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By W. D. Robertson

SINCE the comprehensive paper of Moore, Beckin-sale, and Mallinson,' little consideration has been given to the mechanism of mercury stress cracking of copper-base alloys, apart from extensive work on metallurgical and fabrication variables employing mercurous nitrate as an evaluation test. However, with the phase diagrams now available and the recent considerations of interfacial tension at grain boundaries, developed by Smith,2 it appears that the elements of a detailed solution to the problem are available. The facts that require explanation are: 1—Pure copper is not embrittled by mercury, with or without an applied or residual stress. 2—Cu-Zn and other copper-base alloys, in excess of some undefined solute concentration, are embrittled provided an external or residual stress is acting; cracking is not observed in the absence of stress. 3—The path of fracture is invariably intergranu-lar. 4—Copper and copper-base alloys do not dissolve readily in mercury at room temperature.' Consideration of the Cu-Hg phase diagram% hows that, at room temperature, solution of copper in mercury is probably limited by the formation on the surface of a microscopically thin layer of inter-metallic compound, CuHg, having a very limited range of solubility which effectively restricts diffusion of copper and mercury. But, above 150°C (the highest peritectic temperature) copper solid solution is in equilibrium with a liquid Hg-Cu solution and, consequently, copper should dissolve freely in a large volume of mercury with the formation of an equilibrium dihedral angle at grain boundaries in contact with the liquid phase. Depending on the magnitude of this angle, mercury will or will not penetrate the solid phase along grain boundaries and spread over grain faces. Thus the measurement of the dihedral angle of grain boundaries in equilibrium with the liquid phase above 150°C should indicate whether copper is intrinsically resistant to embrittlement by mercury. In view of the fact that mercury is appreciably soluble in copper, it may also be anticipated that diffusion of mercury will take place at higher temperatures in the absence of the intermetallic compound and possibly at a more rapid rate along grain boundaries than through the grains, resulting in a Cu-Hg alloy of unknown properties. In the case of brass, the ternary system Cu-Zn-Hg is involved and, from the resistance of brass to general solution in mercury at room temperature, it is probable that a compound of limited solubility range also exists, similar to the binary Cu-Hg sys- tem. Also, compared with copper, a change in the dihedral angle at grain boundaries in contact with mercury may be expected to result from the addition of zinc to copper. The preceding generalizations appear to be confirmed by the following experiments. Experimental Results Oxygen-free copper wire, annealed at 700°C for 3 hr in copper foil, was immersed in mercury at 170°C, with and without an applied stress. After 24 hr immersion, specimens which were spring loaded to a nominal stress of 10,000 psi had not failed, and there was no apparent embrittlement as indicated by a 180" bend around a diameter approximately equal to the diameter of the wire (0.125 in.) : General solution of the surface had taken place, indicated by a change in diameter of the wire, and the resulting structure of the surface is shown in Fig. 1. It is apparent that angles have developed at grain boundaries and examination at a high magnification indicates that the angle is in excess of 120°, completely excluding penetration of mercury. In view of the measurements made by Smith n the

Jan 1, 1952

By N. A. Gokcen, M. Ohtani

Thermodynamic intevaction pararnetevs of elements E2(2), for dilute binary solutions of a component "2" in liquid iron, i.e., E(22) = 9 In f2/?N2 where f2 is the activity coefficient and N2 the mole fraction, and E(3) 2 = In f2/ N3 dilute ternary solutions of "2" and "3," and the carbon saturation parameter sc(3) (In f c/ N3) N c/N Fe for N3 - 0, are critically examined and correlated. It has been found that the interaction parameters and the atomic numbers of alloying elements follow regular periodic putterns. PHYSICO-chemical behavior of alloying elements in molten iron have become the subject of numerous investigations during the past 25 years. Consequently, the mutual effects of elements in the iron-rich solutions Fe-C-X, Fe-N-X, Fe-H-X, Fe-O-X, and Fe-S-X where X represents an alloying element, have gradually become better understood. These effects for a given temperature and pressure may be expressed by the interaction parameter of Wagner1, 2 derived briefly in the following manner. The complete differential of the Gibbs free-energy equation at constant temperature and pressure is dF = Fl dn, + F2 dn, + F3 dn3+ . . . [ 1] where F is the free energy; F 1, the partial molar free energy of "I"; and n,, the number of moles of "i." Cross-differentiation of this expression* *Cross-differentials are obtained as follows: Since the order of differentiation of F with n2 and n3 is immaterial, the left sides of the second differentials are equal, hence the derivation of Eq. [2] is obtained. For a dilute solution of components 2 and 3 in solvent 1, with the substitution of RT In f i = Fi xs for Fi where fi is the activity coefficient, and Fixs is the excess partial molar free energy, Eq. [2] becomes O) [3] where N2 and N, are the mole fractions. The interaction parameters are defined by

