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By Carl Wagner

This paper contains solutions of the differential equation of diffusion in binary alloys if the diffusion coefficient is an exponential function of the concentration of one of the components. THE general differential equation for one-dimensional diffusion in a binary system can be written as: where c is the concentration of one of the two components in any suitable units; x, the distance from a reference plane; t, time; and D, the diffusion coefficient. Hartley and Crank&apos; have pointed out that eq 1 with conventional length units for measuring the distance x holds only if the alloy can be regarded as a rigid framework. In general, this is not the case, especially if the lattice parameter varies appreciably with composition. If a modified coordinate system is used instead of an orthodox system based on the centimeter a:: length unit, eq 52 is obtained, which has the same general form as eq 1 and is generally valid. The necessary transformations are presented in the appendix. If&apos; D is independent of concentration, analytical solutions of eq 1 are known for numerous boundary conditions. If D depends on concentration, solutions based on known analytical functions are not available. Among others, Boltzmann2 and Matano3 have shown that the concentration c depends only on (x/t1/2) in the case of diffusion between two semi- infinite spaces with uniform initial concentrations: c = c, for x < 0, t = 0, i.e., x/tl/2 = — x [21] c = c2 for x > 0, t = 0, i.e., x/tl/2 = + a Moreover, Boltzmann and Matano have shown how D may be calculated as a function of concentration over the whole range of composition from c -c, to c = c2 if c as a function of (x/t1/2) for the initial conditions stated in eq 2 has been determined experimentally. Thus, for instance, in principle, the diffusion coefficient in silver-gold alloys may be calculated as a function of concentration for the whole range of composition from only one diffusion experiment with a couple of pure silver and pure gold welded together. If the diffusion coefficient D as a function of concentration c is known, a solution of eq 1 for boundary conditions as stated in eq 2 with arbitrarily chosen values of c, and C2 may be wanted. For instance, if the diffusion coefficient in an alloy A-B as a function of concentration has been derived from an experiment with a diffusion couple involving 0 and 30 pct B as initial. concentrations, the calculation of the concentration distribution in a diffusion couple involving other initial concentrations, e.g., 5 and 20 pct B, may be desired. This problem may be solved by numerical or graphical integration of eq l. The solution of an ordinary differential equation of second order, which results from using (x/t1/2) as an independent variable, can be computed quite rapidly if two conditions for the same value of the independent variable are given. In eq 2, however, two conditions are given for two

Jan 1, 1953

By D. M. Blacknall, N. N. Winogradoff, E. W. Williams

Low-temperature measurements of photolumines-cence were used to evaluate the progvess in materials development. Variation of the impurity type, impurity concentration, and method of growth were used to clarify the chemical origin of defects in GaAs. Melt-g~ozun, epitaxial vapor-, and solution-grown samples were studied. A comparison of measurements at 77" and 20°K shows that more defects can be observed at the lower temperature. Th&apos;vee residual defects were identified in relatively pure GaAs. These were: silicon, copper, and a gallium vacancy-donor complex. Solution growth from a gallium solution inhibits the formation of the latter two. Eleven defects were studied and the "optical" activation energy of some of these, namely, silicon, cobalt, and chromium, has not been reported in the literature before. THE discovery of the injection laser in 1962 prompted extensive measurements of the photoluminescence of GaAs. The measurements were made at 77°K on GaAs doped with shallow impurities at various doping levels and compared with electroluminescence1&apos;2 and absorp- tion data.374 In addition, lower-temperature studies were made on relatively pure GaAS&apos; and on GaAs doped with oxygen,5&apos;" manganese,&apos; and copper.&apos; The observation of defects* in GaAs with photolu- *The word "defects" ~efers to both chemical impurities and native defects. minescence at low temperatures makes photolu mines-cence an invaluable tool in evaluating the progress in materials development. The only previous evaluation was done at 77°K when solution-grown and melt-grown GaAs were compared.O No identification of defects was made but it was shown that some of the deep-level luminescence seen in melt-grown GaAs was absent in solution-grown GaAs. The present work extends the comparison of preparation techniques to lower temperatures and to a study of epitaxial vapor-grown GaAs. It is particularly valuable for thin epitaxial layers since they cannot be analyzed by conventional analytical techniques. In addition, by varying the impurity type and impurity concentration the chemical origin and nature of defects in GaAs was demonstrated. Eleven defects were studied in all. Three of the defects were identified as residual defects which often contaminate GaAs prepared from the melt and the vapor. Only one such defect was observed in GaAs grown from a gallium solution and this was identified as silicon.

