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By N. Parlee, V. C. Kashyap

The solubilities of nitrogen in liquid iron and liquid Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys were measured by the Sieverts method. Measurements were made at 1600° to 1800°C on binary alloys up to 20 pet Ni, 10 pet V, 10 pet Mo; and on ternary alloys containing 0 to 3 pet V with 0 to 5 pet Mo. The results on liquid iron confirm that Sieverts' law is obeyed in the range 50 to 750 mm pressure. The measured solubilities and their temperature coefficients are in general agreement with other modern authors. The logarithms of the activity coefficients of nitrogen in the binaries are approximately linear functions of the pet of alloying element. A method suggested by Wagner, Chipman, and others for predicting gas solubilities in complex alloys from solubility data on binaries was applied to the Fe-Mo-V alloys. Reasonably good agreement was obtained between calculated and experimental solubilities. NITROGEN'S solubility in liquid iron has been studied by a number of investigators. It is reasonably well established that the solubility of nitrogen follows Sieverts' law at least up to 1 atm partial pressure and that the solubility increases gradually with temperature. The solubility of nitrogen in Fe-X binary liquid systems has been investigated in only a few cases. Only the systems Fe-Cr,3-5, 7 Fe-V,3 Fe-Mn,3, 5 Fe-Ni,3, 5 Fe-Si,B, H Fe-C, L, H and Fe-P4 appear to have received any study. The only work on liquid Fe-V was done by Brick and Creevy.3 This was limited to 13.5 pet and 26.5 pet V, but no exact temperatures were recorded. No work whatsoever appears to have been done on liquid Fe-Mo alloys and even work on Fe-Ni alloys is rather scant. The work on liquid ternary systems is still more limited, and the only publication available appears to be that of Wentrup and Reif,7 who studied the Fe-Cr-Mn and Fe-Cr-Ni alloys. Rassbach, Saunders, and Harbrecht17 have reported work on the solubility of nitrogen in stainless steel but this was not a systematic study of any particular system. Commercial alloys usually contain several alloying elements. Thus, it often becomes important to be able to predict the nitrogen solubility in systems containing two or more added elements without the necessity of making measurements. Wagner,14 Chipman," Darken and Gurry," and Morris and Buehl 14 have suggested means by which this may be accomplished, and Langenberg14 has recently applied one of these methods to nitrogen solubility in complex liquid alloys. This paper reports the results of nitrogen solubility determinations on Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys and compares calculated and experimental solubilities in the ternary alloy. Attempted measurements on Fe-Cr alloys were not successful by the experimental method employed. Experimental Method The general method of solubility measurement was that of Sieverts.' The apparatus and procedure were essentially the same as used by Liang, Bever, and Floe."' The equipment consisted of a small vacuum furnace heated by a 6 kw induction unit, gas measuring apparatus, and a gas purification train. The crucibles used were Norton Alundum with alumina sand around them for insulation. The crucibles were charged with 100 to 200 g of material, about 180 g or nearly filling the crucible being found most satisfactory. Hot volumes were determined with argon and ranged from 95 to 130 cu cm (stp). Temperature measurements were made with a Leeds and Northrup optical pyrometer which was calibrated periodically against the melting point of iron in the same apparatus."-'* Good quality nitrogen, hydrogen, and argon gases were further purified and dried in standard purification trains. The sources of the high purity iron and other alloying elements used were as follows:

Jan 1, 1959

By J. W. Freeman, J. P. Rowe, R. F. Decker

HEAT-to-heat variations in properties of an alloy of constant nominal chemical composition have been a perplexing problem to the metallurgist. These heat-to-heat differences have been especially baffling in high-temperature metallurgy. In order to establish fundamental reasons for these heat-to-heat variations, the National Advisory Committee for Aeronautics has sponsored and financially assisted an extended research program on heat-resistant alloys at the University of Michigan. As part of the program to find the contribution of processing variables, Frey, Freeman, and white' studied effects of heat treating on nickel-base alloys and Ewing and reeman' investigated effects of hot-working practice on N155 alloy. To extend the program to the study of effects of melting practice on high-temperature properties, a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 pct A1 composition was selected for experimentation. The objective of this program was to establish the melting-practice variables which influenced the hot-working characteristics and creep-rupture properties and, at the same time, establish the metallurgical mechanisms for the effects. During the course of the investigation of practices using vacuum melting, it became increasingly evident through chemical analyses supplied by industrial concerns that a major variable was melt reaction with the crucible. This paper is devoted to the results of this phase of the melting-practice study. EXPERIMENTAL PROCEDURES Experimental 10-lb heats were induction melted in the University of Michigan vacuum-melting unit with the melting practices outlined in Table I. Aim analysis for the basic alloy, in wt pct, for all heats was as follows: Cr Co Mo Ti Al 20.0 15.0 4.0 3.1 3.1 Mn Si C Ni 0.12 0.12 0.08-0.15 Bal. Small amounts of boron and zirconium were added to certain heats as listed in Table I. These additions