Jan 1, 1961

Jan 1, 1967

By D. N. Dietz

Jan 1, 1969

By C. Wagner

When an alloy solidifies and the composition of the solid differs from the composition of the liquid, atoms of the alloying elements rejected at the solid-liquid interface have to diffuse toward the bulk liquid. Diffusion may be supported by convection. Theoretical calculations have been made for a liquid without convection, for a liquid involving natural convection, and for solidification of a liquid alloy at the surface of a rotating disk as an example of forced convection. WHEN an alloy solidifies, the equilibrium composition of the originating solid phase differs in general from the composition of the liquid phase. Thus, segregation may take place, i.e., the composition of the solid phase formed at different times differs from the bulk composition. The degree of segregation depends on several factors such as the partition ratio of the alloying elements between the liquid and the solid phase, the rate of solidification, and convection. To clarify, a theoretical analysis has been worked out. The following presuppositions are made: 1—Calculations are confined to the solidification of binary alloys in which the concentration of component A (solvent) is much greater than that of component B (solute). 2—The equilibrium concentration of the alloying element B is assumed to be lower in the solid phase than in the coexisting liquid phase. 3—At the solid-liquid interface, partition equilibrium is assumed. 4—The dependence of the partition ratio of the solute between the liquid and the solid phase on concentration and temperature is disregarded since only small concentrations of the solute are considered. 5—The concentration of the alloying element B in the solid phase is supposed to be lower than the saturation concentration for the formation of a second solid phase. 6—diffusion in the solid phase is disregarded, since diffusion rates in the solid state are comparatively low. When the partition ratio of the solute between the liquid and the solid phase is greater than unity, a part of the solute is rejected at the solid-liquid inter- face and has to diffuse toward the bulk liquid. Thus there is necessarily a concentration difference in the liquid between the solid-liquid interface and the bulk liquid as has been pointed out by Hayes and Chipman,' Rutter and Chalmers,' Tiller, Jackson, Rutter, and Chalmers, and others (see Fig. 1). In view of the concentration gradient in the liquid phase, the ratio of the concentration of the solute in the solid phase to that in the bulk liquid differs from the equilibrium ratio, although at the solid-liquid interface, partition equilibrium is assumed. Under certain limiting conditions, the solid may even have virtually the composition of the bulk liquid as is shown below. General Equations Let u be the linear crystallization velocity in cm per sec, D the diffusion coefficient of component B in the liquid phase in cm2 sec-', c',, and c", the concentrations of component B in the liquid and the solid phase, respectively, in mol per cm", and s the distance from the solid-liquid interface toward the bulk liquid at a given time t. The partition ratio is assumed to be equal to a partition constant K. Thus. The difference in the specific volume between the liquid and the solid phase may be disregarded. In view of the discontinuity of the concentration of the solute at the interface according to Eq. 1, u(c', — c",), , , = tic', (S = 0)(1 — K) gram-atoms B per unit area per unit time are rejected at the interface and have to diffuse toward the bulk liquid. From Fick's first law it follows that uc',,(s = 0) (1 ~K) == - D(dc',,/?>s). _-„. [2] The concentration profile in the liquid near the interface depends on the interplay of diffusion and convection as is discussed in the following sections. A schematic concentration profile is shown in Fig. 1. The "effective thickness of the diffusion boundary

Jan 1, 1955

By Fred S. Mulock

THE principal operating and producing properties covered by the Western Operations of the United States Smelting Refining and Mining Company are the U. S. and Lark mine in the Bingham district of Utah, the Bayard department in the Central mining district of New Mexico, the Midvale mill and smelter near Salt Lake City, the lead refinery of its subsidiary, U. S. S. Lead Refinery, Inc., at East Chicago, Ind., and the coal operations of its subsidiary, United States Fuel Company, at Hiawatha, Utah. Operations of lesser importance at this time are conducted either on company account or by lessees in the Centennial, Bullion Beck, and Eagle and Blue Bell mines in the Tintic district of Utah, the Hidden Treasure and Ophir mines in the Ophir district of Utah, and the White Knob mine in Custer County, Idaho. The Richmond-Eureka Mining Company, in which the Company owns a controlling interest, has leased its properties near Eureka, Nev., to the Eureka Corporation Limited. The Gold-road property at Goldroad, Ariz., has been shut down since 1942, and due to high costs of labor and supplies, consideration is now being given to removal of all surface and underground improvements. The mine and mill im¬provements at the Sunnyside property in Colorado, recently purchased by the Sunbank Corporation, a subsidiary of the Company, are now being dismantled.

