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By Heinz W. Duddeck, Hans-Konstantin Nipp

The design of storage space or deep mining in rock salt should take into account not only time dependency of the rock salt behavior but also temperature effects. For deep mining of potassium salt the natural increase of temperature with depth may no longer be negligible. For the storage of cryogenic liquid gas in salt caverns more knowledge is nezded about the propagation of deep temperatures and their effects on the stress-strain-creep behavior of the surrounding salt. High temperature problems arise for nuclear waste storages in caverns or drill holes emitting radiation. A numerical model is proposed for the analysis of displacements and stresses including their time and temperature induced change. For the material behavior of salt constitutive equations are chosen composed of a combination of Hooke-Kelvin-Bingham-Newton-model based on experimental results (excluding at present deep cooling), Langer 1980. The parameters involved are depending on the stress level and the temperature. The finite-element-method is applied to rotationally symmetrical three-dimensional problems. The non-linear calculation method is based on an implicit method with respect to time. A modified Newton-Raphson-method and the initial strain approach are employed. Along with some experiences on suitable numerical procedures, examples are shown for the characteristical effects of time-temperature dependency. Having achieved convergency and reliability a method is now available for practical design and parametric sensibility studies.

Jan 1, 1982

By H. C. Casey, M. B. Panish

The roles of the phase diagram and the diffusion and solubility analyses in the selection of sources for the diffusion of zinc into GaAs are discussed. Isothermal sections of- the phase diagram are described at 1000°, 775°, 744°, and 700°. Below 744° the three solid phases, Zn3As2, GaAs, and ZnAsz, may be in equilibrium. In the composition regions where the three solid phases are in equilibrium, the partial pressures of the components do not vary with composition and there is no liquid phase. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected to yield reproducible diffusion profiles without surface damage. The 5/50/45 ternary source Provides a significant improvement in the reproducibility and planarity of- the zinc diffusion as compared with other zinc diffusion sources that result from starting with elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. Several experimental diffision profiles for the 5/50/45 diffusion source have been determined. The profiles are very steep in the region of the junction and produce devices that exhibit step junction behavior. The junction depth varies as the square root of time. Diffusion at 700°C for 4 hr gives a 5-µ junction depth and a surface concentration of 2.4 x1020 cm-3. The surface concentration is enhanced by a factor of three and the junction depth decreased by a factor of ten as compared with diffusion with a starting source 01- elemental zinc. The differences in dijyusion behavior with these two sources are due primarily to the approximately 10' greater equilibrium As4 partial pressure for the 5/50/45 source. ThE most common technique for the preparation of GaAs p-n junctions for diverse applications ranging from switching diodes to injection lasers has been to diffuse zinc into the solid from the vapor phase. The zinc impurity has generally been provided by introducing into a diffusion ampoule elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. For the purpose of eliminating surface deterioration, zinc has been diffused into GaAs through SiO2 films1 and from zinc-doped SiO2 films.2 During a study of the injection and recombination mechanisms in GaAs junctions, we found that these diffusion techniques either resulted in nonreproducible diffusion profiles and nonplanar junction interfaces or were extremely inconvenient to use. An unpublished report by Allen and pearson3 emphasized that an understanding of diffusion requires relating the diffusion conditions and system compositions to the ternary phase diagram. Recent studies have made it possible to relate the effect of starting source composition on the GaAs sample surface and diffusion profile reproducibility and, in addition, to estimate the expected surface concentration and zinc diffusivity. These studies include the Ga-As-Zn phase diagram,415 the determination of the incorporation reaction for zinc as a substitutional impurity,6 and the analysis of the concentration dependence of the diffusion coefficient.' In this paper the role of the phase diagram in the selection of the starting diffusion source composition is illustrated, and an application of the diffusion and solubility analyses is used to demonstrate their utility in the estimation of surface concentration and diffusivity for various starting source compositions. Consideration of the isothermal sections of the ternary phase diagram shows that below about 744° C a composition region exists where the three solid phases Zn3As2, GaAs, and ZnAs2 are in equilibrium without a liquid phase. In this region the partial pressures of the components do not vary with composition, and thus the surface concentration and diffusivity depend only on temperature. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected. As will be described in detail, this diffusion source yields reproducible diffusion profiles without surface damage, planar junction interfaces, and steep profiles that result in devices with step junction behavior. Only closed diffusion systems are considered. Open or flowing vapor systems require the maintaining of constant vapor pressures in the flowing gas and represent control problems outside the scope of this discussion.