Jan 1, 1959

By J. A. Rowland, C. W. Funk

THIS investigation is a part of the United States Bureau of Mines work in conserving the Nation's resources. The isothermal sections presented were developed as a guide to a comprehensive investigation of the properties and fabricating characteristics of copper-base alloys containing manganese and tin. These alloys are being investigated as possible replacements for the commercial bronzes containing substantial quantities of tin. Development of the isothermal sections has, therefore, been limited to the area between 0 to 20 pct Mn and 0 to 25 pct Sn. Since Heusler1 reported the ferromagnetic properties of the Cu-Mn-Sn alloys in 1903, the system has been the subject of several investigations. These studies were largely concerned with correlation of magnetic properties and crystal structure.2-6 Vero,' however, established the solidus surface of the system, between 20 pct Mn and 40 pct Sn, by thermal and microscopic methods. The a, ß, and y solid solutions were also observed by Vero and reported to extend into the interior of the ternary system. For the present study, the annotated diagram of the Cu-Sn system prepared by Raynor' and the Cu-Mn diagram by Dean and coworkers9 were used as the binary borders of the ternary system. Procedure The metals used in this investigation were electrolytic manganese, washed cathode copper, and three-star tin. The manganese, produced at the Boulder City pilot plant of the Bureau of Mines, had a purity of 99.9 pct; the copper contained less than 0.004 pct Bi and 0.001 pct S; the tin contained 0.070 pct Pb, 0.070 pct Sb, 0.050 pct Fe, and 0.065 pct Si. Heats of 1 lb were melted in alundum crucibles with a 3-kw induction furnace. The heats were chill-cast in iron or copper molds to form 6-in. ingots 3/4 in. in diameter. Molds were washed with graphite or zirconia, depending on the manganese content, and preheated to 150°C. The maximum impurity content of any alloy was 0.03 pct Fe, 0.02 pct Si, and 0.02 pct Al; in most cases, they contained less than half this quantity of any of these impurities. Composition of the alloys and their treatment prior to homogenizing are shown in Fig. 1. Designations adjacent to each composition refer to the heat numbers. With a few exceptions, ingots containing 20 pct Sn or less were hot-swaged. These ingots were swaged, after a 24-hr preheat at 650°C, to obtain a total reduction of 70 pct in cross section. Intermittent reheating was necessary, and reductions were limited to either 0.025 or 0.050 in. in diameter per pass. Selection of a 200-hr homogenizing treatment was based on extensive experiments which indicated that virtual equilibrium was reached after 150 hr. Structures were retained by quenching in water. Grain sizes in the specimens homogenized at 350" and 450°C were generally small. These homogenizing treatments were preceded by a 50-hr anneal at 650°C to facilitate phase identification by increasing the grain size in these specimens. The specimens were furnace-cooled from this temperature to the homogenizing temperature, and the heat treatment was continued for the standard 200-hr period. The homogenized samples were bisected to provide an internal section for metallographic examination. Optimum definition of the microstructure was obtained by successive polishing and etching. Quarter-strength ASTM copper reagent No. 13 gave the most satisfactory results.10 Filings from interior sections of the samples were used for diffraction studies. These filings were annealed in evacuated glass tubes at homogenizing temperatures for periods exceeding 50 hr and quenched in water. During this treatment the manganese content was reduced by significant amounts, probably by vaporization. This change in composition was considered in applying the diffraction data, which were used only as a means of identifying phases where the data were consistent with the metallographic evidence. Phase Identification The a solid solution is readily distinguished by the copper-colored, twinned, polyhedral grains, as shown in Fig. 2, and a face-centered cubic X-ray pattern. Tukon indentations, using a 25-g load, indicate a Knoop hardness of 155 for a quenched from 650°C. Using white light developed by a Wratten 78 A filter, the ß grains in etched specimens have a dark brown tint in contrast to the lighter copper-colored grains of the a phase. Knoop hardness values of 284 were obtained for the ß structure in specimens quenched from 650°C. The ß structure was also distinguished from the a phase by its body-centered cubic lattice. The acicular structure appearing in Fig. 3 was evident in several alloys of higher tin content after quenching from either 750' or 650°C. Since a trans-

Jan 1, 1954

By R. R. Klimpel Discussion by C. C. Harris, L. G. Austin

C. C. Harris (Columbia University) — The authors ' have presented relationships for the random division of a magnitude into r + l parts taking account of the order of selection. Interpreting their model in comminution terms, their Eqs. 7, 9 and 11 refer to the one-dimensional case; that is, to the subdivision of a long thin rod at random. It is assumed that the fragments may be indefinitely small. Real materials, however, are limited in the degree of subdivision which can be attained through the intervention of practical restrictions. One in fine grinding is the depletion of microflaws as material becomes finer. Another is the