Jan 1, 1948

By E. S. Leaver

THE presence of soluble base metals in precious-metal ores usually precludes cyanidation as the best method of treatment. The laboratory experiments described in this paper show the possibility of cyanidation of gold-silver ores containing less than 0.5 per cent, of cyanide-soluble copper and the effect of zinc in the cyanide solution. PART I.-COPPER IN CYANIDATION The proposed process of cyanidation of precious-metal ores containing copper is based on the regeneration of about 80 per cent., of the cyanide used in the dissolution of the copper. The method of regeneration involves a combination of the sulfide and the acid precipitation of the copper and silver. The resultant solution is made alkaline with lime, and the gold is precipitated with zinc dust. Solubility of Copper Minerals in Cyanide Solution In order to determine the solubility of copper minerals, including metallic copper, under the usual conditions for cyanidation, experiments were conducted with synthetic ores. Each ore sample was prepared by mixing the particular pure copper mineral with barren sea sand. Both the mineral and sand were ground to pass 100 mesh before they were thoroughly mixed. The percentage of copper in each head sample was determined by direct assay, excepting the metallic copper sample, which was computed on weights before mixing. Table 1 gives the results.

Jan 1, 1929

Jan 1, 1967

By T. L. Joseph

A study is made of the amount of solution loss necessary to maintain the reducing power of the gas stream in the blast furnace. Curves are presented to show the effect of solution loss, moisture in the blast, and carbon dioxide from the flux on the nitrogen in the THE blast furnace process is based upon the counter flow of gases and solids. As CO, N, and H, flow upward from the combustion zones, oxygen is acquired from the descending charge. In the reduction of iron ore, a portion of CO is converted to CO, and similarly a portion of H, is converted to water vapor. The inert N,, from the air used in combustion, passes through the furnace with little change. Its concentration is, however, decreased by reactions such as direct reduction and solution loss which increase the volume of CO in the gas stream; Similarly the evolution of C02 from the limestone also dilutes the nitrogen. he purpose of this paper is to illustrate an idealized and simplified method of studying furnace processes by following changes in the gas phase between the tuyeres and the stock line. A more specific objective is to evaluate the effect of solution loss upon the CO/CO, ratio in that region of the furnace in which FeO is reduced to metallic iron. This last stage of reduction requires relatively high CO/CO, ratios to exceed the equilibrium requirements. Solution loss or the reaction of COZ with C to produce CO has a pronounced effect upon the ratio of the carbon gases and is necessary to maintain the reducing power of the gas stream if the consumption of coke is low. It will be explained later that indirect reduction followed by solution loss is stoichiometri-cally equivalent to direct reduction. Calculations will be made to show how the composition of the gas in the region of the mantle varies with coke consumption and with different amounts of solution loss. Such calculations show the condi- tions under which gasification of C with oxygen in the charge is needed to maintain the reducing power of the gas. Equilibrium conditions for FeO and the carbon gases will be used to establish a minimum CO/CO, ratio below which reduction will not proceed. The manner in which carbon is gasified in the furnace, at the tuyeres with oxygen in the air or above the tuyeres with oxygen from the charge, will be a basic feature of all calculations. It is hoped that greater interest in the use of top gas as a means of following furnace reactions will be aroused by the calculations and generalized curves which are presented. Bosh Gas Equations Subject to some alteration by the amount of moisture in the blast and by direct reduction, the gas leaving the combustion zones of a blast furnace has a definite composition. Because a relatively small amount of oxygen is acquired from the charge in the bosh and in the crucible, the products of combustion undergo little change until they enter the shaft. Bosh gas is, therefore, essentially the products of combustion of carbon in a deep fuel bed with air. The relative weights and volumes of reacting materials are expressed by the equation: 2~ + 0? + 3.76N, = 2C0 $ 3.76NZ [I] Air Bosh Gas -air = 79% N? = 3.76) 21% 02 Starting with a known mass of C consumed largely by air, Eq 1, but partly by water vapor, Eq 2, the volume and C + H2O = CO $ H? [21 composition of the bosh gas can be calculated and subsequent changes followed as reactions take place at various elevations in the furnace. As shown in

