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By R. E. Campbell

Uranium metal of improved purity was prepared by electrorefining commercial magnesium-reduced uranium in a molten sodium chloride-uranium trichloride electrolyte. The best operating conditions for the preparation of refined metal were established as follows: an electrolyte containing 8.7 to 13.3 weight-percent uranium; initial cathode current densities from 300 to 1,500 amp/sq ft; and a molten salt temperature of 860° C. Ingots produced from electrorefined uranium crystals prepared with these operating conditions were substantially free of metallic impurities. The only impurities in the refined and consolidated metal were present in low or undetectable amounts.

Jan 1, 1965

By R. Schuhmann

Jan 1, 1965

By T. A. Sullivan

High-purity vanadium metal was prepared by electrorefining commercial vanadium in a molten sodium bromide, potassium bromide, and vanadium dibromide electrolyte. Variables investigated were operating temperature, current densities, electrolyte composition, and condition of the anode. The purity of the refined metal was in the range of 99.95 percent vana-dium. Iron and oxygen in the 50- to 250-ppm range were the only major impurities. Metal with hardness numbers of 50 to 60 in the Rockwell F scale was prepared from feed material with a Rockwell B hardness of 90. The arc-melted metal was highly ductile and could be cold-worked into sheet or foil.

Jan 1, 1965

The 8 ft by 91/2 ft drive which joined No. 7 Shaft with Browne Shaft on the 1,480 ft level was extended from both ends and met at a point approximately 12,000 ft from No. 7 (2,000 ft from Browne).The surveying required for this 2 1/2 mile haulage drive called for greater accuracy than was obtainable from South Mine standard methods. Procedures and devices from published information were tried and modified as required to suit local conditions. Several new methods were applied and improved as the drive advanced. The control of angular, linear and level measurements was perhaps considerably in excess of the requirements, but this was offset by abnormally large discrepancies resulting from shaft plumbing. The accuracy of the final breakthrough, although not to the standard desired, was sufficient to complete the connection without inconvenience and added cost.INTRODUCTIONThe acquisition of the Browne Shaft leases in January 1962 presented the management of Broken Hill South Limited with the problem of transporting ore from these leases to its mill. It was eventually decided that diesel locomotivehaulage through a 2t mile drive on the 1,480 ft level between the two mines was the best solution. The drive was advanced from both ends after Browne Shaft was deepened by 80 ft to reach the 1,480 ft level horizon. Each end advancedabout 15 ft/day with the miners working three 7 hr shifts. Blasting was restricted to the end of the shift.The survey work involved five shaft plumbings and 78 theodolite stations in a traverse, underground and surface,of more than 5 miles. Because of the exceptional length of the drive, an unusually high degree of reliability was required.The aim was for a maximum error at breakthrough of 1 ft 1 in 30,000, and to secure this, precise methods of linear measurement were necessary. Shaft plumbing in particular posed special difficulties.

Jan 1, 1965

By J. C. Uy, T. E. Davidson, A. P. Lee

The effects of hydrostatic pressures to 26 kbars on the micro structure of poly crystalline Cd, Zn, Bi, Sn, Zr, Mg, Cu, and Fe were examined. Pressure-induced microscopic plastic flow in the form of boundary migration, slip, multiple slip, or twinning has been observed either singly or in combination in cadmium, zinc, bismuth, and tin. No deformation was observed in zirconium, magnesium, copper, and iron. The occurrence of such deformation, in terms of its intensity and initiation pressure, relates directly to the degree of anisotropy in the linear compressibility. Pressure cycling does not significantly affect the residual tensile properties of a zinc alloy which exhibits pressure-induced deformation similar to that of Pure zinc. CLASSICAL elastic theory predicts that a superim-posed hydrostatic pressure will not induce shear stresses in an ideal material. Thus, in the case of homogeneous and isotropic materials plastic flow will not occur as a result of pressure exposure, regardless of the magnitude of the pressure, unless some form of phase transformation or permanent density change takes place. However, real materials, such as metals, often vary considerably from the condition of homogeneity and isotropy. For this reason, Vu and johannin' examined and observed hydrostatic pressure-induced microscopic deformation in polycrystalline cadmium and, zinc, but not in aluminum, to pressures of 9 kbars and indicated that its occurrence is related to anisotropy in the linear compressibility. In addition, Davidson and omaan' have reported pressure-induced deformation in polycrystalline bismuth below the 1-11 transformation pressure. It becomes apparent then that under certain conditions hydrostatic pressure can induce localized internal shear stresses in some metals of sufficient magnitude to cause plastic flow. In this work, eight pure single-phase metals of different lattice structures and degrees of elastic anisotropy were examined after pressure exposures of up to 26 kbars in order to establish the conditions under which such deformation occurs and the type of deformation as a function of pressure. The effects of pressure cycling on the mechanical proper-

