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By S. Weinig, J. Winter

The grain boundary adsorption of solutes as a function of bulk concentration and solution temperature was studied using internal-frictimz techniques. From the variation of the cor-responding energy of activation for the Phenomenon, the inter-actior2 energy between a solute atom and a high-angle boundary was calculated. Interaction energies in the range of 0.3 ev were obtained, and were used to obtain the actual concentration of solute at the grain boundary. In corroboralory creel, studies the direct grain boundary contribution to the total creep strain was measured. It was found that the interface creep varied with the type and magnitude of the solute adsorbed. Subscribing to the theory of their being energetically favorable sites at the grain boundary for solutes of both Positive and negative size deviations, ternaries were investigated in Which solutes of both types were present. A marked increase in the resistance to grain boundary creep was manifested. THE major difficulty which has been encountered in investigations of the grain boundary segregation of solutes has been the lack of a sufficiently sensitive method of measuring the amount of adsorbed solute at the boundary. For the general case of a high-angle boundary, no direct method of measuring the adsorption at the boundary has been found to date. Internal friction has been used in several studies of grain boundary adsorption1-3 and although it is somewhat indirect, it was demonstrated to have the necessary sensitivity. In this investigation the authors have used internal-friction techniques in conjunction with a study of the grain boundary contribution to the total creep strain. As both parts of the investigation were performed on the same specimens it was possible to combine a highly sensitive technique with a somewhat more direct method in order to obtain information about the adsorption phenomenon. From internal-friction studies the rate of increase of the activation energy was observed to be a function of the difference in size between the solute and solvent atoms. It was proposed that if Gibbs' adsorption isotherm is considered, i.e., where r is the excess solute at the boundary, c is the bulk concentration, and ay/ac is the change in grain boundary energy with bulk concentration, then AH b/ac must vary in the same way as ay/ac and therefore In this way a relative measure of the grain boundary adsorption of solutes is directly obtainable from in-ternal-friction studies. If the previous work in the field of grain boundary adsorption of solutes is examined, certain apparent information is desirable if the phenomenon is to be understood. The most important questions that must be asked are as follows: 1) Is the adsorption of solutes at the grain boundary an equilibrium process? 2) Can the Mott model of the grain boundary be used as a basis of setting up an elastic interaction between the grain boundary and solute atoms? 3) Is it possible to obtain an exact measure of the excess solute at the grain boundary as a function of temperature and bulk concentration rather than merely a relative measure of the adsorption 4) Are the conclusions obtained from an indirect method such as internal-friction studies meaningful in considering gross grain boundary effects such as creep? EXPERIMENTAL PROCEDURE The material used in this investigation was Bureau of Mines "superpurity" titanium (79 Bhn—1500 kg

Jan 1, 1960

By Donald A. Brobst

The minerals barite (BaSO4) and witherite (BaCO3) are the chief sources of the element barium and its compounds needed for many industrial processes and products. Barite, the principal ore mineral, is found the world over and is abundant and widely distributed throughout the United States.3 Witherite is much less common than barite, though more desirable in many ways as a raw material for the production of barium chemicals. England is the chief producer of witherite. Witherite is not mined in the United States at the present time, but it has been mined with barite from a deposit at El Portal, California. Barite is also called barytes, tiff, cawk, or heavy spar. Ordinarily it is a heavy mineral that crystallizes in the orthorhombic system. It is colorless, white, or gray, and transparent to opaque. In some deposits barite is black, yellow, brown, red, green, or blue because of included impurities. The streak is white and the luster vitreous to resinous or pearly. The specific gravity of pure barite (65.7 pct BaO and 34.3 pct SO3) is calculated to be 4.5, but inclusions and impurities in natural barite may reduce this value considerably. Well-formed crystals are generally tabular and have three cleavages. The barite of many deposits, however, has an uneven fracture and an apparent cleavage caused by separation along planes between successively deposited layers. The hardness is 2.5 to 3.5 on Mohs' scale. Commercially the terms "hard" and "soft" are used to refer to ease of grinding. Barite is relatively insoluble in water and acid, and thus can be used as a chemically inert material. Witherite, the natural carbonate of barium (77.7 pct BaO and 22.3 pct CO2), crystallizes in the orthorhombic system. The fracture is uneven and the luster is vitreous to resinous. The hardness is 3 to 3.5. The specific gravity of the pure mineral is calculated to be 4.29. It is transparent to opaque. The color is ordinarily white, gray, yellow, brown, or green. Geology and Distribution of Deposits Workable deposits of barite are widely distributed throughout the world in many geologic environments in sedimentary, igneous, and metamorphic rocks. Most deposits can be classified into three main types: (1) vein and cavityfilling deposits; (2) bedded deposits; and (3) residual deposits. 1. Vein and cavity-filling deposits are those in which barite and associated minerals occur along faults, gashes, joints, and bedding planes, and in breccia zones and solution channels. They also occur in various collapse and sink structures in limestone. Sharp contacts of the veins and cavity fillings with wall rocks are common. Barite cements fault and collapse breccia by replacement of the matrix or by filling voids. Large-scale replacement of the wall rocks beyond ore-controlling structures is rare. Barite in vein and cavity filling deposits is generally dense, "hard," and white to gray. Associated minerals are fluorite, calcite, ankerite, dolomite, quartz, and many sulfide minerals, especially pyrite, chalcopyrite, galena, and sphalerite. Gold, silver, and rare earth minerals occur with barite in some deposits in the western United States. Barite is also a gangue mineral in metallic ore deposits but production as a byproduct from such deposits will be affected by many economic factors. The host rocks are igneous, sedimentary, and metamorphic rocks of pre-Cambrian to

