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By G. W. Toop

Jan 1, 1965

By T. Yoshioka, Paul A. Beck

SILICON, germanium, and tin occur with both the white tine-type structure and the diamond cubic structure. In the latter form these elements are semiconductors; in the former they are metallic. The metallic form of germanium and silicon is obtained only under high pressure.' For all three elements the transition from the semiconductor to the metallic state is accompanied by a decrease in the atomic volume of somewhat more than 20 pctily2 Table I. At such a large compression the widening of the s and p bands is sufficient to make the energy gap of 1.1 ev, or less, of the semiconductor disappear, giving rise to the metallic state.*

Jan 1, 1965

By R. M. Hudson

Equilibrium constants have been determined for the jeaction C (in steel) + H2O = CO + H2 as a function of carbon content (0.013 to 0.74 ujt pct) and temperature (1200° to 1800°F) by using a flow system in which the water-vapor content of various gas mixtures containing hydrogen, carbon monoxide, and nitrogen was systematically controlled. The equilibrium partial-pressure ratio K1 = PcoPH2/PH2O was obtained for two low-carbon steels and four Fe-C binaries from a series of runs made at each temperature. By comparison of Ki with the analogous ratio for the reaction C (graphite) + H2O = CO + H2, the activity of carbon in steel (ac) was comDuted for each temperature and carbon content studied. From these data values of the equilibrium constants for two other carburization-decarburiza-tion reactions of importance were estimated. The chemical compositions of the two steels and four Fe-C binaries used are given in Table I. Specimens of Steel E were cut from a 0.035-in.-thick commercially box-annealed and temper-rolled lot of a low-carbon low-metalloid steel. Steel F was a commercially hot-rolled rimmed steel that was cold-reduced at the Laboratory to a 0.059-in. thickness. Fe-C binaries A, B, C, and D were vacuum-melted and poured, hot-rolled, pickled, and cold-reduced at the Laboratory to furnish specimens 0.035 in. thick. Sheet specimens were cut from all lots to approximately 3/4 by 3 in. by gage and were vapor-degreased with trichlo-roethylene and weighed before heat treatment. Heat treatments were carried out in a hinged-top Hevi-Duty electric furnace with a Vycor-glass tube. When the furnace was at the desired

Jan 1, 1965

By Thomas C. Wilder

Jan 1, 1965

By B. H. Caudle, R. E. Watson, I. H. Silberberg

The production history of an inverted nine-spot injection pattern was studied with a porous plate model similar to Habermann's. Colored fluids were used so the boundary movements could be photographed. By varying the production rates of the side and corner producing wells, the optimum pattern sweep efficiency can be obtained. Results of the laboratory tests indicate that interpolation of the pattern sweep and conductivity ratio data will permit application of the data to predicting fluid injection operations with mobility ratios between 0.1 and 10 and production rate ratios between I and the optimum values. INTRODUCTION The inverted nine-spot injection pattern in Fig. 1 has some unique advantages over other regular injection patterns (five spot, line drive, etc.) used in secondary recovery operations. It has three producing wells for each injection well, while the five-spot and line-drive patterns require an equal number of injectors and producers. Futher-more, of the eight producing wells surrounding each injection well, four are of the "side well" type which lie nearer the injection well than the remaining four "corner wells". This allows the production rates of these two types of wells to be adjusted independently of each other to obtain better pattern sweep efficiency. This latter advantage may well be the reason why the nine-spot patterns have not been studied as extensively as the patterns containing only one type of injection or producing well. The pattern sweep efficiency of the inverted nine spot is affected almost as much by operating with different producing rates of the comer and side wells as by differing mobility ratios. Possibly because of this added operating parameter, published studies of nine-spot systems have been limited in their coverage of the pertinent variables.'-' The model studies reported here covered the mobility-ratio range normally found in waterflood operations, as well as the variation in well production rates necessary to achieve optimum pattern sweep efficiency. Conductivity ratios — a measure of the change in total flow at constant pressure difference — were obtained during each model run. A porous-plate model with miscible fluids representing the in-place and injected fluids was used in this study. This model technique is the same as that used in both X-ray shadowgraph" and visual techniques4 described in the literature. Using miscible fluids eliminates residual oil in the model, and the permeability to the injected fluid is the same as to the in-place fluid. Thus the mobility ratio in the model is given by the ratio of the viscosity of the displaced fluid to the viscosity of the injected fluid. Because of the non-linear nature of the viscosity vs composition curve for two miscible liquids, the mobility change across the boundary between the two fluids is reasonably sharp. This technique thus represents the displacement of a region of one fluid mobility by a region of possibly different mobility in an isotropic system under steady-state flow conditions. Table 1 shows the dimensionless similarity groups used to scale the model conditions and results to

