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By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By D. Kuhlmann-Wilsdorf

A new theory of work hardening is developed which rests on only a few simple principles and is applicable to a wide variety of materials and dislocation structures. It explains, qualitatively, the general characteristics of the three-stage shear stress-shear strain curve of fcc metals, as well as the most important features connected with easy glide. The value of, the work-hardening coefficient in stage 11, is derived quantitatively, from first principles, and is shown to be insensitive to many changes in detailed dislocation behavior. The low rate at which energy is stored during mechanical working in stage 11, the dependence of slip line length on stress, and the so-called Cottrell-Stokes law are explained. Although the theory is primarily developed for fcc metals and alloys, it is largely applicable also to some other materiuls, and in particular apparently to poly crystalline simple steels in theh linear range of hardening. FOR pure fcc metals and alloys, after many different pretreatments and under a great variety of testing conditions, the well-known three-stage work-hardening curve is commonly observed. Moreover, the work-hardening coefficient in stage 11, 011, bears an almost constant relationship to G, the modulus of rigidity, such that K = G/Brr" = 300, within a factor of about 2 either way. The very fact that the three-stage curve and the value of K are so very persistent, can hardly be understood except on the assumption that some quite simple phenomena are responsible. In this light all available theories of work hardening must be judged unsatisfactory: Each of them is based on some quite specific dislocation model, while it is known that metals with similar values of K may have widely different dislocation structures, for example, dislocation tangles in the case of pure fcc metals, and piled-up groups of dislocations in a-brasstype alloys. Thus, while a particular theory might conceivably represent a special case with a reasonable degree of accuracy, it cannot possibly have illuminated the underlying principle. Another severe criticism applying to the presently most widely discussed theories is that they employ empirical or even quite unexplained parameters in order to arrive at a numerical value of K. This indicates that some vital aspect of the work-hardening process has remained unexplained. In the present paper, a new theory of work-hardening is developed which does not suffer from the above shortcomings. It is derived from first principles, and is founded on the realization that the underlying causes for the three-stage work-harden- ing curve and for the persistence of the numerical value of O,, must be few and simple. As a first step it is shown herein that the experimental oklservations on "easy glide" can be explained on the assumption that in this stage dislocations multiply, beginning in a number of restricted area:;, and from there penetrate into crystal regions still substantially free of glide dislocations until a quasi-uniform dislocation distribution has been established. During "easy glide", the resistance to the movement of the foremost dislocations, advancing into still largely a dislocation-free regions, is believed to control the flow stress. This resistance is determined by various factors, among them the reaction of the dislocations against bowing-out into loops, which is due to their line tension. Without such bowing-out no dislocation multiplication would occur, but the corresponding contribution to the flow stress stays practically constant all through stage I. According to the present theory, stage TI begins as soon as there are no more areas left into which newly formed dislocations have not yet penetrated, i.e., as soon :is a quasi-uniform dislocation density has been attaned. Regardless of how, in detail, the dislocations should happen to be arranged at the end of "easy glide", whether in pileups or tangles, on one glide system or on several, the stress necessary to overcome the line tension of the segments must now increase, because the dislocation density increiises while the average free dislocation length decreases. It is argued that all other contributions to the flow stress stay at about the same level as in stage I, and that the said increase in the stress necessary to bow out dislocation segments into loops is responsible for the major part of work hardening in stage 11. Stage TII of the stress-strain curve is explained by largely follouing the ideas of Seeger and his co-workers; however, it is pointed out that the start of stage m may on occasion indicate the onset of "conservative climb" instead of cross slip. Indirect evidence indicates that linear work hardening persists even under the profuse action of cross slip, but at a lower rate. Only when, in addition to cross slip, climb operates extensively, does the work-hardening rat,. drop sharply, ultimately down to zero. BRIEF SURVEY OF EXPERIMENTAL EVIDENCE The stress-strain curve of crystals of many different substances are qualitatively similar. No significant permanent plastic deformation takes place below the so-called "critical resolved shear stress". As the applied stress is raised beyond this level. yielding occurs with little or no work hardening and

