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By R. D. Daniels, T. G. Oakwood

A study was made of the effects of small quantities of hydrogen on the mechanical properties of colum-bium. Tensile specimens, hydrogenated to concentrations of 20 to 200 ppm, were tested at temperatures of 300°, 191°, and 77°K. Although hydrogen was found to have little effect on the strength of columbium, the ductility of Cb-H alloys was found to be quite sensitive to both hydrogen concentration and temperature. At 300°K, an abrupt loss in ductility occurred at a critical hydrogen concentration, although some ductility was observed beyond the tolerance limit. A similar result was found at a lower hydrogen concentration at 191°K. At 77°K, however, a more gradual loss in ductility with increasing hydrogen concentration was observed. Hydrogenated columbium was thus observed to undergo a ductile-brittle-ductile transition. Metallographic examination of fractured specimens revealed extensive porosity at both 77° and300°K which was a distinct function of hydrogen content. At 191°K, although some secondary cracking was noted, the amount of observed porosity was minimal. These observations are interpreted in terms of hydrogen solubility and mobility as a function of temperature and in the role of hydrogen in promoting growth of microcracks. lHE effect of hydrogen on the mechanical properties of the refractory metals is not, at present, completely understood. A number of studies have shown these materials to be susceptible to hydrogen embrittlement. Roberts and Rogers1 have found that vanadium can be embrittled by hydrogen. It was further demonstrated that fracture undergoes a ductile-brittle-ductile transition as the temperature is lowered from 150° to -196°C; i.e., there is a ductility minimum observed at a certain temperature. The ductility is increased by either raising or lowering the temperature from this point. A more complete study by Eustice and Carlson2 on vanadium containing 10 to 800 ppm placed the ductility minimum at about -100°C with variations reportedly due to hydrogen content and strain rate. Ductility minima have also been found at certain temperatures for tantalum containing 7 ppm H3 and 140 ppm H.4 At hydrogen concentrations above 270 ppm, however, the ductility return at low temperatures was considerably reduced.4 In the case of columbium, some disagreement exists in the literature. Eustice and Carlson,5 Wilcox et al.,6 and Imgram et al.4 failed to find a ductility minimum although a composition-dependent ductile-brittle transition was observed. Hydrogen concentrations in these investigations were 20 ppm,5 1 to 30 ppm,6 and 200 to 390 ppm.4 However, Wood and Daniels7 observed a rather pronounced ductility minimum at hydrogen contents ranging from 19 to 252 ppm. Those theories of hydrogen embrittlement involving the precipitation of diatomic hydrogen which have been applies to ferrous metals8-12 do not seem to be applicable to the case of columbium and other exothermic occluders. Such theories propose that extensive crack formation and propagation occurs by the precipitation and expansion of diatomic hydrogen at internal voids and microcracks. However, photomicrographs of hydrogenated columbium do not show any evidence of damage introduced by the sorption and precipitation of diatomic hydrogen; rather, at high hydrogen concentrations, a hydrogen-rich second phase is precipitated.13'14 In addition, a number of these theories require the development of high hydrogen pressures at voids in the structure.8'10'12 This does not appear to be feasible in the concentration ranges discussed in the aforementioned paragraphs. The possible interaction of atomic hydrogen with microcracks resulting from dislocation pile-ups15,16 remains in doubt since pile-ups have not been observed in bcc metals17 including columbium.18 Wood and Daniels7 have put forth the possibility that a hydride precipitation could be responsible for crack nucleation in columbium. Work by Longson19 has shown that hydrogen embrittlement of columbium parallels the bulk solubility limit; i.e., as the solubility increases, for instance with temperature, the amount of hydrogen necessary to cause embrittlement also increases. Although a hydride precipitation appears attractive as a means of nucleating microcracks in columbium, what require more intensive study are the low-temperature anomalies which have been observed, i.e., the ductile-brittle-d'ictile transition characteristics. Also, the hydrogen concentrations where embrittlement occurs are often below the bulk solubility limits determined by Albrecht et al.13,14 and Walter and Chandler.20 This work is an attempt to determine more definitively the effects of concentration and temperature on the mechanical properties of dilute Cb-H alloys. EXPERIMENTAL PROCEDURE Ultrahigh-purity columbium rods, obtained from the Wah Chang Corp., were cold-reduced by rotary swaging. A chemical analysis is given in Table I. The material was cut into cylindrical blanks 1.50 ±0.005 in. long. Individual specimens were either given a stress relief anneal at 750°C or recrystal-lized at 1200°C. Resulting microstructures were either a "bamboo" structure characteristic of a wrought material or a recrystallized structure with a grain diameter of approximately 100 n. All heat treatments were carried out in a vacuum of 10-5 Torr or less.