Jan 1, 1965

By R. J. Reynik, F. R. Meeks

IN the classical paper1 of Mehl and Rhines entitled "The Rates of Diffusion in the Alpha Solid Solutions of Copper", the authors state: "It has been mathematically demonstrated that the treatment of the data as though the diffusion were taking place between two flat plates instead of radially in a cylinder has no appreciable effect upon the results. Were the bars of a much smaller diameter, a modification of the analytical treatment would have been required." Unfortunately, the errors in the reported concentrations are much too large to neglect, as shown in the results below. A planar treatment of diffusion data assumes that the reference planes separated by a nominal distance (AX) have identical areas. An adjustment must be made on the concentration data should the successive diffusion planes differ in area. The Mehl-Rhines' diffusion samples were cylindrical with copper electroplated onto copper-based alloys. Successive surface areas through which diffusion occurs are in the ratio ri/r1, where ri is the radial distance between the center of the sample and the center of the i th shell to which the host (alloy) atoms diffuse, and r1 is the radial distance between the center of the sample and the center of the innermost (i = 1) experimentally reported shell from which the alloy atoms diffuse. Hence, ri/r1 (i = 1, ..., n layers) is a dimensionless correction factor to be multiplied by the reported concentration data before planar-data analysis is attempted. In the forty-seven samples reported, the original interface between the copper alloys and the electroplated copper was located at a mean distance of 8.255 mm from the center of the samples. The successive layers, machined off the samples, were approximately 0.0762 mm thick. The distance (xi) at which concentration (ci) was reported was always a distance measured with respect to the original interface, that is, with respect to the fixed distance of 8.255 mm. Hence, the as yet undiscovered Kirkendall Effect was precompensated. The values of ri and r1 are therefore given by ri = 8.255 + xi and Y, = 8.255 + x,. The illustrative table below lists the position xi (mm), ri (mm), the value of ri/r1, the reported concentration (ci) in weight percent (only valid for radial analysis of data), and the corrected concentration [c'i = (ri/r1)ci] in weight percent (only valid for planar analysis of data). Similar tables can be constructed for the remaining forty-six samples. The corrected data can be used to re-evaluate the diffusion coefficients for the reported systems.

Jan 1, 1965

By Manuel Gomez

Carbon number distributions were obtained for tar acid fractions from five low-temperature tars by low-ionizing voltage mass spectrometry. Quantitative data for phenols representing seven structural compound types were examined by statistical analysis. It was shown that for the phenols discussed, the data could be represented by regression equations expressing phenolic concentration as a function of the reciprocal of the carbon number and the carbon-to-hydrogen ratio of the parent coal. The total concentration of each structural type present was found to depend on the molecular weight and boiling point of the initial member of the group. Carbon distribution data for the tar acid fractions studied support the view that low-temperature tars contain the same chemical compounds but in different proportions.