Jan 1, 1962

By Niels Hansen

The substructure formed by drawing at room temperature in aluminum (99.5 and 99.998 pct purity) and in recrystallized aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum -oxide was examined by transmission electron microscopy, and the flow stress of the drawn materials was measured by tensile testing at room temperature. A sub-grain structure was present after a reduction in area by drawing of 10 to 20 pct, and the subgrain size was observed to decrease with increasing deformation. The tensile data show that the increase in flow stress (0.2 pct offset) by drawing from 10 to 95 pct depends on the reduction in area, not on the composition of the materials. Dispersion strengthening and subgrain bowzdary strengtlzening contribute to the flow stress, and these strengthening processes have been found to be linearly additive. The flow stress (0) can be related to the subgrain size &) by the Petclz relation = uo + k . t, where go is dependent on the composition of the products and k is approximately the same far all materials. THE microstructure of dispersion-strengthened aluminum aluminum-oxide products consists of small oxide plates distributed in an aluminum matrix. The matrix structure depends on the manufacturing history, and in hot-worked as well as cold-worked products the matrix is divided by subgrain (or dislocation) boundaries. For hot-extruded products it has been shown1 that dispersion strengthening and subgrain boundary strengthening are linearly additive, and the flow stress (0.2 pct offset.) at room temperature has been related to the subgrain size (ts) by a Petch equation,2,3 s = so + k . ts-1/2, where s0, increases with increasing oxide content. For cold-worked products containing subgrains no systematic work has been reported, and it was the aim of the present study to examine the microstructure and the relationship between the flow stress and the subgrain size for such products. The behavior of' aluminum aluminum-oxide products depends on the purity of the aluminum matrix, and aluminum of the matrix purity (99.5 pct) was included in the investigation. The literature contains few data about the behavior of this impure aluminum, and aluminum of a higher purity (99.998 pct) was therefore also examined. As regards the relationship between the flow stress and the subgrain size in cold-worked dispersion-strengthened products, no systematic work has been reported. For aged cold-worked structures containing fine precipitates (Fe-Mo carbide) a Petch relation has been found,4 and it has been shown that the k value NlELS HANSEN is Head, Metallurgy Department, Danish Atomic Energy Commission, Research Establishment Riso, Denmark. Manuscriot submitted January 9, 1969. IMD is approximately the same as in iron, whereas the s0 value is higher owing to the presence of the precipi-tates. Investigations of metals such as tungsten,' ferrous metals,4,6 and molybdenum7 cold drawn or swaged at room temperature have shown that the flow stress can be related to the subgrain size by a Petch relation when ts is taken as the subgrain size perpendicular to the direction of deformation. For aluminum no work has been reported on the relationship between the flow stress and the subgrain size after deformation at room temperature, whereas for aluminum tensile strained at different temperatures in the range -183" to 375°C a Petch relation has been found by taking ts equal to the subgrain size.' In the present study two aluminum materials (99.998 and 99.5 pct) and three aluminum aluminum-oxide products (containing 0.2, 1.0, and 4.7 wt pct oxide) were drawn at room temperature to reductions in area from about 10 to about 95 pct. The structures were studied by transmission electron microscopy, and the flow stress (0.2 pct offset) was measured at room temperature. EXPERIMENTAL Materials. The materials are given in Table I together with the chemical analysis. The three aluminum aluminum-oxide products were manufactured from aluminum powder that had been compacted and Table I. Chemical Analysis of Materials Al203 Fe SI Material wt pct wt pct wt pct 99.998 pct* - 0.0004 0.0012 Aluminum 99.5 pctt - 0.36 0.16 Aluminum AlMD13† 0.2 0.16 0.12 Aluminum- -Oxide AlMD105† 1.0 0.26 0.18 Products SAPISML960s† 4.7 0.22 0.19 *Other impurities: O.0004 pct max each of Cu and Zn (supplier's analysis). †Other impurities: 0.03 pct max Cu. 0.02 pct max each of Mn, Mg, Zn, Ti. Table 11. Mean Diameter of Aluminum-Oxide Particles in Extruded and in Cold--Drawn Aluminum Aluminum-Oxide Products Mean Diam. of A1203-Plates* Material State A AlMD105 Extruded 540 Cold Drawn 97 pct 510 SAP ISML 960 Extruded 770 Cold Drawn 95 pct 820 *The standard deviation of the mean is approx. 5 ±pct.