Jan 1, 1969

By Amitava Gangulee, Michael B. Bever

The order-disorder transition in Ag-Mg alloys in the range 17 to 26 at. pct Mg was investigated and some thermodynamic, electrical and mechanical properties of ordered Ag-Mg alloys were measured. A modification of the phase diagram is proposed on the basis of measured transition temperatures. The stability of the ordered structure is analyzed in terms of the quasichemical theory. Kinetic aspects of the order-disorder transition were also investigated. The energies of ordering at 273°K of Ag-Mg alloys were measured by liquid metal solution calorimetry. The electrical resistivities and the tensile Properties of the ordered alloys were measured. The exothermic energy of ordering increased with magnesium concentration up to the composition Ag3Mg; it is discussed in terms of the quasichemical theory. Pronounced order hardening was observed and can be explained by several strengthening mechanisms, which are particularly effective because of a change in crystal structure associated with the ordering transition. IN silver-rich solid solutions containing approximately 17 to 26 at. pct Mg, long- range ordering may occur during appropriate therma1 treatments. Clare-brough and Nicholas1 first detected such long-range order in the solid solution of composition Ag3Mg and suggested that the unit cell of the superlattice contained 256 atoms. x-ray2 and electron diffraction3 investigations confirmed the occurrence of long-range order, but indicated a shifted Ll2-type structure. On the basis of recent X-ray measurements the crystal structure of ordered Ag3Mg has been confirmed as type D023.4 The present paper is concerned with the order-disorder transition in silver-rich Ag-Mg solid solutions and some thermodynamic, electrical, and mechanical properties of the ordered alloys. The effects of short-range order on the properties of silver-rich solid solutions containing up to 26 at. pct Mg are discussed in a concurrent paper.5 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Specimens. Specimens of Ag-Mg alloys containing from 18 to 26 at. pct Mg were prepared in the form of 1.0-mm-diam wires as described in Section 1.1 of Ref. 5. Disordered specimens were prepared by annealing at 773°K for 1 hr and quenching into iced brine. Ordered specimens were prepared by annealing at 773°K for 1 hr and slowly cooling to room temperature over a period of 15 days. The specimens were stored at 78°K. 1.2) Resistivity Measurements. Electrical resistivi- ties were measured by a potentiometric method.' Equilibrium values were obtained at several temperatures. The kinetics of ordering were investigated by following the time-dependent changes of the resistivity of initially disordered specimens during annealing. The specimens were enclosed in copper capsules and immersed in salt pots; the heating up was accelerated by injecting preheated helium into the capsules. 1.3) Calorimetry. The energies of ordering of the alloys were measured in a tin solution calorimeter as the difference between the heat effects of additions of completely ordered and disordered specimens of the same composition. The procedure and the method of calculation have been described.6 Magnesium was used for thermal compensation in most calorimetric runs in order to improve the accuracy.677 1.4) Mechanical Tests. Tensile tests were carried out with wire specimens at room temperature as described in Section 1.5 of Ref. 5. Microhardness measurements were also made.? 2) RESULTS AND DISCUSSION The characteristics of the order-disorder transition of silver-rich Ag-Mg solid solutions will be discussed first. Some thermodynamic, electrical, and mechanical properties of the ordered alloys will then be considered and compared with the corresponding properties of dis-disordered alloys. 2.1) The Order-Disorder Transition. 2.1.1) Thermodynamic and Structural Aspects. The transition temperatures Tt were determined from discontinuities in the slope of the equilibrium resistivity vs temperature curves. Normalized curves for three compositions are shown in Fig. 1. The transition temperature increases with the magnesium concentration and reaches a maximum at the stoichiometric composition Ag3Mg. The transition temperature of the alloy Ag3Mg was measured as 665° ± 2°K and compares with published values of 660°,1 663°,8 and 66°k.3 In the slopes of the resistivity vs temperature curves of alloys containing 22.2 and 22.5 at. pct Mg, discontinuities were observed at two temperatures. Such upper and lower discontinuities indicate a two-phase field. A modified form of the published phase diagram9 is shown in Fig. 2. A two-phase field was found only on the low-magnesium side of the composition Ag3Mg. On the high-magnesium side, the existence of a two-phase field could not be established because of insufficient resolution, but such a field must be present. This part of the phase diagram can be made complete by a eutec-toid-type reaction a = (a' + ß). The existence of a boundary between the two-phase fields (a + ß) and (a' + ß) is also in accord with published lattice parameters.3 The crystal structure of ordered Ag3Mg (type Do23)