Jan 1, 1960

By H. B. Charmbury, D. R. Mitchell

Recovery of fine coal from solids reporting to wash water has become increasingly important. These solids range from about 28 mesh to 0 and constitute 3 to 7 pct by weight of the feed tonnage to a coal preparation plant. In the past they were usually wasted to streams, but present clean stream legislation makes it necessary to remove them from the wash water and, if economically possible, recover the associated coal as a saleable product. Where these solids are not wasted to streams or to slime ponds they are recovered by thickeners and filters. Since filter cake is often high in ash or sulfur, or both, it is not readily marketed or used. Common practice is to mix it with other plant products, generally slack or cleaned run-of-mine. Uniform blending is difficult, not only because the impurity is usually high, but also because during certain operating periods it is possible to get a concentration of this filter cake in a railroad or barge. At some plants filter cake has been derived from the froth flotation clean-up of Dorr thickener underflow. The operating circuits required for a froth flotation plant make this a comparatively high-cost treatment, and in the last few years experiments have been carried out with bulk oil methods. These also are quite expensive and lend themselves only to special situations. Table I gives some characteristics of thickener underflows for plants in the Pittsburgh area treating Pittsburgh seam coal. It will be noted that there is a concentration of impurities in the -200 mesh sizes.

Jan 1, 1960

By C. A. O’Malley, F. W. Kinsey

This paper deals with an experimental study in the use of a preagglomerated burden as a means of increasing the production of sinter. The effect of a wide range of sinter burden was studied, including concentrates produced by a flotation process. Some of the important characteristics of a sinter bed are discussed along with the strength and reducibility of the sintered product. In recent years the use of sinter in blast furnaces has become increasingly important across the country—largely because of the demand for more hot iron from existing plant capacity and the increasing amount of fines in the burden materials available to the blast-furnace operator. In many instances, unfortunately, the demand for sinter has been so great that little time has been available to give the proper

Jan 1, 1960

(There are 82 Local Sections in the United States, 10 Foreign) ADIRONDACK Established June 18, 1952 Official year begins in January Meets next to last Saturday monthly April through October Local Section Dues AIME Mbrs $2 Affiliate Mbrs $3 Severn P Brown, Chairman George E Erdman, Vice-Chairman Patrick F Farrell, Secretary-Treasurer Republic Steel Corp Mineville, N Y

Jan 1, 1960

Year of Election 1959 Andrew Fletcher, New York, N Y "For his outstanding leadership in the lead and zinc mining industries, and for his able and devoted services to the Institute as its Treasurer and President, and as a Director for many years " 1917 Herbert Hoover, New York, N Y 1955 George M Humphrey, Cleveland, Ohio 1950 Zay Jeffries, Ptttsfield, Mass 1942 Essington Lewis, Melbourne, Vic, Australia 1959 John M Lovejoy, New York, N Y "For his distinguished service to the Institute, for his outstanding contributions in furthering the professional status of petroleum engineers, for his pioneering in application of engineering to petroleum production, and for his outstanding record of public service on behalf of the petroleum industry " 1957 Donald H McLaughlin, San Francisco, California 1957 C H Mathewson, New Haven, Connecticut 1938 Albert M Portevin, Parts, France 1957 Fred Searls, Jr, New York, N Y