Jan 1, 1969

By J. C. Martin

A theoretical analysis of steam stimulation is presented for single sands. The analysis includes the effect of steam production and most of the effects of heat conduction. The results show the effects of a number of important variables on the performance of an idealized well under steam stimulation. Calculated responses are presented which indicate the effects of steam production, amount of steam injected, water production, formation thickness and formation damage. Results indicate that steam production can cause large reductions in the heat contained in the formation. This effect can be eliminated by drawdown control. Water production reduces the amount of oil produced during stimulation. The optimum amount of steam to inject depends on economic factors as well as the well response. In many cases, the increased temperature resulting from stimulation reduces oil viscosity near the well sufficiently to overcome the effects of formation damage even if the damage is not removed during steam injection. Calculated responses for thin sands are more favorable than anticipated. INTRODUCTION Little has been published on the theory of steam stimulation'-' despite the interest it has created and the wide variation in well responses. The results of the present analysis provide an insight into steam stimulation, and the methods employed provide a foundation for future work. Analyses presented in Refs. 1 and 2 are very limited and apply to gravity drainage conditions. Ref. 3 contains an analysis similar to the one presented here. The idealized models used and the assumptions made in Ref. 3 are different from those used in this paper. The analysis assumes that after steam injection has heated a small portion of the volume within the radius of drainage of a single uniform sand, a shut-in soaking period is allowed before returning the well to production. The effects of gravity, capillarity, transient pressure and water-sensitive sands are neglected. The injection and soaking times are assumed short compared to the stimulated production time. The initial temperature is assumed uniform; thus, the results apply primarily to first-cycle stimulation. The effects of gas production other than steam are neglected, and the water-oil ratio during production is assumed constant. Steam stimulation involves the simultaneous variation of the temperature, pressure and saturations. General mathematical equations for these variations are complicated and can be very difficult to solve. Simplified equations based on idealized models are used to reduce the mathematics sufficiently to allow approximate solutions to be obtained. DISCUSSION INJECTION An idealized model for which heat conduction is neglected is used to represent the behavior of a well during steam injection. The mathematics for this model is presented in Appendix A which also contains an approximate solution for the behavior of the no-conduction model. SOAKING During soaking, the well is shut in. Only the temperature, pressure and saturation distributions at the end of soaking are needed in the analysis. During soaking the heat is considered to be conducted in a uniform medium from an initially uniformly-heated circular cylinder confined to the producing interval. At the end of soaking the saturations and pressures are assumed to correspond to the cold zone. Analysis of the heat flow during soaking is included in the next section. The radius of the heated cylinder is calculated from the following heat balance (for constant quality steam injection). At the end of the soaking period it is assumed that little or no free gas is present near the well, and that the soaking period has been sufficiently long that the steam zone has had time to expand and the steam has condensed. The condition where there is no soaking is considered in the next section. PRODUCTION In this section, an approximate method is presented for solving the equations of heat and fluid flow associated with the production of oil and water during steam stimulation. Where initial pressure drawdowns are sufficient to cause steam to flow into the wellbore, steam production is assumed to occur within a short initial adjustment period (Appendix B). The production practices followed soon after the well is returned to production can have a large influence on the amount of oil produced during the stimulation cycle. Under most conditions, there is a period of time in which some or all of the water in the heated zone is converted into steam and produced. This flashing of hot water is caused by the pressure in the heated zone dropping below

By A. H. Heim

A method and apparatus for measuring gas porosities of rocks are described. The apparatus can be assembled from commercially available components. In principle, measurements are made by volume substitution at constant pressure. The maximum error is not more than 0.3 porosity per cent. Typical results are given. INTRODUCTION Determining the porosity of rock samples is one of the most important and yet most varied types of measurement in core analysis. Among the many techniques devised are the so-called "gas porosity" methods. An old and well known example is the Washburn-Bunting method.' The U. S. Bureau of Mines2-' described and later improved the apparatus for a now widely used method generally known as the "Boyle's law" method. In the present form of the Washburn-Bunting method,' the volume of air in the pores of a rock sample at atmospheric pressure is extracted and then collected in a graduated burette at atmospheric pressure. The volume of air is read directly as the pore volume of the sample. The absolute error in reading the collected volume of gas is independent of the total volume; thus, the relative error is larger when the volume is small, as it is for rocks of low porosity. In addition, the sample after measurement contains mercury, which limits its use for other analyses. The Bureau of Mines (or Boyle's law) method measures directly the solids volume of a sample from which the pore volume and porosity are derived, using a separate measurement of the bulk volume. Gas at a few atmospheres pressure is introduced into a sample chamber of known volume containing the rock sample. The pressure is accurately measured. Following, the gas is expanded into a burette at 1 atm, and the gas volume is read directly. From the initial pressure p, and the final pressure p2 and volume v,, the initial gas volume v1 is calculated using Boyle's law; that is, p1v1 = p2v2. Volume v, minus the volume of the empty sample chamber is the solids volume of the sample. The accuracy of the method is limited, unless corrections are made, by deviations of the gas from the "ideal" gas-law behavior assumed in the simple form of Boyle's law. The purpose of the present paper is to describe a method for measuring the gas porosity of a rock which avoids many of these difficulties. Gas volumes are measured directly with the same accuracy as the bulk volumes. Pressures of at least an order of magnitude larger than those of previous methods are employed to insure rapid penetration of the gas into the sample. While special equipment may be built to apply the method, the porosimeter may be constructed as well from commercially available components. For simplicity, the apparatus described will be referred to as the "Constant-Pressure gas porosimeter". THE CONSTANT-PRESSURE METHOD Fig. 1 shows schematically the arrangement of components comprising the present Constant-Pressure porosimeter. Briefly, the method is one of volume substitution and may be considered a null measurement. Omitting (for the present) some of the operational details, the method of measurement consists of the following three steps. 1. After evacuation, the volume of the measuring system (a ballast chamber, a manifold, two gauges and their connections) up to the sample chamber is filled with gas to a high pressure (- 1,000 psi). A sample of the gas at this pressure is trapped in one side of a sensitive differential pressure gauge to serve as the reference pressure for subsequent steps. 2. The evacuated sample chamber containing the rock sample is opened to the measuring system. As the gas expands into the chamber, the resulting decrease in pressure unbalances the differential pressure gauge. 3. The pressure is restored by means of a mercury volumetric pump. The volume of mercury injected exactly equals the free or void volume of the sample chamber (volume of empty chamber minus the solids volume of the rock within). From the injected volume and the known empty chamber volume, the solids volume is obtained and the porosity calculated. The pressure and the volume occupied by the gas are the same before and after opening the sample chamber. Expansion and compression of the gas are incidental operations and do not enter into the calculation of porosity. By the pressure balancing or nulling, the free volume of the sample chamber is merely substituted by an equal and measured volume of mercury. Since the measurements are at constant pressure, there are no compressibility corrections necessary for the sample chamber.