Jan 1, 1969

By C. W. Davis, R. S. Dean

AMONG naturally occurring inorganic compounds, magnetite has many unusual and interesting properties, and it is the purpose of this paper to call attention to these properties and review possible uses of magnetite that might be based on them; in other words, to see what uses may be found for magnetite as a physical rather than as a chemical entity, as a mineral rather than as an iron ore. The Mineral Physics Studies initiated in the Metallurgical Division of the U. S. Bureau of Mines a few years ago gathered together much information on mineral properties, and they are therefore the principal source of material for this paper. Magnetic Properties Of Magnetite And Possible Uses As A Magnetic Material Magnetite is unique among minerals for its great magnetic susceptibility, approximately one-third that of soft iron, and some magnetites are permanent magnets, or lodestones. The literature contains many measurements of magnetic properties of individual magnetite crystals, but no systematic survey of the effect of mechanical preparation and heat-treatment was available until the recent investigations of the Bureau of which included not only susceptibility but coercive force and remanence as well. For the purpose of orientation, Table 1 gives the magnetic properties of several samples of magnetite and of a few other substances3. This table indicates that when ordinary magnetite is powdered it decreases in susceptibility and increases in coercive force and remanence, approaching the properties of lodestone. The properties of lodestone are in fact probably due to the development of very large internal surface on fine grain size4.

Jan 1, 1937

By Lyle L. Marsh, David L. Douglas

CORRELATION was made between the heat treatment and hardness of three U-Ti alloys ranging in composition from 8.5 to 50 atomic pct Ti. The following important observations were made: 1) A direct quench of y U-Ti solid solution resulted in the formation of a hard martensitic phase in low-titanium alloys. 2) Subsequent tempering initially increased the hardness by the precipitation of a fine dispersion of U2Ti; further precipitation of U2Ti with tempering time eventually resulted in softening. 3) High-hardness levels were obtained also by isothermal transformation of an 8.5 atomic pct Ti alloy at 400º and 500°C. 4) The crystal structure of the phases present at the solution-treating temperature (one region in the phase diagram excepted) and the temperature within a given phase region affected the hardness of both quenched and isothermally transformed alloys. Introduction It has been known since 1887 that the mechanical properties of metals were dependent upon their microstructure. Sorby pointed out in that year that annealed gray iron castings were softer than chilled iron castings by virtue of the graphite which had replaced hard cementite in the microstructure. Over the years, interest has increased in the effect of microstructure on the mechanical properties of metals, and now high-strength levels may be achieved by bringing about the dispersion of a second phase or by other microstructural adjustments. The nature of a second phase in an alloy strongly influences the properties. For example, the size, shape, amount, and distribution of a second phase plays a very important role in the ultimate properties of an alloy. Microstructural control is achieved by heat treatments. Hence, any alloy system of potential use should be understood in terms of its response to heat treatment and the resultant effects upon the properties.

Jan 1, 1958

By Roy P. Full, Robert M. Grantham

Regional structural adjustments in early Tertiary time resulted in the development of the Republic graben, a major down-dropped block that is from 6 to 10 miles in width and more than fifty miles in length. The graben became the center of extensive volcanic activity during Eocene and Oligocene time, resulting in a thick sequence of water-laid tuffaceous sediments, volcanic flows, and associated intrusives. A younger series of sediments, pyroclastics, and flows were deposited in structural depressions within the graben following the period of widespread volcanic activity. The Republic mining district is located along one of the major intragraben structural zones, where continuing subsidence during the period of volcanic activity resulted in an increased thickness of flows and associated flow breccias and pyroclastics. Intrusive masses in part healed early graben-forming faults, but later subsidence reopened old faults and created new fracture zones which later became the control for the gold-quartz veins. Considerable block adjustment along the subsidence area is evidenced by the structural pattern in the mines, and telescoped vein structures indicate north-south compressional stresses and east-west graben-forming tensional stresses prior to and during the emplacement of the veins. The veins, varying from a few feet to more than 50 feet in width, are filled primarily by fine-grained quartz, commonly chalcedonic or porcelain-like in appearance. Finely laminated dark-gray to black concentric banding within the veins generally distinguishes the better-grade ore zones, which contain finely disseminated sulfides and ore minerals that include principally electrum, stephanite, naumannite, and native silver.