Jan 1, 1965

By J. E. McDonald, J. G. Eberhart

A model is discussed from which the work of adhcslon .tor liquid transition metals on aluminum oxide surfaces can he calculated, A close-packed (00011 oxygen surface on A12O3 is assumed with two different types of surface sites: one type involving metal-oxygen bonds and the other man der Waals into actions. The work of adhesion is thus expressed as the sum of these two bonsding free energies. Calculated works of adhesion for nickel, titanium, chromium, and zirconium on sapphire agree well with the experimentally determined quantities. The model is extentled to the calculation of the work of adhesion and shear stress required to remove a thin metal film from a sapphire substrate and is in good agreement with experimental values. The obsewed dependence of the work of adhesion on the free energy of oxide formation of the metal is shown to also provide an interpretation of the tittle dependence of thin-film adhesion. THIS paper presents a model for the type of bonding which occurs across a metal-A12O3 interface. The model is used to explain the results of two types of experiments in which such an interface exists: 1) the adhesion of thin metal films on Al2O3 substrates and 2) the wetting of A12O3 by liquid metal drops. The adhesion of thin films to various substrates has been the subject of a variety of investigations.'-' Benjamin and weaver3 and Bowie,6 using the scratch test developed by Heavens,10 studied the adhesion of metallic films to glass substrates. Their observations for noble-metal film adhesion agree well with an adhesion model involving a van der Waals type of bonding between the film and the substrate. For films of metals whose free energy of oxide formation. ?F°f, has a negative value. Benjamin and weaver3 and Bowie6 found a time-dependent adhesion with an initial value that can be interpreted in terms of van der Waals interactions but a larger terminal value which was related to ?F°f, Karnow-sky and Estill7 deposited films on sapphire at elevated temperatures and noticed no time dependence of film adhesion but a similar correlation with ?F°f. Because of the kinetic problems associated with thin-film adhesion it is desirable to examine adhesion in an equilibrium system. The wetting behavior of liquid-metal drops on Al2O3 provides such a system. Systems of this metal-ceramic type have been studied extensively.11 Humenik and Kingeryl2 have measured the wetting of A12O3 (and other substrates) by several metals and have pointed out that the wetting ability of these metals increases with increasing values of -?F°f. It is thus seen that thin-film adhesion and metal wetting on A12O3 are both related to the tendency of the metal to react with the surface oxide ions of the Al2O3 substrate and, because of this, both phenomena should be explainable by an appropriate model for the metal-Al2O3 interfacial bonding. In the sections that follow, wetting and adhesion data on A2O3 are reviewed and a model is presented by which these phenomena can be interpreted. ANALYSIS OF WETTING EXPERIMENTS In an equilibrium system involving a liquid-metal drop on a solid Al2O3 substrate, the work of adhesion, WAD, is defined by the Dupre, equation as WAD = ?s + ?L -?sL [1] where ?s and ?L are the surface free energies of the solid substrate and the liquid drop, respectively, and ?sL is the interfacial free energy. The work of adhesion is the work required to separate a unit area of the solid-liquid interface into two surfaces. The work of adhesion is usually determined from a sessile-drop experiment in which yL and the contact angle, ?, are measured. The Young-Dupr6 equation is then used to calculate WAD Wad = ?L (1+ cos ?) [2] The literature of this subject has been examined and Table I shows work of adhesion data for various liquid metals as measured on A12O3 substrates. The standard free energy of oxide formation of the metal at the temperature of the wetting experiment, ?F°f . is also tabulated in kcal per g-atom of oxygen. The data is grouped according to the gaseous atmos-

Jan 1, 1965

By J. G. Eisele

Solvent-extraction characteristics of dodecyl phosphoric acid (DDPA) were investigated to determine its potential as a fractional or selective extract-ant for individual elements in a rare-earth-yttrium mixture. The DDPA is an effective extractant for splitting rare-earth mixtures into light and heavy subgroups. Yttrium normally extracts with the heavy rare-earth elements but may be shifted toward an extraction sequence with the light rare-earth elements by increasing the pH. Elements in the light and heavy ends of the rare-earth series can be separated from middle-group rare-earth elements by using diethylenetriaminepentaacetic acid (DTPA) as an aqueous phase counter-extractant. Hydrogen-ion dependency of the distribution coefficients differs from that reported for similar systems at tracer-level concentration.

Jan 1, 1965

By Ralph H. Whaite

The Bureau of Mines program for microfilming maps of abandoned mines in the Pennsylvania anthracite region is described. A catalog of the maps that have been microfilmed in the Eastern Middle anthracite field--the first area to be covered in the program--is presented. Additional catalogs will be published as significant mining areas are completed.