Jan 1, 1952

Jan 1, 1967

By A. S. Nowick, A. E. Roswell

Anelastic measurements of atomic mobility in an Ag-Zn substitutional solid solution, make possible a study of the rate of decay of lattice defects frozen into the alloy by quenching. A WIDE variety of experimental evidence has accumulated recently in support of the belief that atomic mobility or diffusion in face-centered cubic lattices occurs principally through the movement of lattice defects, as contrasted to a mechanism by which two or more atoms directly exchange lattice positions. The most direct evidence, summarized in a recent review,' includes the Kirkendall-effect measurements and anelastic measurements on quenched alloys. Theoretical calculations' have focused attention on the lattice vacancy as the defect probably responsible for diffusion in the common metals. Later calculations3 have also shown the possible importance of combined pairs of vacancies in producing diffusion. The only defect that has been considered seriously, in addition to the vacancy and combination of vacancies, is the "interstitialcy" (an atom which has left its normal lattice position and entered an interstitial position) ; the calculated energy of formation of an interstitialcy in a close-packed lattice is too large to permit a reasonable probability for the occurrence of this defect In view of these calculations it may be tentatively concluded that the defects producing atomic movements are single or multiple vacancies. Anelastic measurements of atomic mobility in substitutional solid solutions provide a valuable method for the study of lattice defects. By means of this method it was first demonstrated' that defects may be frozen into a lattice by rapid quenching from high temperatures. (It was subsequently shown6 that resistivity measurements may also be capable of detecting the presence of frozen-in defects.) A summary of the principles involved in these anelastic measurements will now be presented. The anelastic method is based on a relaxation phenomenon in substitutional solid solutions, first discovered by Zenera in a brass and subseauentlv investigated extensively in a series of Ag-zn solid solutions.' This relaxation effect may be observed in the usual way either dynamically, as a peak in

Jan 1, 1954

By R. S. Shoemaker, F. W. McQuiston

MAGMA COPPER COMPANY San Manuel Division The San Manuel Division of Magma Copper Company is located about 40 miles north of Tucson. Tons of ore milled in 1973 .were approximately 19 million at a rate of 63,000 tons per day. From this, about 42,600 tons of copper concentrate was produced as saying approximately 1.070 MoS2 and 28.5% Cu. As with many copper ores, the San Manuel ore contains a small amount of gold, but in this particular case, much of the gold follows the molybdenite. Separation of the molybdenite from the bulk sulfide concentrate by flotation produces a moly concentrate containing 9170 MoS2, just under 1.070 Cu, and 0.44 oz Au per ton. Cyanidation of this material for gold recovery is the only practice of its kind known to the authors of this Monograph. After thickening, the final moly concentrate is filtered for subsequent repulping with cyanide and lime. Gold dissolution takes place in three agitators in series with the pulp from the agitators being filtered in two stages in disc filters. Between filtration stages, the cake is repulped with barren solution. Filtrate from both filters is the pregnant solution. The Merrill-Crowe recovery unit is comprised of two solution tanks and the usual clarifying filter, vacuum tower, zinc dust feeder and Merrill precipitate press. Because of the presence of finely divided sooty chalcocite in the molybdenum concentrate, the cyanide consumption of 55 pounds per ton is extremely high. A compensating factor, however, is the low copper, moly concentrate produced. Precipitation of the gold from the highly copper-contaminated solution requires 0.56 pounds of zinc dust and 0.28 pounds of lead acetate per ton, high figures when compared to normal cyanidation practice. The Merrill- Crowe precipitate assays approximately 28.5% Cu, 8% Zn, 156 oz Au and 197 oz Ag per ton. The San Manuel cyanidation plant is an outstanding and innovative development.