Jan 1, 1968

By Robert G. Nisle

The classic theory of pressure build-up in shut-in oil wells as developed by Horner and van Everdingen is based on two-dimensional radial symmetry in the well-reservoir system. Such symmetry does not exist in the case of a well which parfiially penetrates the producing formation. As a result of this lack of symmetry the use of the classic theory in such cases become questionable. In this paper the mathematical theory has been extended to include the case of partially penetrating wells. Numerical solutions illustrating the up-dication of the equations are presented. The effect of partial penetration on pressure build-up is shown by a comparison of synthetic pressure build-up curves derived from the numerical solution of the equation for partially penetrating wells for various degrees of penetration. It is shown that partial penetration is detectable from the characteristic shape of the pressure build-up curve and that formation productivity may be calculated from the pressure buildup data in a manner identical to that described by the classic theory. INTRO DUCTION The use of pressure build-up data on shut-in oil wells is a well-established technique for the measurement of reservoir productivity. The work of Homer&apos; and van Everdingen&apos; is well known. Since the publication of their pioneering work, others"&apos; have elaborated and extended the technique. These authors have dealt exclusively with the case of wells that completely penetrate he producing formation. Two-dimensional radial symmetry is achieved, thereby, and the problem is greatly simplified. This ideal situation is seldom encountered in practice. But, in spite of this, the technique is often employed anyway. The question, therefore, arises: how much confidence can be placed in the results of such calculations when the data are taken on wells that only partially penetrate the producing formation? It is the purpose of this work to answer this question. Only the single-phase fluid case will be considered. van Everdigen&apos; has presented a rigorous solution of the two-dimensional case, but because of mathematical complexity, this solution has not proved to be particularly useful. Horner&apos; utilized Kelvin&apos;s point source solution in two dimensions and showed that it is a sufficiently good approximation for oil reservoir studies. The geometry of the well and the producing formation is illustrated in Fig. l. Geometrically the formation may be described as an infinite slab. The infinite slab is defined as the solid (the porous medium in this case) bounded by two parallel planes. Thus, the slab extends to very great distances in both the positive and negative directions of two of the coordinate axes, but is finite in

By R. E. Hanneman, A. N. Mariano

In conjunction with the need for accurate volumetric data in the Fe-V system for subsequent use in calculating the high-pressure diagrams, room- and high-temperature X-ray diffraction measurements have been carried out. No previous measurements have been published on lattice parameters or volume changes associated with the a transformation for Fe-V alloys. The existing literature on lattice-parameter data for the a and s phases has been reviewed by pearson1 with considerable uncertainty indicated in the data. In order to obtain a good estimate of ?Va-? for thermodynamic calculations of the a D ?(bee D fee) phase stability, high-temperature vacuum X-ray diffraction measurements were made on an Fe-V alloy of 0.92 wt pet V. The term ?Va-? is the difference of molar volumes of the limiting solubilities of the a and y phases at any given temperature; these values can be calculated readily from the appropriate lattice-parameter data. The equipment used was a commercially available MRC (Materials Research Corp.) high-temperature X-ray camera which was fitted to a Norelco diffractometer