M. G. CORSON.'-I am not going to discuss any of the papers presented but merely the question of season cracking of brass in general. Alpha brass has been known for nearly 500 yr. and from the very beginning a number of articles were made from sheets of this alloy by the process of spinning. Metal turning lathes were not yet known but wood turning lathes already existed and the wood turners used to make the mandrils and do the brass spinning themselves. Cases of season cracking were known even then. In 1915 I was connected with a small company doing a certain amount of brass spinning. Before the war its products never gave cause for complaint but their war-time products were cracking too frequently. The reason was, that due to the exigencies of war an excessive speed-up was attempted and the material simply could not take it. Today corrosion cracking of brass is most important in the case of cartridges for small arms ammunition and shell cases for large guns. The cracking takes place in storage and too frequently it is explained by the hypothetical presence of vapors of ammonia. However, I had the experience of purchasing some 20,000 rounds for the old Vetterli rifle from the Swiss government in 1905. The rifle and the cartridges were obsolete for many years and those which I bought were stored for at least 10 yr. None of them was found to be cracked or to crack in use. And the reason again was in the amount of work used in manufacturing the cartridges between anneals. The machinery today is more powerful and the amount of

Jan 1, 1945

By F. H. Ellinger

TI HE crystal structure of neodymium has been re-A ported by Quill1 and by Klemm and Bommer"s to be hexagonal-close-packed, Strukturbericht-type A3, with a, = 3.650.4, c, = 5.890.4, c/a = 1.614. Klemm and Bommer,% owever, pointed out that the observed intensities of the lines of the neodymium powder pattern agreed only in part with the intensities calculated for the type A3 structure, and that the neodymium powder pattern showed extra lines which could not be traced to impurities. They found that these extra lines could be accounted for by doubling the c-axis, but apparently they did not consider their evidence to be sufficiently conclusive to justify reporting the doubled c-axis. In the present work, the structure of neodymium was found to be double hexagonal-close-packed. The neodymium metal used in the present investigation was obtained through the courtesy of F. H. Spedding of the Ames Laboratory. Its major impurity was stated to be 0.03 pct Ca. The author's spectrographic analysis indicated high purity and carbon was determined to be less than 30 ppm. X-ray powder specimens were prepared from filings stress relieved in vacuum at 200°C for 50 hr. Powder photographs were taken in an 114.6 mm diam camera (Straumanis film mounting) at room temperature and in a 19 cm diam Unicam high temperature camera at elevated temperatures. Copper x-radia-tion was used for all the photographs. The powder pattern of neodymium was found to index to a hexagonal unit cell with dimensions, as determined from the high angle Ka doublets, of: a.= 3.655+0.001.4; c, = 11.796+0.004.4; and c/a = 3.227 at room temperature. The measured density of neodymium shows that this cell contains 4 atoms, the calculated density is accordingly D, = 7.02 g per cu cm. The diffraction data for the first 15 lines of the powder pattern are listed in Table I. In a double hexagonal-close-packed unit cell, the 4 atoms would be in the positions (0,0,0), (0,0,%), (1/3, 2/3, 1/4), and (2/3,1/3,%) of space group P 6,/mmc. On the basis of these positions, the relative intensities of the reflections were calculated using the expression: 1+cos2 20 I oc \Frp 1 ' sin2 0 cos 0 where F is the structure factor and p is the multi- plicity factor. Since absorption was not taken into consideration, comparison of observed and calculated intensities should be made only for neighboring reflections. Each atom has 12 neighbors, 6 in the basal plane at a distance of 3.655.4 and 3 above and 3 below at the closer distance of 3.626.4. These distances correspond to an average radius of the neodymium atom of 1.820.4. The description of this structure in terms of A, B, and C close-packed layers of atoms is ABAC ABAC. ...... The structure repeats every fourth layer and the stacking sequence of the second, third, and fourth layers corresponds to cubic-close-packing of atoms. A series of powder photographs taken at successively increasing temperatures up to 680a10"C revealed that the double hexagonal-close-packed structure is stable up to this temperature. Acknowledgments The authw wishes to thank W. H. Zachariasen and A. S. Coffinberry for their helpful comments on this work and also Marion Gibbs for measuring the diffraction films. This work was sponsored by the United States Atomic Energy Commission.

