Search Documents

By G. W. Preckshot, J. W. Gorman

MOLTEN metals offer an excellent medium for the study of molecular diffusion and interphase transfer. In the absence of intermetallic compound formation, solutions of molten metals are solutions of elements. Therefore, complicating factors such as molecular structure, dissociation, association, polarization, and so on, are generally absent. Further, metals remain in the liquid state over a wide range of temperature. Thus, the effect of temperature on transport processes can be studied in more detail. Although some data are available for the diffusion of metals in the molten state at high temperatures,"""".'!' the most useful and accurate data are those for the diffusion of various elements in mercury at room temperature. The effective radius of diffusion for the various elements in mercury may be calculated from the Stokes-Einstein relation.'-These calculated radii are compared with the atomic and ionic radii calculated from X-ray data on crystals." The effective radii of diffusion of the alkali and alkali-earth metals correspond to those of the neutral atom; those of cadmium, silver, lead, zinc, thallium, bismuth, and tin correspond to ionic radii; and those of copper and gold indicate larger radii due to association with mercury or more likely, faulty diffusion data. Independent evidence"' supports the notion that alkali metals are uncharged in amalgams. The concept of metals moving free of their conductance electrons in the liquid state has been discussed by Eyring, et al,'" in connection with studies on the viscosity of pure molten metals. Considering the approximate nature of the tabulated atomic and ionic radii and the variance in the diffusion measurements, the application of the Stokes-Einstein equation to the diffusion of metals in mercury gives gratifying results. It is noted that a number of these metals have article radii eaual to or less than those of the solvent mercury.".'*,"' Soba1,'" sing the inaccurate Roberts-Austin20 data, indicated that the effective radius of diffusion might well be a function of temperature. Additionally in studies of mass transfer between phases, many conflicting opinions have been expressed concerning the assumption of equilibrium at the interface." ,","," The results of the present work on the diffusion of solid copper in molten lead throws light on the tempera- ture variation of the diffusion radius as well as the extent of the interfacial resistance. The theoretical background and experimental procedure are presented here in detail. Results on other systems will be presented in subsequent papers. Nomenclature The following nomenclature is used in the paper: A—cross-sectional area of diffusion column, sq cm C, C,—concentration of solution and saturated solution respectively, g per cc D,D'—-diffusivity, sq cm per sec e—Naperian base h—ratio, k/D k—mass-transfer coefficient, cm per sec L—diffusion column length, cm n—series index q—flux, g per sq cm-sec r—radius, cm or A R—-gas constant t—time, sec T—temperature, K V—volume, cc w—weight of copper-lead alloy on copper cylinder WT—-total copper transferred to lead diffusion, column, g Z—distance from top of diffusion column, cm 2'—distance from copper-lead interface, cm (2' = L-2) u,,—roots of diffusion equation Mathematical Apparatus The model shown in Fig. 1 applies to the diffusion of solid copper into molten lead. Here Fick's first law may be written where all terms are defined in the nomenclature. It is assumed that the volume of the lead column is constant. This is justified since experimental densities compared favorably with calculated densities based on perfect interstitial mixing. Thus there is no counter diffusion of lead. It is clear that 2 in Equation [I] should be measured relative to the interface which moves relative to the diffusion cell but not to the liquid phase. Hence, the frame of reference is the plane of the copper-lead interface. The diffusivity calculated at constant volume, D", is that defined by Hartly and Crank" and is designated herein as D. No Interfacial Resistance—The two situations of the presence and absence of interfacial resistance will be treated. The simplest is the latter which re-

Jan 1, 1959

By W. A. Backofen, D. H. Avery, G. A. Miller

An evaluation has been made of the relative importance of yield strength (?) and stacking-fault energy (y) to the rate of fatigue-crack growth in materials of fcc structure. Pure copper and its solid-solution al-loys with aluminum and nickel were chosen for the study because they provided sufficient range in both quantities of interest that either could be varied independently of the other. Experiments involved alternating tension and compression of flat specimens which were prepared with sharpened internal notches so that most, if not all, of the crack-nucleation interval could be eliminated. Growth rate (dC/dN) was concluded to be proportional to the square of the plastic-strain amplitude (€,,) over a strain range of approximately 6x 10-4 to 6 x 10-3. The factor, k, linking dC/dN and ep in dC/dN = kEp2 increased and decreased with corresponding variations in y, but it did not respond syste?>/atically to change in ay, indicating that y is the significant variable in crack growth at constant plastic-strain amplitude. In polycrystalline material, k varied by a factor of 5 over the available range of y. In a few single-crystal experiments on Cu-A1 alloys the growth rate responded less strongly to change in y. It has been suggested that single crystals behave somewhat differently than poly crystalline material because there is more extetnsive substructure near the grain boundaries in the latter, and this facilitates crack advance by separation along subgrain boundaries. A point of some controversy in current work on fatigue relates to the effects of strength and stacking-fault energy on crack growth. In recent experiments a separation was made between the cycling intervals for crack nucleation and the subsequent growth that eventually ends a specimen's fatigue life.' The study was carried out on Cu-A1 alloys primarily, fatigued in alternating four-point bending to constant deflection. A nucleation interval of about 10' cycles (at a total strain amplitude = 0.2 pct) was found to be insensitive to aluminum content in the range 0 to 7.5 wt pct, while the growth period was increased approximately forty fold over the same compositional range. The increase was not in any sense linear, however. Rather, most of the change occurred below 4 pct A1 or a stacking-fault energy, ?, of about 15 ergs per sq cm. It was argued that the plastic-strain amplitude was approximately constant, and therefore the effect of composition must have grown out of the reduction in stacking-fault energy. Several studies have shown that, with high ?, cross slip is encouraged, subgrain structure is introduced during fatigue, and cracking is aided through propagation along subgrain boundaries.1-5 Therefore, lowering ? sufficiently to interfere with substructure formation would be expected to retard growth rate. On the other hand, it is a general rule that resistance to fatigue cracking increases as strength is raised. Accordingly, there might still have been some doubt that Y was the controlling variable, since strength would be increased as y was lowered by the aluminum additions. To help in dispelling that doubt, an experiment was made on a polycrystalline Cu-Ni alloy similar in strength to the Cu-A1 alloys but of higher ?; the crack-growth interval was found to be essentially that of pure copper.' Further support for this position on stacking-fault energy as it relates to crack growth is derived from work by Boettner and McEvily,6 in which the actual crack-growth rate was measured on samples previously notched so as to minimize the nucleation period. Unfortunately, it was necessary in isolating strength level to compare different alloy systems and grain sizes. Recognizing the complication, it was still concluded that growth may be retarded by a reduction in y, per se. A related study has also been made by Roberson and Grosskreutz.7 The zinc content of a brass was systematically changed to alter strength and stack-ing-fault energy, although not below the 15 ergs per sq cm at which pronounced change in growth interval was found in the earlier work. The results were limited to more or less conventional S-N diagrams so that nucleation and growth events could not be separated. No definite conclusions were drawn, but