Jan 1, 1964

By Jr. Baldwin. William M

WELL known to every metallurgist is the fact that different production schedules will profoundly affect the character of annealed metal strip. Yet the number of conditions [ ] that may be wrought by different combinations of rolling and annealing schedules is so myriad that despite the continual research that is being applied to this subject, the complete picture is not yet known. Copper, like all other metals, during the process of rolling or annealing, develops certain crystallographic configurations which should not be dismissed as being too impractical, for the crystallographic condition existing within the metal is a principal influence upon both the external mechanical properties and the behavior of the material [ ] when it is subjected to such operations as bending, flanging, drawing, and so forth. EFFECT OF ROLLING AND ANNEALING UPON THE CRYSTALLOGRAPHY OF COPPER STRIP The most salient points in the crystallographic reactions of polycrystalline copper to rolling and annealing may be best represented graphically by a "map" such as that given in Fig. I. I. As copper strip is cold-rolled from a randomly oriented structure (pole figure I),

Jan 1, 1942

By A. V. Henry

THE kaolins of the southeastern United States were known to civiliza-tion as early as the latter part of the eighteenth century-and yet the Fig. 1.-KAOLIN PRODUCTION AND IMPORTS. commercial history of Georgia kaolins may be said to begin in the year 1900. The U. S. Bureau of Mines reported for that year a production of 6885 tons of "miscellaneous" clays in Georgia. A comparison of these figures with those of 1934, when the production rose to 284,556 tons (65 per cent of the domestic production), indicates the growing economic and technologic importance of this raw material. Fig. 1 clearly shows that a part of the increase is due to a normal growth in the use of kaolinitic clays and a part is due to replacement of clays formerly imported.

Jan 1, 1937

By Jerry M. Thornton, Richard W. Cannon, Don C. Rotherham

This paper attempts to show the role of induced polarization (IP) and resistivity surveys in the discovery of the ore bodies of Gibraltar Mines Ltd. (N.P.L.) and the importance of conducting large enough surveys to properly evaluate the results. The first IP survey was conducted in the area in 1963. This survey was extended and other IP surveys were added to it for the next seven years. The data from these surveys was finally combined to produce four large scale plan maps of resistivity and percent frequency effect (PFE) results (N = 1 and 3). A halo-type anomalous zone 6000 ft wide and 14,000 ft long was thus outlined in the PFE maps. The four ore bodies of Gibraltar Mines were found to occur along the inside rim of this IP halo.

Jan 1, 1973

By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton&apos; reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler&apos; stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

By A. L. Jr. Pozzi, A. O. Garder, D. W. Peaceman

A new numerical method is proposed for the solution of multidimensional miscible displacement problems. Besides the usual stationary grid associated with numerical procedures, the method uses moving points for which positions and concentrations are computed each time step. Based on the method of characteristics for treating combined transport and dispersion, the method applies equally well to any number of dimensions and, in contrast with other numerical procedures, properly takes into account the physical dispersion, no matter how small. Extensive tests show that accurate solutions of one-dimensional problems can be obtained over a wide range of values of the dispersion coefficient, including zero. They also show that the moving points do not need to be uniformly spaced, and that increasing the number of moving points beyond 2/grid interval does not significantly improve the accuracy of the solution. Two-dimmsional calculations using the new method were carried out to simulate laboratory model displacements in which gravity caused overriding of solvent. Good agreement between observed and computed profiles and measured and computed concentrations of produced fluid was obtained for a viscosity ratio of 1.89; at higher viscosity ratios, fair agreement was obtained Computed results were found to be significantly affected by vertical dispersion, and negligibly affected by dispersion in the direction of flow, in agreement with conclusions based on experimental observations. INTRODUCTION Although miscible displacement processes are potentially of great economic significance, limited progress has been made in developing mathematical methods for predicting the outcome of a solvent flood. Because of the complexity of the partial differential equations which describe multidimensional miscible displacement, numerical methods are a natural approach to their solution. The task of finding suitable numerical approximations to one of the partial differential equations, which involves both dispersion and convective transport, has been particularly difficult. Dispersion in the absence of transport is described by the heat flow equation, a second-order equation of parabolic type. This equation has been very successfully treated by numerical methods. Transport in the absence of dispersion is described by a first-order equation of hyperbolic type. This equation has been treated numerically with some success in one dimension, both by Lagrangian and Eulerian techniques, 1.2 but extension to two or more dimensions has not been satisfactorily accomplished. Usually one of two things happens: either the numerical solution develops oscillations or it becomes smeared by artificial dispersion resulting from the numerical process. When transport and dispersion are considered simultaneously, this numerical dispersion may dominate the low physical dispersivicy that generally characterizes miscible displacement. Stone and Brian2 have developed a new difference equation for treating combined transport and dispersion in one dimension. By suitable choice of certain parameters, they succeeded in markedly reducing both oscillation and numerical dispersion. However, a satisfactory extension to higher dimensions has not yet been found. Peaceman and Rachford3 presented a centered-in-time and centered-in-distance difference equation combined with a 1,transfer of overshoot" procedure which was demonstrated to work well in one dimension. The technique was applied to the two-dimensional miscible displacement problem, but subsequent calculations with zero dispersivity showed little change in results compared with the calculations they presented. This indicates that their method involved a numerical dispersion of the same order as the physical dispersion. The present paper describes an alternate method for solving the combined transport-dispersion