Jan 1, 1956

By Richard H. Zinszer

APPLICATION of electric logs has been used in correlation of subsurface structure to determine the size and shape of the oil reservoir. [ ] Such a knowledge is hardly complete until saturation and productivity are determined for the various horizons. It is difficult to use electric logs successfully for this purpose because of the many factors that influence the curves. In this work an effort was made to establish an empirical correlation between formation resistivity for a series of electric-log curves and water saturation and oil productivity of sand. Electric logs were obtained by recording with 10 different electrode spacings through the same interval of a well. In the analysis of these curves all factors except two, a dependent and independent variable, were held constant. The interval studied had been cored and a large number of samples were analyzed in the core laboratory in order to compare the values of permeability and saturation with the measured values of formation resistivity. Results of this analysis indicate: (I) the depth to which mud filtrate enters a sand body, (2) a correlation between permeability and sand resistivity for shallow penetration depths, and (3) that the water saturation for an oil sand can be determined from the measured sand resistivity after making suitable correc- [ ] tions for sand thickness. The proceduer in the last method depends on a correction for thickness factor and a theoretical curve. The accuracy of the theoretical curve is now being tested in the laboratory.

Jan 1, 1944

By B. B. Betty

H. L. Burghoff.*—Have the authors any information on the effect of grain size in these materials? There is a material difference in the grain sizes shown for the Monel and the Inconel. Is a wide range of grain size normally found for each material, and, if so, what is its effect upon creep strength? 11. L. Eiselstein.—The grain size for Monel shown in the micrograph is the usual size found in that product. The grain size of Inconel is about the same as that, too. However, we have run tests on Inconel at higher temperatures than those reported in this paper, and have found that the coarser grain size has a better creep resistance; and that the grain size that gives the best creep resistance at 1600°F. is about 0.005 in. in diameter. We have no test on Monel with varying grain size. J. J. KANTER.†-It has been known for a long time that Monel metal exhibits ductility anomalies at elevated temperatures. Even in short-time test, it can be demonstrated in the range of 900°F. that there is a distinct falling off of the ability of Mone1 metal to elongate, and in rupture tests this shortcoming is still further accentuated. Knowledge of this rupture anomaly of Monel metal may be one of the reasons for which designer's approach certain high-temperature applications with reservations. The authors of this paper have merely demonstrated that for 900°F. the alloy has an ability to elongate 1.7 per cent over a period of some 2700 hr. Before any conviction can be expected from designers that Monel metal is applicable to stress design in such range of temperature, I think it is desirable to demonstrate the capacity for the material to elongate over a longer period of time than has been done in this presentation.

Jan 1, 1945

Discussion of Papers. Meetings of the Institute offer opportunity for social acquaintance and exchange of ideas, for the presentation of papers, and for discussions thereon ; also incidentally for viewing under especially favorable conditions mining operations and industrial establishments, and for hospitals-ties which demonstrate the brotherhood due to kindred interests. Placing sociability prominent is not to be assumed as relegating other features of meetings to subordinate positions; but during about 40 years of membership in the Institute, the value of acquaintances formed (often ripening into close friendship), and the interchange of data, have frequently demonstrated that the social feature of meetings is of great and lasting value to the membership. Of' a roll embracing 4,011 members, resident in all parts of our country, and scattered in various portions of the world, only a small fraction are able to attend meetings, even if the localities selected are alternately widely separated. Hence, the return which most -members receive for their annual assessment of dues is limited to the publications issued, and the credit of being recognized as a member of a great and worthy organization. Tile greater the value of tile contents of our publication, the fuller the return which goes to members. While the Institute disavows responsibility for views or statements made in papers which appear in its Transactions, the fact that these contributions, after passing proper censorship, are accepted by the Institute and spread before the world may properly be received by the writers as endorsements of their (the writers') ability to present a specific technical or industrial proposition worthy of being carefully read. But the mere presentation and publication of contributed papers falls short of fulfilling one important feature of our meetings. If the purpose is confined to having the writers' views, discoveries, theories, or methods published, this can be obtained through the technical or trade journals and magazines.