Jan 1, 1968

By Harry A. Lipsitt, Douglas Y. Wang

A fatigue study in completely reversed axial tension-compression has been perforried on high-purity titanium and on three high-purity alloys of titanium. The alloys each contain approxi7nately 0.75 at. pct of a single interstitial element; carbon, nitrogen, and oxygen, respectivley. The results corroborate a previously published theory which proposed that strain aging under alternating stress was responsible for the fatigue limit behavior of certain alloys. The present data indicate that in these alloys an increasing strain-talline aging effect under alternating stress is provided by oxygen, carbon, and nitrogen, respectively. CURRENT research on the nature of the fatigue limit in metals suggests that the presence of a fatigue limit in metallic materials is a manifestation of strain aging that occurs under alternating stress.lm5 A comprehensive theoretical model based on the above hypothesis has been developed to explain the existence of a fatigue limit.' This model also provides increased insight into several other fatigue phenomena as under stressing, overstressing, and coaxing effects. The theory, as well, provides equal understanding for those cases where no real fatigue limit is observed. Briefly, this theory assumes that the S-N curve for a pure metal is a smooth function of the applied stress, and the effect of adding an element that is soluble (or forms a precipitate) in the pure metal is simply to shift the S-N curve to the right. If the added element confers the power to strain age, the result is a further shift of the S-N curve, this time upward and to the right. Since strain aging is not expected to be a strong function of stress, and since damage per cycle is known to be quite stress dependent, it is to be expected that there will be some limiting lower stress at which the strengthening due to strain aging will balance the damage due to crack propagation. This stress is the fatigue limit. The position of the fatigue-limit knee was thought to be a function of the magnitude of the strain-aging effect on both the finite and infinite life portions of the S-N curve. Although the strain aging hypothesis seems to be reasonably valid for bcc materials,2'6 it needed to be tested for both fcc and cph metals. This report is the first of a series concerning the fatigue-limit behavior of titanium with varying amounts of the interstitial solutes (C, N,, and 4) that are known to cause static strain aging in titanium. Yield-point effects have been reported for polycrys-talline high-purity titanium alloys containing either carbon, nitrogen, or oxygen.7'9 These effects were observed at testing temperatures in the range 100 to 300'. In addition yield-point and strain-aging effects have been reported for single crystals of titanium containing 0.1 wt pct C plus N.' These yield points were observed over a wide temperature range, but no room-temperature aging occurred. Aging at 180' was required to cause the return of the yield point. The magnitude of the yield phenomena in titanium containing interstitials is not expected to be as large as is observed in bcc metals because of several factors. Titanium has a very high chemical affinity for oxygen and nitrogen. The thermodynamic stability of solutions of oxygen or nitrogen in titanium is recognized. Lattice parameter measurements of titanium containing arbon, oxygen,1° or nitrogen" show that the "c" parameter is expanded more than the "a" parameter, but that up to about 2 wt pct this results in an insignificant change of the axial ratio 'c/a." Ehrlich" has shown that the sites occupied by interstitial atoms in titanium are spherically symmetrical and therefore a lattice expansion, at a constant c/a ratio, results in a simple dilation of the interstitial site. Such a dilation involving no shear has been shown to react only with edge components of dislocations.13 This causes only a weak pinning action. Shear stresses would be anticipated locally when only one of the two interstitial positions was occupied. The carbon atom will cause a symmetrical distortion of the lattice whereas the oxygen and nitrogen atoms have, in addition, the previously mentioned chemical affinity of titanium for these elements. These factors will result in a considerably smaller reduction of free energy upon the association of interstitial atoms with dislocations, and therefore a much weaker pinning than has been observed for the bcc metals. These considerations would lead to the hypothesis that of the interstitial elements considered here carbon would cause the strongest pinning effect in titanium where the amount of interstitial in solution is constant. This hypothesis will be borne out in the analysis of the present results.

Jan 1, 1962

By Albert J. Phillips

IT is a privilege and a pleasure to deliver this, the Twenty-sixth Annual Institute of Metals Division Lecture. Eleven years ago C. A. Edwards addressed this audience on the subject "Gases in Metals." In spite of this relatively recent presentation, I propose to, present to you some quantitative considerations of industrial significance on the separation of gases from molten metals because recent observations and measurements, presented in the literature, have made it possible to evaluate mathematically the gases or gas-forming elements and to develop an understanding of the mechanism of gas separation that should permit, in many cases, the control of this baffling phenomenon. DEFINITIONS Before becoming involved in the subject it seems desirable, for the sake of clarity, to state certain definitions and axioms: I. We are dealing only with gases that separate from the molten metal either during cooling or in the transition from liquid to solid. Gases injected by the liquid stream and trapped in the solidified metal, or those forced into the solidifying metal from the mold due to either thermal or cher4ical effects are not considered. Neither are we concerned with the separation of gases within the metal after solidification is complete for the data on this subject are at least complete enough to permit the practicing metallurgist to satisfactorily control the phenomenon. 2. Only where there is a decrease in solubility or a change in equilibrium of either a gaseous element or an element that reacts to form a gaseous compound, can there be a separation of a gaseous phase from the liquid or solidifying metal. 3. The amount of gas separating from the liquid during solidification can be computed directly from the amount of the element contained in the liquid when freezing commences less the amount of the element found in the solid either as a separate solid phase or in solid solution. 4. There can be no separation of gas bubbles unless the told pressure of the gases in the liquid meld exceeds atmospheric pressure plus the hydrostatic pressure of ' the liquid metal head. (In addition, pres- sure resulting from surface tension in- creases the total pressure requirement for initial gas separation. Probably the remarkable differences in appearance caused by different gases in the same host metal are influenced greatly by the rate of diffusion of the gas in the liquid metal balancing the decrease in pressure as the gas bubble size increases and the surface tension effect decreases. Thus hydrogen with its high diffusion rate in liquid copper separates in the form of relatively coarse cavities for a given rate of heat extraction.) 5. Gas separation can take place at less than atmospheric pressure in the voids created by the shrinkage from liquid to solid, but since the voids are not caused by the gas the presence of gas in the voids is of importance only where it