Jan 1, 1965

Prof. J. W. Richards, South Bethlehem, Pa. (in reply to several questions):—The cut representing some of the round briquettes which were under test shows that, at the brcaking-stresses, they break into lumps, and do not disintegrate into powder. The process is simplicity itself. I have followed the different processes for sintering iron-ores and flue-dust, am interested in all of them and wish them all success; but this process appealed to me strongly by its simplicity. It is in line with a method which I once tried to work out myself, but which never came to anything, namely, the agglomeration of fine iron-ores by means of Portland cement. As small an amount as 5 or 6 per cent. of Portland cement will enable fine ore to agglomerate and set into a briquette, but when I came to estimate the cost, I found it was a little too high. The Schumacher process, curiously enough, does not work well on iron-ore, but flue-dust thus treated does harden and give a strong briquette. In my attempts to find a reason for this difference, it has occurred to me that possibly the particles of flue-dust had been coated over with some sublimed silica, which might be an agent in the setting. But I found by experiment that neither sublimed silica, nor ordinary silica, nor ordinary alumina, would briquette. Chemically pure iron oxide briquetted quite hard; but the application of pressure is a necessary part of the operation. If simply moistened with the solution and allowed to stand it does not set hard, but the more pressure applied to it the hardcr it sets. Evidently the flue-dust particles must be pressed very close together in order to get the small proportion of active material wet, so that the particles shall act at their points of contact; for it is evident that only at the points of contact does the cementing action take place. The reactions are facilitated by considerable pressure, bringing the acting particles close together, and may go on with

Jan 1, 1913

By Lester Tarnopol, Ralph Hultgren

A considerable interest in the subject of superlattices has been manifested by many papers and reviews that have recently appeared, both in physical and metallurgical publications. This interest is due largely to the apparent simplicity of the ordering process, which permits the explanation of many phenomena on the basis of elementary theory. Moreover, ordering may cause important changes in the physical properties of alloys. In this paper, we shall discuss the causes of superlattices in terms of simple properties of the elements that give rise to them, together with a series of experiments performed to test our conclusions. Evidence is presented that in some cases the process of ordering is more complex than might be supposed. While the different species of atoms are usually found in random positions in alloy lattices, in some cases unlike atoms tend to be nearest neighbors. Bethe&apos;s1 "order of neighbors" is a statistical measure of thib tendency. At suitable compositions it is possible for atoms in large regions to be regularly arranged, which causes superlattice lines to appear. in X-ray diffraction patterns. Bragg and Williams2 haw dealt with this "long-distance order" in their fundamental work 011 superlattices. Excellent discussions of superlattices are to be found in current reviews TheRmodynamic Considerations Thcrmal vibration tends to destroy order. The magnitude of the effect can be determined from the entropy of mixing, which is calculate from first principles. Since the ordered state has the lower entropy, it must also have a lower internal energy to be stable at any temperature. The difference in internal energy determines the critical temperature at which long-distance order disappears. According to the, theory of Bragg and Williams,~