Jan 1, 1967

By P. Beardmore, B. W. Howlett, B. D. Lichter, M. B. Bever

The heats of formation at 273°K of the compounds Mg2Ge, Mg2sn, and Mg2b, the heats of fusion and melting points of Mg2Sn and Mg2Pb, and the heats of solution of magnesium, germanium, and lead in liquid tin have been measured. The excess free energies of the liquid alloys and the free energies of formation of magnesium-Group IVB compounds at their melting points and their standard free energies of formation at 298°K have been calculated. The stability and bonding of the compounds are discussed with reference to these properties. Some thermodynatnic aspects of the liquid phases in the systems Mg-Sn and Mg-Pb are also considered. THE compounds of magnesium with the Group TVB elements, silicon, germanium, tin, and lead, have often been considered to constitute a nearly ideal homologous series. In particular, their thermodynamic stability has been assumed to decrease with increasing atomic number of the Group IVB element.' The binary-phase diagrams of the magnesium-Group IVB elements given by Hansen and Anderko2 have the same form. Each system has a single con-gruently melting compound of limited homogeneity range. The structures of these compounds, which have the formula Mg2X, are anti-isomorphous with the calcium fluoride structure. A recent investigation has found evidence of a second compound in the system Mg-Pb.3 The solid compounds Mg2Si, Mg2Ge, and Mg,Sn are semiconductors, while the conductivity of Mg2Pb approaches that of a metallic conductor. This difference suggests that other properties may also show a discontinuity. The investigation reported here is concerned with the thermodynamic properties of magnesium-IVB compounds and particularly their variations with the period of the Group IVB element. The heats of formation at 273°K of the compounds MgzGe, Mg2Sn, and Mg2Pb and the heats of fusion and melting points of Mg2Sn and Mg2Pb have been measured. The results, combined with published data, are interpreted in relation to the stability and the bonding characteristics of the compounds. Some thermodynamic aspects of the liquid phases in the systems Mg-Sn and Mg-Pb are also considered. In the course of the investigation the heats of solution of magnesium, germanium, and lead in liquid tin have been determined. 1) EXPERIMENTAL PROCEDURES 1.1) Samples. Samples of the compounds Mg2Ge, Mg2Sn, and Mg2Pb, supplied by Professor P. Aigrain, Compagnie Générale de Télégraphie Sans Fils, were used in measuring heats of formation, heats of fusion, and melting points. Samples of Mg2Sn and Mg2Pb, supplied by Dr. V. B. Kurfman, Dow Metal Products Co., samples of Mg2Sn, prepared at the Air Force Cambridge Research Laboratories, and samples of MgzPb, prepared in this laboratory, were used for additional measurements of the heats of fusion and the melting points. The samples were stored in evacuated Pyrex capsules or under nonreacting liquids. 1.2) Heats of Formation. The heats of formation at 273°Kof the compounds Mg2Ge, Mg2Sn, and Mg,Pb were measured by tin-solution calorimetry. In this method, samples of the compound and of a mixture of the constituent elements are added alternately from 0°C to a tin-rich bath. The difference between the heat effects, corrected for the change in composition of the bath, is the heat of formation of the compound. Details of the method have been given elsewhere. 4 The bath was maintained at 350°C for the dissolution of the compounds MgzSn and Mg2Pb. Since at this temperature the dissolution of Mg2Ge was too slow, a bath temperature of 400" or 450°C was used with this compound. At least three calorimetric runs, each of approximately six additions, were made with each compound. 1.3) Heats of Solution. The determination of the heats of solution of magnesium, germanium, and lead in tin was included in this investigation because they were not well-established at the time this work was started. To obtain the heat of solution, the difference

Jan 1, 1967

By John E. Hockett

The need for basic information about the relationship between resistance to dejormatim (flow stress), temperature, strain, and strain rate, for the solution of metal-fovming problems, is pointed out. Some early attempts to satisfy the need are mentioned. A brief description of a machine called a Cam Plastome-ter is given, including the processing of results of testing in the machine. Next, a program of testing aluminum in compression over a wide range of constant true-strain rates (0.1 to > 200 sec-1) and a modevately broad range of temperatures (223° to 673°K) is described. The results of this program are presented in the form of true-stress us true-strain cuvves. The data in these curves are presented in the form of relationships between true stress and true-strain rate in sermilogarithmic and log-log form, as functions of temperatures—for several true strains. Finally, true stress, for a given true strain, is displayed as a function of log true-strain rate and absolute temperature, i.e., a surface. SINCE the publication of Hill's book1 on plasticity theory, increasingly rapid advances have been made in analytical solutions to forming problems. Methods in common use are the slab method, the uniform deformation energy method, the limit analysis method, the slipline field method, and the semiexperimental method called "visioplasticity". These approaches, and examples of their use, are covered in detail by Johnson and Melloor2 and by Thornsen, Yang, and Kobayashi.3 unfortunately, practically all of the above work has had to rely upon a number of basic assumptions, e.g., homogeneous deformation and Coulomb (sliding) friction; and virtually no dependence of the mechanical behavior of the deforming metal, upon temperature, strain, and strain rate, has been included. It is with this dependency that this paper is concerned. Loizou and sims4 looked at the above relationship for lead using both a constant compression-speed Cam Plastometer and a constant true-strain-rate Cam Plastometer designed by Orowan.5 Alder and Phillips8 investigated the relationships for aluminum, copper, and steel in the same constant true-strain-rate Plastometer. cook7 tested twelve steels at temperatures ranging from 1170° to 1473°K in the same Plastometer over a range of true-strain rates of 1.5 to 100 sec-'. The writer tested commercially pure aluminum at room temperature and depleted uranium at temperatures from 573" to 873°K at strain rates from 10-3 to 1.0 sec-1 in a Cam Plastometer designed and built at Los Alamos Scientific Laboratory.8 During the past few years the Cam Plastometer at Los Alamos has been used for a number of relatively minor experiments on brass, mild steel, duralumin, Armco iron, and depleted uranium. In this time the machine has been continually modified and improved. It was decided to utilize fully the wide range of strain rates now available with the machine by testing a material about which some information was already in the literature. Prior work on commercially pure aluminum6 appeared to deserve confirmation and expansion. So it was decided to explore the resistance to compression of this material over the currently available range of constant true-strain rates and a convenient range of temperatures. This paper is a report of that exploration. I) EQUIPMENT AND PROCEDURE The principal item of equipment is, of course, the Cam Plastometer, the working part of which is shown in Fig. 1. In this figure, an aluminum specimen may be seen between two tungsten carbide platens, in position for a room-temperature test. Above the upper carbide platen is a load cell. Output from the load cell is amplified and applied to a galvanometer in a recording oscillograph. Auxiliary equipment includes the oscillograph, the control console, a counter, and a time-mark generator. The counter is first used in adjusting the time base. Then it registers the count, of sixty pips per revolution generated by the rotating cam, in each second. These pips and the time base are also applied to galvanometers in the oscillograph. Thus, load, time, and cam position are recorded simultaneously. Heating of a specimen prior to compression is done

Jan 1, 1968

By G. T. Hahn, C. N. Reid, A. Gilbert

An evaluation is made of the possible cautsal relationship between twinning and fracture in molybdenum. For both single and poly crystalline material no instance of twin-induced fracture was observed. Instead brittle fracture was found to be slip-induced at heterogeneities. For single-crystal material, the yield stvess in compression and the fracture stvess in tensiow obey a similar angular- relationship which follows approximately a 1/cos2 ? law. where 0 is the angle between the specimen axis and the nearest (100) plane. This sittlilarity between yield and fracture behavior casts doubt on the interpretations made previoltsly that a 1/cos2? relationship supports a critical normal fracture stress criterion. SINCE fracture in brittle materials takes place at stresses an order of magnitude lower than the theoretical strength of the lattice, it must be postulated that some stress-concentrating effect is operative during the fracture-initiation process. Several mechanisms have been proposed whereby the necessary stress concentrations could be produced. The well-known Cottrell mechanism1 describes a dislocation interaction which can lead to the formation of an incipient cleavage crack on a cleavage plane, and both zener2 and stroh3 have discussed models which predict the stress concentration at the intersection of a slip band with a grain boundary. When twinning occurs twin/twin intersections and twin/grain boundary intersections represent another possible means of fracture initiation. Although still controversial, the concept of twin-induced fracture is supported by a weighty mass of evidence, which has been reviewed in a recent paper.4 This investigation was conducted in order to assess the extent to which the brittleness of molybdenum can be ascribed to this cause. Emphasis was placed on seeking direct metallographic evidence for twin-induced fracture such as arrangements of twins located at the fracture origin. EXPERIMENTAL PROGRAM Materials. The experimental materials are described inTable I. From the chemical analyses and estimates of the amounts of interstitials likely to be retained in solution,5 it is concluded that all were mul-tiphased systems. X-ray diffraction experiments6 showed no evidence of preferred orientation in the polycrystalline materials. Single crystals were grown from Molybdenum X and Y using the floating-zone technique,' in a vacuum of better than 3 x 10-5 Torr. However difficulties were experienced with Molybdenum X due to violent gas evolution from the molten zone, and additional crystals (Crystals 3 to 6) were produced by annealing for 5 1/2 hr at 2300°C under a vacuum of 10-4 Torr. Techniques. A series of tension, compression, and bend tests was conducted. Tension tests were used to demonstrate brittle behavior, to measure brittle-fracture stresses, and to provide fractured specimens for metallographic inspection. Compression tests were employed in order to obtain some ductility and a measure of the yield stress. Furthermore, it was considered that compression loading would permit the study of crack nucleation in the absence of propagation. The bend tests were conducted to facilitate identification of the fracture origin, which would be expected to be at, or near, the tensile surface of the sample. Tests were carried out at temperatures between 78" and 298°K attained by means of a liquid-nitrogen evaporator of modified Wessel design.' Specimens were fashioned by mechanical grinding, and, prior to heat treatment, were electropolished at 10 v in a 3:l mixture of ethyl alcohol and sulfuric acid, using a stainless-steel cathode. Except where noted, a strain rate of 4 pct per min was used. All specimens had a gage section 0.75 in. long; diameters of 0.10 and 0.20 in. were adopted for the tension and compression specimens, respectively, the former of single shoulder design, the ends being gripped in split collets with a conical bearing surface. In the bend test, electropolished specimens measuring 0.080 by 0.25 by 1.25 in. were deformed at 78°K by four-point loading. The bending device had spans of 1 in. between the outer and 4 in between the inner fulcra; it was stressed between the compression anvils of the Instron machine at a constant deflection rate. EXPERIMENTAL RESULTS Polycrystals. Tension and Compression Tcsls. It is apparent from Fig. 1(a) that above 170°K fracture of Molybdenum X takes place at stresses equal to or greater than the compressive yield stress whereas