Jan 1, 1960

By T. D. Murphy

This chapter deals with those types of silica raw materials that have been segregated and refined by natural processes into nearly monomineralic deposits and hence, by virtue of their high degree of purity, have become the sources of commodities having special and somewhat restricted commercial uses. In some instances, these raw materials occur in nature as unconsolidated quartzose sand or gravel and can be exploited and used with very little preparation and expense. More often, they occur as sandstone, conglomerate, quartzite, quartz mica schist, or massive igneous quartz which must be crushed, washed, screened, and sometimes chemically treated before commodities of suitable compositional and textural characteristics can be successfully prepared. The occurrence and distribution of silica raw materials is summarized and an effort has been made to bring commodity definitions, critical properties, and specifications up to date. Presentation of mining and processing methods is considered beyond the scope of this article; they are, for the most part, conventional and well known. New production techniques are currently reported in the trade journals and are later adequately described in technical publications as promptly as competitive restrictions allow. Discussion on Basis of Use ABRASIVE USES Industrial silica used for abrasive purposes falls into three main categories: (a) blasting sand; (b) glass-grinding sand; and (c) stone-sawing and rubbing sand. Blasting sand is a sound closely-sized quartz sand which, when propelled at high velocity by air, water, or controlled centrifugal force, is effective for such uses as cleaning metal castings, removing paint and rust, or renovating stone veneer. It is commonly referred to as Sand Blast sand. Multicycle quartz sand is an efficient blasting agent by merit of its survival characteristics which are soundness, toughness, and hardness. Steel grit and shot have supplanted it to a large extent but owing to their higher cost and tendency toward deterioration in storage, are still not universally used. It is conceded that angularity promotes faster cutting but this is offset by a higher loss in fines. The peening action of a rounded grain is a desirable feature in achieving a satin finish for certain light metal castings but a subangular grain is unsurpassed for fast heavy cutting. Specifications are chiefly based on size frequency distribution but it is mandatory that the grain be free of adhering clay or irony coatings. Material that dusts upon handling will not be tolerated. There is no uniform trade designation for the many blasting sand grades. Most producers sell on the basis of numbered grades; that is, No. 1, No. 2 and so on, this generally connoting fine to coarser grades. Designation of grade by the two sieve sizes between which most of the material lies, is practiced in some areas. Thus, in a No. 1220 grade, 98 pct of the material passes a 12 mesh sieve and is retained on a 20 mesh sieve. Blasting sand specifications vary according to use. Coarse grades range from 4 mesh to 12 mesh, medium grades range from 12 mesh to 30 mesh, finer grades may range from 20 mesh to 100 mesh or finer. Specifications generally call for narrow limits of gradation, requiring precise sizing methods. The fact that most blasting sands are retained

Jan 1, 1960

By W. V. Green

The creep-rupture behavior of commercial powder-metallurgy tungsten rod is reported for temperatures of 2250°, 2500°, 2700°, and 2800°C, stresses up to 7000 psi, and times up to 4 hr. The temperature dependence and the stress dependence of creep rates are evaluated. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher stress results reported by pugh.4 THE tensile strength of single-crystal wire1 and of polycrystalline wire2 have been measured by Goucher. More recently Bechtold3 and pugh4 have studied the mechanical properties of tungsten rod between room temperature and 1200°C. Since tungsten has the highest melting point of all metals, it should retain useful strength to very high temperatures, and should find many applications in missiles, rockets, and so forth. Therefore, the mechanical usefulness of polycrystalline tungsten rod was investigated in the 2250" to 2800°C temperature range by short-time creep-rupture tests. MATERIALS TESTED Creep specimens were machined from 1/2-in. round commercial tungsten rod which was manufactured from powder by cold pressing, sintering, and hot swaging. Purity reported by the vendor was 99.95 pct W. Spectrochemical analyses showed "traces" (less than 0.01 pct) of silicon, iron, and titanium, and "faint traces" (less than 0.001 pct) of calcium and manganese. Carbon content was 30 ppm and nitrogen content was 70 to 110 ppm. No oxygen analysis was obtained. Room-temperature stress-strain tests on the as-received tungsten gave badly scattered results. Threaded end specimens broke at the threads. When these specimens were retested using shoulder grips, the specimens broke at the shoulders. No fractures occurred in the gage lengths. The fracture stresses were: 127,000; 137,000; and 154,000 psi for three specimens which fractured at the shoulders. The microstructure of the as-received tungsten rod is shown in Fig. 1. SPECIMENS USED Fig. 2 shows the two types of creep specimens tested. The threaded-end type specimen, which was used in most tests, had a 3/4-in. gage length and 1/4-in. gage diam. The cone-end specimen, which was used primarily to investigate the effects of a smaller gage diameter and the practicability of the modified grips and specimen, had a 3/4-in. gage length and a 1/8-in. gage diam. In both cases, the gage length terminated at 0.005-in. high shoulders which served as fiducial marks for optical strain measurements. Surface finish on the gage length was 16 µ-in. rms. Creep rates and rupture times were not significantly different for the two types of specimens and were not affected by electropolishing the specimens before testing. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.5 In it the specimen is held vertically by grips of similar material and on the axis of a cylindrical tungsten or tantalum heater-tube. The specimen is loaded by means of the specimen grips, a pull rod (which is sealed to the chamber lid by a vacuum-tight bellows), a mechanical lever system, and hanging dead weights. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. An optical system views the incandescent specimen through slits in the radiation shielding and heater-tube. The optical system projects an enlarged image of the specimen gage length on a ground-glass screen. Periodic gage-length measurements are made on this image with two cathetometers. Thorium oxide coatings on the specimen threads or conical end surfaces completely prevented diffusion-welding of specimens to grips, and were used