Jan 1, 1939

By Lester Tarnopol, Ralph Hultgren

A considerable interest in the subject of superlattices has been manifested by many papers and reviews that have recently appeared, both in physical and metallurgical publications. This interest is due largely to the apparent simplicity of the ordering process, which permits the explanation of many phenomena on the basis of elementary theory. Moreover, ordering may cause important changes in the physical properties of alloys. In this paper, we shall discuss the causes of superlattices in terms of simple properties of the elements that give rise to them, together with a series of experiments performed to test our conclusions. Evidence is presented that in some cases the process of ordering is more complex than might be supposed. While the different species of atoms are usually found in random positions in alloy lattices, in some cases unlike atoms tend to be nearest neighbors. Bethe&apos;s1 "order of neighbors" is a statistical measure of thib tendency. At suitable compositions it is possible for atoms in large regions to be regularly arranged, which causes superlattice lines to appear. in X-ray diffraction patterns. Bragg and Williams2 haw dealt with this "long-distance order" in their fundamental work 011 superlattices. Excellent discussions of superlattices are to be found in current reviews TheRmodynamic Considerations Thcrmal vibration tends to destroy order. The magnitude of the effect can be determined from the entropy of mixing, which is calculate from first principles. Since the ordered state has the lower entropy, it must also have a lower internal energy to be stable at any temperature. The difference in internal energy determines the critical temperature at which long-distance order disappears. According to the, theory of Bragg and Williams,~

Jan 1, 1939

By F. Wartenweiler

Much has been written on milling and cyanidation as practiced on this gold field, therefore the purpose of this paper is to record its development only briefly and to describe in more detail the contemporary state of the science and art of this branch of metallurgy. It is a pleasing task, because a steady evolution is to be recorded. Definite trends influenced the development. Some have the stamp of original thought and observation; many have been achieved from a logical sequence of planned experimentation and research; while others have resulted from the drive of sheer necessity. The large scale of operations and capital outlay has compelled conservative progress. Banket ORe For a better understanding, a review of the characteristics of the ore may not be out of place. The Witwatersrand gold ore is named "banket" from the similarity of the oxidized outcrop ore to the Boer almond cake of that name. The inter bedded orebody is commonly called "reef." It is a conglomerate composed of various sizes of pebbles, principally non-gold-bearing white quartz, which constitute about 70 per cent of the bulk, within a matrix of cementing material consisting of fine-grained quartz, sericite, chlorite and chloritoid and containing the precious metals and mineral sulfides. Argillaceous components in the mil pulp may be as high as 32 per cent. Of the sulfide minerals, pyrite and pyrrhotite are predominant. Most base-metal sulfides are present, but sporadically and generally only found in highly concentrated mill products. In the latter, osmiridium is recovered in varying amounts; from 1 oz. in 3000 tons to 1 oz. in 10,000 tons of ore. Most of the oxidized ore has been mined, so milling is confined principally to the sulfide ore. A typical analysis of sulfide ore is: silica (SiO2), 86.76 per cent; pyritc (FeS2), 2.75; ferric oxide (Fe2o3), 2.65; alumina (Al2o3), 6.91; lime (CaO), tr.; magnesia (MgO), 0.70; sp. gr., 2.7. Milling grade at present price of gold (137 shillings per ounce) varies from 3.5 to 8.5 dwt., with one mine milling ore as high as 16 dwt. The