Jan 1, 1975

By P. G. Winchell, J. K. Jackson

The strtcture of body-centered Fe-Ni-C alloys (0 to 16.5 wt pct Ni) containing less than 0.015 wt pct C was investigated by measuring the carbon-diffusion peak at low frequencies with a torsion pendulurrr. By determining the Snoek damping in ferrite and in quenched alloys of identical composition, the effects of nickel content and heat treatment were separated, and the existence of a structure in which Snoek damping is greatly reduced was revealed in the quenched ternary alloys. The relative amount of this structure increases with increased nickel content and cooling rate. It is proposed that this structure may be highly imperfect or tetragonal. In Fe-Ni-C alloys containing only ferrite the addition of nickel (0 to 5.1 wt pet) decreases tke area of the carbon-diffusion peak and shifts its position to lower temperatures but broadens the peak only slightljl. The decrease in peak area with increasing nickel implies that short-range interactions with the nickel atoms prevent some of the carbon atoms from participating in the relaxation process. The shift in the peak position indicates a long-range effect of nickel on the movement of carbon atoms so that at 300°K the diffisivity of carbon in -ferrite is increased by about 35 pct by the addition of 5.1 tut pct Ni. The results are presented as distributions of relaxation strength 072 the activation energy under the assumption that the frequency factor is invariant. BODY-CENTERED iron-base solid solutions dissolve carbon interstitially in the octahedral sites. The occupation of an octahedral site produces a tetragonal distortion of the surrounding lattice. These sites fall into three sets according to the orientation of the tegragonal distortion associated with each and may be identified by their lattice coordinates as: type 1/2 0 0, type 0 1/2 0, type 0 0 1/2. At low carbon levels in cubic ferrite the carbon atoms are distributed at random1 among these sites. In high-carbon body-centered iron-base solid solutions, which are unstable with respect to several two-phase mixtures, a tetragonal structure occurs as the product of the diffusionless transformation of austenite. This transformation is commonly accompanied by appreciable microstrain and its product is called martensite. The tetragonality of martensite, a supersaturated solution of carbon in a iron, is maintained prior to decomposition even though local diffusion of carbon occurs as evidenced by carbide precipitation. The tetragonality is taken as evidence that one set of octahedral sites is preferentially occupied by carbon. (This preferential occupation is called ordering below.) Support for this view is presented by the absence of strain-induced carbon-atom diffusion in high-carbon solid solutions (martensite). Such diffusion occurs in ferrite and produces the 40°C internal-friction peak observed at 1 cps frequencies.' Thus, there appears to be qualitative evidence favoring the view that at sufficiently high carbon levels tetragonality arises spontaneously as a result of the ordering of the carbon atoms; however, no experimental evidence exists concerning an equilibrium between cubic and tetragonal body-centered solid solutions. Moreover, attempts to estimate the energy of ordering7-' predict a value too low to maintain the tetragonality observed at medium carbon levels, 0.3 to 0.6 wt pct C. In the present work an attempt using internal-friction measurements is made to establish the presence or absence of tetragonality in low-carbon body-centered solid solutions formed by quenching austenite. Fe-Ni alloys containing about 0.01 wt pct and 0 to 15 wt pct Ni were selected for the study. While the work was in progress Gilbert and Owen10 reported that the transformation which occurs in these alloys during quenching at rates up to 5000°C per sec is not martensitic but is more properly categorized as massive. Thus, the solid solution

Jan 1, 1964

By W. M. Weigel

LESS advances in the technology of non-metallic minerals than for several years past mark 1931, and the cause is easily found. The universal depression and decreased markets for non-metallic as well as other mineral commodities has forced the producers to cut out all unnecessary expense and reduce operating costs to a minimum in order to keep going, even on a reduced output, and to prevent insolvency. The result. has been that but 'little research has been carried on, and such as has been completed has in but few cases been put into commercial practice on account of the expense involved in new equipment and plant changes. The trend in the industry has been more economic than technologic, and the greatest effort put on market studies and sales attempts to expand markets and scrutiny of present operating 'practice leading to reduction of cost of production. This tendency has been increased by highly competitive conditions and the buyer's market which has prevailed and to the fact that price has been a greater factor than quality in placing orders. Only in cases where improvements in technology would immediately and effectively reduce costs or where in special cases there was but little competition with almost a monopoly control has actual technical development taken place.