Jan 7, 1913

By L. A. Tarshis, H. E. Cline

A stability criterion for a lamellar eutectic interface was derived previously1 assuming that the wavelength, A,. of the perturbation which grows most rapidly is much larger than the lamellar spacing. A. This assumption was required to permit averaging of both the interface temperature and composition over the complicated geometry of a lamellae. If this assumption is invalid, as has been suggested.2,3 then the problem becomes too complicated to solve completely. The first of these analyses1 did not calculate the wavelength. A,. of the initially unstable perturbation. whereas the more recent analysis.' which led to a contradiction of this assumption. did not include one of the key factors for determining this wavelength. To rigorously determine the wavelength, the effect of the curvature of the perturbed interface (not considered by either of the above treatments) must be included. By omitting this term, one would be led to an incorrect conclusion regarding the magnitude of A,. but to an accurate criterion for stability as evidenced by the excellent agreement with experimental observations.' In the case of single-phase alloys. the critical wavelength. A,. for instability can be calculated from the Mullins and Sekerka4 (M.S.) analysis which includes the effects of capillarity. In the following discussion, the M.S. analysis is applied to lamellar eutectics and the critical wavelengths calculated for reasonable growth conditions in Pb-Sn eutectic alloys. In order to apply the M.S. analysis to eutectics. one may substitute i) the effective liquidus slope.1 m*. for the single-phase liquidus slope and ii) the ratio of the bulk alloy composition. C,. to the average interface composition in the liquid (Ci = CE where CE is the equilibrium eutectic composition) for the distribution coefficient to give:

Jan 1, 1970

By Charles Larkey

NUMEROUS papers have been published on the use of graphic methods to determine the best curve to be used in estimating the production decline of oil wells but, as far as the writer has been able to ascertain, nothing has been published dealing directly with the subject as to how curves may be worked out mathematically, which will conform most closely to the production data under consideration in any given instance; hence the writer has endeavored to show by means of a few concrete examples just how such appli-cation can be made. Among valuation engineers, two types of curves are in current use for the representation of the decline in production of oil wells. One may be represented by the equation, y = krx, sometimes known as a percentage curve, for the reason that the production for any period is multiplied by a constant rate or percentage to obtain the production for the succeeding period. This curve appears as a straight line on semi-logarithmic cross-section paper. The other curve may be represented by the equation, y = kxn, and is shown as a straight line on logarithmic cross-section paper. In each of these equations, y represents the number of barrels produced over a given period of time, and x the successive periods of time. The other letters are constants to be determined for each well or group of wells considered in arriving at the most probable curve to represent the rate of production for a given property; from which the underground reserves may be estimated by extrapolation, or the extending of the curve beyond the last known period of production to show the most probable production values for the future.

Jan 7, 1923

By J. D. Edwards, C. S. Taylor, A. S. Russell

Solubilities and densities are reported for alumina hydrates in NaOH solutions under the conditions of the Bayer process employed to purify alumina for aluminum production. The equilibrium constants for reactions to form A102- accurately correlate the effects of NaOH concentration on the solubilities; the temperature coefficients of the equilibria lead to heats of solution of 7.34, 4.76, and 5.24 kcal for the a trihydrate, a monohydrate, and ß trihydrate, respectively. Moderate calcination does not change the solubility of the a trihydrate but increases that of the a monohydrate. At solution temperatures above 100°C, the trihydrates transform rapidly to a monohydrate. Hydro-thermally produced a monohydrate is the stable phase above 20°C. CORNERSTONE of the aluminum industry, the Bayer process for alumina production is based on the difference in solubility of hydrated alumina in NaOH solutions between 170" and 40°C. Solubilities and densities in this system were determined thirty years ago by M. Tosterudl under the direction of J. D. Edwards and C. S. Taylor. The solubility data, which still appear more concordant than those in the literature, are employed to sort out the complex equilibria in this system. The nomenclature for the alumina hydrates is that presented in The Aluminum Industry' and more recently summarized in Alumina Properties.3 a trihydrate is the purified phase analogous to gibbsite, a monohydrate is similarly akin to boehmite, and ß trihydrate is sometimes known as bayerite. Literature Goudriaan4 reviewed the early literature on alumina in NaOH solutions and presented data on the solubility at 30°C of several forms. The gel precipitated from aluminum sulphate or chloride with ammonia and dried at 130" to 140°C had the highest solubility but was unstable, its solubility being cut to one-tenth on standing in NaOH. The solubility of the gel was decreased one-third on calcination at 300" to 400°C, while that of the gel transformed in NaOH at room temperature to a crystalline trihydrate was unchanged on calcination. The preparation produced by slow hydrolysis of sodium aluminate solution with CO, in the air gave solubilities in rough agreement with later values for a trihydrate. The solubility of this form was increased slightly by the calcination. Fricke and Jucaitis5 extended the work to 30" and 60°C with a trihydrate. They also gave solubilities for ß trihydrate (bayerite b), although the residue belonging to the left branch of the solubility curve corresponded to a trihydrate. The residues at high NaOH concentrations were mono and trisodium aluminates, the latter being 3Na2O . AL2O3 • 6H2O. Solubilities of a trihydrate at 95°C and of a monohydrate at 150" and 200 °C come from the work of Magarchak.6 a trihydrate transformed to a monohydrate above 95°C. A few measurements on the solubility at 25°C of an alumina trihydrate prepared by slow hydrolysis of NaAIO, solutions were presented by Sprauer and pearce.? Their analyses showed the monosodium aluminate to have the composition Na2O.Al2O3-2.5H2O.