Jan 1, 1935

By E. G. Banks

This paper is presented in the belief that metallurgists and chemists will be interested in the practice of grinding in tube-mills in connection with stamps, especially since the records of working here given extend over a lengthy period of time (since May, 1905). The ore from the Waihi mine—more especially that produced in the upper levels—contains a large proportion of hard, chalce-donic quartz, and the gold exists in an exceedingly fine state, conditions which necessitate very fine crushing in order to obtain a high extraction of the precious metal. Before the introduction of tube-mills at the 90-stamp Waihi mill, it was found necessary to stamp through 40-mesh (1,600 holes per sq. in.) woven wire-screens, having a fairly high discharge. The pulp then graded : Per Cent. Per Cent. On 50-mes11, .- 0.1 On l20-mesh ..8.77 On 60-mesh, . 8-74 On 150-mesh,.... 7.48 On 80-mesh,... 16.06 Passed 150-mesh,... 55.19 On 100-mesh,.... 3.66 The stamp-dnty was 2.89 short tons per stamp per day, or a total of 260 tons daily. Although the extraction on this pulp was: gold, from 88 to 90 per cent., and silver, from 74 to 78 per cent., it was recognized that finer grinding of the sands would prove beneficial, provided a machine could be found to do this work economically. Various grinding-mills and pans were tried, but without satisfactory results, the particles of sand being so hard that the capacity of any of the machines was too small to be economical. The results of grinding in tube-mills in other countries were so satisfactory that three tube-mills mere erected at the Waihi

Jan 1, 1908

By C. Wert, D. Keefer

The results of this study indicate that sudden increases in aging temperature lead to reversion phenmena in carbon in the a, iron system. These phenomena are thought to be associated with the dissolution of carbide precipitates. Reversion is studied with respect to three variables: 1) Specimen grain size, 2) the initial amount of carbon in solution, and 3) difference between initial and final aging temperature. It is found that of these variables the initial carbon concentration has the greatest effect on reversion. THE solid solution of carbon in n iron has been the subject of numerous investigations throughout the past few years. Despite the great amount of effort which has been put forth toward understanding this system, however, there persist a number of interesting aspects of the system which are open to further research&apos; Studies Of the precipitate which forms as a result of aging a supersaturated solution of carbon in a, iron appear to be particularly interesting. The present work is an attempt to determine certain

Jan 1, 1960

(Butte Meeting, August, 1913.) IN metallurgical circle it is. known widely, but somewhat vaguely, that the ease of reduction of metallic .oxides. depends largely on the way they have been prepared. It is likewise known that. different forms of carbon have different and greatly varying reducing powers. It is the purpose of, this paper to show somewhat more definitely and scientifically these facts. Sonic years ago the writer published an account of pyrometric determinations of the reduction temperature of zinc oxides variously prepared and of several kinds.1 In said paper it was shown that the temperature at which zinc oxide evolves zinc according to the equation, ZnO+C? Zn+CO depends upon the nature of -the two reacting bodies. The determinations bad a range of accuracy of from 2°to 6°C.,whereas differences were found to, amount to an extreme of 90° C. So the differences are real ones and must have a definite cause. The equation of boiling water, (H2 O)4 = 4 (H20) has a fixed temperature for? equilibrium of 100° C. at 760 mm. pressure. In general, all equations reacting in the liquid or the gaseous phase have well-defined constant physical conditions which govern the equilibrium point and reaction velocities.

Jan 7, 1913

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös&apos; law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By R. J. Quigg, G. S. Doble