Jan 1, 1965

By R. M. Asimow

The magnetization curves for specimezs containing superparmagnetic particles are considered. It is shown that the curves may differ from a Langezlin function because of particle anisotropy, particle interactions , and the presence of a size distribution of particles. The various causes of particle anisotropy are considered, and magnetization curves for specimens with cubic and uniaxial anisotropy are presented. The magnetization curves depend on the In the particle-size below 100A it is quite difficult to obtain quantitative size and shape information on precipitate particles. All of the available techniques have their limitations; however, quantitative applications of superparmagnetism have not been developed as fully as possible due to a lack of analysis of the complete magnetization curve. With such an analysis it appears possible to obtain from a single magnetization curve of a specimen containing randomly oriented SPM (superparamagnetic) particles a quantitative volume distribution and a description of the particle shape.* sign of the anisotropy energy and in the case of a negative uniaxial anisotropy (prolate spheroids) the resulting curves may differ very considerbly from a Langevin function. A graphical technique is developed whereby it is possible to separate out the effects of the size distribution, the particle interaction, and the particle anisotropy. Thus it is possible to obtain quantitative values for both the particle shape and the size distribution. Langevin function2 I/Is = ctnh(HVIs/k T)-k T/HVIS [ 1 ] where I, is the saturation magnetization, V the particle volume, H the applied field, T the particle temperature, k the Boltzmann constant, and I the magnetization in the direction of the applied field. Such behavior is rarely if ever observed in actual systems. One explanation for this is that the SPM particles do possess a significant anisotropy and thus the magnetic energy associated with the particle depends on the direction of magnetization in a more complicated way than for the isotropic particle of Eq. [I]. In general the magnetic energy E of an isolated SPM particle embedded in a nonmagnetic matrix can be expressed as a sum of several contributions: E = Eh + Ed+Es+Ec [2] where Eh is the external field energy, Ed the energy resulting from the particle demagnetizing factor, E, the magnetostriction energy, and E, the crystalline anisotropy energy. In each term we consider only the part dependent on the orientation of the magnetization vector and the particle axes as the shape of the magnetization curve will be determined by these contributions. Following the same procedure used in deriving the Langevin function,