Jan 1, 1969

By A. Kelly, S. Sato

Tensile tests have been performed on aluminum single crystals of 99.99 pct purity at 196°K. The resolved shear stress when the stress-strain curve becomes concave to the strain axis depends on orientation, being always higher for crystals with an initial orientation close to the sides of the unit triangle. Observations have been made, with the optical microscope, of the appearance of slip lines on polished surfaces of the crystals. Particular attention has been paid to the first appearance of cross-slip. It is confirmed that marked cross-slip is first seen when the stress-strain curve becomes concave to the strain axis. Measurements are reported of the lengths of the slip lines observed on top and side faces of the crystals at various stages of the deformation. The lengths of the slip lines vary inversely as the flow stress for all crystals, independent of crystal orientation. From measurements of the lengths and separations of the slip traces it is possible to estimate the number of dislocations which are annihilated at each cross-slip site. It is concluded that the annihilation of screw dislocations of opposite sign is the most important cross-slip process occurring. FRIEDEL1 recently pointed out that the stress-strain curve of many pure metals of face-centered-cubic structure can be considered as composed of three stages. Plastic flow commences with a region showing a small rate of hardening which is approximately linear. This has been called "easy glide*. It is followed by a region of more rapid hardening in which the slope of the curve is again approximately constant and this, in turn, is superseded by a final part of the curve which is concave to the strain axis. Following Diehl2 we may designate these regions as stages I, II, and III respectively. The onset of stage 111 occurs at lower stresses at higher temperatures. The appearance of the slip lines formed during these various stages has been described by a number of workers?-5* The object of the present work was to make detailed observations of the lengths and separations of slip lines for a number of crystals of different orientations deformed at the same temperature and strain rate. Although much previous work has been published on the deformation of aluminum single crystals the importance of measurements of these quantities has only recently been realized—they are essential for experimental tests of recent theories of work hardening.' 9 In aluminum, deformed at room temperature, stage 11 of the stress-strain curve is very weakly marked, as the stress for the onset of stage 111 is attained soon after the end of easy glide. In the present experiments it was decided to use a temperature lower than room temperature so that stage II of the curve was better developed. However, at temperatures as low as 90°K slip lines are not measured easily with the optical microscope.5 For this reason 1960k was chosen as a suitable temperature. Even at 1960k however, stage III of the curve commences at glide strains of 6 to 10 pct and hence

Jan 1, 1960

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

PREVIOUS work' on a four-component system (Cu-Mn-Ni-Fe) resulted in the development of consistent relationships between the chemical composition and the electrical properties of these manganin-type alloys. The present study was undertaken to develop alloys with temperature coefficients of resistivity and thermoelectric properties more desirable than those of the manganin type, and to determine whether the relationships which had been found for the Cu-Mn-Ni-Fe alloys could be extended to five-and six-component alloy systems. PREPARATION OF ALLOYS The five- and six-component alloys were made from OFHC copper rod, ARMCO iron, electrolytic nickel, manganese cathode chip, and special high-purity aluminum and indium. A Cu-Mg master was used for deoxidation. The compositions of these materials are given in Table I. The alloys were melted and cast as indicated previously,' except that no cover was used and the melts were teemed. EXPERIMENTAL PROCEDURE The finished wire size of 0.0808 in. diam was again selected for the reason that the test specimens would be self-supporting, thus eliminating any extraneous effects which might have been introduced by winding smaller diameter wire on spools or forms. The following tests were performed on the finished wires: A) Chemical Analyses—All of the components of these alloys were determined by premium gravimetric methods. The principle residual impurity contained in these alloys is 0.008 pct Mg (by weight), maximum. Tables II and 111 present the mean analyses computed from at least four determinations of each constituent. B) Electrical Characteristics—The test procedures forthe determination of the thermal emf vs copper, resistivity, and the resistance-temperature relationship are given in detail in Ref. 1. It was also shown that the resistance-temperature relationship is of the form Pt = P,n + At -B/2, [1] where P, is the resistance at t C expressed in percent of a given standard resistance, P, is this per- 0 centage at 0°C, and A and B are constants for a given, properly treated, composition. The results of the electrical tests are also given in Tables II and 111. INTERPRETATION OF DATA The modified Linde2 formula, known to be valid for dilute binary solid solutions, was applied to the complex Cu-Mn-Ni-Fe type alloys. This relationship is of the form where Ap is the increase in resistivity. Zb the valence of the solute, Zn the valence of the solvent, and K and K are designations assigned by Robinson and Dorn3 to the constants for the periodic group to which solute element belongs. The units of K, are -cm per valence difference squared per at. pct; those of K2 are pa-cm per at. pct. For the sake of brevity, these units are not repeated in the following discussion. Calculations were made to determine if this formula was accurate for five-component systems. No experimental studies were made of the Cu-In and Cu-A1 binary systems. The effects of indium additions upon the resistivity of copper are given by Linde. These data, along with those of the effects of Mn and Fe, permitted the calculation of the effects of Al.