Commercial stress -relieved TD Nickel bar was shown to retain room- and elevated-temperature tensile strength after exposure up to 2501°F. Cold swaging increased both room -temperature and 2000°F tensile strength. After annealing at 2500°F the strengthening due to swaging was retained at 2000°F hilt eliminated at room temperature. Annealing produced changes in hardness and X-ray half peak width indicating the presence of recovery processes as 1071° as 1000°F but no recrystallization of swaged material was noted at any temperature. In contrast to swaging, rolling induced a recrystal-lized structure after annealing. The tensile strength of this recrystallized structure was comparable to the cold-worked condition. High-temperature tensile properties of as -received bar were highly anisotropic with the transverse tensile strength being one fifth the longitudinal value. The aniso-/ropy is affected by working direction and may he partially reversed by changing the direction of metal flow. The divergence in tensile strength, beginning above 550°F or- approximate one third the absolute melting point, is strain-rate dependent. T D Nickel is a commercial dispersion-hardened alloy containing 2 vol pct thoria. The dispersion, consisting of spherical particles 0.030 to 0.050 in diameter with an interparticle spacing of less than 1 is reported to maintain stable properties up to 2400°F.1 This stability of second phase results in maintenance of elevated-temperature strength at higher temperatures and longer times than normal nickel-base superalloys.2 The purpose of this paper is to describe the effect of various mechanical working operations on the strength and microstructural stability of TD Nickel bar. MATERIAL AND PROCEDURES All material used in this study was commercial TD Nickel bar. This material is produced by a chemical process which results in a nickel powder containing a dispersion of thoria particles. The powder is then pressed, sintered, extruded, and subsequently worked to bar stock. Three starting materials from three separate lots were used: as-extruded bar. 1-in.-diam stress-relieved bar, and 1/2-in.-diam stress-relieved bar. Since TD Nickel bar stock is cold-worked without a recrystalliza-tion anneal, the accumulated deformation or degree of cold work in these materials increases as the bar diameter decreases. Some of the 1/2-in.-diam bar was swaged to 1/4 in. diameter at room temperature in order to produce an as-worked condition for comparison with the stress-relieved stock. Tensile testing was performed on an Instron Tensile Tester at a constant crosshead speed of 0.020 in. per min. The 0.2 pct offset yield strength was measured from the load-crosshead movement plot. Specimen gage dimensions were 0.080 in. in diameter by 0.40 in. in length, producing a strain rate of approximately 0.050 min-1. Specimens were tested in air and heated within a resistance-wound furnace controlled to ±5°F. A 15-min soak at temperature was employed before testing. Samples were heat-treated in air and specimens machined after exposure with sufficient material removed to eliminate any surface contamination. X-ray line breadth was determined from a diffractometer scan of a transverse face of a bar using copper K, radiation. Metallographic preparation utilized standard mechanical polishing with Carapella&apos;s etch. Specimens for electron microscopy were electropolished in a 1:7 sulfuric/methaol solution and chromium-shadowed collodion replicas prepared. RESULTS AND DISCUSSION I) Effect of Elevated-Temperature Exposure on the properties of TD Nickel. The effect of various elevated-temperature exposures on the room-temperature tensile strength of TD Nickel is shown in Table I. In the unexposed condition the tensile strength, reduction in area, and hardness all increase with increasing accumulated deformation while the elongation decreases. After exposure at 2500°F the strength of all three materials decreases to about 65,000 psi and the elongations increase slightly. The apparent increase in strength of the 1-in. bar after a 2000°F treatment is probably experimental scatter. These results indicate that the room-temperature strengthening due to additional deformation is annealed out upon elevated-temperature exposure. In contrast to the room-temperature data, the 2000°F tensile strengths increase in order of increasing deformation even after exposure. Although some loss of strength occurs after exposure, much of the effect of working is still maintained at 2000°F. The room-temperature hardness after various