Jan 1, 1965

By Paul Gordon

The distribution coefficient, k, of interest in zone refining is generally defined as the ratio of the solid to the liquid solubilities of one element in another at the normal melting point of the solvent. In practice, distribution coefficients are frequently calculated from solubilities at temperatures well below the melting point of the solvent, e.g., at a eutectic temperature. This is done because of the general lack of accurate data on the liquidus and solidus curves in most phase diagrams. The practice is equivalent to assuming that the liquidus and solidus curves are straight lines in the temperature range between the melting point of the solvent and the temperature at which data for the solubilities are known. It is recognized that the k values so derived may be in serious error; we have found evidence in recent zone-refining operations that a case in point is silicon in aluminum. The phase diagram found in the literature for silicon in aluminum indicates a eutectic on the aluminum-rich side at 12.5 at. pct Si and at 577°C,1 and a solid solubility of silicon in aluminum at this temperature of 1.59 pct.2 It also shows the liquidus and solidus as nearly straight lines from 577°C to the melting point of aluminum (660°C)1,2 The k value obtained from this data is 0.13. This is almost exactly the same as the k value (about 0.14)' obtained in a similar way for copper in aluminum. Yet we have found by mass-spectrograph analyses* of three bars of zone-refined aluminum that copper is efficiently removed from aluminum by zone refining but silicon is not. Two of the three bars of aluminum were zone-refined in our laboratories, the other in the laboratories of AIAG Metals, Inc. The former two bars, designated bars PG2 and PG3, were 30 in. long by 1 in. in diameter during refining; each was processed in a high-purity graphite boat* and kept under refining stage of the process consisted of thirty unidirectional zone traverses at rates of about 1 to 2 in. per hr, with a zone length of 1 to 2 in. At approximately the middle of the refining period a 6-in. piece of the impurity-laden finishing end of the bar* was cut off and replaced with new start- ing material. Following refining, the purest 20-in. section of the bar (obtained by discarding approximately 2 in. of the starting end and 8 in. of the finishing end of the bar) was leveled and then analyzed. The AIAG bar was 16 in. long and about 1.2 in. in diameter; it was purified by eight passes of a 2-in. zone at a rate of 1.6 in. per hr, the bar being contained in a sintered alumina boat lined with loose alumina powder of the highest purity. Data for the silicon and copper contents of the three refined bars are given in Table I. Derived data for the efficiencies of the zone-refining operations are listed in Table 11. It is clear from these two tables that the copper is removed much more efficiently—by a factor of 10 to 50 times—from aluminum during zone refining than is silicon. For example, in bar PG3 the thirty zone passes reduced the copper content from 10 to 0.02 ppm, i.e., by 500 times, whereas the same treatment lowered the silicon content by only a factor of about 16. It seem virtually certain, therefore, that the distribution co efficient, k, for silicon in aluminum is well above that for copper and is very likely not much below unity. This also implies that the solidus line on the aluminum-rich side of the A1-Si phase diagram is very probably appreciably curved near the aluminum melting point since the phase-diagram data indicate such curvature is unlikely in the liquidus.

Jan 1, 1965

By R. A. Spurling, C. G. Rhodes

SATISFACTORY metallographic sample preparation of very soft metals, such as lead and its alloys is generally difficult. The prime requisite of any technique must be that the result gives an undis-torted microstructure for the microscopist to examine. A small amount of mechanical polishing followed by a chemical or electrolytic polish is usually the most desirable way to obtain an undis-torted surface. Several chemical-4 and electrolytic3-' polishing solutions have been developed for dilute lead alloys. Perchloric acid mixtures (with acetic anhydride, ethyl alcohol, or water) are among the most prominent electropolishing solutions used for lead; however, the presence of bismuth in the alloy precludes the use of any perchloric-containing solution. The other solutions1-7 were found to be unsatisfactory on alloys ranging from 10 to 65 wt pct Bi in lead. With increasing bismuth content, the microstructure shows a lead (terminal solid solution), 0-6 mixture, E (peri-tectically formed hexagonal phase), and E bismuth mixture (eutectic at 56.7 wt pct Bi).9 The metallographic samples were mounted in "Araldite" epoxy (the heat generated during polymerization does not alter the microstructure), ground by hand on well-waxed silicon carbide papers (400 and 600 grit), and polished with 3- and 0.25-CL diamond paste on billiard and microcloths, respectively. The use of the various polishing and etching solutions reported in the literature resulted in the formation of irremovable reaction products on the sample surface when applied to "as-ground" or "as-polished" surfaces. The E phase was the most difficult to clean chemically and in the development of an etchant for this system several solutions which satisfactorily etched the bismuth or a phase were unacceptable because of their reaction with the E. It was found that a mixture of 50 ml lactic acid 30 ml nitric acid 20 ml (30 pct) hydrogen peroxide (Solution #1) was a satisfactory etchant for the a-matrix alloys. The samples were prepared as before and etched after 1 min of polishing with 3-p diamond paste. The etchant was applied by swabbing (light pressure) for 30 sec to 1 min and the sample was then rinsed in running water. The E has a slight stain and the a is fairly bright, Fig. 1.