Jan 1, 1947

By E. Gregory, C. G. Goetzel

The outstanding elevated temperature properties of materials made from sintered aluminum powder have been well established in recent years.1,2 and considerable investigation has been carried out on the structures which appear to be responsible for this type of strengthening.2,3 The maximum operating temperature of such materials is severely limited, however, by the low melting point of the aluminum matrix; and, therefore, considerable interest was aroused in methods of introducing the

Jan 1, 1959

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By Sandip K. Mitra, John E. Dorn

The Basinki-modified Seeger equation for deformation of metals by means of thermally activated intersection of dislocations was used to ascertain the various factors responsible for the strain hardening of poly crystalline aluminum and a series of a solid solutions of magnesium in aluminum. The analyses were based principally on the rate of change of strain rate with stress and the Cottrell-Stokes ratio. From measurements of these quantities on a series of strain-hardened states, the force displacement diagram for intersection, the density of dislocations in the entanglements, and the contributions of the athermal local stress and long-range stress interactions were deduced. Poly crystalline aluminum was observed to have the same force-displacement diagram for intersection as single aluminum crystals, and the corresponding diagram for the magnesium alloys differed in a manner that suggested that small amounts of magnesium may decrease slightly the stacking fault energy of aluminum. Although poly crystalline aluminum had about the same initial density of dislocations as the single crystals, the density of dislocations increased much more rapidly with strain in the polycrystals. This factor and the higher back stresses generated in the poly crystalline aluminum were the major factors responsible for the higher strength of the poly crystalline aluminum, As the magnesium content of the alloys was increased, the initial density of the dislocations also increased. Most of the alloy strengthening arose from this factor; alloying effects due to short-range order strengthening, Suzuki locking, Cottrell pinning, and so forth, were estimated to be quite small. The gveater rate of strain hardening in the alloys was deduced to be due primarily to the greater increase in the density of the dislocations with strain as the magnesium content was increased. It is the purpose of the present investigation to shed additional light on the average plastic behavior of a grain in a polycrystalline aggregate, by analyses, based on dislocation theory, of appropriate experimental test results. These deductions when compared with those from single-crystal data will then serve to illustrate the major items of difference between the plastic behavior of single crystals and the average behavior of a grain in a

Jan 1, 1963

[MINING AND EXPLORATION DIVISION Established as Mining, Geology and Geophysics Division, Sept. 27, 1949 Name changed February 19, 1958. Lyman H. Hart, Chairman Robert J. Lacy, Assistant Chairman Vice Chairmen: John C. Wangaard, Membership J. M. Ehrhorn, Program John G. Hall, Publications C. E. Nelson, Secretary American, Smelting and Refining Co. 120 Broadway New York 5, New York Editor, Rock-in-the-Box: J. W. Chandler.]

Jan 1, 1961

By R. H. Martinson, E. Teghtsoonian

The effects of magnesium-rich surface layers of varying thickness on the mechanical properties of LiF have been studied. The yield stress, critical tensile stress, and work-hardening slope increase linearly with layer thickness, while the strain to fracture decreases yapidly with increasing layev thickness. The results of tension tests, supplemente!d by metallogvaphic evidence, indicate that the yield stress and the critical tensile stress of LiF are not determined by surface-source operation. DESPITE many studies, which have recently been reviewed,' certain fundamental aspects of the plasticity of LiF remain obscure. For instance, one question still awaiting a satisfactory resolution is: does the nucleation and/or multiplication of dislocations in LiF occur preferentially near the crystal surface? It is now well-known that mobile dislocation half-loops are readily introduced into LiF by surface damage and that the mechanical properties of LiF are affected by such surface damage. However, it is not known whether, in the absence of large numbers of artificially introduced surface sources, dislocations arise more easily near the crystal surface than in the crystal interior. It is also not known to what extent existing mobile dislocations multiply preferentially near the crystal surface. The present work is an experimental study of these matters. A short investigation of the effect of magnesium -alloyed surface layers on the deformation of LiF single crystals has been published by Westwood.~ Some relevant conclusions drawn from this research are restated here for purposes of comparison with the present work. 1) Tests on as-cleaved, chemically polished, coated and uncoated specimens show that a coating can restrict the operation of artificially introduced surface sources, thereby raising the yield stress. A coating also decreases the initial rate of work hardening of as-cleaved LiF crystals by reducing the number of active dislocation sources, so that mutual dislocation interference effects are lessened. 2) A catastrophic breakthrough of groups of edge dislocations piled up against the coating can cause stress drops in the stress-strain curve. 3) A surface coating can act as a stable barrier to the egress of dislocations, causing pile-up,

Jan 1, 1965

By D. D. Pollock, D. I. Finch

Relationships between the compositions of specially prepared manganin-type alloys and some of their electrical properties have been established. Empirical equations, based upon the electronic configurations of the alloying elements, are given which describe the resistivity, temperature coefficient, peak temperature, and thermoelectric power of Cu-Mn-Ni-Fe alloys at approximately room temperature. Calculations based upon these relationships are correlated with experimental data. SECURING suitable alloys for the construction of stable resistors, for use in precise electrical measuring devices, has been important ever since the art of electrical measurement was begun. German silver, Pt-Ag, and Platinoid are examples of some of the alloys in early use. These early alloys were un- satisfactory for one or more of the following reasons: l—insufficient stability of electrical properties with time, 2—poor reproducibility of electrical characteristics from melt to melt, 3—excessive temperature coefficients of resistance, and 4—excessive cost. Weston introduced the Cu-Mn-Fe and Cu-Mn-Ni-Fe alloys of the type now generally known as manganins. His patents are believed to represent the first disclosure of any alloy with a negative temperature coefficient of resistance. After this work, the German company, Isabellenhutte, in conjunction with Feussner and St. Lindeck, produced alloys of