Jan 1, 1970

By James C. M. Li

The Petch relation between the flow stress and the gain size is derived from a consideration of gain boundary sources of dislocations without the need of dislocation Pile-ups. Three mechanisms for inierpreting the yield stress: the gain boundary strength, the unpinning of Frank-Read source near a grain boundary, and the generation of dislocations from the grain boundary are compared and the condition of their equivalence is shown. The effect of the average angle of misfit of pain boundaries is found to be sma11 and so is that of the average angle of misfit of subboundaries having impurities. The effect of impurities on the ledge density in the grain boundary is treated thermodynamically and a relatwn is proposed for the variation of Petch slope with impurity activity. The effect of temperature on the Petch slope is interpreted as due to the change of ledge structure in the grain boundary. It is indicated that the effect of annealing temperature may be more important than that of the test temperature and therefore should be studied. The effect of plastic strain on the Petch analysis is deduced from a work-hardening equation in which the generation of dislocations has first-order kinetics and the annihilation of dislocations has second-order kinetics. It is concluded that the Petch slope will decrease with plustic strain if the rate of annihilation of dislocations is sufficiently large. Critical experiments which may shed light on the mechanism for the Petch relation are suggested. THE relation between the yield or flow stress, 0, and the grain size, l, was first proposed by all' and later studied more extensively by Petch and co-workers, who also proposed a similar relation for the fracture stress and deduced from these a grain-size effect of the ductile-brittle transition temperature. The microscopic mechanism used by all' and petch2 involves a pile-up of dislocations of like sign generated from a Frank-Read source. The yielding or flow takes place when the pile-up exerts sufficient stress at the grain boundary so that the plastic deformation can propagate from one grain to another. If the average strength of the grain boundary is ai and the average length of the pileup is lp, the Petch slope, k, is given by" where p is the shear modulus, b the Burgers vector, and v the Poisson ratio. This slope will be independent of the grain size if l/lp is a constant. This is possible, since, if the Frank-Reed source is situated near the grain boundary, lp = 1, and if it is situated in the middle of the grain, Ip = 1/2. cottrell,12 also using the pile-up mechanism, proposed that the stress concentration at the grain boundary will initiate Frank-Read sources near the grain boundary and in this manner a Lüders band can propagate from one grain to another. Assuming that the average distance between the Frank-Read sources and the grain boundary is 1, and the unpinning stress of the Frank-Read sources is op, Cottrell obtained the following Petch slope: This slope will be independent of the grain size if ls is independent of the same, which is not as obvious as the condition, Ip = I for Eq. [2]. In addition to this assumption, the direct relation between the Petch slope k and the unpinning stress, up, was recently questioned by Johnsonon grounds that it is inconsistent with the following observations: the independence of k with temperature and strain rate, and the small k in columbium, which, like iron, has a sharp yield point. As pointed out by ohnson," the most important objection both to the Hall-Petch mechanism, in which the strength of the grain boundary plays the role in yielding, and to the Cottrell mechanism, in which the unpinning of Frank-Read sources plays the role in yielding, is the lack of direct observation of the pile-ups. The dislocation structure in deformed iron has been examined recently in the electron microsope.'-' Dislocations appear to be generated from grain boundaries or other interfaces; they form clusters and tangles within the grain at very early stages of deformation, even in the Lüders band, if the deformation is slow or at normal and elevated temperatures. Although it is still too early to interpret bulk properties from thin-film observations, it does seem worthwhile to look for a mechanism for the Petch relation which does not require dislocation pileup. SUBBOUNDARY SOURCES In order to show that a consideration of grain boundary sources can lead to the same Petch relation as does the consideration of the strength of the grain boundary, we shall first discuss the case of a simple tilt boundary whose elastic properties have been studied in detail.17 The strength of a partially

Jan 1, 1963

By E. Lifshin, R. E. Hanneman

QUANTITATIVE applications of the electron micro-beam probe frequently involve the evaluation of complex mathematical expressions and/or the analysis of large amounts of experimental data. The purpose of this communication is to describe briefly a versatile and useful computer program system that is applicable to analyze rapidly a wide variety of practical microprobe problems. This system consists of a group of ten FORTRAN programs that can be stored on tape, cards, or in the memory disc of the computer. These programs, or links, can be run individually or in any prespecified sequence without interrupting the operation of the computer or without destroying information which is being transfered from one link to another. For the program system described here a GE-235 computer with disc storage was used, so that the DCHAIN method of program linking was employed. Included in the library are programs to: 1) initiate analysis of a new set of data and transfer control between all other programs in any predetermined manner; 2) generate theoretical calibration curves of composition vs relative intensity; 3) generate empirical deviation parameters from least-square fits of experimental calibration data from standards of known composition; 4) convert raw X-ray data to corrected composition; 5) determine inter diffusion coefficients by Matano analysis of con centrat ion -distance data on a uniaxial diffusion couple; 6) determine activation energies and frequency factors of temperature-activated processes such as diffusion; and 7) generate calibration curves for determination of the thickness of thin films using microanalysis. A detailed description of these computer programs and their underlying principles is available on request from the authors."' The first program to generate theoretical calibration curves of corrected relative intensities vs composition uses the Poole and Thomas atomic number correction' and the Philibert absorption factor' with a voltage-dependent mass absorption coefficient for electrons in the alloy. A modified Castaing fluores- cence correction is also used which includes the effects of both Ka and KO radiation and over voltage.' Once the theoretical curves have been calculated in 1 wt pct intervals, these results are least-squares fit to obtain Ziebold deviation parameters' which are stored in COMMON in the computer memory. The net discrepancies between the original theoretical calibration curve and the regenerated curve using the Ziebold parameter are computed. Although this link is explicitly written for K-K fluorescent interactions, it can be applied to K-L, L-K, and L-L interactions as previously disc~ssed."~ Similar programs have also been written to utilize the Wittry fluorescence correction, Birks combined corrections, and various other corrections.' These modified programs have proved to be quite useful for quantitative comparisons of the results of the various theories. The program for conversion of raw X-ray data to corrected composition includes corrections for drift, backround, and instrumental dead time. The corrected intensities are converted to composition by use of the Ziebold equation"2 and parameter obtained from the program system. The results can be obtained for either atom or weight fractions. In addition to accurately computing interdiffusion coefficients the Matano analysis program calculates least-square smoothed values of concentration, concentration gradient, and curvature for each point on the raw input concentration profile. In order to obtain high accuracies a unique method of performing a least-square polynomial fit to incrementally advancing profile segments which overlap is used.' This program has been successfully modified for use in ternary diffusion problems3 and can readily be modified to handle analysis of diffusion profiles which include phase boundary discontinuities. This link is generally applicable to analysis of interdiffusion data obtained by other techniques as well as by the microprobe. The primary function of the next program is to least-squares fit experimental diffusion data to the normal Arrhenius function: D = Doexp(-Q/RT), to obtain values of Do and Q. In addition the probable error and one, two, and three u statistical confidence limits of DO, Q, and log D are evaluated. This program is also directly useful for analysis of any other simple temperature-activated processes including conductivity, and certain deformation and chemical processes. The program to generate calibration curves for film-thickness determination using the microprobe is based on a numerical integration of the equation derived by Cockett and ~avis.' Values of film thickness obtained by this program for copper on various substrates are in good agreement with measurements made by other techniques. Versions of the above program system have been prepared for use with or without a remote teletype connection to the computer for processing on either a real-time or time-share basis. The instrumentation coupling a microprobe to a teletype for automatic data collection and analysis by the presently described program system has been reported elsewhere by the authors.' If teletype equipment is not used to communicate with the computer, standard methods of card reading and tape reading can be used. In either