Jan 1, 1960

By R. F. Sheldon

Largest uranium deposit in the Northwest is Dawn Mining Co.'s Midnite mine on the Spokane Indian Reservation. The orebodies lie along the contact of granite and metamorphosed sedimentary rock and are controlled by faults and shear zones near the granite contact. In the oxidized zone the deposits consist mainly of the secondary uranium mineral meta-autunite; sooty uraninite and primary uranium minerals are known to occur at greater depths. Elevations in the mine area range from 2500 to 3500 ft. The rolling hills and low, rounded mountains are covered with grass and evergreen trees. HISTORY AND DEVELOPMENT Original showings were discovered with a geiger counter in the spring of 1954 by prospectors Jim and John LeBret. High radioactivity in several schist outcrops was found due to scaly coatings of a greenish-yellow, fluorescent mineral, later identified as meta-autunite. Prior to this time autunite was not known to occur in the state of Washington, and no significant uranium deposits had been found in the Pacific Northwest. Outcrops in the area were few, and most of the ground was mantled with 2 to 10 ft of overburden, but three other radioactive zones were discovered by prospecting the ridge southward along the strike of the schist near its contact with granite for three quarters of a mile. Midnite Mines Inc. was formed

Jan 1, 1960

Established as Mining, Geology and Geophysics Division, Sept. 27, 1949 Name changed February 19, 1958 Robert J Lacy, Chairman John G Hall, Assistant Chairman Vice-Chairmen Peter Joralemon, Membership J M Ehrhorn, Program John C Wangaard, Publications A W Ness, Secretary American Smelting & Refining Co 600 Crandall Building Salt Lake City 1, Utah

Jan 1, 1960

By W. A. Tiller, J. P. McHugh

HE majority of liquidus and solidus surfaces in phase diagrams have been determined by the conventional cooling- and heating-curve techniques.' These techniques have two main shortcomings: 1) the solidus may be in considerable error due to the difficulty involved in completely homogenizing the solid and 2) the determination of liquidus and solidus in more than a two-component system does not enable one to determine tie-lines connecting the specific equilibrium solid and liquid compositions. However, in a recent paper by one of the authors,' a method was suggested whereby the liquidus and solidus surfaces plus tie-lines in an n-component system may be determined. This method utilizes a controlled solidification technique and assumes that interface equilibrium exists during freezing. The present work was undertaken with a twofold purpose; first, to determine the liquidus and solidus lines in the pseudo-binary system Bi2Te3-Bi2Se3 by heating- and cooling-curve techniques and, second, to determine the partition coefficients of Te and Se in the BizTe3-,Sex system by controlled solidifica- tion techniques. The two sets of results can be compared to test the accuracy of the controlled solidification method. EXPERIMENTAL I—The starting materials for this study were 997999 pct Bi, Te, and Se, obtained from the American Smelting and Refining Co. The compounds BizTe, and Bi2Se3 were each prepared by melting together stoichiometric amounts of the elements, followed by twelve zone-refining passes. This produced homogeneous bars of the compounds for use in the phase-diagram studies. The apparatus used to obtain heating and cooling curves is illustrated schematically in Fig. 1. The alloy samples were located in a graphite crucible placed in a stainless steel canister. The canister was supported in a heavily lagged pit furnace by a device which oscillated the canister about its vertical axis at a frequency of about 3 cycles per sec during heating and cooling-curve runs. The graphite crucible was designed to minimize the thermal coupling of the sample to the furnace. A thin graphite sleeve separated the alloy sample from the stainless steel tube that housed the thermo-

