of the spreading ridge association are fairly ubiquitious through most of geologic history and can be recognized by the lithologic assemblage and primitive lead isotope ratios; (2) most metals in the island arc association are not derived entirely from a subducting oceanic plate, and have a partly continental affinity; (3) subduction beneath a continental plate generates ores which are derived either from the downgoing plate or from the lower crust; (4) the heating of a continental plate by thickening or by mantle plumes may develop a metallogenic province involving extraction of metals from the curst; (5) rifts and grabens developing thick sections of marine sediments with evaporites may be the locus of base metal mineralization by movement of reducing brine solutions resulting from diagenesis and bacterial reduction of sulfates

Jan 1, 1978

By F. E. Luborsky, K. T. Aust

RECENT interest has been shown in utilizing solid-state techniques for obtaining large oriented grains in the Alnico Alloys.1-4 Unfortunately, due to the inherent brittleness of these materials it is difficult to introduce sufficient imperfections by deformation to support the nucleation and growth of new, recrystallized grains. As a result, recrystal-lization methods for obtaining large grains, such as the strain-anneal technique, do not appear to be feasible. Steinort et a1.2 used a combination of a thermal gradient and internal strains to obtain large single crystals of Alnico 5 from a poly crystalline casting by annealing at temperatures above 1200°C. It was suggested that the strains were the result of the precipitation of the y phase which exists between -850° and 1200°C. The purpose of the present study was to determine if the grain size of the cast Alnico alloys can be markedly increased by solid state techniques involv-

Jan 1, 1963

By E. T. Turkdogan, M. T. Hepworth, R. P. Smith

The permeability of oxygen in 0 iron in the tempera-ture range 700" to 900 C and in 6 iron at 1450°C was determined by the rate of internal oxidation of iron, containing -0.1 pct Al. The solubility of oxygen in zone-refined iron was determined by equilibration with hydrogen-water vapor gas mixtures at 1450" and 1510°C; oxygen solubilities , for iron in equi1ibriu.rn with molten oxide, are found to be 66 and 83 ppm for these two temperatures, respectively. The diffusivity of oxygen in iron at 14500C3 as calculated from the permeability and solubility data, is (4.1 * 0.6) x 10 "B sq cm per sec. OXYGEN is one of the most common impurities present in iron or steel, mainly in the form of oxide inclusions. In the study of many metallurgical problems concerning solid iron, it is often desirable to know with a reasonable accuracy the solubility and diffusivity of oxygen over a wide temperature range. The solubility of oxygen in solid iron has been the subject of numerous studies yielding highly discordant results as seen for example from the literature surveys made by Meijering &apos; and Schenck et a1.&apos; As shown by Kitchener et aL3 and by Sifferlen, the high oxygen solubilities reported by many investigators are the result of oxidizable impurities which are often present in iron. In addition, there have been experimental problems associated with icaccuracy of oxygen analysis of iron containing less than 100 ppm 0. A number of studies have been made on the permeability of oxygen in a and y iron using Fe-Si, Fe-Mn, and Fe-A1 alloys in the internal-oxidation experiments.1&apos;2&apos;5&apos;6 However, no direct measurements have been made of the diffusivity of oxygen in iron. In the present work two sets of experimental measurements were made: permeability and solubility studies at 1450" and 1510°C and permeability studies only in the range 700 to 900°C. In both sets of permeability measurements slab-shaped specimens containing small predetermined amounts of aluminum in solution were exposed at constant temperature to gas mixtures of hydrogen, water vapor, and argon for varying times. These specimens were quenched, sectioned, and examined for oxygen penetration by metallographic observation of aluminum oxide particles which formed. From these data, it is possible to calculate the ratio of the diffusivity of oxygen in iron, D, to the equilibrium constant K for the reaction Hz(g) * O (dissolved in iron) = H,O(g). EXPERIMENTAL Permeability Measurements at 1450°C. An ingot of vacuum-carbon deoxidized iron containing 0.086 pct A1 was prepared, using commercial "Type lO4A Plas-tiron"; after hot rolling, specimens were machined into slabs a by 2 by 2 in. The impurity contents were: S, P < 0.002 pct; C, Mn < 0.01 pct; each of all other Usual impurities < 0.004 pet. The amount of oxide inclusions in this material, determined by a bromine-methyl acetate extraction, corresponded to about 20 ppm 0 in the iron which agreed well with the results of vacuum-fusion analysis. Each specimen was annealed at 1450°C for 1 hr in purified hydrogen, polished to a smooth surface, and then introduced into a controlled oxidizing atmosphere in a recrystallized alumina tube at 1450°C. The constant temperature zone (*3"C) was about 3 in. in length. The gas composition was controlled by mixing argon with hydrogen (using calibrated constant-head flow meters) and passing the mixture through a column of a mixture of oxalic acid dihydrate and 10 pct anhydrous oxalic acid, to establish a required water-vapor content in the gas mixture. The temperature of the oxalic acid dihydrate column was controlled by a thermostat. The total gas flow was in the range 800 to 1000 cu cm per min. The exit gas from the reaction tube was passed through a weighing bottle containing a desiccant, to cross-check the degree of water-vapor saturation, which for all experiments was about 97 pct of those derived from the data of Baxter and Lansing.1 For a typical experiment, a specimen was introduced into the furnace in a stream of dry argon and hydrogen. The specimen was then rapidly raised by a Pt-Rh alloy wire into the hot zone and allowed to reach the reaction temperature, at which time the oxidizing gas mixture was introduced. The oxygen potentials employed were sufficient to oxidize aluminum but not to cause liquid iron oxide to form. After a specified time, the experiment was ended by dropping the specimen onto a water-cooled copper block at the bottom of the reaction tube. The depth of the internally oxidized zone, hereafter called the "case", was determined by sectioning the specimen at right angles to the long direction. The section was then examined under a microscope equipped with a micrometer stage. In general, the oxide particles were fairly uniform in size and distribution, forming a reasonably well-defined interface between the oxidized and unoxidized region. A typical cross section as observed at X30 is shown in Fig. 1. A thermal macroetch was used in one selected specimen to delineate the case. A cross section of a previously oxidized slab was polished and reheated at 1450°C in a hydrogen atmosphere for about 10 min. Upon quenching, the surface relief shown in Fig. 2 was produced; causes of this effect are unknown. Permeability Measurements Below 900°C. A slightly