Jan 1, 1965

Jan 1, 1965

By Hugh M. Roberts

In the spring of 1915, then a 30-year old geologist in the employ of the E. J. Longyear Co., of Minneapolis, Minn., I accompanied prospectors to ex- amine outcrops of supposed nickel ore situated a mile or two in from the shore of a lake in the Kenora district of northwestern Ontario. The deposit proved to be bog iron ore containing traces of nickel. We were stormbound there for three days, a circumstance which gave rise to a tale that was told at our fire one night. It seems that Sandy and Jock, two prospectors, were crossing the bay of a large lake in a canoe. They were bucking headwinds; the waves grew higher. Jock called out from the stern, "Sandy, can ye na pray a little." Sandy pressed his knees a little closer into the bow and, between strokes of his paddle, sought for words, which came haltingly, "Save us this time . . . Oh Lord . . . and we promise . . ." when Jock, peering through the spray sang out, "I would na commit yourself, Sandy, I think I see lond ahead."

Jan 1, 1965

By R. F. W. Pease, R. A. Ploc

A scanning electron microscope with a resolving power better then 100Å has been developed for the direct examination of surfaces. This instrument was used to study iron undergoing oxidation at 500°C. It was found that the electron current in the scanning electron microscope was low enough (about 10-atrzp) to have no observable effect on the growth of the oxide. "Armco " iron, when oxidized, exhibited an oxide film whose thickness and whiskey population varied with pain orientation; but purer iron, when oxidized, exhibited no such pain dependence and whisker occurrence appeared to be caused by impurities. UNTIL recently most surfaces of opaque specimens could either be studied with a light microscope or, if higher resolution was required, by viewing a replica of the surface in a transmission electron microscope. Direct electron microscopy of a surface has, in general, proved difficult owing to excessive foreshortening and the poor image quality obtained. The scanning electron microscope, however, offers an alternative method of directly viewing a surface without these disadvantages. At low magnification it offers a much larger depth of focus than the light microscope, and at high magnifications it offers much higher resolution (about 100Å). PRINCIPLE OF THE SCANNING ELECTRON MICROSCOPE A schematic diagram is shown in Fig. 1. The electron optical system consists of a gun followed by a series of lenses which focus the electron beam onto the surface of the specimen. The beam is scanned in a rectangular raster across the specimen surface and, by amplifying the secondary electron current from the 'pecimen, a picture of the specimen surface is built UP sequentially on the face of the display cathode-ray tube. The magnification of such a system is given by the ratio of the scan amplitude on the display cathode-ray tube to