Jan 1, 1967

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

By W. A. Backofen, R. L. Fleischer

Single crystal, bicrystal, and polycrystal tensile tests of aluminum at 4.2°K, 77°K, and 300°K have been used to examine the role of grain boundaries in the deformation process. Results indicate that a grain boundary may affect the extent and slope of easy glide. The stage II hardening rate, on the other hand, is independent of the presence or absence of grain boundaries. This conclusion allows the size of the region of multiple slip caused by an incompatible grain boundary to be determined. For the size of bicyystal sample used in this study, multiple slip occurs in about half of the cross section. PREVIOUS studies of the stress-strain characteristics of bicrystals of face-centered-cubic metals have been limited to aluminuml-5 at room temperature. Recent results, however, indicate that the stress-strain curves of single crystals of such metals may be separated into at least three stages6 in which different deformation processes are occurring7 provided testing is done at sufficiently low temperatures.' Since for aluminum a well-defined stage II develops only below room temperature, previous studies have not been able to relate effects of grain boundaries to all of the three stages of deformation. It is therefore to be expected that low-temperature deformation of aluminum single crystals and bicrystals should clarify the effects of grain boundaries on the different processes of deformation. EXPERIMENTAL PROCEDURE Single crystals and bicrystals were grown from the melt by the standard techniqueg with aluminum reported by Alcoa to be 99.993 pct pure. Ridges in the boat were used to guide the grain boundary during growth, assuring that the boundary would bisect the sample.10 The rate of furnace motion during growth was 1.0 cm per hr. During growth zone purification resulted, as evidenced by the ability of the first material to freeze to recrystallize at room temperature following severe deformation. Samples were approximately 4.4 X 6.6 mm in cross section and 103.5 mm in length between grips. Samples were annealed at 635" i 5°C for 40 hr and furnace cooled over a 7-hr period. They were then electropolished in a solution of 5 parts methanol to 1 part perchloric acid at a current density of 15 amp per sq dm for about 30 min at temperatures below 0°C. Tensile testing was performed at 295" (room temperature), 77" (sample in liquid nitrogen), and 4.2"K (sample in liquid helium) on the hard-type machine indicated schematically in Fig. 1. The machine con- sists basically of a tube surrounding a rod; one end of the sample is attached to each member, and the rod is pulled up the tube to extend the sample. The rod is rigidly mounted and is moved vertically by a system described by asinski." The pulling force is measured continuously by an electrical strain gage load cell, and the relative displacement of the tube and rod is also recorded continuously by a soft cantilever beam with electrical strain gages. Maximum stress and strain sensitivities were ±2g per sq mm and * 3-10-5. In all tests the strain rate was approximately 5.10-5 per sec. The thin wires in the tensile apparatus introduce softness, which may be corrected for, however, by measuring load vs displacement with the sample replaced by an elastic member. For loads greater than 15 kg the spring constant is 1.875.106 g per cm. The flexible wires also served to reduce substantially the large shearing forces which may arise in the case of grips having horizontal rigidity.'' As in any gripping system, however, bending moments will arise in the course of deformation by single slip. Engineering stress, s = (load)/(original cross-sectional area), and strain, E = (increase in length)/ (original length), are used for stress-strain curves unless otherwise indicated. Tables list resolved shear stress, T=mo and shear strain ? = dm, where m is the usual Schmid resolved shear stress factor for the primary slip system at the start of deformation. The first group of samples to be described forms an isoaxial set, all of the crystals making up the single crystals or bicrystals having the same tensile axis, the orientation of which is indicated by the cross in Fig. 2. For this orientation the primary slip plane and slip direction make angles of 45 deg with the tensile axis and the Schmid factor m has its maximum possible value of 0.5. Rotations about the tensile axis are indexed by means of an angle 0 between the small-area surface of the samples and the projection of the primary slip direction onto the cross section, as defined in Fig. 3. In single crystals, values of 0 were 0 and 90 deg, while in bicrystals 0 values were (0 deg, 180 deg), (90 deg, 270 deg), and (0 deg, 90 deg) as indicated in Fig. 4.