Jan 1, 1960

By D. Kramer

HASEN1 has published a phase diagram for the zirconium-nickel system. This phase diagram has been redetermined by Hayes, Roberson, and paasche2 in the range 0 to 50 at. pct Ni. Recently, Smith and Guard3 have published a tentative diagram for the

Jan 1, 1960

By Raymond B. Ladoo

Wollastonite is a calcium metasilicate, with the formula CaSiO3; containing theoretically 48.3 pct CaO and 51.7 pct Si02. It is one of many natural and synthetic silicates with varying CaO/SiO2 ratios, with and without water of crystallization. While it is a very common mineral, deposits of sufficient size and purity to be of commercial interest are unusual. There is only one producer (1958) of wollastonite for industrial use in the United States, Godfrey L. Cabot, Inc. at Willsboro, New York. There has been a small production of surface material for ornamental use from near Blythe, California. Carload tests have been made on California wollastonite for making mineral wool and a commercial plant for this purpose was projected in 1957. Properties Wollastonite is monoclinic and commonly occurs in masses or aggregates of bladed or needle-like crystals. It has a perfect cleavage parallel to the long prismatic axis. It is rather brittle and some types grind easily to a very finely fibrous product, but other types, due to interlacing of fibers, are tough and difficult to grind. Mobs hardness is 4.5 to 5; specific gravity 2.8-2.9; index of refraction 1.616 to 1.631; melting point 1,512°C. Color when pure is a brilliant white, but when less pure it may be gray or brown. Luster is vitreous, transparent to translucent. Common mineral associates are garnet (several varieties), diopside, calcite and quartz. The nature of the mineral impurities determines to a large degree the commercial value of a deposit. At Willsboro, New York, the impurities consist chiefly of iron garnet and iron diopside which are both magnetic and so are easily removable by magnetic separation, yielding a nearly theoretically pure product. Some deposits in California contain calcite and quartz which cannot be removed cheaply, thus limiting market possibilities. Occurrence Wollastonite is a contact metamorphic mineral occurring in most places within or associated with impure limestones. The deposits at Willsboro, New York1,2,3,5 consist of two or more beds dipping 15-50°E and striking NW-SE. The main bed, 30 to 70 ft thick, may be traced on the surface for at least 2 ½ miles. In this belt, the Pre-Cambrian Grenville limestone has been injected and partially replaced by the more liquid portions of an anorthositic magma. Buddington and Whitcomb3 have described the rock as "Mixed gneisses, pyroxenite and garnetiferous gneisses and skarns." Prospecting revealed the wollastonite at ten different places in the belt, overlain in most places by a garnet rock. Diamond drilling has proven several million tons with probable reserves around 15 million tons. Interbedded with the wollastonite are beds of garnet from a few inches to several feet in thickness. In the wollastonite ore itself the chief and almost only associated minerals are garnet (mostly almandite but some andradite and grossularite) with small amounts of green hedenbergite. Inasmuch as the almandite and diopside are magnetic they are easily separated from the wollastonite in high intensity magnetic separators. If grossularite should occur in quantity other means of separation would be needed. Wollastonite has been reported at 35 localities in California12 but only those in the Big Maria and Little Maria Mountains, 16 to 20 miles north of Blythe, Riverside County, are

Jan 1, 1960

By A. A. Bauer, M. S. Farkas, F. A. Rough

An investigation of the d-phase relationships between the uranium-zirconium and uranium-molybdenum systems was conducted. A ternary cut joining U-31.5 at. pct Mo to U-74 at. pct Zr is presented on the basis of differential thermal analysis, metallographic and X-ray diffraction data. HyDothetical isothermal ternary sections, inferred from the determined d-phase relationships, are presented for the uraniztm-zirconium-molybdenum system. A ternary eutectoid, at 454ºC, was found in zirconium-rich alloys. Its composition, based on metallography and electron-beam micro-analysis, is estimated as U-61.7 at. pct Zr-7.1 at. pct Mo. URANIUM binary systems have been studied extensively in the past to supply basic information needed in reactor-fuel development. Alloys of uranium with zirconium, molybdenum, and titanium are of particular interest because, in these binaries, extensive or complete solid solubility between the body-centered-cubic forms of these elements and y uranium exists. In addition, an intermediate phase of limited solid solubility forms in each of these systems by transformation of the high-temperature ?-uranium phase. Previous investigation of the phase relationships existing between the intermediate 6 phases in the uranium-zirconium-titanium and the uranium-molyb- denum-titanium ternaries have already been reported.1,2 The results of an investigation of the phase relationships existing between the 6 phases in the uranium-zirconium-molybdenum system is reported here. The phase equilibria that occur in the solid-state portions of the pertinent binary systems are shown in Fig. 1. Phase nomenclature appearing throughout the report is as shown in these diagrams. The crystal structure of the phases in this system are given in Table I. EXPERIMENTAL PROCEDURES Alloys were cast and fabricated to 1/4-in.-diam rod. Specimens were heat treated and examined by metallographic and X-ray techniques. Thermal-analysis data were obtained.