Jan 1, 1957

DISCUSSION, M. Cohen presiding A. H. Geisler and D. L. Martin (GeneTal Electric Research Laboratory, Schenectady, N. Y.)—We were rather interested to note the author's conclusion that the cubic to tetragonal transformation may be of the second order, for we have been able to show that the order-disorder transformation in an analogous alloy system is a first-order transformation with a discon-

Jan 1, 1952

By A. E. Bibb, F. W. Kunz

A platelet form of zirconium hydride was found in zirconium and ZY-1 wt pct U single crystals containing hydvogen in the range of 50 to 100 ppm. The habit planes for the hydride plateletg in the zirconium crystals were found to be {1012}, {1121}, and (1122) while the habit planes in the ZY-1 wt pct U crystals were {1121), {1123}, and (1.231). With the exception of the {1231} plane, these have been identified as the twin planes in zirconium. The different effect of hydridc on the mechanical puoperlies of zirconium at high and low strain rates has been explained in terms of the defornzation mechanism and the habit planes of the hydride. ZIRCONIUM and zirconium-base alloys are considered for many nuclear reactor applications, where the pick-up of hydrogen is a distinct possibility, if not an unavoidable occurrence. An excellent example of this is the absorption of hydrogen by zirconium and its alloys during aqueous corrosion, where as much as 30 pct of the hydrogen produced by the corrosion reaction is picked up by the metal. Under the proper conditions, the absorbed hydrogen would precipitate as zirconium hydride and consequently alter the mechanical and physical properties of the zirconium-base alloys. The knowledge obtained from a study of the crystallographic aspects of the hydride precipitation is necessary for the interpretation of the observed changes in the mechanical and physical properties. The deleterious effect of hydrogen on zirconium-base materials is not always observed in normal slow tensile loadings at or above room temperature, but becomes immediately obvious under impact loading, where the energy absorbed decreases with increasing hydrogen content,' and in notched specimens where triaxial loadings are attained.2 This effect is of serious consequence in the applications of Zr where shock loads or high strain rates are experienced. The purpose of this investigation was to determine the crystallographic planes of the Zr and Zr-1 wt pct U matrices upon which zirconium hydride will precipitate and to correlate these with the observed mechanical property data. PROCEDURE Crystal Growth—Single crystals of Zr and Zr-1 wt pct U alloy were used in this investigation. The Zr crystals were made from sponge that had a typical analysis as shown in Table I. Large grains were grown in this material by rapid cooling an arc-melted charge in a button furnace. This operation undoubtedly lowered the volatile impurity concentration below those listed in Table I. Back-reflection Laue patterns of these large grains showed the presence of considerable substructure and lattice distortion within each grain. It was found that an 18-day anneal in an argon atmosphere at 840°C (a high a heat-treatment) followed by furnace cooling, resulted in the further growth of the large grains and removed the detectable substructure ana lattice distortion. Equiaxed crystals with a cube edge of approximately 1/4 in. were produced in this manner. Large crystals of Zircaloy-2 (1.5 wt pct Sn, 0.15 wt pct Fe, 0.1 wt pct Cr, 0.05 wt pct Ni) also were produced by this technique but the large amount of substructure formed could not be removed by annealing. The Zr-1 wt pct U solid solution crystals were produced from an alloy rod consisting of Westing-house-Foote hafnium-free crystal bar zirconium and depleted uranium. The chemical analysis of the alloy is also given in Table I. Three-inch sections were cut from an 0.120-in.-diameter alloy rod and tapered to a fine point on each end. The samples were sealed in evacuated Vycor tubes, homogenized for 5 hr at 1000°C in the ß-phase field, and slowly lowered in a gradient furnace into the a phase (800°C), annealed for 60 hr at this temperature to produce grain growth and furnace cooled. This technique produced large grains approximately 1/2 to 3/4 in. long over the entire cross section of the rod, which were free of observable substructure. Metallographic examination up to X1000 did not show the existence of any second phase in these grains. Crystal Orientation—All crystals were abraded on fine emery paper to produce two flat surfaces 90 deg to each other. The crystals were analyzed by the standard Back-Reflection Laue technique to obtain the crystal orientation with respect to the abraded surfaces. The Back-Reflection Laue Photograms of all crystals used were clear and sharp indicating that the crystals were free from any substructure that could be detected by these means. Hydriding—Only samples containing four to five grains were used for hydriding. Samples that exhibited fine grained patches were discarded. The samples were hydrided using the following technique. After etching in 48 vol. pct HNO3, 48 vol. pct H2O, and 4 vol. pct HF (48 pct) solution, the specimens