Jan 1, 1961

By R. L. Bell, T. G. Langdon

A technique was developed- for determining the grain strain, and hence the grain boundary sliding contribution, occurring during the high- temperature creep of a magnesium alloy, from the distortion of a grid photographically printed on the specimen surface. The results were compared with those obtained from measurements of grain shape, both at the surface and interrwlly, and it was concluded that the grain shape technique may substantially underestimate the grain strain and overestimate the sliding contribution due to the tendency for migration to spheroidize the grains. ALTHOUGH a considerable volume of work has been published on the role of grain boundary sliding in high-temperature creep, many of the estimates of Egb (the contribution of grain boundary sliding to the total strain) have been in error due to the use of incorrect formulas or inadequate averaging procedures.' One of the most easy and convenient measurements from which to compute Egb is that of v, the step normal to the surface where a grain boundary is incident. Unfortunately, this parameter is also the one associated with the treatest number of pitfalls. Values of v have been used to calculate Egb from the equation: egb =knrVr [1] where k is a geometrical averaging factor, n is the number of grains per unit length before deformation, v is the average value of v, and the subscript ,r denotes the procedure of averaging along a number of randomly directed lines. If the dependence of sliding on stress were assumed, it would be possible, in principle, to calculate k from the known distribution of angles between boundaries and the surface. This in itself is difficult because the distribution depends on the history of the surface,' but the problem is even further complicated by the fact that v depends on other factors such as the unbalanced pressure from subsurface grains.3 However, the great simplicity of the measurement procedure for v makes it highly desirable that this problem of k determination should be overcome. In the present experiments, this was achieved by the use of an indirect empirical method in which the grain strain, eg, at the surface was determined by the use of a photographically printed grid. The assumption here is that the total strain, et, is simply the sum of that due to grain boundary sliding, egb, and that due to slip or other processes within the grains, eg. SO that: Et = Eg + Egb [2] Thus k is given by: In practice, it is customary to indicate the importance of sliding by expressing it as a percentage of the total creep strain; this quantity is termed y (= 100Egb/Et). The determination of Eg from a printed grid within the grains avoids the difficulties due to boundary migration which should be considered when the grain strain is calculated from measurements of the average grain shape before and after deformation. As first pointed out by Rachinger,4,5 however, this latter technique has the particular advantage that it can also be applied in the interior of a polycrystal. Recently, several workers have produced evidence on a variety of materials6-'' to support the observation, first made by Rachinger on aluminum,4,5 that 7 can be very high, 70 to 100 pct, in the interior, even when the surface value, determined from boundary offsets, is very much lower.10'11 Although there have been criticisms both of the shortcomings of the grain shape technique'' and of the different procedures used to determine y at the surface,' it seemed important to check whether measurements of sliding by grain shape gave values of y which were truly representative of the material. In the present experiments, grain shape measurements were therefore made both at the surface and in the interior for comparison with one another and with the independent measurements of grain strain using the surface grid technique. EXPERIMENTAL TECHNIQUES The material used in this investigation was Magnox AL80, a Mg-0.78 wt pct A1 alloy supplied by Magnesium Elektron Ltd., Manchester. Tensile specimens, about 7 cm in length, were prepared from a 1.27-cm-diam rod, with two parallel longitudinal flat faces each approximately 3 cm in length. The specimens were annealed for 2 hr in an oxygen-free capsule, at temperatures in the range 430° to 540°C, to give varying grain sizes, and, prior to testing, the grain size of each was carefully determined using the linear intercept method. This revealed that the grains were elongated -0.5 to 5 pct in the longitudinal direction. Testing was carried out in Dennison Model T47E machines under constant load at temperatures in the range 150" to 300°C. At temperatures of 200°C and below, tests were conducted in air with the polished flat faces coated with a thin film of silicone oil to prevent oxidation; at higher temperatures, an argon atmosphere was used. To determine v,, each test was interrupted at regular increments of strain and the specimen removed from the machine. At the lower strains, when v, was less than about 1 pm, measurements were taken on a Zeiss Linnik interference microscope;

Jan 1, 1969

By E. J. Eisenach, Edward Matsen

AT the present time the Climax Molybdenum Co. is the largest molybdenum producer in the world and the operator of the largest underground mine in North America. It has grown steadily and rapidly since its beginning in 1917. Only 250,000 lb of MoS2 were produced during the first year from 1917 to 1918 when the company was formed. Operations were suspended shortly thereafter because of the lack of a market and knowledge of the uses of molybdenum. During World War I it was used as a substitute for some rare metals and for minor chemical purposes. After 5 years of intensive research and sales promotion, Climax metallurgists succeeded in finding proper applications for the newly discovered metal and the mine was reopened in 1924. Demand for molybdenum increased gradually and in 1930, 3.5 million lb of MoS2 were produced. In the meantime, research work for additional uses of molybdenum continued until it had established itself as one of the most important alloying elements in producing high quality steels. After the start of World War 11, from January 1942 to October 1953, 43 million tons of molybdenum ore were mined and 484 million lb of MoS2 were produced. Climax mine is located in Colorado, 100 miles southwest of Denver and 12 miles northeast of Leadville on the Continental Divide of the Rocky Mountains. The principal mine workings range from 11,170 to 12,000 ft in elevation. Topographically, it lies in the base of a large cirque that is surrounded by Mt. Bartlett to the north, Clinton Peak and McNamee Peak to the east and Ceresco Ridge to the south. This cirque opens to the west and to the Ten Mile Valley.