Jan 1, 1967

By T. E. Scott, D. H. Sherman, C. V. Owen

Mechanical properties and optical metallographic characteristics of vanadium containing 53 ppm (wt) H were investigated from, 77° to 298°K. A sharp ductile to brittle transition induced by the presence of hydrogen was observed between 238° and 223°K and a mar-tensitically formed hydride appeared at 200°K. While there appears to be a subtle relationship between the hydride formation and the ductile-brittle transition, it was concluded that the hydride per se was not sufficietzt to cause the severe em brittletnent. On the basis of the metallographic experiments and the results of a Petch analysis it is suggested that the mechanism of the embrittlement involves a reduction of the true surface energy, or cohesion, of the uanadiunz. THAT hydrogen can severely embrittle vanadium is well-documented;'-5 however, the mechanism by which hydrogen induces the observed embrittlement has not been established. It is not known whether the embrittlement of vanadium is caused by the formation of vanadium hydride or by a more subtle role of hydrogen. Until very recently6>' the solid solubility of hydrogen in vanadium at temperatures in the,range of the embrittlement was not known to a useful accuracy. In general, a severe embrittlement of the type produced by the presence of hydrogen in vanadium can be caused by changes in either of two properties of a metal. Either the yield stress of the metal is raised to the extent that plastic deformation at the tip of a crack cannot occur or the cohesive properties of the metal are reduced, at least locally, to the point at which cleavage is the natural response to applied loads. Of course a combination of these is possible. It is not known which of these properties of vanadium is influenced most by the addition of hydrogen. The purpose of this investigation was to determine the role of hydrogen in the embrittlement of vanadium. Accordingly, the solubility of hydrogen in vanadium in the temperature range where embrittlement is most severe was determined, the appearance of vanadium hydride was examined in relation to the initial ductile to brittle transition temperature, and an attempt was made to evaluate the effect of hydrogen on the yield stress and cohesive properties of vanadium. MATERIAL AND PROCEDURES Sample Preparation. The vanadium used in this investigation was prepared by the iodide refining process described by Carlson and owen.' Three ingots, 3 in. diam by 6 in. long, were cold-swaged to 0.096 in. diam, cut into short lengths, and then arc-melted under purified argon into one ingot. This process was repeated to insure a uniform composition in the final ingot. Chemical analysis of the metal is given in Table I. On the basis of work of Loria et a/ .' the following sequence of treatments was performed in order to obtain a uniform equiaxed ultimate grain structure: a) cold swage q-in.-diam ingot to 0.230 in. diam; b) anneal 6 hr at 1000°C in vacuum; c) by cold swaging reduce 81 pct in area in three steps: 0.230 to 0.187 in. diam, 0.187 to 0.150 in. diam, 0.150 to 0.096 in. diam. This sequence provided the desired grain structure after subsequent annealing treatments. Because annealing in evacuated quartz capsules resulted in contamination by oxygen, all anneals in this investigation were performed in a 304 stainless-steel chamber under a dynamic vacuum of 10- I Torr with the vanadium wrapped in tantalum foil. Prior to all annealing treatments the wires were electropolished for 1 min at 16°C in an 80 pct methanol-20 pct sul-furic acid electrolyte at 12.5 v. Following the final reduction the 0.096-in.-diam wire was cut into 2-in. lengths. A 1-in. gage section was reduced to 0.090 in. diam by electropolishing as above. Five different grain sizes were obtained by annealing the 2-in. samples at different temperatures for 8 hr to insure uniform grain size and residual hydrogen removal. The annealing temperatures used and the resulting grain sizes are given in Table 11. The final step in sample preparation was to charge half of the specimens of each grain size with hydro-

Jan 1, 1969

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,' is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors' sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958

By E. S. Machlin

The wzodel of Blandin and Diplunt;, generalized to include a phase factor, is applied to the carbon-carbon interaction in iron. Darken&apos;s "energetic" model is generalized to include not only first neighbor interactions but further neighbor interactions as well. On the bases of these generalized models relations are derived for the activity of carbon in both austenite and ferrite in terms of the carbon-carbon Pair interaction energies. A single function then yields the pair interaction energies consistent with the experimental activities of carbon in both ferrite and austenite. Thus, a simple explanation is given for the observation that the nearest-neighbor interaction between carbon is repulsive in austenite and attractive in ferrite. Certain consequences of this approach are explored. OnE object of the present paper is to attempt to take into account the consequences of electrostatic contributions to the carbon-carbon pair interaction energy for carbon as a solute in iron. Friedel&apos; has shown that oscillations in electrostatic potential are to be expected about a solute atom in a metallic solution. Blandin and 6lant6&apos; have shown that such oscillations yield an interaction energy between pairs of solute atoms that obeys the relation: W{ = A cos(2ftFri + 4>)/(kFri)3 [l] where kF = Fermi wave vector, ri = distance between solute atoms comprising the pair7 <p = phase factor dependent only on electronic nature of solute and solvent, A = coefficient dependent only on electronic nature of solute and solvent. Machlin3 found that Eq. [I] accurately described the pair interaction energy derived from short-range order measurements based on field ion microscope observations of dilute alloys of platinum. He also found that the value of the phase factor $ derived from residual resistivity measurements agreed well with that obtained from the analysis of the short-range order data. Harrison and paskin4 were able to predict the long-range ordering energy of 0 brass using Relation [I] and residual resistivity values to predict the value of the phase factor $. Machlin5 has repeated their analysis and applied it to the prediction of the long-range ordering energy in AgZn and AgCd with excellent agreement between prediction and experiment. Both A and $ are independent of the crystal structure. The Fermi wave vector depends uniquely upon the conduction electron concentration per unit volume in the spherical approximation of the Fermi surface. Thus, Eq. [I] is expected to apply to both fer- rite and austenite with only one set of values of A and $. Mossbauer studies6 yield the result that iron has one 4s electron. We shall make an assumption found to hold previously for platinum3&apos;7 and nikel, which is that only the s electrons are involved in shielding the perturbing potential of carbon. With this assumption, kF = 1.35 A-l. Although A and $ may be obtained from certain mdels&apos;&apos;&apos; we shall take A and $ to be empirical constants in the spirit of Kohn and osko.&apos; Thus, Eq. [I] involves two adjustible parameters. Consequently, two independent relations in A and $I are required in order to evaluate them for carbon as a solute in iron. We may use a recent analysis of Aaronson, Domain, and poundg who showed that Darken&apos;s energetic model,1° as well as others, can be used to describe the activity-temperature data for carbon in iron in both the aus-tenitic and ferritic phases. Darken&apos;s model takes into account only first neighbor pair interactions. For our needs, all neighbor pairs need to be taken into account. It is convenient to generalize Darken&apos;s model. The result for the partition function for austenite is: over the temperature range 800" to 1200°C and where the uncertainty corresponds to one standard deviation. Eq. [4] effectively yields only one relation. Another relation is required to obtain unique values for A and $. One property of Eq. [4] is that it is independent of crystal structure. Hence, data for a iron can be used to obtain another relation. To arrive at this relation we must generalize Eqs. [2] and [3] so that they may be applied to the bcc a iron. The result is that:

Jan 1, 1969

By J. L. Taylor, Pol Duwez

THE present knowledge of the Ti-Al system is limited to the portion of the diagram extending from pure aluminum to the intermetallic compound TiAl3&apos; A preliminary investigation of the titanium-rich Ti-A1 alloys revealed that the solubility of aluminum in titanium is quite extensive and that the transformation temperature of titanium is raised by alloying with aluminum. From an X-ray diffraction study of alloys containing up to 75 atomic pct Al (TiAl3), the phase boundaries at 750°C were located as follows: the a titanium solid solution extends from 0 to about 36 atomic pct Al, a two-phase region exists from 36 to 46 atomic pct Al, and an intermediate phase of varying concentration extends from 46 to 62 atomic pct Al. The purpose of the present paper is to describe the crystal structure of this new phase. The alloys were prepared by melting in a helium arc furnace on a water-cooled copper plate, using a furnace essentially the same as that described in ref. 2. The titanium metal was of the iodide type furnished by the New Jersey Zinc Co., and a piece of pure aluminum (99.99 pct) was obtained through the courtesy of the Aluminum Co. of America. After melting, the samples, weighing approximately 5 g, were sealed in evacuated fused silica tubes and homogenized for 4 hr at 1000°C. The specimens were then held for 10 days at 750°C and rapidly cooled to room temperature. Filings were then taken from each sample, sealed in evacuated vials, annealed at 750°C for 4 hr, and rapidly cooled to room temperature by quenching the vials in water. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using K copper radiation filtered through a nickel foil. Structure Determination The X-ray diffraction patterns of the alloys containing 46, 50, 55. 60, and 62 atomic pct Al were identical, except for a slight shift in the positions of the reflections. The alloy containing 55 atomic pct Al was chosen far structure determination. The powder pattern contained 37 reflections and the a, doublets were well resolved in the back-reflection range. The relatively small number of reflections and the sharpness of the pattern were considered as an indication of a simple atomic arrangement in a relatively small unit cell of high symmetry, and an attempt was therefore made to solve the structure without single crystal work. A satisfactory fit was found on a large scale Hull-Davey tetragonal chart for an axial ratio of approximately 1.45. All the reflections were readily indexed and the tentative unit cell dimensions were computed to be a - 2.81 kX, c - 4.07 kX, and c/a = 1.448. The indices (hkl) and the values of d and sin2 A are given in Table I. The agreement between observed and computed sin2 is quite satisfactory. Once the unit cell was known, the details of the structure were readily found. First, it is obvious that the number of atoms per unit cell cannot exceed two, since more than two atoms would lead to a density greater than that of pure titanium. The next logical step is to assume that the two atoms occupy the corner and center of the cell. If this assumption is correct, the structure may be described as follows: space group D1, - P 4/mmm; one titanium atom in a: 000; one aluminum atom in d: 1/2 1/2 1/2: and no extinctions. Assuming this structure to be the correct one. intensities were computed by means of the usual equation: sin2 0 cos 0 where F is the structure factor; 8, the Bragg angle. and p, the multiplicity factor. The calculated values of intensities are compared in Table I with the visually estimated intensities. The agreement is quite satisfactory and the structure is therefore confirmed. The crystal structure of TiAl just described is the same as that of AuCu ordered. The AuCu ordered

Jan 1, 1953

By E. C. Ekedahl, R. J. Heath

Introduction Potassium, together with nitrogen and phosphorous, is an essential nutrient required for growth. Since all living things need potash, the major demand for potash - about 95% of the total - is as a fertilizer. Agricultural productivity has increased dramatically in recent times. This increase in crop yields requires substantial amounts of added nutrients to keep the soil fertile. It follows then that potash will always be in demand. There is no substitute. Other fertilizers that contain phosphorous (P) and nitrogen (N) are complementary and not competing products. Fireplace ashes (pot-ashes) have a relatively high potassium content. Their value as a fertilizer had been recognized for centuries. But today&apos;s potash industry did not begin until deposits of potassium-rich ore were discovered and exploited in Europe during the 19th century. Canadian potash development Potash in Saskatchewan was first recognized in 1943. It was discovered as a byproduct of an oil exploration program. But it was several years later before the existence of a major commercial deposit was acknowledged, and not until 1951 that the first attempt at development occurred. That attempt was unsuccessful. The shaft flooded and was abandoned. It did, however, demonstrate the need for new technology to penetrate the waterlogged Blairmore layer. This was eventually developed and the first mines were brought into production in the early 1960s. Once the technology was available, and the extent and quality of the potash beds became known, a number of companies proceeded to develop mines. By 1970, seven mines were in operation and three more were nearing completion. Combined, total capacity then was 7.6 Mt/a (8.4 mil¬lion stpy) K20. At that time, world potash consumption was about 15 Mt/a (16.5 million stpy). This increase in supply from Canada produced a large potential surplus that shattered the prevailing balance between supply and demand. Although world demand increased steadily throughout the 1960s and early 1970s, it was several years before world supply and demand were again in balance. Saskatchewan capacity has been expanded a number of times. It now stands at 10.7 Mt/a (11.7 million stpy) K20. Actual production has not approached this figure, however. Two new mines in New Brunswick have recently been built with a combined annual capacity of 1.2 Mt (1.3 million st) K20. Total Canadian capacity of about 12 Mt/a (13 million stpy) now amounts to 30% of world capacity. Central offshore marketing organization Canadian Potash Exports Ltd. (Canpotex) was created in 1970 as the offshore marketing organization for Canadian producers. Canpotex is owned by Saskatchewan producers and is their exclusive marketing organization for offshore business. Each company handles its own sales in Canada and the US, but all sales to other markets are handled through and by Canpotex. The Saskatchewan industry has an ore body of a size and consistency unmatched anywhere in the world. Large efficient mines have production costs that compare favorably with other producing countries. On the minus side, Saskatchewan is remote from most major markets. It therefore needs the ef¬ficiencies that stem from one organization that coordinates all offshore shipments and minimizes distribution costs. Agriculture guides potash market In the period following World War II, potash was a classic growth industry. World demand increased each year from 1945 to early 1970s. Since then, demand has been more erratic. Some years show substantial increases, but are followed by significant declines. For about the last decade, the pattern has been unclear and future demand has become correspondingly difficult to predict. North America and Europe together account for about 40% of the world potash consumption. In both areas, farming is characterized by surplus production, declining crop prices, and expensive government support programs. Under those circumstances, farmers respond by minimizing input costs. Fertilizer is one of the items they reduce. Potash is retained in the soil. It is possible to reduce potash application with no immediate deterioration in crop yield. The lower yields occur only when potash levels are depleted. So, farmers can econo-