Jan 1, 1960

By D. Gupta, S. Weinig

This investigation comprises the study of dislocation-oxygen interactions in a! titanium and its effect on the ductile to brittle transition in titanium. Internal friction techniques using a low-frequency lorsion pendulum were used to study the oxygen atom interactions with dislocations in "superpurity" titanium. A calculation of the interaction energy between an oxygen atom and a dislocation, based on the "breakaway" strain resulted in a value of 0.015 ev as compared to theoretical values of 0.022 and 0.035 ev for edge and screw dislocations, respectively. Both the saturation of the room temperature decrement and the transition from ductile to brittle behavior occurred at 1.5 at. pct 0. It was proposed that the embrittlement was due to oxygen atoms immobilizing the dislocations. It was possible to increase the ductility of the Ti-0 binary alloys by decreasing the oxygen pinning. The increase in uniform elongation was 30 pct for an increase in the preanneal temperature of 300°C. ThE room-temperature ductility of a titanium is significantly affected by interstitial solutes. Although oxygen has a solid solubility of 15.5 pct by weight, the room-temperature ductility extends only to 0.6 pct.' The ductility precipitously falls at this concentration and the fracture characteristics change from ductile to brittle.2 The small effective bulk composition of solute required to destroy the room-temperature ductility of the titanium must be indicative of an in-homogeneous distribution of solute atoms. Internal friction techniques were used in this investigation to

Jan 1, 1960

By H. J. McQueen, G. C. Kuczynski

ThE useful properties of k6-Alfenol and the thermenol alloys (summarized by J. E. Nachman and W. J. Buehler') have encouraged research into those alloys which, having compositions near 25 at. pct Al, 75 at. pct Fe, undergo an ordering transformation between 500° and 550°C. The equilibrium diagram of the iron-rich iron-aluminum alloys was first determined by Bradley and Jay.2,3 They distinguished three structures: the disordered, which is bcc; FeAl, which is simple cubic with one Fe atom and one Al atom per lattice site; and Fe3Al, which is fcc with three Fe atoms and one Al atom per lattice site. This last structure may be conceived as eight body-centered cubes with Al atoms at the centers of alternate ones, so that Al atoms have only Fe as first and second nearest neighbors. Later, Osawa and Murata4 determined the boundaries of the different superlattice regions in the iron-rich Fe-Al solid solution by dilatometric and X-ray methods. Two of the six phases, which they found between 0 and 50 at. pct Al, were never identified by other workers. A. Taylor and R. M. ones,' concurrently with and independently of this research, redetermined this diagram by measuring lattice parameters at temperature. Further reference will be made to their results. EQUILIBRIUM DIAGRAM A) Experimental Procedure—The alloys were prepared from NRC gas-free iron (99.9 pct Fe) and 99.99 pct Al. They were melted in alumina' crucubles under vacuum in an induction furnace. If the ingots were unsound or showed more than a 3 pct weight loss, they were rejected. The ingots were homogenized at 1100°C for 24 hr before hot-rolling at 700" to 900°C from 1 in. to 0.25 in. thick. It is interesting to note that alloys containing more than 28 at. pct Al were able to take an 80 pct reduction of area in the ordered FeAl region. The dilatometer specimens and specimens for chemical analysis were cut from these plates. A Leitz dilatometer was used to measure the coefficient of linear expansion as a function of temperature. The specimens were slowly cooled from 900" to 300°C where they were annealed for 10 hr before slowly cooling to room temperature. The expansion was recorded photographically as the alloys were heated and cooled at 1.5oC per min between 100" and 1000°C. The magnetic measurements determining the Curie points were performed on the dilatometer specimens in the dilatometer, by using direct current in the furnace windings both to heat the specimen at 1.5°C per min and to serve as the primary coil. The regular specimen holder was replaced by a thin alundum tube on which was wound, as a secondary, a closely spaced coil of fine copper wire. A reversal of current in the furnace windings produced, in the secondary, an emf which was proportional to the induction in the specimen, and which could be detected on a galvanometer. In this way, it was possible to determine the Curie points of alloys to within * 5°C. B) Results and Discussion—The coefficients of linear expansion, as obtained from the dilatometer curves, are plotted as a function of temperature and composition in Fig. 1. Since in many cases the heating and cooling curves were superimposed, it was decided to measure slopes of heating curves only. Definite high peaks, due to the transformations, were observed on each curve between 400" and 520°C, and, for alloys containing more than 23 at. pct Al, a second set of smaller peaks at temperatures above 660°C. The sharpness of the peaks indicates that ordering to Fe3Al is a first-order reaction. The compositions and the temperatures of these peaks are listed in Table I. When these temperatures are plotted as a function of the composition, the result is the constitution diagram presented in