Jan 1, 1965

By K. N. Weaver

In the early 1950's the cement industry began putting a new emphasis on geology. This article points up some of the industry's raw materials problems that geologists are uniquely qualified to handle. Portland cement can be made from relatively abundant industrial minerals and rocks, and this may explain why cement producers placed little emphasis on geology during the early days of the industry. After World War 11, however, the industry began to recognize the need for geological exploration and some of the larger companies began to build a permanent geological staff. This development has its roots in: 1) The rapid expansion of the industry. After World War II and continuing into the early 1950's the demand for cement far exceeded the production capacity. This placed a great deal of pressure on the producers to enlarge capacity at their plants and to develop new sites. 2) The closing of many cement plants due to inadequate raw materials. Producers feared lack of raw materials due to inadequate exploration and evaluation. 3) An ever increasing pressure for upgrading of the quality of portland cement, necessitated upgrading the quality of raw materials. 4) The increasingly large capital investment needed to build new cement plants required a higher degree of accuracy in reserve calculation. These reasons are more or less self explanatory and will not be elaborated on. They are outlined to illustrate the probable evolution of thought among cement management to justify the development of a geological staff. In the author's personal experience the geologist must continually readjust to changing conditions within the industry. For example, cement production capacity grew so rapidly that today production is only about 70% to 75% of rated capacity (73.8% in 1963). Therefore, whereas the geologist's function during the active expansion of capacity was primarily one of exploration, one of his major functions today is the development of existing reserves. This assumes of course that reserves at existing plants have been proven to be adequate in terms of the company's reserve policy. Through the proper development of raw materials, the geologist can markedly influence quality control, production and long range planning. Examples of several of the operations of Medusa Portland Cement Co. will illustrate how proper attention to geologic detail pays off in the above areas. Because limestone is the major raw material of port-land cement, the examples will be concerned with it. DEVELOPMENT OF GEOLOGIC DETAIL One of the prime objectives of an exploration or development project should be the establishment of the stratigraphy and structure of the deposit. The basic tool for exploration and development is still the core drill, and the geologist must gain a maximum amount of information from a minimum amount of drilling. In order to obtain this objective the following is essential: 1) Adequate detailed geologic logging of cores. The core is first logged and separated into lithologically distinct units. In order to make the lithologic breaks as meaningful as possible, representative pieces of core (not all) are etched in dilute HCI. This removes the "drill polish", brings out the structure of the rock and indicates the proportion of dolomite and argillaceous material because dolomite and argillaceous material etch in relief. In this way the lithologic breaks become clearer and one gains a general idea of the chemical makeup before analysis. This method of logging lessens the probability of including two types of stone, e.g. limestone and dolomite into the same sample for chemical analysis. 2) Representative sampling for chemical analysis. After logging, the lithologic units are sampled for chemical analysis. A representative analysis can be obtained by extracting a 1-in. sample for every foot of core. For example, a lithologic interval of 10 ft to 20 ft would yield ten 1-in. samples taken at 11 ft, 12 ft, 13 ft... and 20 ft. These samples are then crushed, pulverized and split into a sample for chemical analysis. This sampling method represents a significant saving of time over splitting the entire core. 3) Preparing the core as a record. Because of the expense of storage and the difficulty of handling large amounts of core, only representative samples of each lithologic unit are saved for reference. An

Jan 1, 1965

The Industrial Minerals Milling Section of the Mineral Processing Division has been engaged for the past three years in a study of the separation of minerals, by means of electronic sorting equipment, on the basis of their colour. Considerable knowledge of the subject has been built up. Because the object of this study is application as a means of beneficiation, a number of examples of the separations achieved are presented. Introduction T 0 the mineral collector, the colour of a mineral may be pleasing, even fascinating; to the mineralogist, student or professional, it may also be practical. It serves, to some extent, as a distinguishing feature in many minerals, and helps to fix with reasonable accuracy the identity of a few. It may now become a useful tool of the mineral dresser. The idea of using a difference in colour as a means of separation of one mineral from another is not new. Hand sorting dates back to ancient time. However, the means by which this can be done mechanically was developed only during the past decade. As far as the Mineral Processing Division is concerned, interest dates from March, 1960, when the following item was observed in the

Jan 1, 1965

By R. L. Solmer

During 1959-61, the Bureau of Mines investigated the strain and deformation induced in rock and concrete linings around mine openings by retreat panel caving at the Climax Molybdenum mine. Two concrete-lined slusher drifts on the Phillipson level of the mine were instrumented with both electrical strain gages and extensometers. Changes in strain and deformation were recorded over an 18-month period during the undercutting and caving of the mining panel. General agreement was found between the strain and deformation measurements and the hypothesis that the vertical component of the stress field on the openings is almost completely removed by undercutting. This phenomenon is a possible explanation for the structural failures that occur in the slusher drifts during the undercutting cycle.