Jan 1, 1965

By D. M. Kehn

A method has been devloped for chromatographic analysis Of the vapor and liquid phases Of a a system containing methane to components having 20 or more carbon atoms. The method uses a windowed equilibrium cell in which volumetric phase behavior of the system can be observed accurately and from which small samples of gas or liquid can be withdrawn for analysis. Analyses are made using two chromatographs, one for the lighter and one for the heavier components in a sample. Combination of the two analyses yields a detailed analysis of the gas or liquid sample. The complexity of the condensate heavy ends is evident from the chromatograms of these fractions, and the predominance of the paraffin hydrocarborn serves as a useful marker in interpreting the chromatograms. The K-values obtained in this analytical method are presented for a high-pressure condensate system and predict closely the observed volumetric behavior of the system. INTRODUCTION Quantitative analysis of hydrocarbons from natural gas reservoirs is necessary for several reasons—to calculate the amount of sales gas produced, to calculate the amount of natural gasoline produced, to plan a liquid recovery system, or to calculate the potential economic value of a reservoir produced under one or more of several different conditions. Analysis of natural gas fluids produced to the surface consists of identifying and computing the mol fraction of each component of the mixture. Although methane is the predominant component, varying amounts of ethane, propane, butane, pentanes and heavier components are also present. Materials containing up to 30 carbon atoms occur in amounts which decrease with increasing molecular weight. However, the quantities of components in the 20 to 30 carbon atom range are usually so small that their importance is negligible, and they are undetect-able in natural gas by ordinary analytical methods. All the components up to those having 20 carbon atoms may sigsficantly affect phase behavior, however. Commonly, only the methane-through-pentane fraction is analyzed quantitatively for each component, while components heavier than Pentane are lumped and repored as "hexane- plus". Expensive, tedious techniques are required for analysis of this fraction. Consequently the detailed analyses needed for prediction of reservoir behavior are usually undertaken only when major gas fields are being developed. The need for complete analyses of condensate systems is apparent when it is recalled that most gas fields are produced by pressure depletion. As the pressure declines, some of the heavier hydrocarbons are lost as liquids which are in the reservoir. In many instances the amount of liquid in equilibrium with the gas phase at high pressure constitutes only 1 or 2 mol per cent of the total system. Flash calculations generally must predict the actual amount of liquid with an accuracy of a few per cent in order to be useful. This retrograde condensation has been understood for years, but accurate correlation methods to permit quantitative prediction of phase behavior in the retrograde region are not presently available. The increasing importance of natural gas has made accurate prediction of phase behavior and composition of produced natural gas streams an economic necessity. The work reported here was undertaken to provide a rapid, economical method for obtaining the vapor-liquid equilibrium information needed to predict accurately the composition of the fluids produced from a gas reservoir throughout its life. TO develop this method, a pressure cell equipped with windows was designed and built for observing the volumes of liquid and gas present at reservoir pressures and temperatures. Use was made of established chromatographic methods for rapid and detailed analysis of both phases. This paper describes the equipment and techniques developed for obtaining vapor-liquid equilibrium data, presents the results of analyses of a condensate system, and indicates the usefulness of these data in predicting hydrocarbon phase behavior. DESCRIPTION OF EQUIPMENT USED The equipment used in obtaining the required information on phase behavior and the complete analysis of hydrocarbon mixtures through C, will be described first, followed by a discussion of the operation of the equipment. It will be helpful, however, to consider first a brief outline of the technique used. A sample of separator gas and liquid is charged to the windowed cell (see Figs. 1 and 2) where volumetric equilibrium phase behavior at reservoir pressures and temperatures can be determined. Then samples of the coexisting phases are withdrawn. The methane-through-pentane fraction is analyzed with a chromatograph equipped with a hot-wire detector, and the pentane-plus fraction is analyzed with a second chromatograph equipped

Jan 1, 1965

By R. H. Ernst, H. R. Ogden, D. J. Maykuth

AT present, no theories exist which allow prediction of the effect of alloying additions on the thermoelectric properties of metals. Nevertheless, Battelle and others1 have observed that, at high temperatures, the peak thermal electromotive-force output (relative to a platinum standard) occurs with metals in Group VI of the Periodic Chart. The authors suspected that this peak was associated with the fact that maximum electronic bond stability is achieved with these metals which have six bonding electrons per atom. On the basis of current electron-concentration theory for transition metals and alloys:' it was surmised that the addition of valency electrons to metals of Groups IV and V (accomplished by the addition of metals from Groups VI, VII, or VIII) should progressively increase the thermoelectric-power output of the resulting alloys until an alloy composition is reached at which the number of valency electrons per atom is six. A further increase in the ratio of valency electrons per atom should then decrease the thermoelectric power. In contrast, the addition of bonding electrons to Group VI, VII, or VIII metals should decrease their thermoelectric power since the electron per atom

Jan 1, 1965

By E. L. Howard, R. S. Barney back

E. L. Howard (Chief Testing Engineer, Pacific Cement & Aggregates, Inc., San Francisco, Calif.) We have made concrete with all the materials mentioned by Mr. Barneyback, including sawdust. He has highlighted the principal problems and effects found when these light materials are used as concrete aggregate. We can only agree with the inter-relationship he has emphasized between grading, specific gravity and unit weight. Uniformity in these characteristics helps to assure good concrete. Mr. Barneyback says the design of lightweight concrete mixtures "is a complete mystery to most engineers". He is wholly right in his evaluation of our ability generally to put together a concrete using lightweight aggregate. A study of the references he has appended will yield little comfort in the matter of proportioning. Much remains to be done in this area of concrete. We believe Mr. Barneyback has treated the subject, though briefly, in an excellent manner.