Jan 1, 1960

By C. Land, R. Hultgren

Heat contents of four Cr-Ni alloys were determined in a diphenyl ethev calorimeter. Aside from ferromagnetic effects, Kopp's law of additivity of heat capacities is approximately fol-lowed, in disagreement with earlier results of A. W. Foster. In 1934 Foster1 reported heat-capacity measurements of dilute solutions of chromium in nickel, primarily as a study of the effect of alloying on the ferromagnetic Curie temperature. He found that, apart from the Curie temperature effect, the general level of heat capacities was reduced 10 pct by the addition of 1 pct Cr; 20 pct by the addition of 2 pct Cr. His measurements of pure nickel essentially agreed with accepted values. These results indicate that small amounts of dissolved chromium cause an increase in the Debye temperature of nickel, presupposing a change of frequency of interatomic bonding vibrations which is much larger than should be expected. If Foster's results were verified, therefore, they would have important implications for bonding theory. The only other heat-capacity measurements in this system seem to be those of Taylor and Hinton,' who studied anomalies which they attributed to super-lattice formation at 25 at. pct Cr. At temperatures above the anomaly, Taylor and Hinton found heat capacities at this composition were quite normal, approximately obeying Kopp's law of additivity. EXPERIMENTAL WORK In order to verify or disprove the remarkable results of Foster, the heat contents of four dilute solid solutions of chromiunn in nickel were measured in a diphenyl ether calorimeter. This instrument, described elsewhere,, operates on the principle of the Bunsen ice calorimeter, but uses diphenyl ether as the working substance. Diphenyl ether melts at the convenient temperature of 26.S°C and supplies a more sensitive measure of heat than ice. The hot sample, in an atmosphere of argon, is dropped from a furnace at a measured temperature into a chamber which is surrounded by a mixture of solid and liquid diphenyl ether. The heat from the hot specimen melts some of the solid without chang- ing the temperature of the calorimeter. The amount of solid melted, and therefore the number of calories released by the specimen, is measured from the increase of volume of the mixture, which pushes mercury down a graduated capillary tube. The apparatus has been standardized against the known heat content of pure platinum. Heat loss during the dropping of the specimen was estimated by comparing the heat content of an empty platinum capsule with a solid platinum ball of the same radius and degree of polish of the surface. Repeated tests demonstrate the precision of measurement to be closer than *0.3 pct. Smoothed experimental results are listed in Table I. The tabulated values for pure nickel are taken from kelley, several measurements were made which agreed closely with this tabulation. For chromium, however, no similar agreement was found. The values tabulated were taken from a thorough study of chromium with the diphenyl ether calorimeter which will be published elsewhere.= Suitable plots of the data showed the expected ferromagnetic anomalies in the low-chromium alloys, while the 11 pct alloy shows no ferromagnetic anomaly, but a different, small anomaly below 900°K. This is perhaps the same anomaly found in CrNi, which was once attributed to superlattice formation,' but is probably due to some other cause, such as antifer-