Jan 1, 1961

By R. W. Powers, M. V. Doyle

ThE solution of a diatomic gas such as 0, or N2 in a metal usually follows Sieverts' law; i. e., Here C is the solute concentration at equilibrium and P, the gas pressure. The proportionality constant Ks is also the equilibrium constant for the reaction 1/2 02 (at pressure, P) - 0 (in solution at [21 concentration., C). to use oxygen as an illustrative gas. Sieverts' law is therefore interpreted to indicate that diatomic gases go into metallic solution atomically and that the solute "gas" atoms interact negligibly with each other. Of course, this interpretation is strictly valid only over the temperature interval in which the reaction indicated in [Z] can be investigated. At temperatures several hundreds of degrees below this interval, the possibility of interactions between solute atoms is conceivable. Indeed, from internal-friction measurements some evidence for the existence of groupings of oxygen atoms in tantalum solid solutions was presented a few years ago.1,2 Over a range of solute concentration, the experimental oxygen internal-friction peak in tantalum, measured as a function of temperature at constant frequency of vibration, can be described as the sum of two elemental peaks, each corresponding to a separate relaxation process. At 0.7 cps, the height of the elemental peak found at 137°C is proportional to the oxygen content, whereas the height of the one at 162°C varies as the square of the oxygen concentration. The 137°C peak was presumed to arise from the stress-induced ordering of oxygen atoms among various classes of octahedral sites in the manner proposed by Snoek.3 The 162°C peak was attributed to a somewhat similar stress-induced ordering process, in which each oxygen atom was interacting with a neighboring oxygen atom. Similarly, the experimental peak due to nitrogen in tantalum can also be described as the sum of two peaks. The height of one varies as the nitrogen concentration and the other as the square of this quantity. In fact, some evidence of solute interactions exist for all oxygen and nitrogen solid solutions of Group V transition metals. However, the interaction energy was not obtained previously for any alloy. The determination of this quantity, as a part of a more intensive study of the interaction between oxygen atoms in solid solution in tantalum, is reported in this paper. PRINCIPLE OF THE EXPERIMENT Consider an equilibrium in a solid solution of tantalum between oxygen atoms which are bound together pairwise and those solute oxygen atoms which are not so associated. 20 (Ta) - O2 (Ta) [3]

Jan 1, 1960

By C. H. Cheng, C. E. Birchenall

The fundamental problem in the thermodynamics of solid solutions is the determinatiorl or calculation of the activities of the components as a function of temperature and composition. Since the theory of metals is not suficiently developed to allow a priori calculation of these quantities, they must be obtained from experiment. C. Wagner1 has reviewed the literature of this subject for the period before 1940. Although several important and extensive studies have been made in the meantime, the number of systems to which any sort of quantitative information can be assigned is vanish-ingly small. These data have become of great potential importance in studies of the structure of solid solutions2 and intermetallic compounds, the nature of the diffusion process,3,4 and perhaps even the mechanism of mechanical deformation.5 For these reasons, it. seems very worthwhile to extend the experimental data in this field. Although there is little use in duplicating Wagner's review, attention should be directed to the most recently reported investigations. A brief enumeration of the methods of measurement previously employed also should be valuable. The most direct method is the determination of the partial pressure of the components in the vapor phase in equilibrium with the solution. Both equilibrium and kinetic methods have been tried in metal systems, but almost exclusively on liquid phases. Only in the ease of carbon in iron alloys and in the copper-zinc system have extensive measure- ments been made which include solid phases. When one of the components is an element, such as nitrogen or carbon, which forms compounds which are very volatile and stable at normal temperatures and pressures (CH4, Co2, CO NH3), it is frequently possible to equilibrate mixtures containing these (such as CH4-H2, CO2-CO, NH3-H2) independently with the elernents (C, X) and with the metal (Fe, Ni, etc.). Such measurernents have been made for carbon in iron, iron-silicon, and iron-manganese alloys by Smith6 and in iron and iron-nickel alloys by Toensing.7 Differences between carbon activity values at the same temperature and carbon content when carboil is introduced from CH4-H2 rnixtures or CO-CO. mixtures indicate that the effects of hydrogen and oxygen in the system are not negligible, and one can only hope that the true value lies somewhere between these sets of results, probably nearer the CH4-H2 data since hydrogen is less soluble in iron than oxygen. This is essentially an equilibrium method, although flowing gas is employed. A kirletic method has been employed which consists of sweeping an inert gas (generally hydrogen) over the alloy at a series of rates, condensing the metal vapor out,, and analyzing it. The metal content can be extrapolated to zero flow rate (equilibrium). Wejnarth's8 work on Cd-Mg and Zn-Mg is a good example of this frequently used method. A variant of this consists of equilibrating a known volume of inert gas with the alloy, sweeping it out quickly, and analyzing for metal. In common with the above method, it has the disadvantage that the "inert" gas is generally somewhat soluble in the alloy. Moreover, the former continuously displaces the system from equilihrium and may give low values if solid diffusion is involved. The dew point method applied by Hargreaves9 to the alpha and beta brasses and by Schneider and Stolll0 to A1-Zn avoids the introduction of another component to the system, but is useful only in systems in which one component is much more volatile than the other. The alloy sealed in one end of an evacuated silica tube is heated to the desired temperature. The temperature of the other end is lowered until droplets of the volatile component condense. When the temperature is raised slightly, the droplets will evaporate. By careful adjustment of temperature, the range between evaporation and condensation can be narrowed appreciably. An independent determination of the vapor pressure of the . pure volatile component is necessary to give the partial pressure over the alloy. This is the method employed here to determine the vapor pressures of zinc and cadmium over their silver alloys up to 34 pct in cadmium and 76 pct in zinc. The former involves only the a solid solution, but the latter covers the a, ß, y, and e fields. In recent determinations, Herbenar, Siebert, and Duffenbarkl1 used the