Jan 1, 1932

By S. G. Lasky

EVENTS during and since the war indicate that the nations of the world are trying to initiate an era of international co-operation. Definitions and objectives include social, economic, and human considerations no less than political considerations. The mineral resources of the world and the absolute and relative position of each nation enter into this situation. The possible use of armed might, the application of sanctions, the international flow of commerce, the ways in which this flow may encourage or hamper international well-being, and the influence of international and domestic well-being upon one another are all matters that must take mineral resources into account. If the United States is to act wisely and forthrightly in such matters we must be thoroughly informed as to our position with respect to mineral resources. What is the mineral position of the United States? A variety of widely conflicting opinions are held in authoritative and intelligent quarters: (1) For practical purposes our mineral resources are already exhausted.

Jan 1, 1946

By J. L. Jernegan

In the summer and fall of 1875, the author was present during a short smelting campaign at the Hall Valley works, and having had occasion to make a number of chemical analyses of the ores, fuel, and fluxes, deems that the results of the same, and also an account of the smelting operations, may be found of interest to members of the Institute. The mines and reduction works of the Hall Valley Silver—Lead Mining and Smelting Company (limited) are situated at Hall Valley, Park County, Colorado. The smelting works are located about half way from the mouth to the head of the above-named valley, and the mines high up on the mountains, near its head. The three principal mines of the company are the Whale, Leftwick, and Coldspring. They are all on different veins, running parallel to one another, with a general trend from southwest and northeast. The

By J. L. Jernegan

IN the summer and fall of 1875, the author was present during a short smelting campaign at the Hall Valley works, and having had occasion to make a number of chemical analyses of the ores, fuel, and fluxes, deems that the results of the same, and also an account of the smelting operations, may be found of interest to members of the Institute. The mines and reduction works of the Hall Valley Silver-Lead Mining and Smelting Company (limited) are situated at Hall Valley, Park County, Colorado. The smelting works are located about half way from the mouth to the head of the above-named valley, and the mines high up on the mountains, near its head. The three principal mines of the company are the Whale, Leftwick, and Cold¬spring. They are all on different veins, running parallel to one another, with a general trend from southwest and northeast. The

Jan 1, 1877

By H. Biloni, G. F. Bolling

The microsegregation in tin specimens containing 0.2, 0.5. or 1 wt pct Pb has been studied m detail. The specimens were grown from the melt in a controlled fashion and exhibited a well-developed cellular substructure. In general, a severe microsegre-gation can be observed in all the photomicrographs presented. Some observations of special interest are: the distribution of a second phase, the presence of a eutectic in several forms, the evidence for dif- THE Smialowski or cellular substructure which forms during solidification has been extensively studied during the past decade.'* Many of the im- *Most references to the cellular substructure except for the last 2 years are reviewed by Winegard.' portant characteristics of this substructure, such as its occurrence and variability with growth conditions, its association with the phenomenon of constitutional supercooling, and its effect on dislocation production and mobility, have received quantitative fusion of solute in the solid, and the enhancement of segregation at a dislocation subboundary network ("striations"). On the basis of the metallographic observations, it can be deduced that the segregation observed is representative of the solute segregation produced during crystal growth. Some deductions are also made about the interplay of the two substructures, cells and striations, and about the mode of cellular growth. investigation both experimentally and theoretically. However, the concentration profile of the solute segregated during crystal growth has not been examined in detail. Tin crystals grown from melts containing various concentrations of lead have been most extensively studied. In a recent investigation of Sn-Pb alloys, Kramer et a1.2 were able to measure the effective solute distribution coefficient, k,, at the most advanced points of the solid-liquid interface, over a large range of growth conditions, finding it to approach the value of k,, the equilibrium distribution coefficient. As will be shown, this must lead to drastic segregation. Another recent study of several Sn-Pb alloys was made by Plaskett and winegard3 who investigated the variation of growth conditions