Jan 1, 1956

By E. Buehler, E. Berry

HE magnetic properties of dilute palladium alloys are of fundamental interest.''' Neutron diffraction studies3 have indicated that a better understanding of the behavior of these alloys could be realized with the availability of high-purity single crystals of palladium. Crucible melts of 99.999 pct pure palladium were found inadequate for such research. In a successful effort to fill this need, floating zone refining of palladium was undertaken. In this note the results of the initial experiments are reported. Zoning was accomplished in an argon atmosphere using 450 kc rf generator for an energy source. Samples 5 to 6 mm in diam were suspended in a gastight quartz envelope which could be moved vertically through the rf coil. A nominal upward traverse rate of 1.5 mm per min was maintained during a pass. Close coupling was found to be essential for stable retention of the liquid in the zone. Single crystals averaging 3.5 cm in length were obtained. Laue photography showed them to be continuous single crystals without gross imperfections. Several criteria were used for evaluation of the purity of the zoned material: magnetic behavior, low-temperature specific heat and residual resistivity ratios. Table I shows the residual resistance ratios obtained for two samples, one subjected to a single pass, the other zoned four times. It is appilrent that palladium can be zone refined with the electrically active impurities being transported toward the tail end. A decrease in susceptibility for zone-melted specimens over any previously measured material from 1.5" to 80'~ has been obserted by H. J. Williams and R. C. Sherwood4 substantiating the residual resistance data. The specific heat measurements are currently being made3 and will be published at some later date. Discussions with J. H. Wernick and S. C. Abrahams are acknowledged. We also wish to thank G. F. Brennert for the residual resistance measure ments.

Jan 1, 1962

By B. B. Rath, Hsun Hu

In wedge-shaped bicrystals of zone-refined aluminum it is observed that (111) pure tilt boundaries migrate under the driving force of their own inter-facial free energy. The boundary velocity is a power function of the driving force. The driving force exponent decreases with decreasing angle of misorien-tation. For example, at 64O°C, the exponent decreased from 4.0 for a 40 deg to 3.2 for a 16 deg tilt boundary. An evaluation of the driving force acting on the boundaries during their motion indicates that for low driv-forces, up to about 2 x l03 ergs per cu cm, the velocity is relatively independent of misorientation, whereas at higher driving forces a 40 deg tilt boundary exhibits the highest velocity. The measured activation energy for boundary migration approaches that for bulk self-diffusion at low driving forces, decreasing from 33 to 27 kcal per mole as the driving force is increased from 1 x l0 to 5 x l03 ergs per cu cm. These results are compared with current theories of grain-boundary migration. In previous experimental studies of grain boundary migration the driving force has been limited to a difference in stored energy across the boundary. This stored energy has been introduced into the crystal either by prior deformation1-3 or by grown-in lineage structure. A part of the energy stored in the deformed crystal is released by recovery either prior to or concurrently with grain boundary migration, thus introducing an uncertainty as to the magnitude of the driving force responsible for grain boundary migration. The grown-in lineage structure, though thermally stable during annealing, neither provides conditions under which different levels of energy may be stored in the imperfect crystal nor provides a control of orientation difference across the migrating boundary of a growing grain. Furthermore, because of variation in the lineage structure, it is difficult to determine accurately the energy stored in the imperfect crystal. Several investigations of grain boundary migration during normal grain growth have also suffered from difficulties in estimating the driving force because of uncertainties in the principal radii of curvature.~ In the present investigation the velocity of pure tilt boundaries in zone-refined aluminum bicrystals of selected orientation (40, 30, and 16 deg around the [Ill] tilt axis) has been measured in the absence of a dislocation density difference across the moving boundary, thus eliminating the previous experimental difficulties. The driving force for boundary migration is derived from a gradient of the total interfacial free energy of the migrating boundary in wedge-shaped bicrystals. A similar method was attempted by Bron and Machlin in a study of grain boundary migration in silver. However, they found that one of the crystals was deformed and consequently the motion of the boundary was partly due to a difference of stored energy across the boundary. The observed behavior of boundary velocities as affected by the driving force is examined in the light of the predictions of the current theories of grain boundary migration.7"10 The effect of boundary misorientation on velocity is compared with the theory of " which is based on a dislocation core model for high-angle boundaries. EXPERIMENTAL METHOD Seed-oriented bicrystals of zone-refined aluminum, 2.5 cm wide, 0.5 cm thick, and 12 cm long, containing tilt boundaries with a common (111) axis, were grown from the melt in the direction of this axis. Spectro-graphic analysis, reported earlier,'' indicated the purity of the crystals to be 99.999+pct. Three such bicrystals containing 16, 30, and 40 deg tilt boundaries were used. Wedge-shaped specimens were prepared from these bicrystals by spark cutting followed by electrolytic polishing. The angle of the wedge was usually 40 deg and the specimens were usually 0.25 cm thick. The intercrystalline boundary was located within 0.2 to 0.5 cm from the tip of the wedge. Fig. 1 shows a section of an oriented bicrystal containing an outline of a wedge-shaped specimen. The crystallographic directions shown in Fig. 1 represent the orientation of one of the crystals (the larger section of the bicrys-tal); the orientation of the other crystal differs only by rotation around the common [lil] axis. The parallel faces of the wedge always corresponded to the common (171) planes in both crystals, whereas the orientation of the side faces varied, depending on the misorientation angle. The bicrystal orientations were determined