Jan 1, 1965

By Raymond D. Daniels, Frank E. Rizzo, James D. Gerber

ThIS discussion describes a method for the addition of small amounts of oxygen to columbium (niobium) in an accurate and reproducible manner. The method is based on the complete reduction by columbium of a carefully weighed amount of another metal oxide. The equilibrium Pq associated with Cb-CbO mixtures is extremely low, e.g., 10"25 atm at 100O°C, and the pressures over Cb-0 solutions are even lower. The equilibrium Pq associated with a given metal-metal oxide mixture can be easily obtained, with the aid of a Richardson-Jeffes chart.&apos; Although columbium should effectively reduce almost any metal-metal oxide combination, the proper choice of a metal-metal oxide system is complicated by the low rate of oxygen transport in the gas phase at low oxygen pressures and the difficulty in reducing any columbium suboxide formed during the reduction of the oxygen source material. Thermodynamically, oxide formation on columbium will be avoided so long as the oxygen partial pressure over the columbium is below the equilibrium pressure associated with the mixture Cb-CbO. The logical choice of a source for oxygen would appear to be a mixture of Cb-CbO, since oxide formation would be precluded by nucleation difficulty. But calculations using the kinetic theory of gasses indicate that, for a temperature of 900°C, the reaction would proceed too JAMES D. GERBER, formerly Research Assistant, University of Oklahoma, Norman, Okla., is Research Metallurgist, Air Force Weapons Test Laboratory, Kirtland Air Force Base, N. Mex. FRANK E. RIZZO, Junior Member AIME, formerly Assistant Professor of Metallurgy, University of Oklahoma, is Associate Professor of Metallurgy, University of Texas at El Paso, El Paso, Tex. RAYMOND D. DANIELS, Member AIME, Professor of Metallurgical Engineering, University of Oklahoma, is an NSF Fellow, Institute de MBtallurgie Structurale, Universite de euch:tel, Neuchitel, Switzerland. Manuscript submitted October 28, 1968. IMD

Jan 1, 1970

By A. A. Bauer, H. A. Saller, F. A. Rough, J. R. Doig

among uranium alloy systems are the U-Zr, U-Ti,and U-Mo binary systems, in that an intermediate phase, of limited solubility range, exists in each system. These intermediate phase alloys offer a promising field of investigation, both as binary alloys and as ternary alloy combinations. While a limited amount of work has been done on the binary alloys, none has been done on ternary combinations of these alloys. As a possible prelude to more intensive investigation of these systems, a study of the phase relationships between the 6 phases of the U-Zr and U-Ti systems was undertaken. The solid-state portions of the binary constitutional diagrams for the U-Ti,1 Zr-Ti,2 and U-Zr3 systems are shown in Fig. 1. The solid to liquid transformations are not shown, as these transformations were not studied in the ternary system. The phase designations employed are based upon those shown in the uranium constitutional diagrams. The crystal structures of the various phases are given in Table I. Experimental Materials and Methods The ternary section presented is based upon the results of thermal, metallographic, and X-ray analyses of a series of alloys ranging in composition between the phases of the U-Zr and U-Ti systems (U-74 atomic pct Zr to U-35 atomic pct Ti). After preparation of the alloys, thermal data were obtained. On the basis of these data, specimens were heat treated and examined metallographically. Specimens were then selected from those heat treated for X-ray determination of the phases present in what were considered critical phase regions. Alloy and Specimen Preparation—Alloys for this investigation were prepared from selected as-reduced uranium and crystal-bar zirconium and titanium. For nominal compositions, see Table 11. Charges were arc melted from five to seven times under a helium atmosphere, finally being cast into wire-bar form for fabrication. A zirconium getter button was used to clean the furnace atmosphere prior to melting. The alloys were homogenized 20 hr at 900 °C and furnace cooled. A portion of each bar was then removed for thermal analysis; the remainder was saved for fabrication. Alloys 8 through 14 were placed in steel tubes along with zirconium getter chips and, after flushing with argon, the tubes were welded shut and rolled at 1500 °F to a 50 pct reduction in diam. The remaining alloys were annealed 24 hr at ll00°F to insure transformation of the ? phase to the 8-U2Ti phase and were then hot rolled from a salt bath. Attempts to roll alloys 6 and 7 at 1100 °F were unsuccessful. Following this, attempts were made to roll pieces of alloys 1 through 5, which had cracked rather severely during casting, at 1200 °F, but these efforts were also unsuccessful. These alloys were, therefore, further treated in their cast and homogenized condition. All alloys were pickled to remove oxide formed during rolling. Thermal data were obtained on these alloys by conventional differential thermal analysis at a heating rate of 30C per min, and by a high-speed heating method at rates of approximately 10°C per sec. For the latter method of analysis, a 36-gage Chromel-Alumel thermocouple is spot welded between two slivers of alloy, the sandwich being en-

Jan 1, 1958