Jan 1, 1950

By J. B. Newkirk, W. G. Martin

Oxidized cobalt powder is known to have a magnetic hysteresis loop which is asymmetric with respect to the magnetization axis. The experiment described herein shows that the orientation relationship between the basal plane of hexagonal cobalt and the oxide which forms upon it at 400°C is {111}ux//{100.1 }co <110>ux//<11.O> This orientation relationship allows a magnetic interaction between the antiferromagnetic oxide and the ferromagnetic substrate which could account for the offset hysteresis loop. Oxidized nickel powder has a symmetrical hysteresis loop and so is apparently not influenced by any magnetic interaction between metal and oxide. The orientation of the oxide (cubic) was found to be identical with that of the nickel substrate when the oxide forms on a polished surface parallel with {111} Ni. IN 1956 W. H. Meiklejohn and C. P. Bean discovered that fine particles of cobalt which had been prepared in a certain way have a magnetic hysteresis loop which in a strong field is asymmetric relative to the magnetization axis.&apos; The cobalt powder exhibited this unusual magnetic property only after it had been oxidized in air or oxygen; it lost the shifted hysteresis loop when the oxide was reduced in hydrogen. X-ray and neutron diffraction&apos; experiments showed the presence of cobaltous oxide (COO) and hexagonal cobalt in samples exhibiting the biased hysteresis loop and specifically showed no indication of any other compound with the exception of mercuric oxide.* The magnetic hysteresis loop becomes symmetrical above the Nee1 temperature (paramagnetic state) of COO. Therefore, it was concluded that the anomalous magnetic behavior is associated with the influence of cobaltous oxide upon the metallic cobalt. It has been proposed that crystallographic coherency may exist between the cobalt and a plane of some antiferromagnetic material which has unbalanced spin distribution and sufficient magnetic anisotropy to hold its spin in the direction which existed when the specimen was cooled. COO has these properties. Therefore, Roth&apos; has suggested that cobaltous oxide may form with a {111} plane parallel and coherent with the basal plane of the hexagonal cobalt metal and proposed that, as consequence of the antiferromagnetic interaction between COO and the underlying cobalt, the magnetization direction in oxidized fine Co particles may be ro-lated from the easy c-direction.2 Such a relationship, he proposed, would explain the observed magnetic effect in oxidized cobalt powder. The main purpose of this study was to determine the orientation relationship, if any, between the basal plane of cobalt and the oxide which forms upon it. Attempts to produce a film of COO which was strong enough to be handled were not successful. However we did succeed in making a film of CoCo2O, which was strong enough to be removed from the cobalt substrate and mounted on an electron-microscope grid. Because of the close structural similarity of COO and CoCo2O, we believe the orientation relation found for CoCo2O, on cobalt probably also holds for COO on cobalt. The epitaxial relationship of NiO and Ni also was investigated. To date no shifted hysteresis loop has been observed with nickel powder. However, the similarity of atomic array in cobalt and nickel leads to the prediction that a {111} of NiO may be parallel with a (111} of nickel. Experimental Method Cobalt-Cobalt Oxide—A coarse-grained specimen of a (hexagonal) cobalt was prepared by allowing a large crystal of fee cobalt to transform slowly at 400°C. The crystal was then cut to expose a surface parallel with the basal plane. A back reflection Laue X-ray photograph showed that the 00.1 plane was within 2" of the cut surface. The surface was mechanically polished and then electro polished in 85 pet orthophosphoric acid after which the crystal was held for 30 min at 400°C in air. During this heat-treatment the surface darkened slightly due to the oxide film which formed. The film was not thick enough to give an X-ray diffraction pattern, even by a glancing-angle technique. Glancing-angle electron diffraction was not possible either, owing to the interference of the electron beam with the high magnetic fields which exist at the 00.1 surface of the cobalt. However, it was possible to make an electron-diffraction photograph of the oxide film by stripping it from the cobalt substrate using the method described later. By maintaining reference marks carefully, it was possible to preserve the orientation relationship between the stripped film and the substrate on which it was formed. The oxidized surface of the crystal was first covered with a 1 pet solution of collodion (cellulose nitrate) in amyl acetate. When the film was dry, small rectangles were scored on the surface with a needle point. The specimen was then repolished

Jan 1, 1959