Jan 1, 1970

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori' molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,' using the data of Parravano and Malquori.' Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

By Clyde E. Williams

The purpose of this report is to supply the Coal Classification Committee' with information for use in the formulation of a system of classification of coals according to their uses. Consideration is given here only to the nonferrous metallurgical operations that consume relatively large amounts of coal or coke; i. e., the smelting of copper, lead, zinc and aluminum. For all of these uses, coal of certain definite qualities is desired. Geographical location, however, often determines whether these qualities can be specified. In some instances the preferred qualities must be specified, regardless of cost. In others, quality may be sacrificed for lower cost, although the best quality consistent with cost is usually the determining factor. These considerations will be outlined in the following discussion under the various uses, which, however, will illustrate the impracticability of preparing definite specifications for coal used in the majority of the nonferrous industries. Coal and Coke in Copper Metallurgy From the standpoint of coal consumption, copper smelting and refining operations are the most important of the nonferrous metallurgical uses of coal. As nickel ores treated in the United States and Canada are associated with copper, the first step in their recovery is really a copper-smelting operation; accordingly, the following considerations under copper smelting apply equally to nickel. Copper Smelting in Reverberatory Furnaces.—For a long time, rever-beratory copper-smelting furnaces were fired with lump coal burned on grates in a fire box. Later, lump coal was displaced by pulverized coal or oil burned directly in the smelting chamber. Recently, natural gas has been used in several plants, although producer gas was used for this purpose at Great Falls as early as 1903.2 Requirements for coal used in

Jan 1, 1932

By Kenneth Cottingham

The year 1941 brought a considerable increase in drilling activity in Ohio. In 1940, the total of wells completed was 1228, whereas in 1941 it was 1561, or an increase of approximately 27 per cent. Of the 1561 wells, 333 were oil wells, 701 gas wells and 527 dry holes. The completions for the past five years are shown in Table I; the number of productive oil or gas wells for the year 1941, arranged by producing formations, are given in Table 2; the number of wells, oil, gas or dry, completed in each county in 1941, in Table 3, and wells by sands in Table 4. The production of oil increased by about 500,000 bbl. in 1941, nearly all of the increase being in Pennsylvania grade. In 1940, the total production was 3,052,000 bbl. from 25,500 wells. In 1941 the total production was 3,547,534 bbl. from 24,801 wells. The increase in production is chiefly due to the Clinton pool in Clayton township, Perry County, which is briefly men- tioned later in this review. The number of oil wells, by grades of oil, and the total quantities produced are shown in Table ;. Annual oil production for five years is listed in Table 6. The average prices paid for crude in 1941 were slightly higher than in 1940 These 1941 prices, with dates of change, are shown in Table 7. The maximum production of natural gas in Ohio was in the year 1915, when the total was just under 80 billion cu. ft. The maximum consumption occurred in the year 1916, and was approximately 169 billion cu. ft. For the past several years, Ohio has ranged from eighth to eleventh, in order of gas production for the different states, being in tenth place in 1940. In the matter of consumption, however, Ohio remains in fifth place. Preliminary figures for 1940 indicate that production of natural gas increased II per

Jan 1, 1942

By Kenneth Cottingham

The year 1941 brought a considerable increase in drilling activity in Ohio. In 1940, the total of wells completed was 1228, whereas in 1941 it was 1561, or an increase of approximately 27 per cent. Of the 1561 wells, 333 were oil wells, 701 gas wells and 527 dry holes. The completions for the past five years are shown in Table I; the number of productive oil or gas wells for the year 1941, arranged by producing formations, are given in Table 2; the number of wells, oil, gas or dry, completed in each county in 1941, in Table 3, and wells by sands in Table 4. The production of oil increased by about 500,000 bbl. in 1941, nearly all of the increase being in Pennsylvania grade. In 1940, the total production was 3,052,000 bbl. from 25,500 wells. In 1941 the total production was 3,547,534 bbl. from 24,801 wells. The increase in production is chiefly due to the Clinton pool in Clayton township, Perry County, which is briefly men- tioned later in this review. The number of oil wells, by grades of oil, and the total quantities produced are shown in Table ;. Annual oil production for five years is listed in Table 6. The average prices paid for crude in 1941 were slightly higher than in 1940 These 1941 prices, with dates of change, are shown in Table 7. The maximum production of natural gas in Ohio was in the year 1915, when the total was just under 80 billion cu. ft. The maximum consumption occurred in the year 1916, and was approximately 169 billion cu. ft. For the past several years, Ohio has ranged from eighth to eleventh, in order of gas production for the different states, being in tenth place in 1940. In the matter of consumption, however, Ohio remains in fifth place. Preliminary figures for 1940 indicate that production of natural gas increased II per