Jan 3, 1954

By C. Max Bauer

THE most important development in the petroleum industry in Montana, during 1924, was the bringing in of the Hepp well on May 12, by the Midwest Refining Co. This followed three years of active prospecting and drilling in the state by this company. The well is located 35 miles west of Billings, in Stillwater County, and makes a high-grade paraffin oil from the Dakota sand at a. depth of 3825 ft. After flowing for several months at the rate of 150 bbl. per day, the well has been shut in for lack of storage, awaiting further development in the field. TABLE 1. Production Cat Creek and Kevin-Sunburst Fields Month Kevin-Sunburst Pipe- Estimated Cat Creek Pipeline Estimated line Runs Fuel Oil Used Runs Fuel Used January 3,214 0 133,400 140 February 3,250 0 134,248 490 March 11,989 595 163,129 910 April 116,897 1,155 125,918 980 May 179,726 2,310 152,179 770 June 126,131 2,697 122,270 910 July 132,173 2,170 118,034 770 August 202,001 2,695 142,313 1,120 September 187,201 2,135 110,012 350 October 162,589 1,995 121,683 350 November 130,392 2,520 139,900 350 December 107,465 1,780 124,169 0 Total 1,363,028 20,052 1,581,255 .7,140 There are two producing oilfields in the state-the Cat Creek and the Kevin-Sunburst, which produced a total of 2,971,475 bbl. in 1924. The only other field of proved value is Soap Creek, which contains a heavy black oil and is shut in for lack of marketing facilities. Gas is produced for local use at Havre, Chinook, and Baker, and a carbon-black plant is located at Baker.

Jan 3, 1925

By D. Turnbull, A. M. Turkalo

It is well known that if copper that has been severely cold-worked by rolling (70-98 pct) is heated to high temperatures a small number of large grains are formed at the expense of the fine grained structure that appears upon primary recrystallization. Dahl and Pawlek,' Cook and Mac-Quarie,2 Ward,3 and Boas and Bowles4 have studied this phenomenon in copper. It has been reported as taking place with measurable velocities in the temperature range 700-1080". Boas and Bowles have reported that the time necessary for the transformation is of the order of days at 700°C. According to Ward3 the number of secondary grains which appear in OFHC copper decrease with increasing perfection of cubical alignment after primary recrystallization; also the perfection of cubical alignment increases with decreasing grain size prior to the final reduction. In this investigation two heats, A and B, of especially high purity copper (99.999 pct) supplied by the American Smelting and Refining Co., were used. The behavior of samples prepared from the two heats was qualitatively very similar providing that the grain sizes established prior to the final reduction were about the same. We observed that in specimens prepared from bars which were relatively coarse grained prior to final reduction secondary recrystallization took place at a rapid rate at temperatures as low as 500°C. This is about 200-300°C lower than the temperature necessary to obtain fairly rapid transformation in OFHC copper. A 0.22 in. thick rectangular bar of lot B was cold-reduced 60 pct by straight rolling and given a penultimate annealing treatment at 250°C. Following this it was cold-reduced 90 pct and heated to various temperatures in the range 450-1040°C. The specimens were about 8 mils thick

Jan 1, 1950

By George A. Bell

THE mine and milling plant of Demonstration Gold Mines, Ltd., is near the city limits of Baguio, Mt. Province, P. I. The mine road connects with the main highway to Manila. The nearest railway point is near sea level, approximately 40 miles distant. The Baguio district is very mountainous and has one of the heaviest rainfalls in the world. It is therefore difficult to maintain roads or to impound tailings and mine dumps. All supplies are trucked into the district direct from Manila or the nearest railway point, which means uncertain deliveries and high freight rates. Installation of equipment is difficult and costly. The average elevation at the mine is 4000 ft. and the climatic conditions are ideal except for a three months rainy season. The company generates its own power for mining and milling operations with three 400-hp. Ruston Diesel engines direct connected to 250-kw. General Electric alternating current generators. Labor conditions have been excellent, although at present social security laws are causing some unrest. Labor receives a higher average wage rate in this district than other labor in the Islands. The company also furnishes free living quarters, hospitalization and work- men's compensation. Taxation has been reasonable up to the present time, but some of the new mining legislation may make it difficult to operate and pay dividends. The future depends largely upon the continuation of $35 gold and the political outcome in the Islands. HISTORY The Demonstration ore body was worked by the Igorots for many years, as evidenced by old stopes and fill encountered in present operations. Attention of Americans was first attracted soon after the Spanish- American war. During the building of the Benguet road to Baguio, the engineers and foreman became interested in the geology of the district.