Jan 1, 1967

By Morris A. Steinberg

Because of the broad scope of my topic I will discuss my subject from the point of view of a present status of the metallic materials that are used in structures and will dwell primarily on those structures related to high- performance aerospace systems. Thus, I can best portray the status of these structural materials as related to existing transportation systems, delineating some of the highlights of alloy development, fabrication, and properties obtained. I shall point out what are, in my opinion, the needed solutions to pressing unsolved metallurgical problems connected with certain selected metals: aluminum alloys, beryllium, titanium, steels, superalloys, refractory metals and some metal-matrix composites. Aluminum Alloys For a number of years a series of strong aluminum alloys used for airframes has had an important bearing on the development of minimum- weight, highly efficient structures. Among these alloys are such familiar ones as 2024-T3, 2014-T6, 7075-T6, 7079-T6 and 7178-T6. A review of the development and use of strong aluminum alloys in aircraft structures indicates that before about 25 years ago there was very little application of products other than forgings in the high-strength tempers produced by precipitation heat treating to T6- or T8-type tempers. 1 As stated by Dix in 1944, "There has been a gradual evolution in engineering viewpoint regarding the mechanical characteristics which are required in a structural material suitable for aircraft. Formerly, emphasis was placed on a generous spread between yield and tensile strengths, on elongation, on impact strength and on resistance to corrosion. Aircraft structural engineers still differ widely as to the importance which they attach to these proper tie.” 2 It is fair to say that this evolution is still taking place, that the problem is much the same in 1970 as in 1944 - except that strength levels have advanced some - and the question remains as to how far we can go in that direction. In the meantime, a new group of alloys has received acceptance and widespread use. The first alloy of this group, 7075-T6, was formally introduced by Dix&apos;s 1944 paper. The drastic changes that have taken place in the size and configuration of components employed in air-