Jan 12, 1987

By F. Garofalo

It has been shown by various investigators that during constant stress creep the dependence of minimum creep rate, 6,, on stress, o, is given by em = A onat low stress levels, md by 6, = A&apos; exp [ß s] at high stress levels. In these relations A, n, A&apos;, and ß are constant at constant temperature. A single relation has been found which satisfies conditions for both high and low stresses and agrees well with experimental results. This relation is 2, = AN (sinh a s)n, where A" is a constant at constunt temperature and a = p/n. This relation also satisfies the linear relation, 6, = k s, found at temperatures near the melting point at low stresses. EXPERIMENTAL creep results have led to a number of empirical relationships between minimum creep rate, 6,, and the applied stress, s. Under conditions of constant stress it is generally found that at low-stress levels,&apos;-&apos; the dependence of minimum creep rate is given by 6, = Asn. At high-stress levels&apos;74 the experimental results fit the relation, 6, = A&apos; exp [po l. In these relations A, n, A&apos; and ß are constant at constant temperature. A model based on climb-of-edge dislocations from a pile-up array leads to a relation similar to that found experimentally at low stresses.&apos; On the other hand. theories based on chemical-reaction rate,5 nonconservatively moving dislocation jogs, and jog migration and climb-of-edge dislocations4 lead to a relation similar to that found experimentally at high stresses. No difference in mechanism between low and high stress levels has been clearly defined; it is questionable whether such a difference really exists. In any event, the major argument usually given in substantiation of a change in mechanism from low to high stresses is that no single relation exists for defining the stress dependence of the creep rate over wide ranges in stress. However, such a relation has been found and is of the form, dm = A" (sinh a s)n, where A" is a constant at con- stant temperature and a = ß/n. This relation agrees well with experimental results over wide ranges in stress and temperature for copper, aluminum, an A1-3.1 pct Mg alloy, and an austenitic stainless steel. STRESS DEPENDENCE OF MINIMUM CREEP RATE At low stress levels the minimum creep rate, gm, depends on the stress, 0, under conditions of constant stress creep through the relation em=Aon [1] The quantities A and n have been defined previously. In the range in which this relation applies, a linear dependence is found in a log em,-log o plot. Above the stress range of application of relation [I], the minimum creep rate increases much mar; rapidly than predicted by relation [I]. This behavior is shown in Fig. 1 for a series of creep tests on copper4 at various temperatures ranging from 673 o to 973°K. Relation [I] is satisfied at the lower stresses, although the results at 973°K are quite limited. In all cases the transition beyond the applicable range of relation [I] is a gradual one indicating no abrupt change in mechanism. For all test temperatures, values of n have been determined from the results in Fig. 1. These are reported in Table I under Alog tm/hlog o. At high stress levels the stress dependence of minimum creep rate under conditions of constant stress is given by im = A&apos; exp [ß a] 2] All factors have been defined previously. In a log em-0 plot, relation [2] predicts a linear function. Experimentally, a pronounced deviation from the prediction of relation [2] is found at lower stresses. As the stress is lowered, the minimum creep rate decreases more rapidly than predicted by relation [2]. This shown for copper in Fig. 2. Again it is found that the transition from high to low stresses is gradual and no really sharp change is found. Values of p determined from the high stress results are given in Table I. The dependence of minimum creep rate on stress at constant temperature for all ranges in stress

Jan 1, 1963

By M. J. Marcinkowski, Gordon E. Lakso

An extensive investigation has been made of the deformation behavior associated with the Fe3Si super-lattice using transmission electron microscopy techniques. Above 243°K the stress-strain curve exhibits three stages. Stage I occurs at a very low stress level and is related to the generation of perfect superlat-tice dislocations. Stage II is characterized by an extremely rapid rate of work hardening and is associated with the Taylor type locking of these superlattice dislocations. Finally Stage III is related to dynamic recovery processes since the work hardening rate is very small. Below 243ºK, only Stage I is observed, but it occurs at a much higher stress level. This latter observation is related to the generation of imperfect dislocations in Stage I with the consequent production of second nearest neighbor antiphase boundaries. The reason for this is that insufficient thermal energy is available at these low temperatures to generate the complete and perfect superlattice dislocations. It has been shown that the fully ordered FeCo alloys, i.e., those possessing the B2 type structure, exhibit three distinct stages of work hardening whereas the corresponding disordered alloys show only one.&apos;" This difference in behavior between the disordered and ordered alloys has been attributed to the fact that dislocations in the former case travel only as ordinary 1/2ao(111) types whereas in the latter case the move through the lattice as coupled 1/2a0(111) dislocations separated by an antiphase boundary (APB), i.e., the so-called superlattice dislocation. Although some preliminary work has been carried out concerning plastic deformation in ordered alloys possessing the DO3 type superlattice,3 no detailed analysis similar to that described in Refs. 1 and 2 has been attempted. Specifically, it has been suggested that the superlattice dislocation in this particular type structure should consist of four ordinary 1/2ao<111> types bound together by first and second nearest-neighbor APB&apos;s. Fe3A1 and Fe3Si are the two classic alloys possessing the DO3 type lattice; however, because of the somewhat higher ordering energies associated with the FesSi alloy, which in turn assures that dislocations will travel through the lattice as perfect superlattice dislocations under at least some conditions, it was chosen for the present investigation. Because of the extreme brittleness of Fe3Si, all deformation was done in compression. Stress-strain curves were obtained using both polycrystalline samples as well as single crystals. In the latter case the crystals were oriented so that deformation could be controlled either by single or double slip. They were then wafered parallel to and at various angles to the operative slip planes. These wafers were in turn examined by transmission electron microscopy (TEM) techniques in order to determine the extent of the interaction from the dislocation configuration contained therein. EXPERIMENTAL PROCEDURE The alloys used in this investigation were arc melted under helium from electrolytic iron of greater than 99.90 wt pct purity and transistor grade silicon of 99.99 wt pct purity. A typical analysis of interstitial impurities showed 120 ppm 0, 15 ppm N, and 65 ppm C Because of the extremely low ductility of the Fe3Si alloys, it was necessary to spark cut 0.230-in. diam polycrystalline cylinders 0.400 in. long from arc-melted fingers using a thin-walled brass tube as a cutting tool. The polycrystalline alloys could not be recrystallized since very little strain was induced in preparation. However they were annealed at 1273°C for 15 min in evacuated vycor capsules to relieve any cooling stresses that may have developed during solidification and then air cooled. The resulting grain size of the alloy was 0.50 mm. According to warlimont4 1273ºC is just within the single phase field where FesSi possesses the DO3 type lattice. In addition because of this high critical ordering tem-ature, air cooling from this temperature was believed sufficient to fully order all of the Fe3Si samples used in the present investigation. For the same reason, no attempt was made to achieve any degree of disorder by quenching. In fact, rapid quenching from 1123°K caused cracking. Such cracking was first suggested by sato5 with respect to the experimental observations of Glaser and Ivanick.6 Single crystal compression specimens were spark cut from single crystal ingots grown in a Bridgman type furnace. The iron and silicon for the crystals was prealloyed by arc-melting two 130-g buttons which were cut into small pieces before remelting in the furnace. This procedure resulted in a long-range inhomogeneity of 0.5 at. pct Si between the top and bottom of the 2-in.-long single crystal ingot, which was assumed to be negligible in the present investigation. The single crystals, after orienting and spark-cutting, were about 0.37 in. by 0.37 in. in cross section and about 0.5 in. long. True stress-strain curves were obtained using an Instron Tensile Testing machine in conjunction with techniques described previously. 1,7 The strain rate was 0.05 in. per in. per min. Prior to testing, the ends of all the compression cylinders were hand polished using a special jig to insure parallelism after which the sides of the samples were electrochemically polished to eliminate stress risers and to facilitate slip line observations. Test temperatures between 77" and 823°K were obtained using various cooling and heating media as described in Ref. 7 while at the upper end of this temperature range, a mixture of equal