Jan 1, 1960

By W. M. Lehrer

RECENT development of high-temperature brazing alloys has required information regarding the eutec-tic temperature and composition of the Pd-rich section of the Pd-B system.. Literature on this subject was found to be scanty with no complete system yet determined. Buddery and welch1 report an inter-metallic compound occurring in the Pd-B system at 6.33 wt pct B (PdsBz). Another source, Sieverts and Bruning,2 indicates that after annealing at 700°C, a 1.6 and a 2.0 wt pct B alloy were two phase whereas a 0.75 pct B alloy was single phase. Recent work3 using a hot-stage microscope has proposed a eutectic temperature of 743OC. This method utilized the observation of the onset of incipient melting at grain boundaries. The eutectic composition, however, was not determined. METHODS AND PR0CEDURES Five alloys were prepared by triple inert arc-melting high-purity palladium (95.98 pct) with additions of 2 to 6 pct purified amorphous boron. The alloys were crushed within a hardened steel mortar with a steel pestle. The 2 pct alloy, however, was too tough to be crushed in the above manner so was crushed by successive reductions through a rolling mill. Approximately 17 to 18 g of the crushed alloy was used in the thermal analysis. The alloys were melted in pure quartz crucibles. The thermocouple protection tubes were also of quartz and fused along the inside wall of crucibles to prevent floating of the thermocouple. This was an expediency as centering of the thermocouple in the melt would have been preferable. Melting was done in a tube furnace with a slow flow of tank helium maintained as a protective atmosphere. Heating and cooling rates were maintained at 3.5OC per min through the critical temperature ranges by means of a synchronous motor hook-up to a furnace controller. All specimens were heated to 100°C over the indicated liquidus on heating prior to reversing to the cooling cycle. Specimens emerged from the furnace with mirrorlike brightness attesting to the protective quality of the helium atmosphere. Thermal arrests were detected by the differential thermocouple technique using chrome l-alumel couples and nickel as the reference specimen. Arrests were recorded on a Leeds-Northrup automatic X-Y recorder. The specimen temperature and temperature difference were read to + 7.5OC and ± 1.5OC, respectively. These readings were well within the sensitivity of the instrument amplifier. Chromel-alumel couples were used in lieu of Pt-Rh as very few arrests were contemplated in excess of 1200" to 1300°C, the approach of instability. No standardization was performed on these thermocouples subsequent to their use. RESULTS The thermal arrest temperatures obtained are plotted in Fig. 1 as a function of wt pct B. The composition function was obtained by chemical analysis of portions of the specimens after the thermal analysis was completed. The 2 to 6 pct nominal alloys were found to have 1.80, 2.35, 3.65, 4.18 and 5.90

Jan 1, 1960

By R. E. Reed, R. D. Leggett, Paxton, H. W.

TECHNIQUES have been developed for growing monocrystals and bicrystals of Fe-20 Cr, Fe-20 Cr-20 Ni, and Fe-18 Cr-8 Ni alloys by both the strain-anneal and the Bridgeman techniques. None of the techniques are new but since they are simple and many people have expressed interest, they are described here quantitatively as they could be modified for other single-phase "commercial" materials of high melting point. CRYSTAL GROWTH BY STRAIN ANNEAL Flat tensile specimens with a tapered gage length were initially studied to deduce the approximate critical strain. Normal flat tensile specimens were then used. The optimum procedure for the austenitic steels (Fe-Cr-Ni) deduced from a variety of cold reductions, recrystallization treatments, tensile strain, and growth anneals was as follows: cold reduce 70 pct, recrystallize (after machining tensile specimens) at 1000°C for 1 hr, strain in tension 2.5 pct, and then heat to 1350°C as rapidly as possible. A time of 100 hr at 1350°C is usually sufficient to pro-

Jan 1, 1960

By J. W. Rutter, K. T. Aust

The motion of individual grain boundaries under a constant driving force was investi,qated for zone-refined lead, with and without solute tin additions. The rate of boundary migration was found to depend strongly on tin content and on the orientation relationship between the adjacent grains. The results are compared with the theory of impurity-controlled grain boundary miqration developed by Lucke and Detert. Evidence was found that grain boundaries separating grains which have the Kronberg-U&apos;ilson orientation relationships of 38 and 22 deg about <Ill> and 28 deg about <100>, correspond to boundaries of high mobility. The results are discussed in relation to the formation of annealing textures in metals and the structure of high-angle boundaries. It is generally known that small amounts of impurities in solid solution greatly influence the re-crystallization behavior of metals. For example, the addition of 0.005 at. pct of tellurium to copper,&apos; or 0.005 at. pct of silver to lead,2or 0.01 at. pct of manganese or nickel to aluminum3 greatly decreases the rate of recrystallization of these metals. However, this effect may be the combined result of a decrease in the rates of both nucleation and growth; recrystallization experiments do not separate these two factors. Bolling and winegard4 determined the effects of small quantities of tin, silver, and gold on grain growth in polycrystalline zone-refined lead.

Jan 1, 1960