Jan 1, 1965

By Gilbert M. Farrior

The electrical resistivity the coefficient of electrical resistivity the Hall coefficient, and the absolute thermoelectric power were determined in this Bureau of Mines investigation for nine compositions of the TiB2-CrB2 sub-system. The numerical values of the electrical resistivity and the thermo-electric power were greater for the intermediate compositions than for the end members. The absolute values of the Hall coefficients and the coefficients of electrical resistivity were less for the intermediate compositions than for the end members. The electrical resistivities and Hall coefficients were about the order of magnitude of most metals--from 34 to 202 microhm-cm and from about 0 to -23.3 X 10-4 cuP/coulomb. The thermoelectric power was somewhat greater than that of most metals--up to 15.6 microvolts per 0 C.

Jan 1, 1965

By J. M. Kuchta

Experimental data are presented on the autoignition temperature (AIT) characteristics of the hydrocarbon jet fuel, JP-6, in various oxygen-nitrogen atmospheres under conditions of constant volume and constant pressure. AIT's of this fuel in air varied little with fuel injection pressure but increased greatly with decreasing fuel content at low fuel-air-ratios. They also increased with decreasing oxygen content of the fuel vapor-oxidant atmosphere. Consistent with thermal ignition theory, the ignition temperatures increased with decreasing initial pressure, ignition delay, and vessel radius; expressions are given which define the observed variation of AIT with these variables for JP-6 fuel vapor-air mixtures. The significance of autoignition temperature data obtained using various ignition criteria is discussed to show the usefulness of such data in evaluating fire and explosion hazards. In addition, data are presented on the extent of oxidation that occurs prior to autoignition of this fuel in air at various temperatures.

Jan 1, 1965

By M. R. Geer

Samples of coal from six beds in the Roslyn-Cle Elum field of Washington were subjected to float-and-sink tests to determine their amenability to the production of high-ash boiler fuel for on-site power generation. Grindability tests and analyses of ash were made. All of the coals would require some degree of cleaning to insure a product of 25 percent ash. With two of the coals the entire size range would have to be washed. With the other four, it would suffice to clean only the coarse coal and bypass the raw fines.

Jan 1, 1965

By J. E. Harris

By elimination of other possible nucleation processes, it has been demonstrated, for commercially pure magnesium and a Mg-Al alloy, that at stresses less than that necessary for triple-point cracking creep cavities are most probably nucleated heterogeneously at second-phase particles. Evidence for the existence of such particles is presented and the role of grain boundary sliding in the nucleation process is examined quantitatively. DURING creep deformation of polycrystalline magnesium and its dilute alloys in the temperature range 0.45 to 0.7 Tm (Tm = absolute melting temperature) cavities form mainly along grain boundaries oriented normal to the stress axis and failure eventually occurs by their growth and impingement.' The possibility of low-ductility creep failure of magnesium-alloy reactor cans during service has prompted a number of studies of cavity formation in these materials.2-5 In this paper divergent theories of cavity nucleation6-10 are examined critically and conclusions drawn regarding the most probable mechanism of formation of cavities in magnesium. The paper is divided into two parts. The first section consists of the review and quantitative assessment of the possible role of grain boundary sliding in the nucleation process. In the second part an experimental program is described where an electron-microscope technique has been used to determine if second-phase particles exist in as-received commercially pure magnesium and in a magnesium alloy 1) THEORETICAL REVIEW Possible nucleation sites for creep cavities are: a) high-angle grain boundary triple points,11-14 b) subboundary/grain boundary intersections,15-18 c) ledges in the grain boundary, 19-25 d) second-phase particles. 9,26-30 Each of these possibilities is now considered with special reference to deformation of magnesium. 1.1) Triple-Point Cracking. The stroh31 condition to nucleate fracture is: " > vr [1] where ss = applied shear stress, ? = surface energy, C = shear modulus, L = length of sliding interface. This relationship is independent of the nature of the interface and it is possible to calculate the stress concentration at the end of a sliding high-angle grain boundary and thus deduce, approximately,* the minimum applied stress necessary to nucleate triple-point cracking. Such theoretical predictions for Nimonic alloys have been made by McLean13 and found to agree quite closely with the minimum stress determined by experiment. Stresses capable of nucleating triple-point cracking should also be sufficient to nucleate fracture at a grain boundary due to intragranular slip, for the lengths of sliding interface in the two cases are approximately equal. Thus the minimum stress for triple-point cracking should represent a demarcation between failure due to general "cracking" and that due to cavitation. Hauser, Landon, and Dorn32 have demonstrated that for polycrystalline magnesium in the temperature range 78° to 298°K the fracture stress is inversely proportional to the square root of the mean grain diameter. As pointed out by stroh31 this result indicates that Eq. [I] describes the fracture characteristics of magnesium at low temperatures. Heal3 has reported that for rapid deformation (112 pct hr-1) of polycrystalline magnesium the transition from cracking to cavitation occurs in the temperature range 175" to 275°C. He also presented the fracture-stress values for the same material tested under similar conditions. From Eq. [I] taking G = 1.3 x 10" dynes , ? = 600 ergs . cm-2,33 and L = 0.017 cm, a Stroh-McLean13,31 tensile stress of -266 kg. cm-2 is calculated, corresponding to a transition temperature of -190°C; this is in