Jan 1, 1939

By A. J. Weinig

The Liberty Bell cyanide precipitate is unique in that it is apt to vary widely in composition in the course of very short periods of time, and a method of refining and melting that would prove highly satisfactory at one cleanup would yield7almost a hopeless "mess" at a second. Table I gives a general conception of the wide range in grade and composition of those raw precipitates. It is evident that no one standard flux could be expected to produce a high-grade bullion with such a widely variable precipitate, and that any method of treatment with acid requires most careful consideration. Refining by Acids Naturally, our first efforts to improve our precipitates were directed along the lines of acid treatment. Table II embodies the results of careful sampling and analysis of one cleanup at the time when wet refining reached its maximum development at this mill. We have now discarded all methods of wet refining, successfully replacing them by a more scientific method of flux calculation described herein, but it is believed that a general description of this wet refining is warranted as it throws some interesting side lights on acid refining in general. Table I.—Range of Composition of Raw Precipitates Per Cent. Gold and silver.................................... 25.0 to 75 Zinc.............................................. 18.0to 30 Lead............................................. 0.5 to 52 Copper........................................... 0.5 to 20 Silica............................................ 1.0 to 5 Calcium oxide...................................... 4.0 to 8 Sulphur.......................................... 0.5 to 8 Column A gives the analysis of the raw precipitate; column B, that of the precipitate after heating with steam, with frequent addition of hydrochloric acid until a point was reached where the batch had a strong tend-

Jan 1, 1917

By Howard S. Bryant

The year 1928 has recently.passed from the picture and it is at this time that the various divisions of the oil industry are giving thought to plans for the present year. The outstanding characteristic of the industry in 1928 was the successful curtailment of oil production to the market's needs. It has been thought advisable to look ahead and endeavor to anticipate the oil demand for the coming year, and thus determine the volume of oil that can be safely produced without causing major additions to surface stocks. The year has been one of smaller additions to stocks than in 1927, a record demand for oil products, and a further developed spirit of cooperation among oil producers, as well as various other achievements. It is well to pause and take stock of ourselves. Present Status of Crude Oil Supply and Demand The total daily new supply of oil is at this time1 about 2,960,000 bbl. per day, made up of 2,585,000 bbl. domestic crude production, 125,000 bbl. casinghead gasoline, and 250,000 bbl. of imports. With the present low consumption, due to the falling off in the winter season demand, it is estimated that about 150,000 bbl. a day are now being run to storage, and that the first three months in 1929 will see large-sized additions to storage. Consumption plus exports of oil have increased at a regular rate from year to year, and although oil production in 1928 passed the 1,000,000,-000 bbl. mark for the second time in the history of the United States, with a production of 25,000,000 bbl. more than in 1927, only 30,000,000 bbl. were added to storage during 1928. This is compared to an addition of 65,500,000 bbl. in 1927.

Jan 1, 1929

By L. H. de Wald, J. Walter Scott

It is usual practice in the copper industry to use open horizontal molds for casting tough-pitch copper wire bars.' A wire bar cast in this manner is partly characterized by heavy wrinkles and a comparatively deep skin of oxide on the top of the bar, corresponding to the open side of the mold. On the theory that the rough, high-oxide surface might have an adverse effect on the rolling and drawing properties of a wire bar and might account for some of the irregularities of mill behavior, several bars which had been planed to remove the wrinkled surface were processed into wire. These bars responded to mill treatment more satisfactorily than did the regular wire bars. Realizing that machining the surface of one face of each bar would not be commercially feasible, it was decided that casting the metal into a vertical mold and cropping off the pouring end would accomplish approximately the same result. Several wire bars of commercial size (250 Ib.) were so cast and processed into wire for comparative test with bars cast in the usual horizontal molds. It is the purpose of this paper to present the results obtained from this investigation, in which commercial bar sizes and processing technique were used throughout. The results show that in general copper wire bars cast vertically are superior to those cast horizontally. Experimental Procedure A horizontally cast bar and a vertically cast bar were obtained from each of several regular reverberatory furnace heats of copper which had been refined and poled to tough-pitch metal in accordance with usual methods.' Both bars were cast from the same part of the melt and within five minutes of each other, in order to produce as nearly as possible, in each case, wire bars of identical composition.

Jan 1, 1930

By E. C. Dominguez, H. B. Scharf

THE Sparrows Point plant of Bethlehem Steel Co., southeast of Baltimore, is the largest Bethlehem plant, with an annual rated capacity of 6.2 million ingot tons. There is considerable diversity of product, but a high percentage is sheet, tin plate, galvanized sheets, and rod and wire. The large amount of light-weight end product requires a number of pickling installations that necessarily consume large quantities of sulfuric acid. In the coking operations sulfuric acid is also consumed in recovery of ammonia as ammonium sulfate and in treatment of recovered light oil derivatives. Total sulfuric acid consumption in the plant is currently approaching 10,000 tons per month, of which 55 to 60 pct is required for pickling. In 1951 the acute sulfur shortage caused grave concern as to future sulfuric acid supply for the Sparrows Point plant. Raw materials for acid making were already at hand in the form of hydrogen sulfide and pyrites sufficient to produce nearly half the sulfuric acid required at that time. It was also known that the Bethlehem mining activities would produce additional pyrites in the future. Late in 1951 Bethlehem management decided to build a 250-ton sulfuric acid plant at Sparrows Point to utilize these raw materials. The plant was built and put in operation in May 1953. The steel plant has expanded considerably since 1951, and it is now necessary to operate the acid plant far over rated capacity in order to supply plant demand. Production of acid in 1954 amounted to 93,000 tons. Raw Materials for Acid Making: Coking operations at Sparrows Point produce a residual fuel gas in large quantity which has a net heating value of 525 to 545 Btu. Prior to 1950, plant surplus coke oven gas was sold to the local utility company. In