Jan 1, 1970

By H. H. Podgurski, J. C. M. Li, Y. T. Chou, F. N. Davis, R. A. Oriani

When an Fe-2 pct A1 alloy is nitrogemted at 500ºC with a gus tnixture (NH3-H2) in which the nitrogen activity has been kept Lou] enough to avoid the formation of iron nitride, a two-phase alloy is generuled which consists of AlN particles and a ferrite phase cotaining a heavy network of dislocations. The amount of nitrogen contained in such an alloy, when equilibrated with the nitrogenating atmosphere, far exceeds both that needed to satisfy the normal solution requirements of a Fe and that needed to convert all of the aluninuwi to AlN. This excess nitrogen is accounted for as being trapped on dislocations, adsorbed at the ferrite -AlN interface, and as an en-Iuznced lattice solubility in strained ferrite. This excessive uptake of nitrogen had previously been attribuled by other investigators to the formation of a nonstoichiornetric aluminum nitride. Isotope exchange experiments revealed various amomts of exchargeable N14 present in the originally nitrided samples that could not be removed by reduction with HS at 500ºC. This exchangeable nitrogen has been identified us that bound to the AlN -ferrite interface. Estimates of inter facial areas in alloys containing -3 pct by weight of A1N are as high as 10 sq m per g of alloy. ThE first1 of this series of papers described the experiments forming the basis for the elucidation of the mechanism of the formation of aluminum nitride particles within an Fe-A1 alloy. It was found that not only are dislocations necessary for the nucleation of the AlN particles but also the nitriding reaction in turn produces a dense network of dislocations in the ferrite matrix. It was also observed that nitrogen in excess of that needed for the formation of stoichiometric AIN is taken up by the alloy without the formation of an iron nitride. The present paper is an analysis of the excess nitrogen sorbed by the nitrided Fe-A1 alloy which considers the structure generated by the formation of the aluminum nitride particles. Because of the high density of dislocations, this system has proved to be quite useful in studying nitrogen-dislocation interactions. Wriedt and Darken2 have already reported such studies in a cold-worked ferritic steel. EXPERIMENTAL Nitrogen Sorption. The specimens of this alloy were cold worked (50 pct reduction) to 0.011 in. thickness and chemically cleaned in a 2:1 concentrated phosphoric acid-50 pct hydrogen peroxide solution before nitrogenation. The flowing nitrogenating atmosphere (11 pct NH3-89 pct H2) was established before the ni- trogenating temperature was reached. The same gravimetric and gas-flow equipment described in an earlier paper1 was also used in this investigation. Changes in nitrogen concentration were followed gravimetrically when establishing the isotherms. In the isotope exchange experiments, concentration changes were followed volumetrically. In some instances chemical analyses (Kjeldahl method) were used to check for material balances in both the gravimetric and volumetric procedures. Our objective was to obtain reversible nitrogen sorption isotherms for alloys equilibrated with NH3-H2 gas mixtures over a large range of nitrogen activity* and temperature. The *Defined as equal to PN H /P3/2 ,where P corresponds to partial pressure in atmospheres. Actually the nitrogen activity, aN, in the alloy equals K PNH3 /p3/2H2, where K is the equilibrium constant for the reaction NH3 = N + 3/2H2. upper limit for nitrogen activity was below that which would produce iron nitride; for reasons which will become apparent later, most of the sorption studies were made in the temperature range between 400" and 500&apos;C. The alloy sample studied most extensively in this investigation was given a series of successive reductions (100 pct H2) and nitrogenating treatments at 500°C to attain a stabilized structure. Presumably some dislocations were lost during these treatments. Throughout most of the sorption studies, temperature was held at ± 1°C and the gas-phase composition was held to k0.2 pet NH3. Based upon the results of numerous diffusion experiments with this alloy* the &apos;Results to be published in a third paper of this series. times chosen for equilibration were considered more than adequate, Nitrogen Isotope Exchange. The first exchange experiments were carried out by circulating a measured quantity of H2 and NH3* (with a predetermined isotopic *The NH3 was synthesized over a synthetic ammonia iron catalyst using H2, and N2, enriched with N15. AS the NH3 was formed it was removed continuously from the gas phase by circulating the mixture through a refrigerated (78ºK) trap. When most of the nitrogen had been converted to NH3, it was distilled from the trap into a glass storage vessel. composition, N15/N14) over a nitrided specimen at 450°C in a closed glass system. Attempts to reach the exchange limit isothermally, i.e., an isotopic ratio (N15/N14) in the gas phase identical with the extractable nitrogen in the nitrided alloy, were futile. The exchange rate between the gas phase and the alloy was too slow, involving many days. To circumvent the slow exchange with the gas phase, measured amounts of N15 and N14 were introduced into the alloy by nitrogenating with an NH3-H2, mixture at 500°C containing an N15/N14 ratio of 7.76; the charged specimens were then sealed by allowing an oxide film to form over them in air, and in this final condition the specimens were subjected to 500°C in vacuum for various times during which isotope exchange was allowed to proceed within the specimen. It was estab-

Jan 1, 1970

By Peter R. Morris

The effecl of preferred orienlation on X-vay dzffvaction measurements of retained austenzte was investigated for four precipitation-hardening staznless steels in sheet form. A method is preserzted for estimating the ervor in measurement associated with a given samplirig direction. The method was used to select an "optimum" sampling direclion in order to minimize errors in measurement due to preferred orientation. hleasuremenls of retained austenite content employing lhe proposed sampling direction are conzpaved to measuretnents enzploying the more commonly used normal direclion for a series of sawzples. THE first application of X-ray diffraction to the measurement of retained austenite in steels is due to Sekito, 1 who employed a photographic technique in which the (111) reflection from a thin strip of gold affixed to a cylindrical sample was employed as a standard. Averbach 2 introduced the "direct comparison" method in which the ratios of observed to calculated random intensity are assumed proportional to the austenite and/or martensite contents. Averbach&apos;s work forms the basis of most subsequent X-ray diffraction methods for the determination of retained austenite. Subsequent improvements are due to: Averbach and Cohen,3 who employed a sodium chloride crystal to monochromate cobalt radiation; Averbach et a1.,4 who introduced a bent sodium chloride monochromator; Mager,&apos; who used a bent quartz crystal to monochromate chromium radiation ; Littmam, who first used a geiger counter diffractometer for this purpose; Beu and Beu and Koistinen, 11,12 who studied effects of absorption factor, surface preparation, sample geometry, integrated intensity vs peak height, choice of radiation, monochromator, and filter. The possibility of errors in measured values due to orientation effects was noted by Miller,13 who suggested examination of a surface other than the plane of rolling. Lopata and Kula 14 have developed an experimental technique in which the preferred orientation is measured in each sample. They illustrated the method for a sample containing 42 pct retained austenite. Application of their technique to the 1 to 15 pct range typical for the precipitation-hardening stainless steels does not appear feasible. EXPERIMENTAL PROCEDURE The nominal compositions of the precipitation-hardening stainless steels investigated are listed in Table I. Ingots were solution-treated, hot-rolled to approximately 0.2 in., and reduced to 0.050 in. by a suc- cession of cold rolling and annealing operations. After this treatment the 17-4PH sample was in the marten-sitic condition, while the 17-7PH, PH 14-8Mo, and PH 15-7Mo samples were in the austenitic condition. Samples of 17-7PH and PH 15-7Mo steels in the mar-tensitic condition were obtained by heating to 1750&apos;F for 10 min and holding at -100°F for 8 hr. A sample of PH 14-8Mo steel in the martensitic condition was obtained by heating to 1700°F for 1 hr and holding at -100°F for 8 hr, followed by aging at 950" for 1 hr. POLE FIGURE DETERMINATIONS Samples were thinned to 0.003 to 0.005 in. by etching in a solution containing 250 ml reagent-grade phosphoric acid (85 to 87 pct H3PO4), 250 ml technical-grade hydrogen peroxide (30 to 35 pct H 2 O 2), and 50 to 100 ml reagent-grade hydrochloric acid (37 to 38 pct HCl). The specimens were placed in an "integrating" sample holder which provided a 1-in. oscillation in the plane of the sample. The diffractometer was aligned to measure the intensity diffracted by planes of the particular {hkl} type being studied. The sample was Set for a given latitude angle, a, measured from the plane of the sheet, and diffracted intensity recorded as the longitude angle, 0, measured in the plane of the sheet from the rolling direction, was increased from 0 to 360 deg. After a 360-deg scan of B, a was incremented by 5 deg, and the process repeated. Random standards obtained by spraying suspensions of powdered iron (bcc structure) and nickel (fcc structure) in lacquer were used to correct observed intensities for absorption and geometrical effects. Zirconium-filtered molybdenum radiation was used to determine the transmission regions of the (111) (0to 45 deg), (200) (0 to 60 deg), and (220) (0 to 45 deg) austenite and (110) (0 to 45 deg), (200) (0 to 50 deg), and (211) (0 to 35 deg) martensite pole figures. Vanadium-filtered chromium radiation was used to