Jan 1, 1965

By A. J. Jacobs

THE purpose of this note is to draw attention to a set of tables, recently compiled in Rocketdyne Research Report No. 64-19, under the title "Crystal-lographic Data for Indexing Cubic Twin Reflections and Cementite (Fe3C) Reflections in Electron Diffraction Patterns."' These tables were an outgrowth of electron-diffraction work conducted over the past several years on steels, precipitation-hardening aluminum- and nickel-base alloys, molybdenum, tantalum, and tantalum-base alloys. The first table lists the indices of possible twin reflections for all the possible twinning planes in bcc and fcc lattices. The twin reflections correspond

Jan 1, 1965

By W. I. Duvall, D. E. Stephenson

A theoretical solution is given for the energy that is radiated outward when either a cylindrical or spherical cavity located underground in a uniform stress field is suddenly created or enlarged. The method of derivation shows that the stress field in the solid rock surrounding the opening does work on the rock because of elastic displacements that result when the size of the cavity is increased. The amount of this work is sufficient to account for both the increase in the strain energy in the rock surrounding the opening and the seismic energy that radiates outward. Thus, the source of the radiant seismic energy is mainly the gravitational potential energy and not the strain energy stored in the rock. The amount of the radiant seismic energy is directly proportional to the volume of the rock removed from the opening or relieved of stress. Seismic energies from rockbursts are compared with earthquake energies. Also, the amount of gravitational potential energy released by underground explosions is calculated and found to be small compared to the seismic energy generated by the detonation of the explosive. A review of the early literature on rockbursts shows that a number of investigators calculated the amount of energy released by rockbursts. 1-5 However, none of these papers give the formula used to make these calculations or a reference to the derivation of any formulas. The general impression that one obtains from these early papers is that the main source of the seismic energy released by rock-burst is the strain energy stored in the rock before it is fractured. However, a few of the early papers appear to have considered the solid rock at a distance from the mine opening as a possible source of the seismic energy. Recently Black and starfield7 gave a theoretical solution for the strain energy in a stressed plate with and without a circular hole. Also, Press and Archambeau8 gave the theoretical solution for the seismic energy released when a spherical cavity is created in rock subjected to a three-dimensional stress field. Both of the above theoretical papers start with the condition of no opening and calculate the strain energy before and after the opening is suddenly formed. Neither of these papers appear to have calculated the work done by the applied stress field as the cavity is enlarged. The rockburst problem associated with deep mining is concerned with the failure of the solid rock surrounding an underground opening. Therefore, it seems appropriate to consider theoretically the problem of suddenly enlarging the size of an existing opening. The purpose of this paper is to present the theoretical solution for the energy that is available for release as seismic energy when an underground circular tunnel or spherical cavity is suddenly enlarged in diameter. To keep the mathematics as simple as possible, a uniform radial applied stress field is assumed and the rock is assumed to be isotropic, homogeneous and perfectly elastic.

Jan 1, 1965

By R. D. Pehlke, J. V. Gluck

The effect of small additions of silver on the actiziity of zinc in dilute solution with molten bismuth has been determined ill the range 450° to 650°C. Experimental measurements were made in a multi-electrode galvanic cell. All zinc activities showed large positive deviations from Raoult's Law. The results are expressed in terms of the interaction parameter EJ, as defined by Wagner. In the binary Zn-Bi system, Henry's Law was followed at zinc concentrations below 5 mol pct, thus indicating that the binary or self-interaction parameter of zinc in bismuth is essentially zero. The Henry's Law con- THE determination of thermodynamic interaction parameters requires accurate knowledge of solute activities in the dilute-solution region. Dealy and Pehlke1 have summarized the basis for interaction relations, discussed some theoretical implications, and presented a compilation of interaction parameters calculated for molten nonferrous alloys from stant ranged from 2.43 at 650°C to 3.96 at 450°C. The binary zinc activities were consistent with published data for higher zinc concentrations . The ternary interaction parameter ranged from -1.90 at 650°C to -3.30 at 450° C, varying linearly with the reciprocal of the absolute temperature. The negative value for the parameter reflects the fact that addition of silver decreases the activity of zinc in solution with bismuth. data available in the literature. Most of the data were for two-component systems from which only the self-interactions, Ei, could be calculated. Concentration ranges were often such that a considerable extrapolation was required for calculations at lnfinite dilution. The data for ternary systems were quite limited and often unavailable in suitable systematic fashion—thus few values of the parameter e| could be obtained. Knowledge of both the binary and ternary interaction parameters is necessary for the estimation of the activity coefficient of a given dilute solute in