Jan 1, 1971

By R. R. Judd, H. W. Paxton

The rate of dissolution of cementite was studied in three low-carbon materials: a zone-refined Fe-C alloy, an Fe-0.5pct Mn-C alloy, and a commercial low-carbon steel. The materials were spheroidized, ad then held isothermally at temperatures above the Al. The isothermal anneal was interrupted periodically by a water quench and the specimens were analyzed by quantitative metallography for the amount of aus-tenite formed during the anneal. The results of this study were compared with an analytical model for the process, which assumes that carbon diffusion in aus-tenite is the rate-controlling step for the cementite dissolution process. The correlation between the model and the experimental data is excellent for the zone-refined Fe-C alloys; however, the Fe-0.5 pct Mn-C alloys and the commercial steel deviate from the calculated model. This deviation is thought to be a result of manganese segregation between the carbide and the matrix. The rate of nucleation of austenite at carbide interfaces was reduced by the manganese addition and enhanced by the presence of ferrite-ferrite grain boundaries. PREVIOUS investigations of the nucleation and growth of austenite from ferrite-carbide aggregates are not entirely satisfying for at least one of several reasons. The most prevalent of these is a lack of quantitative data. Engineering studies have been run on many steels with little control over important parameters such as composition and initial aggregate structure. The data obtained are valid only for material with identical chemistry and thermal history. A more informative approach to the problem of aus-tenitization would be to determine the mechanism that controls the rate of solution of carbide in austenite and how it is modified by alloying elements. This information could then be used to calculate an austeniti-zation rate for any material, provided its composition and structure are known. The object of the present work is to establish the rate-controlling step for cementite dissolution in Fe-C austenite and to investigate the modification of this rate by small manganese additions. The composition and structure of the material used were carefully controlled and all measurements were designed to allow a quantitative analysis of the kinetic process that controls the austenitization rate. A MODEL FOR DISSOLUTION OF CEMENTITE Cementite dissolution has been analyzed mathematically by a model that approximates the material used in the experiments. This model postulates a regular ar-array of identical cementite spheroids with 4 C( diam, embedded in a grain boundary- free ferrite matrix. The analysis provides a detailed description of the dissolution of one carbide spheroid and a generalization of the solution by summation over all the carbides in the material. The carbides may be isolated by defining identical, space-filling cells of ferrite around them. If the cell dimensions are greater than the diameter of the austenite sphere resulting from complete dissolution of the carbide, and no interaction (through diffusion in ferrite) takes place between cells during the dissolution process, the model need concern only one cell, since the solution in each cell is identical. In the experimental material, the dimensions of the cell, the carbide, and the final austenite sphere are approximately 24, 4, and 8 p, respectively; use of the single cell is therefore justified. The experimental observations are made on the austenite nodules that form around each carbide during the dissolution process. The model concerns the growth of these austenite nodules. The attendant shrinking of the carbide can be obtained from the same analysis by an extension of the calculations. Several a priori assumptions are necessary to make the analysis of the growth problem tractable. They are: 1) carbon diffusion through the austenite nodule is the rate-controlling process; 2) local equilibrium exists at all interfaces, 3) the austenite nucleus that forms on each carbide instantaneously envelops the carbide; 4) during the austenite growth process, the diffusion flux of carbon in ferrite is insignificant; 5) a quasi-steady state exists in the austenite concentration field; that is, at any instant during the dissolution process, the austenite carbon concentration gradient closely approximates that for a steady-state solution; and 6) the effects of capillarity on the dissolution rate of the carbides can be neglected. Referring to Fig. 1, a mass balance at the y-a interface for an infinitesimal boundary movement gives: Where rb is the outer radius of the austenite shell, C1 and C are carbon concentrations at the interface in austenite and ferrite, respectively, see Fig. 2, is the diffusion coefficient of carbon in austenite for the concentration of carbon at the interface, and t is time. The fifth assumption permits the austenite carbon concentration to be approximated by the Laplace solution for the spherical case. Therefore, where C(Y) is the carbon concentration at r, and A and B are constants. Local interfacial equilibrium fixes the boundary conditions for the diffusion problem. They are:

Jan 1, 1969

By Robert D. Pike

IN November 1939, on behalf of the Harbison-Walker Refractories Co., the author undertook the study of the problem of utilizing the dolomite of northwestern Ohio for the manufacture of calcined magnesia suitable for use in refractories. Grateful acknowledgment is made of the unfailing assistance and encouragement throughout this work from the executive and technical staff of Harbison-Walker Refractories Company. The dolomite of the Niagara formation that is exposed or near the surface of a wide area in northwestern Ohio1 constitutes a vast supply of almost pure dolomite. It offers a virtually unlimited supply of cheap raw material of uniform dependable analysis for the manufacture of magnesia. A typical analysis of dolomite from the vicinity of Luckey, Ohio, follows: [ ] Brines containing magnesium chloride or sea water can be reacted with calcined dolomite to produce magnesia.2,3 In such reactions the MgCl2 of the brine supplies some of the magnesia and the amount of dolomite required is thereby reduced by an equivalent amount, but brines of commercial importance containing magnesium chloride are some distance away from the purest grades of the dolomite of northwestern Ohio. It was decided therefore to concentrate upon the development of a suitable process for separating the lime and magnesia of dolomite, depend¬ing upon the dolomite itself as the sole source of magnesia. This would make it possible to place a plant at the dolomite quarry, thus eliminating the cost of transporting the stone and also rendering the calcined magnesia available at a most convenient production point, considering the cost of delivery throughout the steel industry. The selection of a process depending solely upon the dolomite as a source of magnesia also necessarily entails production of the lime content of the dolomite as a by-product. It was recognized that if such a lime by-product could be produced in a suitable form, a plant location in northwestern Ohio would also be advantageous for marketing the lime. The problem, therefore, was the discovery and development of a low-cost process for separating the magnesia and lime of the dolomite of northwestern Ohio and producing each in a form relatively free from the other, and meeting the respective requirements of established markets. A satisfactory solution of this problem has been found, and it is the

Jan 1, 1947

By J. A. Eisele, D. J. Bauer, L. E. Schultze

Approximately 100 million mt of magnetic reject tailings, which contain apatite and about 1% yttrium and rare-earth elements, exist in the eastern U.S. as a result of iron ore mining operations. At the present time, no economic process is available for recovering yttrium from this material. The U.S. Bureau of Mines (USBM) studied the problem to determine if an effective low-cost method could be found, thereby increasing our domestic yttrium reserves. [Fig. 1] is a line drawing of a photograph taken during microprobe analysis of a sample of the tailings, and shows the distribution of yttrium. Typical analysis of this material is 0.14% yttrium and 1.1% rare-earth elements (mainly lanthanum through neodymium). Over half of the yttrium is present as a hydrated Ca-Y silicate deposited along interfaces in the grain structure; whereas, the remainder of the rare-earth elements occur as Ca-Fe-RE silicates. The remaining yttrium and rare-earth elements are in solid solution with the

Jan 1, 1977

By AIME AIME

BY COMBINING the sessions on reduction and refining of copper, lead and zinc it was possible to devote an entire day to nonferrous metallurgy. Four interesting papers were presented at the morning session and four more in the afternoon. In the discussion of papers on copper, F. R. Pyne acted as chairman, with H. M. Shepard as vice-chairman, whereas for those on lead and zinc, F. F. Colcord acted as chairman, with C. R. Hayward as vice-chairman. The paper by P. D. I. Honeyman on the smelting of raw concentrates in the reverberatory furnace was presented by Mr. Pyne and discussed by Messrs. Mazany and Hayward. The interesting paper by E. S. Bardwell, com- paring the use of various fuels in copper-refining furnaces at Great Fails, Mont., was presented by Mr. Shepard and discussed by Messrs. Boggs, Gronningsater and Hayward. That by R. G. Knickerhocker, describing the stationary basic copper converter at Messina, Transvaal, was presented by Mr. Pyne, together with a written discussion by c. R. Kuzell, of the United Verde Copper co. It was an interesting illustration of how well-known processes may sometimes be modified to fit into unusual conditions.