Jan 1, 1959

By Robert J. Hite, Samuel S. Adams

Potash, the generic term for a variety of potassium-bearing minerals, ores, and refined products (Table 1), owes its importance as an industrial mineral to the potassium requirement of growing plants. The term potash originally referred to potassium carbonate produced by the leaching of wood ashes. This process, for which the first US patent was issued in 1790, was the basis for the largest United States chemical industry in the early nineteenth century. The agricultural use of potash soon eclipsed the chemical applications following the German discovery in 1840 that potassium is essential to plant growth. The initial discoveries of large deposits of soluble potassium minerals, essential for agriculture applications, were made in 1857 in Germany and in 1914 in the United States. More than 90% of the 27.5 Mt K20 produced in the world in 1980 (Searls, 1981) was derived from marine evaporite deposits and approximately 90% was used in fertilizers. The potassium content of an ore, mineral, or product is customarily expressed as % K20, a unit of measure which is neither a natural nor synthetic compound of potassium (1.0% K is equivalent to 1.2046% K2O). Geology Potassium, the seventh most abundant element in the earth's crust, is present in silicate minerals in igneous, sedimentary and metamorphic rocks. Potassium is also a major constituent of many surface and subsurface brines (Table 2). Economic potash deposits are essentially restricted, however, to widespread, thick accumulations of marine chloride evaporite deposits. These deposits yield high grade, large tonnage ore bodies, many of which are amenable to low cost mining and beneficiation. The products from these deposits are, moreover, ideal for use in fertilizer because of the high relative solubility of the potassium chloride and sulfate evaporite minerals. World potash production and reserves for such deposits so vastly overshadow other sources of potassium that the following discussion will be limited largely to potash deposits in marine evaporites with brief reference to certain potash-rich brines. Approximately 85% of current domestic production is from bedded salt deposits and much of the balance is from brines. Marine evaporite deposits are accumulations of salt minerals deposited in structural sedimentary basins through the evaporation of seawater or mixtures of seawater and other brines. The salt minerals are precipitated in assemblages and sequences of assemblages as determined by the compositions of the brines and the solubility relations in the salt systems (D'Ans, 1933). The evaporation of seawater normally yields carbonate minerals as the first precipitates (Table 3). Further evaporation and concentration of the brine leads to the precipitation, in succession, of sulfate, chloride, and supersaline mineral assemblages including the salts of potassium and magnesium. The common minerals, ores, and products of potassium deposits are listed in Table 1. Many potash deposits contain accessory evaporite minerals together with a variety of detrital and authigenic silicates (Braitsch, 1971). The structural basins within which marine evaporites occur are of two main types: (a) cratonic basins formed by broad epirogenic movements (for example, the Michigan Basin of the midwestern United States and the Permian Zechstein Basin of eastern Europe), and (b) grabens, commonly related to continental

Jan 1, 1983

By N. L. Hancox

Previous researchers have used the cutting and rejoining model to represent a porous body when attempting to place Archie's law on a theoretical basis and calculate rock permeabilities (F = Ø-m, where F = formation factor, = - porosity and m = a constant). In using the model, a porous solid is assumed to consist of sections with parallel sides containing straight. continuous pores of total porosity 4 (pore to total volume or, for a homogeneous body, pore to total area). The joining of pores at an interface between two sections is assumed to be random which results in a common pore area Ø2. This reduced area Ø2 is then taken as that area which limits electrical conduction or fluid flow in the body. Agreement between experimental results and results calculated using a model is not always good Because of this, various modifications of the model are presented — for instance, the random nature of the joining is questioned. Formation factor measurements on specially constructed porous specimens are described in this paper. it is concluded that the common pore area limits flow completely only if sections containing straight pores are very thin, and that, in most natural materials, the common pore area at an interface must be greater than that given by random joining. However, the model is still useful in permeability calculations, provided that the fractional area limiting flow is determined from formation factor measurements. INTRODUCTION Two important properties of porous media are permeability k, which describes the ease with which a fluid can flow through a porous medium, and formation factor F, defined as the ratio of the resistivity of a saturated specimen to the resistivity of the saturating liquid which describes the electrical properties of the saturated material. k is defined by Darcy's law,l k= µqL/P Ae . . . . . . . . . . . . . . . [1] where µ = liquid viscosity, q = flow rate, L = length of specimen, p = pressure across the specimen and = - the effective area over which flow occurs, F is given experimentally by Archie's law,2 F = Ø-m ,..............(2) where 4 is porosity defined as the pore to total volume or, for a homogeneous body, the pore to total area; and m lies between 1.3 for loose sand and 2 for cemented sand. Consider a porous body of total cross-sectional area A and length L, saturated with a liquid of resistivity R and with an effective area for conduction of Ae. Then, from the definition of F given previously, F=A/Ae , ................(3) or, from Eqs. 2 and 3, Ae = A Øm ..............(4) Thus, in any attempt to calculate k or F, some assumptions must be made concerning the pore structure of the body and a value derived for A,. To determine Ae, Childs and George3 and Wyllie and Gardner4 suggested an elementary statistical representation often referred to as the cutting and rejoining model of a porous body. The body is assumed to be composed of two or more parallel-sided sections of porosity 4, containing straight, continuous pores with a common pore area of Ø2 at an interface between two sections. The value is given by a random joining of the pores in either section. Two such sections,

Jan 1, 1969

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

CONTENTS KANSAS-H. S. BRYANT 3 TEXAS, EXCEPT GULF COAST-M. C. CHENEY 14 GULF COAST-L. P. TEAS 21 TEXAS PANHANDLE-W. E. HUBBARD 29 LOUISIANA, ARKANSAS AND MISSISSIPPI L H. K. SHEARER 37 ROCKY MOUNTAINS-R. C. COFFIN 43 CALIFORNIA-V. H. WILHELM 51 MICHIGAN AND THE TRENTON FIELDS OF OHIO AND INDIANA-M. G. GULLEY 65 ILLINOIS, WESTERN KENTUCKY AND WESTERN INDIANA-A. H. BELL . . . 73

Jan 1, 1932

By AIME AIME

AN outstanding session of the Annual February Meeting was one held under the joint auspices of several groups on Tuesday afternoon, Feb. 22, as a symposium on the question of preserving peace in the postwar era through the control of the supply of sundry minerals vital to the Axis nations. D. H. McLaughlin and R. C. Allen were associate chairmen. And C.K. Leith led the discussion.