Jan 1, 1965

By Robert C. Johnson

Single crystal whiskers of ZrO2 and TiO2 were grown by solution and crystallization of these oxides in molten baths. Mixtures of Na2B407 and LiC1 were the most suitable growth media for zirconia. Sodium borate alone and Na2CO3 plus SiO2 were best suited for titania. The solubilities of zirconia and titania in molten sodium borate were determined, Whether zirconia whiskers were dendritic or nondendritic depended on the temperature used. The best single crystal whiskers were grown below 1,100° C. Titania whiskers always grew as single crystals. The tensile strengths of zirconia and titania whiskers were about 15,000 psi and 50,000 psi, respectively. Modulus of rupture was about 49,000 psi for zirconia whiskers and 75,000 psi for titania whiskers. Chemical analyses showed the zirconia and titania whiskers to be pure. The zirconia and titania whiskers were shown by X-ray analysis to be, respectively, baddeleyite and rutile.

Jan 1, 1965

By J. H. Brophy, A. L. Prill, H. W. Hayden

An error lzas been found in the conventional way of determining the time exponent of linear shrinkage for the solution-precipitation stage of liquid-phase sintering. Large amounts of shrinkage due to initial rearrangenzent result in erroneously low exponents and tni si dentification of the rate-controlling process. Two alternative, mathematically correct, methods of calculation are applied to existing data on Fe-Cu, WC-Co, and Tic-Ni-Mo. This results in reidentifi-cation of the rate-controlling process and somewhat better agreement with related data. In each case the solution-precipitation process is solution-controlled and not diffusion-controlled. THE liquid-phase sintering process has been the object of a considerable amount of research for many years. Linear shrinkage vs time data at various sintering temperatures have been used recently in an attempt to identify the prevailing mass-transport processes in a number of metallic and nonmetallic systems. There is an analytical error inherent in the methods previously used for handling data during the "solution-precipitation" stage of shrinkage which must be recognized before the correct rate-controlling processes can be determined. It is the purpose of this paper to show how the error has affected previous conclusions and to suggest corrections. A number of mechanisms have been proposed to explain experimental observations during sintering in the presence of a liquid phase. The earliest of these is due to Price, Smithells, and williamsl who attributed the observed growth of the solid phase to the simultaneous solution of smaller particles and growth of larger particles. From the work of Lenel et al.2,3 and Gurland and Norton4 has come the suggestion that the liquid-phase sintering process may be divided for analysis into three steps: 1) rearrangement upon formation of the liquid phase; 2) solution and reprecipitation of the solid phase in the liquid; and 3) "coalescence" or a final stage of sintering, characteristically slower than the solution-precipitation process. The sequence of steps is shown schematically in Fig. 1. Kingery5 presented a thermodynamic and kinetic analysis of the first two "stages" of the liquid-phase sintering process in which the functional dependence of lineal shrink- age on time at temperature was used to identify the rate-controlling mass-transport process. Table I summarizes the time dependences and processes considered by Kingery.5 This method of data presentation has been employed by Kingery and coworkers for Fe-CU,6 WC-Co, and a number of nonmetallic systems," and bv Whalen and Humenik for Tic-Ni-Mo and Fe-cu.8 In each of these studies, the rate-controlling step during the "solution-precipitation" stage was identified from the slope of the curve in that stage on a logarithmic plot such as Fig. 1. However, in all of the previous studies, at a certain composition, relatively large amounts of shrinkage due to rearrangement preceded the solution-precipitation stage. Under these conditions, the larger the amount of rearrangement shrinkage the