Jan 1, 1957

By A. E. Harnsberger

IT is obvious that details such as the physical and chemical properties and methods of heat-treating of the materials mentioned must be omitted in a paper on the subject of materials used in oil-refinery pumps1. Only sufficient identification is given to enable the reader to find additional information from already published data. Also, the subject covers many operating conditions, but only the most important services can be discussed here. To the oil refiner, the pumping equipment is of vital interest. Practi-cally every refinery operation, from the charging of crude oil to a dis-tillation unit to the shipping of refined products, involves some form of pumping machinery. Intermediate refining stages involve a great variety of pumping machinery to carry out successfully the aims of the refinery technologist. Temperatures at which oils are handled vary from -50° F. to 900° F. Pressure may vary from subatmospheric to 2000 lb. per, sq. inch. The selection of the proper materials involves a careful consideration of the conditions under which the particular pump must operate. The four most important considerations are temperature, pressure, corrosion, and abrasion or wear. Consideration of temperature may be divided into three parts: (1) extremely low temperatures of the order of -50° F.; (2) temperatures at atmospheric or slightly above; (3) temperatures from 200° to 900° F. Pressures fall into two groups: (1) pressures reached by ordinary trade pumps of the order of 200 lb. per sq. in., (2) extreme pressure conditions involving pressures as high as 2000 lb. Noncorrosive and corrosive oils can be treated differently. Under the latter falls corrosion in the presence of water, which will occur up to 250° F. The second type of corrosion occurs in high-temperature pump-ing equipment, with temperatures from 450° to 900° F., largely caused by sulfur compounds. There are also other corrosive conditions met with

Jan 1, 1935

By Daryl R. Tweeton, William H. Engelmann, Orin M. Peterson, Jon K. Ahlness, Gregory R. Anderson

The Bureau of Mines measured the geochemical changes as H2SO4 was used for in situ uranium leaching by Rocky Mountain Energy Company near Casper, Wyoming. Cores and ground water were analyzed before leaching. Water samples were taken from observation wells located between injection and production wells as the leach solution was brought up to full strength in several steps. Measurements were made of pH, Eh, temperature, conductivity, total dissolved solids, dissolved oxygen,HC03, U. V, Na, K, Ca, Mg,S04, CI, Mo, Mn, Fe, AI, Si, F, P, As, and Se. The data were gathered to assist in geochemical modeling of leaching and to study the potential environmental effects of acid leaching. Environmental considerations appear favorable. For example, the concentration of Se, a toxic element often found in uranium deposits, stayed below the EPA standard for drinking water.

Jan 1, 1979

By Robert D. Pehlke, Kazuhisa Okajima

ThE prediction of the activity coefficient for a solute in a multicomponent liquid metallic solution based on measurements in the related binary systems has been the object of study for some time, particularly in iron-base alloys.1,2 Very few measurements, however, have been made on nonferrous systems; furthermore, measurements made for the specific purpose of testing various prediction equations are almost nonexistent. The measurements here described of the activity coefficient of cadmium in liquid lead alloys were directed toward this goal. One of the most direct means by which the activity coefficient can be calculated has been based on the independent influences of each solute. When solute metals i,j, k, and so forth are present, the activity coefficient, y, of one of these (i for example) may be expressed as a product of factors which represent the effects of each of the other components:

Jan 1, 1964

By William E. Ford, Edward Salisbury Dana

The monoclinic Wolframite Group and the tetragonal Scheelite Group are included here. Wolframite Group WoIframite (Fe,Mn)W04 a : b : c = 0.8300 : 1 : 0.8678 B = 89' 22' Hiibnerite MnW04 048362 : 1 : 0.8668 89' 73' WOLFRAMITE. Monoclinic. Axes a : b : c = 0.8300 : 1 : 0.8678; B = 89' 22'. mm"', 110 A 1TO = 79" 23'. ay', 100 A 101 = 62' 54' at, 100 A 102 = 61" 54'. $', 011 A 011 = 81" 54'. Twins: (1) tw. axis c with a (100) as comp.-face; (2) tw. pl. k (023), Fig. 449, p. 171. Crystals commonly tabular (1 a (100); also prismatic. Faces in prismatic zone vertically striated. Often bladed, lamellar, coarse divergent columnar, granular. Cleavage: b (010) very perfect; also parting (1 a (100), and 11 t (102). Fract,ure uneven. Brittle. H. = 5-5.5. G. = 7.2-7.5. Luster submetallic. Color dark

Jan 1, 1922