Jan 1, 1932

By R. W. Fountain, M. Korchynsky

The precipitation phenomena occurring in cobalt-tantalum alloys have been investigated in the temperature range frm 500" to 1050°C by correlating the results of metallographic, X-ray, micro-and macrohardness, and electrical resistivity studies. The property andmacrohardness,changes were found to depend on 1) general precipitation, and 2) lamellar precipitation. Two new intermetallic phases have been identified: 1) a Co3Ta, a metastable ordered face-centered-cubic compound, and 2) a stable ß Co3Ta phase of hexagonal structure. In addition, the previously reported Co2Ta phase was found to exist in two allotropic modifications: the hexagonal MgZn,-type and the cubic MgCu2-type Laves phases. SINCE a large variety of structures can result as a consequence of the decomposition of a solid solution, predictions on the nature of property changes are difficult, if not impossible, to make. For any rational attempt to correlate properties and structures of a precipitation-hardenable alloy, a detailed understanding of the kinetics of decomposition and morphology of phase separation, as well as knowledge of phase relationships, appears to be prerequisite. Information of this type has been accumulated in the past for many alloy systems, both of theoretical and pastforpractical importance.1,2 Although the presence of intermetallic compounds has been reported in cobalt-base alloys,3 the amount of published information on precipitation-hardenable cobalt-base systems is very limited. A survey of the binary phase diagrams of cobalt indicates that cobalt-tantalum alloys might be of interest as typical of other cobalt-base systems in which Laves phases of the A,B type can be precipitated from solid solution. The present work has been undertaken, therefore, to study the kinetics and morphology of the precipitation reaction in this system and to establish a base for a correlation between the structural aspects and properties in this class of alloys. PREVIOUS WORK The only available phase diagram of the cobalt-tantalum system is based on the work of Koster and Mulfinger. According to these authors, the maximum solubility of tantalum in cobalt is about 13 pct (at 1275°C) and. less than 7 pct at room temperature. Tantalum additions lower the temperature of allotropic transformation of cobalt (about 420°C), and at 7 pct Ta, the high-temperature face-centered-cubic modification (ß cobalt) is retained at room temperature. The precipitating phase was originally designated as Co5Ta2 compound (55.2 pct Ta, about 1550°C melting point), but subsequent investigations by wallbaum5" identified this constituent as the A,B-type Laves phase. Wallbaum&apos;s data indicate that there are two modifications of this intermetallic compound: one richer in cobalt (Co2.2 Tao.8)of the hexagonal MgNi, type; and another of a higher tantalum content (Co2Ta) of the cubic MgCu, type. On the other hand, Elliott7 found that the cobalt-rich alloy (CO2.10,Tao.~l) was predominantly the cubic MgCu, type at 800°C and a mixture of both the MgCu2 and the hexagonal MgZn,-type Laves phases at 1000°C. At 1200°C, Elliott found only the MgZn, type while at 1400°C, he observed only the MgCu2 type. At the stoichiometric composition, Co2Ta, Elliott reported only the cubic MgCu2-type Laves phase in the temperature range of 600oto 1600°C. The precipitation of the cobalt-tantalum intermetallic compound is accompanied by a marked increase in hardness. According to Koster&apos;s4 data, the Brinell hardness of an 8 pct Ta-Co alloy increases from 230 to 340 upon short-time aging at 800°C. EXPERIMENTAL PROCEDURE The binary cobalt-tantalum alloys investigated contained 5, 10, and 15 pct Ta. The range of tantalum additions was thus slightly broader than the reported minimum and maximum solid solubility limits of tantalum in cobalt (7 and 13 pct, respectively)4 The alloys were vacuum-induction melted in a magnesia crucible using cobalt rondelles and technically pure tantalum sheet as raw materials. Deoxidation of the melt was accomplished with carbon, and the chemical analysis of the alloys is given in Table I. The effect of isothermal aging treatments on the progress of precipitation was studied on samples cut from cast ingots. These samples were solution treated for 2 hr at 1250°C and water-quenched. Aging was conducted in the temperature range from 500" to 1050°C for periods between 15 min and 1000 hr and followed by water-quenching. To prevent contamination from the atmosphere, all samples were sealed in evacuated Vycor or quartz tubes for heat-treatments. For solution treatment, argon at 0.2 atmospheric pressure was introduced prior to sealing of the capsule to prevent collapse at high temperature, and titanium sponge was placed at one end of the capsule to act as a getter. MACROHARDNESS The effect of aging on Vickers hardness (Dph) of

Jan 1, 1960