Jan 1, 1942

By Frank Gilbreth

THE problem, of the crippled soldier in industry is not a problem of war work only; it is a problem of industrial development. As individuals, each one of you is seeking to provide our maimed heroes with such teaching as will render them, in the shortest possible amount of time, productive and satisfied members of the community. As individuals you are interested in the organizations that are preparing to receive these men, to train them and to place them at that work for which they are best fitted. As an organization, it is now your duty to take up the industrial end of the problem, to investigate existing conditions in the industries, to discover where the opportunities for employment lie, and so readjust industrial practice that the cripples may be utilized to their own and the community's good with the least shock to themselves or to the industries, and with the greatest amount of permanent benefit to all concerned. We have divided industrial opportunities suitable for cripples roughly, into three classes. First, such as already exist in the industries, which can be set aside for cripples only, present occupants being transferred to other work for which they can be fitted but which is not suitable for cripple work; second, opportunities in the industrial world that, through changes in the working equipment or tools, or through appliances attached to the cripple himself, can make the cripple a competitor of the sound worker; third, opportunities not existing at present in the industries, but which could be introduced for the good of the community, without placing the cripples into competition with any existing class of workers.

Jan 4, 1918

By R. F. Mitchell, G. F. Dillon, A. F. Armington

In this paper the present methods of boron preparation are discussed with emphasis on the iodide intermediate. Several methods of boron triiodide preparation were investigated, the most satisfactory method being the preparation from the elements. A yield of 60 pct based on iodine is found for this method. Zone-refining, sublinzation, distillation, and fractional-recrystallization results are given for the boron triiodide, with distillation producing the best results. Several methods of decomposition are also discussed. The purity of the resulting iodide boron approximates the puritjl of the best available bromide boron, ELEMENTAL boron has been suggested as a possible high-temperature semiconductor by several workers,' but has never been exploited as a device material. The principal difficulty with boron is the unavailability of pure crystalline material from which accurate information on electrical properties could be obtained. Most boron crystals presently produced are very imperfect in structure and of questionable purity, particularly in relation to carbon content. Several methods of boron purification have been reported in the past few years, all of which produce material with a purity better than 99.0 pct. Most of these methods have been the subject of a recent review by Starks' and will not be elaborated upon in this report. However, of all the purification methods reported, only those using halide intermediates produce a purity approaching that usually required for electronic applications. The bromide intermediate has been most used for the preparation of high-purity boron.'y3 This material is easily prepared from the elements and can be effectively purified by distillation and decomposed by hydrogen reduction. The resulting product contains a trace of silicon, and an uncertain amount of carbon, believed to be approximately 100 ppm. It has been recently reported by Russian workers that high-purity boron can be produced using an iodide intermediate.' In the work cited, boron is reported free of spectro-scopically determined impurities, but the reported detection limits are quite high (- 100 ppm). In addition, no data is given on the carbon content of the product. In the present paper, boron triiodide was chosen as the intermediate for several reasons. First, carbon tetraiodide, which could be a major impurity, is reported to be unstable above 200" and hence could be easily separated from the boron triiodide by its decomposition, since temperatures greater than this are attained during the purification process. The low melting point (45°C) and boiling point (20B°C) and the relatively high vapor pressure of boron triiodide should allow the application of any physical purification technique to the material. The possibility of a lower decomposition temperature than that used for the bromide process is another advantage which might cut down extraneous contamination. The iodide, however, does have certain disadvantages when compared with the bromide, the production cost being the most significant. This is the result of a higher halide-to-boron weight ratio, which means more intermediate must be employed. The cost of the starting material is also greater for the iodide. This cost could be considerably reduced however, by recycling the iodine byproduct. Epitaxial growth of boron, which is probably the best method of producing junctions, should be possible with either the bromide or the iodide as the intermediate. However, this has been attempted only on a limited scale up to the present time because of the unavailability of good crystals. The authors have been relatively successful in laying down a heterotaxy of boron on silicon, however. This will be reported at a later date. Several crystalline modifications have been reported for boron, four of which are now believed to be real.' These are the a! and 0 rhombohedral and the a, and 0 tetragonal. In general, the a! rhombohedral is the low-temperature form and the B rhombohedral is the high-temperature form. The tetragonal structures are detected between 1000"

Jan 1, 1964