Jan 1, 1965

By Hsun Hu

Based on Kurdjumoiv-Sachs orientation relationship for the fee bee transformation in metals, the jirzal crystal orientation resulting from successive transformations of bee-fee-bee has been analyzed mathematically. There are 528 different variants; many of ther are crystallograpyically equirvalent. Specific examples show that, for equal probability of all the variants, the principal crystallographic axes [100 ], [110], and [111] of the initial bcc crystal can be transformed into vairous axes in the fina1 crystal However, fur each of these principal crystallographic axes, a continuous range of orientation within certain regions of the unit triangle is completely avoided by the finctl Crystals. For uses of higher indices, the final orientations are more uniformly distributed throughout the unit triangle. Results from the PI-esent analysis are in good agreement with preferred Oientations Observed in a zone-meltecl iron bar. THE allotropic forms of iron are characterized by the unusual fact that at both high and low temperatures a bcc structure is stable, whereas at intermediate temperatures (1400" to 910°C) the metal is fcc. Hence, during cooling from its melting temperature, iron undergoes successive phase transformations ofd—? —a with corresponding changes in the crystal structure of bcc — fcc -bcc. while numerous studies have been made in the past of the 1 — a transformation in iron and in various iron-base alloys, no information is available in the literature as to the mechanism of 6 — l transformation and the lattice orientation relationship between these two phases. Experimental difficulties have apparently prevented researchers from undertaking these studies. The laltice orientation relationship between the parent and the new phases of iron resulting from

Jan 1, 1965

By Ralph Hultgren, Prodyot Roy

Manganese vapor pressures from 1250° to 1500°K were measured by conventional Knudsen and torsion-effusion methods in twelve Fe-Mn alloys with compositions from 9 to 80 at. pct Mn. The Knudsen re-sults agveed approximately with previous measurements found in the literature which indicated the solutions were nearly ideal. However, except for the higher manganese compositions, the initial torsion readings indicated much (up to 50 pct) higher vapor presszcres than the Knudsen method. These high readings decreased steadily with time. The results are interpreted as due to depletion of surface concentration of manganese during evaporation. Thus the initial torsion readings are the most nearly correct and Knudsen methods on alloys are to be regarded with suspicion unless it can be demonstrated that diffusion rates are rapid enough to replenish surface concentrations depleted by evaporation. For the lowest manganese contents and highest temperatures, depletion causes initial torsion readings to be too low. FEW thermodynamic data are available for alloys of the high-melting transition metals due primarily to experimental difficulties at the high temperatures involved. Measurement of vapor pressure is one of the most promising techniques to be applied to this problem. From the vapor pressure of a component of an alloy phase, its activity or its partial molar Gibbs energy can be directly calculated. From measurements over a sufficient range of temperatures and compositions the partial and integral Gibbs energies, enthalpies, and entropies may be determined through Gibbs-Duhem integration. For solid phases of variable composition, which commonly are found in alloys, measured vapor pressures are low because of depletion of the surface concentration of the more volatile component as it is selectively vaporized. Diffusion from the interior tends to restore the depleted concentration. The seriousness of the effect depends on the relative rates of diffusion and vaporization. Although depletion has been recognized as a factor,' direct measurements of its rate are lacking and quantitative estimates of its effect on measurements are uncertain. In the present work the vapor pressures above a series of Fe-Mn alloys have been measured by the torsion-effusion method. This method permits a measurement of the vapor pressure of manganese as soon as the sample comes to temperature and continuously throughout the run. The rate of decline of the apparent vapor pressure measures the rate of depletion and the torsion reading at zero time should be correct. At high manganese concentrations (70 and 80 at. pct Mn), the torsion reading remained nearly constant; surface depletion was negligible. There was a slow drop in measured pressure due to bulk loss of manganese from the sample. However, for lower manganese contents, especially at high temperatures, the depletion effect was considerable and the apparent vapor pressure decreased steadily with time. For these alloys the Knudsen method should give pressures which are too low. The measurement of pressure in the Knudsen method cannot be made until enough manganese has been vaporized to be weighable. The Knudsen result is therefore an integrated average between the initial and final vapor pressures. To verify this, conventional Knudsen measurements were also made with results in approximate agreement with previously published Knudsen measurements for these alloys. As expected, for the lower manganese contents the initial torsion readings of pressure were as much as 50 pct higher than the Knudsen. THE APPARATUS The apparatus, shown in Fig. 1, is capable of operating to temperatures up to 2000°K. A vacuum of 5 x 10"6 mm Hg can be maintained. Temperatures were measured to +3° by a W-Re thermocouple placed in the dummy cell, N. The torsion cell consisted of two alumina crucibles with holes in their covers. They were placed in the molybdenum holder shown suspended from the torsion wire. Rectangular torsion wires (1 by 4 mm) were found to have superior sensitivity and less residual distortion than circular (2-mm-diameter) wires. The precision of angular measurement was found to be *0.025 deg; the variation is no doubt due to temperature fluctuation and vibration. For the Knudsen experiments the alumina cell was set on the support, N. SAMPLE PREPARATION 800-g samples were prepared by melting together electrolytic iron and electrolytic manganese and pouring the melt into a water-cooled copper mold. Melting and pouring were done under a helium at-