Jan 1, 1968

By M. J. Marcinkowski, D. B. Crittenden, A. S. Sastri

A study co.mbining stress-strain .measurements in conjunction with transmission electron microscoPy has been made with near equiatomic Fe-Cr alloys which were aged for various times at 500°C. Associated with this aging is a marked increase in deformation twinning. The outstanding feature of these twins is that they generate stress fields sufficiently great so as to give rise to spontaneous dislocation loop nucleation nearly normal to the propagating twin. This observation is in agreement with the theoretically predicted elongation of the stress field of a dislocation Perpendicular to its direction of motion as it moves near the speed of sound. Dislocation loop nucleation is more difficult in the longer aged alloys so that this energy absorption mechanism is not effective in hindering twin propagation. Since crack nucleation can readily occur near the tip of a twin, the aged alloys become extremely brittle when deformed in tension. Iron-chromium alloys in the vicinity of the equiatomic compositions become severely embrittled when aged at about 500°C. Fisher et 01.&apos; have shown that this embrittlement is related to the decomposition of the original random Fe-Cr solid solution into a chromium-rich and an iron-rich phase. In addition, Mar-cinkowski et a1.&apos; have shown that twinning becomes an increasingly more important mode of deformation as the aging time is increased. These results have been recently corroborated by the transmission electron microscopy study of Mima and amauchi . The Fe-Cr alloy thus seems ideal for verifying the predictions made in Parts I4 and 115 of this investigation where the behavior of large static or blocked twins and those of large dynamic or propagating twins, respectively, were investigated numerically. It was thus decided to measure the stress-strain curves generated by embrittled alloys that were aged for various times and to examine sections by transmission electron microscopy. EXPERIMENTAL PROCEDURE Electrolytic iron and electrolytic chromium were vacuum-melted and poured into ingot form. The composition of the resulting alloy was found to contain 46.0 wt pct Cr (47.8 at. pct), the remainder being iron. The resulting ingot was swaged above 850°C into 0.250-and 0.400-in.-diam rounds. Compression samples of 0.250 in. diam and 0.400 in. long were cut from the smaller-diameter rounds. These samples were then sealed in evacuated quartz tubes and annealed for 30 min at 1150°C to produce a uniform and equiaxed grain size of mean diameter equal to 1.73 mm. They in turn were rapidly quenched from 850°C so as to preserve the condition of random solid-solution characteristic of the elevated temperature. The samples were then aged for various times up to 300 hr at 500°C in a massive Pb-Bi alloy bath. The samples were next polished and tested in compression at room temperature as described in Ref. 6 using an Instron tensile testing machine. The strain rate used was 0.05 in. per in. per min. The remaining larger round was converted into compression specimens of 0.325 in. diam and 0.500 in. long. This larger diameter enabled wafers of sufficient size to be prepared for examination by trans-mission electron microscopy techniques after subjecting them to a suitable strain. Foil preparation is described in some detail in Ref. 6. All foils were examined in a type HU-11A Hitachi electron microscope operating at 100 kv. RESULTS AND DISCUSSION Fig. 1 shows the effect of aging at 500°C on the room-temperature stress-strain curves of the FeCr alloys. For greater clarity the origin of each curve has been displaced upward. The same origin has been used for both the 0 and the 0.1 curves. It is apparent that with increased aging times a sharp drop in load is observed at the yield stress which becomes more pronounced as aging proceeds. A loud sonic burst accompanies this drop and subsequent metallographic examination shows the sample to contain numerous twins. For intermediate aging times, a number of smaller twin bursts follow the initial large one. The total plastic strain associated with the twinning mode of deformation can be obtained by adding up the contributions AE~ from all i twin bursts, i.e., £,¦££,-, in the manner illustrated schematically in Fig. 2. The contraction of the specimen, as measured from the strip chart of the Instron, after suitably correcting for the elasticity of the machine, was converted into true strain using the assumption that there was no volume change and that the sample remained cylindrical. The dashed lines are all drawn parallel to the

Jan 1, 1970

By Fred Leighton

INTRODUCTION Dynamic (seismic or microseismic) methods of determining the stability of structures in rock are based on detecting and analyzing the characteristics of seismic energy that has originated from or traveled through the rock mass. This seismic energy can be in the form of naturally occurring rock noise energy resulting from structural adjustments within the rock or can be introduced into the structure by physical means, such as by blasting or impact. In either case, the seismic energy radiating through the rock mass can be detected using standard equipment and can be analyzed by established techniques to reveal a wide variety of information concerning the condition and stability of the rock mass through which the energy has traveled. In the following sections, the basic instrumentation required for seismic and microseismic studies is described, and some of the presently used applications of these methods are discussed to exemplify the state of the art. INSTRUMENTATION Seismic disturbances in a rock structure generate two types of seismic wave radiation, body waves and sometimes surface waves, which radiate outward in all direc¬tions from the source of the disturbance. Underground mining applications are generally concerned only with discerning the characteristics of the resulting body waves, i.e., the compressional (p-wave) and the shear (s-wave) energy. As these two forms of energy travel through the rock structure, the particles of the rock mass are caused to vibrate, and the vibration character¬istics resulting from each of the two types of wave are distinct. Some important differences are: 1) Compressional and shear waves travel at different velocities through the rock structure. 2) The frequency at which each wave causes particles to vibrate is different, and may range from about 50 to 100 000 Hz. 3) The amplitude or energy level of each wave is different, with the shear energy usually being the greatest. These differences form the basis for equipment se¬lection for individual studies and for modern data analysis techniques. The following sections describe the basic equipment necessary to detect and record seismic wave energy data and show several examples of analysis procedures and how these procedures have been used. In principle, seismic equipment is very simple. It consists of a geophone (or geophones) to detect the seismic energy vibration and convert that vibration to an electric signal, an amplification system to increase the level of that signal, and a means of monitoring and/or recording the signals detected. Fig. 1 is a block diagram of a typical system. The following sections offer a very brief discussion of system components and their individual functions. A more complete discussion is given by Blake, Leighton, and Duvall (1974). Geophones The function of the geophone is to detect the vibrations caused by the passing of the seismic wave energy and to convert that vibration into an electrical signal that displays both the amplitude and frequency characteristics of the vibration. Particle motion or vibration can be quantified and measured by measuring displacement, velocity, or acceleration of the particles. Thus, there are three types of geophones: displacement gages, velocity gages, and accelerometers. The choice of gage depends on the characteristic frequencies of the seismic energy to be monitored and the sensitivities of each type of geophone. In general, displacement gages are used for low-frequency monitoring (periods to 1.0 Hz), velocity gages for medium-frequency monitoring (1.0 to 250 Hz), and accelerometers for high-frequency monitoring (250 to 10 000+ Hz). Experience has shown that in underground studies, the choice of which gage to use lies between velocity gages and accelerometers. An easy, accurate method for selection of gage type is discussed by Blake, Leighton, and Duvall (1974). Once the type of geophone has been selected for use, it must be properly installed, and in the installation procedure the most important step is insuring that the gage is firmly attached to a competent portion of the rock structure. Poorly mounted geophones may entirely fail to recognize low-level seismic signals and will distort the information from signals they do see. Amplifiers Seismic events associated with mine structures occur over a very broad range of energy which results in a broad range of geophone output levels. In general, geophone output levels occur in the microvolt to low milli-volt range, and it is necessary to amplify these signals in order to drive recording or monitoring equipment. Because either an accelerometer or a velocity gage might be used as the geophone, the amplification system must