Jan 1, 1944

By David J. Reddish, Barry N. Whittaker

The characteristics of surface ground strains due to longwall mining are reviewed with special reference to U.K. coal mining observations. The current empirical method of estimating ground strain is discussed. A method of determining surface ground strain above a longwall extraction is described whereby strain can be accurately represented along a line in any direction. The discussion is supported with examples of its application to common subsidence engineering problems.

Jan 1, 1984

Alfred Noble Joint Prize Committee F B Foley, '56 American Documentation Institute F B Foley, '56 American Geological Institute J L Gillson, Nov '56, H A Meyerhoff, Nov '57 Committee on Government Relations J L Gillson, '56 American Power Conference Paul R Nichols, '56 American Standards Association Mining Standards Board E R Borcherdt, Jan '58, Otto Herres, Jan '58 Alternates E W Bullard, Dec '56, and J K Richardson, Dec '56

Jan 1, 1956

The First Conference of the Powder Metallurgy Committee convened in the East Foyer of the Hotel Waldorf-Astoria, New York City, at 9:45 a.m., on Feb. 21, 1944, Mr. John Wulff, General Chairman, presiding. THE CHAIRMAN.-In behalf of the American Institute of Mining and Metallurgical Engineers I welcome all members and guests to this conference on Powder Metallurgy. We hope that this meeting will give expert and novice in the field a chance for discussion. Unfortunately, the subject has been overemphasized by some, and, of late, severely criticized by others. We have here today powder producers, fabricators, and engineers of different viewpoints, who can make the meeting a success. Such success depends not only on the caliber of the papers presented but more so on the discussion. To give you time for a free exchange of views, the papers have been shortened purposely. With the hope that you will all benefit by this conference, I shall turn the meeting over to the Chairmen of the morning session, Mr. Roland P. Koehring, of Moraine Products Division of General Motors, and Dr. R. K. Waring, of the New Jersey Zinc Company. SESSION ON DESIGN FACTORS IN POWDER METALLURGY R. P. Koehring and R. K. Waring presiding The opening paper of the session was presented by Mr. Fred P. Peters, as follows:

Jan 1, 1945

By P. Shahinian, J. Weertman

Minimum creep rates of nickel samples were measured in the stress region of 2.5x107 to 2.8xl0 dyne per sq cm and the temperature region of 400° to 1100°C. The creep rate seems to be proportional to (stress) at stresses below 7x10H dyne per sq cm. The activation energy of creep is approximately 65,000 cal per mol. IN a recent theory' of steady-state creep which is based on Mott's dislocation climb mechanism, the following creep equation was derived for creep in polycrystalline metals (if where K is creep rate, Q the activation energy of self-diffusion, S the entropy of activation of self-diffusion, L' the grain size, L the subgrain size, b the length of the Burgers' vector of a dislocation, u the shear modulus, u the stress, a the critical shear stress, M the density of active Frank-Read sources, v the vibrational frequency of a vacancy, and kT has its usual meaning. This equation predicts a creep rate which depends on the stress through a power law at low stresses. At high stresses the creep rate increases much more rapidly with stress. The theory breaks down for stresses great enough that the inequality holds true. It was the purpose of the present in-

Jan 1, 1957

By P. Somasundaran, K. P. Ananthapadmanabhan

A knowledge of the role of effects and interactions of chemical species is important in developing an understanding of the behavior of mixed minerals and natural ores in beneficiation processes such as flotation and flocculation. In this study the role of such species was examined for the calcite-apatite system by conducting flotation of each mineral in various supernatants prepared by mixing with water. Supernatants of apatite and even that of calcite depressed the flotation of calcite markedly in the pH range of 5 to 13. Addition of Ca(NO3)2, K2C03, and K3P04 also produced definite effects under various pH conditions. Apatite flotation was also affected by the mineral supernatants and by carbonate and phosphate solutions. The results are analyzed in terms of the surfactant's solubility properties and the mineral's electrochemical and dissolution properties. While depression of calcite flotation by the dissolved species is found to be governed by depletion of oleate by bulk precipitation, the depression of apatite flotation is caused by the carbonate and phosphate species in the system. Turbidity measurements and a thermodynamic analysis of possible interactions in the system support these considerations. The effect of the supernatant of minerals on their own flotation suggests the important role of kinetics of various surface interactions in comparison to that of mineral dissolution.