Jan 1, 1965

By K. Barron

The glass insert stressmeter, or photoelastic stressmeter, is an instrument designed to determine stress changes occurring in rocks. It has several potential advantages over other such devices in that it is a biaxial device, it is simple and it is cheap to make. The object of this study was to assess the behaviour of the meter under biaxial loads and to examine some of the problems associated with measurement and interpretation of the fringe pattern. This assessment has been carried out by comparing theoretical and laboratory behaviour of the meter. It has been shown that: a) There are certain optimum measuring points in the meter at which measurements should be made for best accuracy. The position of the points depends on the ratio, n, of the biaxial stresses. b) The meter&apos;s sensitivity can be assumed to be independent of the rock modulus E provided that the rock modulus is < 2.5 x 106 psi and not, as previous workers have assumed, if E < 5 x 106 psi. c) There are several methods of separating the principal stresses; some of these are unsatisfactory. A new method is proposed and discussed. d) The meter sensitivity decreases as the ratio of the biaxial stresses approaches unity; the accuracy thus also decreases. e) The axes of symmetry of the fringe pattern give an excellent indication of applied stress direction. f) Laboratory calibrations are in good agreement with theory. The glass insert or photoelastic stressmeter is an instrument designed to determine stress changes occurring in rocks. It has several potential advantages over other such devices in that it is a biaxial device, it is simple and it is cheap to make. This stressmeter has been described in detail.l,2 Basically it is a hollow glass cylinder that has at one end a light source and filters producing circularly polarized light. The glass cylinder and source are grouted into a borehole in rock and the face of the cylinder is viewed through a quarter wave plate and an analyser. If, after installation, a stress change occurs in the rock, then a distinct colored isochro-matic fringe pattern is seen in the meter. The fringe order at any point in the meter can be determined by counting the fringes and measuring the fractional fringe orders by the Tardy compensation method. The relation between the fringe order at any point and the applied stress change can be determined either by calculation or by calibration. The object of this study was to assess the behavior of this stressmeter under biaxial loading conditions and to examine some of the problems of interpretation of the fringe pattern. THEORY Hiramatsu et a14 have determined the stress distribution in a hollow cylindrical inclusion in an elastic host material when subject to uniaxial stress. Using this solution, the biaxial case of stress p in the x direction and stress q in the y direction (Fig. 1) can be solved by superposition. This has been done in Appendix 1. It is shown that the principal stress difference (s1 -s2) at any point (r,?) in the cylinder is given by:

Jan 1, 1965