Jan 1, 1982

By Harry C. Swanson

TRANSPORTING concrete from mixer to forms has always been a problem. Twenty-five years ago this task was generally accomplished by means of wheelbarrow or concrete buggy. On large dam jobs, as the number of these projects increased, the gantry crane or highline came into use. Today several methods of handling concrete are employed on smaller surface construction jobs, for example, transit-mix trucks or dumpcrete trucks, which have crawler cranes with buckets for placing concrete into forms. In 1944, during early stages of developing Mather mine A shaft, several large underground concrete jobs were necessary. At this time the Cleveland-Cliffs Iron Co, purchased the first pump-crete machine, introduced by the Chain Belt Co. of Milwaukee. The machine was used to pour approximately 200 cu yd of concrete for a dam, or bulkhead, located 400 ft from the shaft. Concrete was mixed on surface, lowered down the shaft 1000 ft in a 2-cu yd bucket hung under one skip, spouted into the bowl of the pumpcrete machine from the bucket, and pumped directly into the forms. Since the day of the first pipeline concrete in 1944 to the present time, other equipment and other methods have been developed to permit transportation of concrete by pipeline through vertical and horizontal distances totaling 1 mile from mixer to forms. Much of the efficiency in present handling of underground concrete can be credited to the Bethlehem Cornwall mines, where concrete was transported through 6-in. pipe for great distances down an inclined shaft and along levels into forms.&apos; During initial development of Mather mine B shaft, with concrete work under way on two or more levels at one time, the pneumatic concrete placer, Fig. 1, was selected as best adapted for underground concrete transportation. The 3/4-cu yd pneumatic placer is a small machine readily moved from one location in the mine to another. It can be equipped with two sets of mine car wheels, which will permit moving on regular mine tracks. It is therefore possible to send concrete through the pipe at great velocity; the pipeline is clean after each shot except for the film of cement adhering to the inside. With the proper slump in the concrete, it is possible to shoot concrete 2000 ft with this machine, using the mine supply of compressed air at 95 psi. This equipment was first used at Mather mine B shaft to concrete slusher drifts, Figs. 2 and 3, and finger raises located about 2000 ft from the shaft. In several instances there were bends into crosscuts and up vertical distances into the forms. For the first pours two placers were used. The first was located near the shaft where the concrete could be spouted into it from a 2-cu yd concrete bucket on the cage. The second was set on the side of the drift at a point approximately 1500 ft from the shaft. The concrete was shot directly into the second placer from the first unit and from the second machine directly into the forms. After completion of several pours with the two machines, a trial pour with only one placer located at the shaft proved that the second placer could be eliminated. Since then all pours have been successfully completed with only one placer underground. As production of iron ore from the mine increased and the development program expanded, use of the cage for handling mine supplies and concrete became a major problem. This brought about the first attempt at shooting concrete vertically down the shaft for 2600 ft. A 6-in. pipeline with victaulic couplings installed during shaft sinking was used for the trial. One placer was set on surface 250 ft from the collar of the shaft so concrete could be spouted directly into it from the mixer. This machine shot the concrete 250 ft horizontally on surface to the shaft, 2600 ft vertically down the shaft, and 100 ft horizontally into the second placer located near the rib of the shaft station or plat. The second machine shot the batch into the forms, about 2000 ft. Total distance horizontally and vertically was 4800 ft. The entire time cycle for a ¾-cu yd batch of concrete from the mixer on surface to the forms underground totaled about 5 min. During the past two years the two-placer method from the mixer on surface to the forms underground has proved a very efficient means of transporting underground concrete. Advantages of using pipeline concrete are as follows: 1—Interference with normal mining operation is eliminated. When the cage, skips, mine cars, or mine openings are used for transporting concrete and materials used for making concrete, mine operation suffers in one way or another.

Jan 1, 1955

By L S. Shekhawat, M P. Roy, R K. Paswan, P K. Singh, A Joshi

Blasting in the mining industry is being transformed, and can no longer be treated as an art or a practice purely dependent upon experiences of individuals. Examples of key drivers that have demanded consistent and more accurate blast results are initiatives to control pit-wall damage to help mine steeper pit slope angles, to control damage to underground opening operating in close vicinity of the open pit mine. Such situation exists at Rampura Agucha open pit lead zinc mine, which is producing 5.7 Mt/a of ore and has started its underground part, which is slated to produce initially 2–2.4 Mt/a and 4.5 Mt/a in the near future. The open pit mine is currently working at 326 m depth and is designed to reach 421 m deep. It has been planned to operate the underground mine maintaining 50 m parting from the planned ultimate level of the open pit mine.Presently, open pit and underground mines are being operated simultaneously. The present average depth of underground working lies between 370 and 410 m below the surface level. Sometimes explosives up to 95 978 kg are being detonated in a blast round in open pit mine. These blasts are often apprehended as a danger to the safety and stability of underground openings. It was decided to document the impact of open pit blasting in the openings of underground workings, so that preventive measures may be taken for the safety and long-term stability of the underground mine. The impact of 86 open pit blasts has been documented in the underground openings and 258 blast vibration data has been recorded. The vibrations were recorded simultaneously in the roof, side walls and at floor levels. The highest levels of vibrations were recorded in the roof and the lowest levels at the corresponding floor levels. The pillars experienced lower level of vibrations than the roof. Blast designs were optimised at open pit mine to control vibration in view of long-term safety and stability of the underground openings. The vibrations generated due to detonation of explosives with shock tubes and electronic delay detonators have been recorded in underground openings for comparative assessment. Ground vibration recorded at roof, pillar and floor were analysed separately and threshold value of the vibration for the safety of underground workings has been determined based on the rock mass rating of the roof rock.CITATION:Singh, P K, Roy, M P, Paswan, R K, Shekhawat, L S and Joshi, A, 2015. Protection of underground mine structures due to adjoining open pit mine blasting, in Proceedings 11th International Symposium on Rock Fragmentation by Blasting, pp 279–288 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Aug 24, 2015

By Mohamad Omarei, S. M. Sadrameli

"The aim of this research work was to produce biodiesel (fatty acid methyl esters, FAME) from canola oil using KOH loaded on y-Al203 support as a heterogeneous catalyst. Different parameters such as effects of the molar ratio of methanol to oil, catalyst amount and reaction time on the yield were investigated. Scanning electron microscope (SEM) and X-ray diffraction (XRD) were used for characterization of the catalysts. A biodiesel yield of 86.67% was obtained under catalyst preparation and transesterification conditions of calcinations temperature of 773 K, 4 h of reaction time at 338 K, and using 3.5 wt% catalysts and molar ratio of methanol/oil of 15:1. The leaching of potassium species in the spent catalyst was observed.1. IntroductionBiodiesel is an eco-friendly and alternative energy source for diesel engines that can be synthesized by transesterfication of vegetable oil or animal fat with alcohols [1 ]. There are four principal approaches to the synthesis of biodiesel involving the transesterification of the triglycerides of the plant oils and animal fats: base catalysis [2], acid catalysis [3-5], employing supercritical alcohol conditions [6] and enzyme catalysis [7]. The commonly used homogeneous catalysts are NaOH, KOH and their alkoxides. Homogeneous alkali-catalyzed transesterification is much faster than acidcatalyzed transesterfication [8]. However, a large amount of water is required to transfer the catalysts from the organic phase to a water phase after the reaction. Therefore, it is considerably more costly to separate the catalyst from the produced solution [9]. These disadvantages could be removed by use of a heterogeneous catalyst [10]. The use of heterogeneous catalysts eliminates the neutralization step, hence it results much easier to separate from liquid products. Also, they can be designed to give a higher activity and selectivity and to have longer catalyst lifetimes [11]. A large number of different heterogeneous catalysts have been synthesized for biodiesel production. For example, calcined Mg-Al hydrotalcites [12], zeolite and metal catalysts [13], metal oxides such as calcium oxide (CaO) [14], magnesium oxide (MgO) [15], zirconium oxide (Zr02) [16], and supported catalysts [17] have been investigated as heterogeneous catalysts. CaO and MgO are most frequently used heterogeneous catalysts for biodiesel production [18]. In this present work, we aimed at developing an efficient catalyst for transesterification of canola oil. We have prepared KOH/ Al203 by impregnation and applied to determine the optimum conditions for biodiesel production. Three different variables including reaction time , alcohol to oil molar ratio and catalyst loading with may influence the quality of the produced biodiesel were optimized. Moreover, SEM (scan electron microscope), XRD (X-ray diffraction) and XRF were used for characterization of the catalysts."

Jan 1, 2012