Jan 1, 1985

(Members are urged to send in for this column any notes of interest; concerning themselves or their fellow-members.) Members and guests who called at Institute headquarters during the period Nov. .10, 19 16 to Dec. 1.0, 1916: Chester Atkinson, La Fundicion, Peru. , Paul Llewellyn, East Chicago, Ind. F. J. Brule, Toronto, Ont., Canada. Harry March, London, England. Sterling H. Bunnell, New York, N. Y. E. P. Mathewson, Toronto, Ont., Canada. G. H. Cunningham, Hobart, Tasmania.' E. W. Moore, Budapest, Rumania. Courtenay DeKalb, Tucson, Ariz. W. J. Pentland, Guadalajara, Mex., E. H. Dickenson, New Y.. Heinrich Ries, Ithaca, N. Y. E. B. Durham, Mount Kisco, N. Y. W. E. Saunders, Philadelphia, Pa. L. B. Eames, Pueblo. Colo. J. G. Scrugham, Reno, Nev. N: H. Emmons, 2d, Copperhill, Tens. - W. H, Seagrave, Kennecott, .Alaska. R. E. Hoffman, Hannibal Mo.'s H. B. Small, Magangue, Colombia. B. B. Hood, Chronic, N. J. W. H. Staver, Washington, D. C. H. E. Jackman, Rochester, N. Y. R. K. Stockwell, Santiago, Chile. F. H. Jackson, Joplin, Mo. Warren D. Thompson, Boston, Mass. Knight S. Jordan, Provo. Utah. Thor Warner, Kingman, Ariz. William Kelly, Vulcan, Mich. S. T. Wellman, Cleveland, Ohio. W. H. Lanagan, San Francisco. Cal. F. H. Willcox, Pittsburgh, Pa. H. H. Lauer, Northampton, Pa. Arthur K. Adams has been appointed geologist to the Andes Copper Co.

Jan 1, 1917

The following is am incomplete list of members and guests who called at Institute headquarters during the period May 10, 1918 to June 10, 1918. Arthur K. Adams, Potrerillos, Chile. J. M. Mahoney, Wilkinsburg, Pa. John Carter Anderson, Tucson, Ariz. Benjamin L. Miller, South Bethlehem, Pa. George S. Blair, Camp Cordon, Ga. Wilbur A. Nelson, Nashville, Tenn. W. A. Deane, Summitville, N. Y. Miles G. Nixon, Chicago, Ill. Charles H. Fulton, Cleveland, Ohio. Walter G. Perkins, San Francisco, Cal. Rudolf Gahl, Inspiration, Ariz. G. M. Ponton, Ottawa, Canada. C. C. Griggs, Eureka, Utah. D. A. Powell, Columbus, Ohio. J. F. Hanst, Potrerillos, Chile. H. W. Reed, Salt Lake City, Utah. Stanley C. Herold, Pittsburgh, Pa. J. C. L. J. Seelig, Padong, East. Indies. Floyd D. James, Boston, Mass. Oberlin Smith, Bridgeton, N. J. Charles Janin, San Francisco, Cal. Harrison Souder, Cornwall, Pa. E. Horton Jones, Copper Cliff, Ont. Stanley A. Spellmeyer, Camp Meade, Md. William Kelly, Vulcan, Mich. Roger S. Sperry, Waterbury, Conn. Ichiro Kitsunezaki, Tokyo, Japan. D. R. Thomas, Toronto, Canada. P. K. Lucke, San Antonio, Tex. Thor Warner, Phoenix, Ariz. E. Francis McCrossin, Birmingham, Ala. L. Douglass Anderson, formerly superintendent of the United States Smelting Co., Midvale, Utah, is now manager of smelters, Intermountain District, United States Smelting, Refining & Mining Co., Salt Lake City, Utah.

Jan 7, 1918

By Horace Pops, L. L. Isaacs

SOLID-STATE transformations at low temperatures are frequently studied by optical metallography. Greninger and ooradian' and Hull and Gar-wood2 have examined the martensitic-type transformations in 0-phase Cu-Zn alloys during continuous cooling below room temperature. The lowest range of temperatures in the apparatus described by these investigators is limited to approximately 110°K. Present studies of reversible first-order phase transitions near liquid-helium temperatures have necessitated the design of a new cold-stage cryo-stat for optical metallography. The features of interest of this instrument are as follows: a) temperatures down to 4.Z°K are obtainable; b) the specimen is always under vacuum, thereby avoiding the condensation of moisture; c) specimens can be rapidly cooled or heated at varying rates, thus permitting studies of transformation hysteresis. Fig. 1 shows the details of the cryostat. All major parts are made of type 304 stainless steel. Both helium and nitrogen cans are Heliarc-welded to the helium filling tube, permitting the use of a common shielding can. Hence, the over-all weight and the area of the evacuated surface are mini- mized. The copper sample holder is screwed into the bottom of the helium can. To assure good thermal contact between the sample holder and the refrigerant, an indium ribbon is placed on the threads