Jan 1, 1963

By C. L. Meyers, A. V. Levy, G. Y. Onoda, R. J. Kotfila

This paper presents the hypothesis that solid-solution hardening of regions in the order of tens of angstroms thick along grain boundaries is the most important mechanism controlling the ductile -brittle transition behavior of poly crystalline bcc refractory metals. Further, a physical model is developed and a general equation is derived to describe the dependence of the solute concentration at grain boundaries on temperature, nominal impurity concentration, thermal treatments, vain size, and prior plastic deformation. Analytical curves of the solute concentration at grain boundaries us temperature, calculated by means of the derived equation, are found to have the same general form as curves of ductility us temperature plotted from experimental data. Senziquantitative relationships between the transition temperature and metallurgical variables can he determined by using the physical model. The room-temperature brittleness of the poly-crystalline refractory metals (tungsten, molybdenum, and chromium) is a result of their high ductile-brittle transition temperatures. Recently studies on single crystals have revealed that, when sufficiently pure, these crystals have much lower transition temperatures than polycrystalline specimens of similar purity.'-3 For example, the transition temperature (measured by reduction in area in tensile tests) for very high-purity tungsten crystals has been reported to be as low as -50°F whereas polycrystalline specimens of similar purity had a transition temperature near 400" ~.' These results suggest that the ductile-brittle transition behavior of these polycrystalline metals can be attributed principally to the influence of grain boundaries on plastic flow and fracture. This paper contains a discussion of the manner in which grain boundaries influence the ductility of the poly-.crystalline bcc refractory metals and proposes that the segregation of impurities to grain boundaries is the most important mechanism for controlling the ductile-brittle transition behavior of these metals. Further, this paper contains an analysis of the effect of the compositional and structural variables on the grain boundary-ductility relationship, and introduces a semiquantitative model that can provide a foundation for more theoretical treatment to describe the influence of these variables on ductile-brittle transition behavior. PHYSICAL MODEL FOR PREDICTING DUCTILE-BRITTLE TRANSITION BEHAVIOR Grain Boundary Segregation of Impurities. Based on their own observations and on theoretical grounds, numerous investigators have suggested that impurities segregate to the grain boundaries. Such segregation would be expected because regions exist where both large and small foreign atoms fit with less strain than within the undistorted crystal structure. Therefore, the concentration of impurities should be higher at boundaries than within the grain body. TO estimate the degree (i.e., the ratio of grain boundary to nominal bulk concentration) to which an interstitial solute tends to segregate at boundaries within a solvent metal, the solubility rather than the size misfit could be used as a guide because solubility expresses the joint effect of both elastic and electronic factors.5 The solubilities of interstitial elements such as carbon, hydrogen, nitrogen, and oxygen are low in the group V-A metals and very low in the group VI-A metals.6 These low solubilities suggest that segregation to grain boundaries should occur for each of these solutes in both refractory metal groups. The difference between the ductility of single-crystal and polycrystalline bcc refractory metals can be described in terms of two distinct effects.4 The first of these is the general observation that grain boundaries hinder slip within grains and slip transfer between grains, and the second is that deformation is more complex in each grain of a polycrystalline specimen than it is in a single crystal. Mc Lean has pointed out, furthermore, that strong slip-hindrance effects at grain boundaries should occur in metals having strong segregation of impurities to grain boundaries. Therefore, the effect of grain boundaries on the hindrance of slip is expected to be the dominating influence on the ductile-brittle transition behavior of these polycrystalline refractory metals. cahn5 has suggested that temperature and solute mobility should influence solute equilibrium segregation at grain boundaries, and Fig. 1 illustrates

Jan 1, 1965

By Leon Dominian

(Wilkes-Barre Meeting, June, 1911.) I. INTRODUCTION. THE lack of Aryan roots for the names of metals commonly known among the Aryan settlers of Asia Minor, as well as the later colonizers of Europe, indicates that these races were generally ignorant of the use of metals until they came into contact with Semitic peoples. Practically all mining-terms in current use among the earliest Greeks resemble very strongly their distinctly Semitic equivalents, which can be traced all the way in a broad belt beginning in Lower Mesopotamia, and extending westwardly to the Syrian shores of the Mediterranean. The Greek word " "metallon," for instance, used indiscriminately to designate mine or ore, probably came from the earlier Semitic equivalent, " matal." Again, the Greek words " chrysos " (gold) and " chalkos " (copper) seem to be descended from the Semitic forms " throats " and a chalak." It is a natural inference that primitive mining-methods were evolved by the dwellers in the mineralized areas of Asia Minor, from whom later Greek, Roman, and even North European miners obtained their first notions of the reduction of metallic ores, by virtue of a general westward migration of mining and metallurgy. Some traces of its passage through Turkish territory will be noted in this paper. While European Turkey can boast of one ancient gold-field, the Asiatic dominions of the Sultan may lay claim to at least two well-defined and widely-separated gold-producing districts. These three regions may be distinguished as the Thracian, the Pontic, and the Anatolian gold-fields. II. TURKEY IN EUROPE. . The Thracian Gold-Field. The most conspicuous topographic feature of the lowland between Constantinople and Salonica is the uplifted Archaean

Nov 1, 1911