Jan 1, 1965

By E. R. Gilbert, D. E. Munson

Creep of copper under 75 to 1.50 kg per sq cm stresses at temperatures near the melting point was found to he a complex reaction controlled by three mechanisms acting in parallel. In order of appearance with decreasing temperature, the auerage activation energies, Qc , are 168, 79, and 24 kcal per mole. Stress dependence of the minimum creep rate was found to he an exponential for the two high-Qc processes and a power law for the low-Qc, process. Transition of control occurs from one mechanism to another. The relative transition temperature depends upon the applied stress, and the range oiler which the transition occurs depends upon the difference in the activation energies of the mechanisms. The creep behavior at high temperature is explained by the climb of dislocations through thermally or mechanically formed jogs, CREEP in pure fcc metals at temperatures in excess of one half the absolute melting point is normally controlled by dislocation c1imb.1,2 A climb model which seems applicable, according to an extensive analysis of data,3 was derived by Weert-man.4 This model assumes jog-saturated dislocations and predicts an activation energy, Qc, nearly equal to that for self-diffusion, USd. Although the requirement of jog saturation is restrictive, agreement between theory and experiment seems adequate. Many other theoretical treatments, including an early model by Mott,5 include detailed consideration of jog formation as an initial requirement for climb. These models predict activation energies for creep which differ from those of self-diffusion. Seeger6,7 postulates an observed activation energy related to the stacking-fault energy. Thus, Usd <Qc<5Usd + Uj where Uj is the jog-formation energy. Seeger incorporated qualitatively the influence of the relative numbers of thermal and athermal jogs. Expanding this concept, Shoeck8 explicitly states a function based on formation mode and relative numbers of vacancies: e r ci exp {-uf/k T} exp {-Um/k T} [ 1 ] where Uf and Um are energies of vacancy formation and migration, respectively. The concentration of jogs, Cj, depends upon the manner of jog production. For intersection jogs, Cj is not sensitive E. R. GILBERT, Junior Member AIME, formerly with De- to temperature; for thermal jogs, Cj is proportional to exp {—Uj /k T}. Schoeck regards each mode as a distinct mechanism; therefore, the mechanisms may act together.299 The diversity predicted by theory, surprisingly, has not been substantiated by experimental results. A significant investigation must include the extremes in stacking-fault energy. Extensive creep studies of aluminum10 and nickel,11,12 high stacking-fault energy metals, have been made. Comparable studies on a low stacking-fault energy metal, such as copper, have not. It is the purpose of this paper to report the results of an investigation of the creep of copper under conditions which favor thermal jogs. EXPERIMENTAL Cylindrical compression creep specimens (0.240 in. in diameter by 0.400 in. long) were machined from cold-drawn rods of electrolytic tough-pitch copper containing 0.0007 Mg, 0.002 Fe, 0.001 Ni, 0.0005 Ag, Cd < 0.005, and Pb < 0.005 wt pct impurities. Undetected spectrographically was a nominal 0.04 wt pct 0, which occurs as a Cu2O constituent distributed discontinuously at grain boundaries. Vacuum annealing at 900°C for 15 min produced a stable 0.03-mm average grain diameter. Testing was carried out using apparatus similar to that described by sherby,13 modified by enclosing platens and a push rod in a vacuum cylinder. Normally this arrangement resulted in pressures less than 10 Only a slight surface tarnish, less than 0.0005 in. in thickness, occurred during the test. The applied stress, corrected for atmospheric pressure, was maintained within 2 pct of the desired true stress by the addition of lead shot at fixed strain increments. Creep strain was measured with dial gages as a relative displacement of the upper and lower platens; accuracy of measurement was 0.0001 in. Two creep-test methods were used, the differential or cyclic temperature14 and the isothermal, to obtain creep data at stress levels of 150, 100, and 75 kg per sq cm over the temperature range of 620° to 1032°C. Minimum creep rates were used from both test methods; this was considered proper because comparable temperature tests or cycling to the same temperature gave the same creep rate, within experimental error. The cold vacuum test chamber, with the unstressed specimen in place, was heated to temperature by placing a preheated furnace over the chamber. Temperature equilibrium was attained within 30 min. For the cyclic tests, the stress was removed during the 5 to 10 min necessary to effect the temperature change and re-

Jan 1, 1965