Jan 1, 1964

By P. D. Zemany, G. W. Sear, B. W. Roberts

Vanadium metal is embrittled by hydrogen at a temperature as low as 250°C when held in the presence of manganese metal and water vapor in a rough vacuum. It is established that the property changes are caused by the catalytic decomposition of water vapor at the vanadium surface and the diffusion into and solution in the vanadium of the resultant hydrogen. It is found that manganese is a necessary component of the catalyst. The manganese is transported in the vapor phase by an unknown molecule. A deuterium tracer experiment demonstates the role of water vapor in the embrittle-ment process. VANADIUM metal foils were observed to become embrittled' at a temperature of about 300 °C when held in the presence of manganese metal and a small amount of moist air, This paper describes the investigation to find the embrittling agent and an understanding of the relatively low temperature reactions that are involved. Experimental The vanadium metal foil used was prepared by cold-rolling and pack-rolling 32 mil sheet" in a series of steps down to 1 mil foil. The original observation was confirmed by sealing vanadium foils of 3 x 10 sq cm into individual Pyrex tubes with manganese powder† and a con- trol tube containing only the vanadium foil. These tubes were evacuated to 10 -5 mm Hg without baking and sealed. After heat treatment for 200 hr at 300°C, the control foil showed no change in duetility, whereas the foil contained in the manganese— containing tube was embrittled. The visual appearance of each was unchanged. A series of Pyrex sample tubes, about 2.5 cm diam and 25 cm long, were prepared, each containing a 3 x 10 sq cm piece of foil and 5 g manganese powder at the lower end of the tube. By reducing the time of anneal and the temperature of these samples, it was found that embrittlement could be created at 250°C in a time as short as 1 hr. Since the vanadium metal used here has been drastically cold-worked by rolling, it is assumed that it contains a maximum number of dislocations. To check the possible necessity of dislocations in this low temperature reaction, a vanadium foil sample was annealed in Vycor for 2 hr at 800°C to re crystallize and reduce the dislocation concentration. Metallographic examination showed grains which were not visible before annealing. The embrittlement procedure was carried out at 300°C and 3 hr. Upon checking the foil no embrittlement was observed. Further experiments demonstrated that about 6 hr at 300°C are required to create embrittlement in the foil. This delay in the onset of embrittlement in the vanadium foil suggests but does not prove that dislocation channels play a role in the embrittlement phenomena. If manganese metal is necessary for this low temperature embrittlement, do other elements in the transition metals group yield the same result? To check this qualitatively, a group of elements of similar atomic radii were obtained and sealed as before into Pyrex tubes with a sheet of vanadium foil. These tubes were annealed at 250°C for 6 hr and included (with radii)-2 A1 (1.4A), As (1.25A), Be (1.2A), Co (1.25A), Cr (1.45A), Cu (1.25A), Fe (1.25A), Ga (1.2A), Ge (1.25L%), Mn (1.3A), Ni (1.25A), Si (1.2A), Ti (1.45A), Zn (1.3A), air, H,O, 10 cm Hg of dry hydrogen, and MnO, powder. Upon testing the above sample foils for brittleness, only the manganese-containing tube yielded a brittle foil. Manganese Transport—To eliminate contact of manganese metal powder and vanadium foil, sample tubes were prepared with fritted glass barriers. The embrittlement reaction was still found to occur. Thus, the mode of transfer of manganese is certainly vapor transport. A vanadium foil was embrittled by this mechanism in an evacuated Pyrex tube for 8 hr at 300°C. By means of X-ray fluorescence analysis,' the amount of manganese added to the surface was established at 5 ±2 x 10 -6 g per sq cm. Since the average rate of manganese deposition is known, an effective average pressure of an assumed carrier compound can be computed. ___ P = M/T v2p mkT

Jan 1, 1959

By W. R. Hibbard Jr., R. W. Guard, N. G. Ainslie

Evidence is presented that copper-base solid solutions of different solutes having equal grain sizes, no preferred crystal-lographic orientation, equal electron-atom ratios, and, within experimental scatter, identical initial yield strengths, need not have identical stress-strain curves at strains larger than about 0.04. The stress-strain behavior is rationalized in terms of the proposed Suzuki chemical interaction between solute atoms and extended dislocations using what is thought to be a somewhat different means of representing stress-strain data. ALTHOUGH the effect: of alloying element upon the strength characteristics of sold solutions is a subject which has received considerable attention in the past, the exact relationships between the common deformation parameters and certain common variables are not really known in some cases. As a result some of the experiments reported in the literature in which these variables are inadequately controlled lose some of their persuasion regarding underlying principles. Nonetheless, facts are known which bear pointing up: When the true stress, a, and true plastic strain, E, of tensile deformatic~n are plotted on a double logarithmic coordinate system, one may observe a straight-line relationship at strains greater than 0.02. The form of the curve in the linear region is given by a = Ken! where a represents true stress, E, true strain, and K and tn, constants. If the relationship holds, K and m define the flow characteristics of the material being tested. m and K, however, may vary with other parameters. Hollomon found that in a-brass, m is influenced by grain size. French and HibbardZ found in alloys of copper that inverse relationships existed between m and 1) the solute concentration for a given solute, 2) the 0.01 yield strength, and 3) the constantK. Lacy and Gensamer3 observed (du/d~) (= U/Em) to increase with increasing values of K in systems of alloyed ferrites (although with considerable scatter of data which may be attributed to uncontrolled grain size). Brick, Martin, and Angier* deduced in copper-base alloys a straight-line relationship (with some scatter) between the change in the Dph number due to solid-solution strengthening and the change in the Dph number due to work hardening which suggested that copper-base alloys having equal yield strengths might have identical stress-strain curves in the plastic flow regions. French and HibbardZ concluded that the yield strength of copper-base solid solutions is the proper basis for comparing the effects of solute elements. Also, Allen, Schofield, and ate' showed that, within their experimental variation, copper-base alloys of zinc, gallium, germanium, and arsenic having the same electron-atom ratios have the same true-stress true-plastic strain curves. Dorn, Pietrokowsky, and ~ietz' also found that with aluminum-base alloys the stress-strain curves in the flow regions are approximately the same if "equivalent" concentrations of alloying elements are used. Solute valence and lattice parameter distortion were the parameters used to determine equivalency. The present report describes an investigation in which an attempt was made to obtain copper-base solid-solution alloys of four solute elements having within close tolerances equal grain sizes and yield strengths, and to see if the level of yield strength does indeed define the flow curve regardless of solute type. During analysis of the data certain unexpected features of the stress-strain curves became apparent which gave rise to some speculation and are discussed at length in the paragraphs that follow. EXPERIMENTAL PROCEDURES Alloy Preparation—Using the data of French and HibbardZ as a first approximation, four different binary copper-base alioys were designed so as to have the same yield strength. In addition, other alloys were prepared in which the solute aoncentrations varied slightly from those calculated above so as to span a range of yield strengths, see Table L The yield strengths of all alloys prepared except the copper-tin alloys were subsequently found to Lie fairly close to one another. The copper used in the alloys was produced by the American Smelting and Refining Co. and was of very high purity (99.999 pct). The alloy additions and their initial purities are as follows:

Jan 1, 1960

By R. W. Armstrong, P. C. Jindal

The hardness dependence on grain size for polycrys-talline cartridge brass and a leaded brass has been measured by Brine11 and Rockwell B testing. In each case, the hardness, H, depends on the average grain diameter, 1, according to: H =Ho + kHl-1/2 where Ho and kH are experimental constants. Diamond pyramid hardness values have also been measured as a function of the indentation size and grain size to give additional information on the nature of the hardness test and the dependence of hardness on micro-structure. The hardness of polycrystalline brass depends on its grain size. Bassett and Davis' demonstrated this as early as 1919 by making Brinell hardness measurements on cartridge brass. Since then, the hardness of this type of material has been measured as a function of grain size by making Rockwell,2'3 Vickers,4 and Brinell5 tests. he hardness dependence on grain size has also been measured for other materials. Angus and summers6 investigated the grain size dependence of the Brinell hardness of polycrystalline copper and a Cu-4.5 pct Sn bronze. In other studies, nickel,? Armco iron,Big an Fe-0.07 pct C alloy,I0 and an 0.39 pct C-12.45 pct Cr stainless steel" have been investigated. In some of the preceding cases, the hardness results have been analyzed to show that the hardness varies with the average grain diameter, 1, according to an l-l\4, l-1/4 or I-2 dependence,11-13 The studies of the influence of grain size on hardness have not been based on any theoretical model. This may be because the hardness of a material is itself a complicated property. However, attempts have been made to correlate, experimentally and theoretically, the hardness of a material with its unidirectional stress-strain behavior.14-l6 On this basis, Hall" proposed that the polycrystal hardness dependence on grain size might follow directly from the Hall-Petch18,19 relation for the grain size dependence of the yield stress. Thus, the hardness-grain size relation was given as: H = Ho + kHl-1/2 [1] where Ho and kH were taken as experimental constants. The relation was applied to the measurements on brass,' copper,6 bronze,= and Armco iron.' More recently, this relation was shown by Armstrong and jindal20 to adequately describe the measurements on cartridge brass made by Bassett and Davis' and Babyak and Rhines.5 In this case, the relationship was taken a step further by independently relating the values of Ho and kH to the values of oyand ky, previously reported by Armstrong, Codd, Douthwaite, and petch21 from measurements of the yield stress dependence on grain size for this type of material. In the present investigation, new Brinell and Rockwell B hardness measurements have been made as a function of grain size for a cartridge brass and a leaded brass. In addition, diamond pyramid hardness values were measured as a function of the indentation size. All these results are applied to a further analysis of the hardness dependence on grain size. MATERIALS AND EXPERIMENTAL METHODS Cartridge brass and a leaded brass were selected for this investigation for two main reasons: it was anticipated 1) that these materials could be cold-worked and recrystallized to a wide range in grain size and 2) that the results to be obtained on these typical industrial materials could be usefully compared with previous investigations. The chemical analyses of the actual materials which were employed are given in Table I. The as-received 1/2- and 3/4-in.-thick plates were given various reductions in thickness by cold rolling. The rolled material was heat-treated at various temperatures between 330" and 850°C for differing time periods from 5 min to 9 hr to achieve a variation in the average grain diameter between 0.0339 and 0.000543 cm.22 During heat treatment, the brass was protected from zinc loss by packing it in chips or foils of the same composition material. Reasonably equi-axed grain structures were obtained in each case. The metallurgical grain sizes of the specimens were determined from measurements of the average linear intercept on a random line. Annealing twin interfaces were not counted along with grain boundaries. The

Jan 1, 1970