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By George M. Fowler, J. P. LYDEN

T HE relationship of geological structure to orebodies and to the great masses of chert in the Tri-State mining district is of such significance that it prompts a brief recital of the existing information regarding the various periods of structural deformation. We began to note a relationship between structure and orebodies early in our studies of the field, and further work revealed a like relationship of structure to the great masses of chert so commonly associated with the ore-

Jan 1, 1934

By Nicholas J. Grant, H. C. Chang

TRANSCRYSTALLINE fracture surfaces of the cleavage type have been examined by microscopy and X-rays for several metals.' These investigations revealed that the fractured surfaces were not flat and invariably had cleavage and other deformation markings on them. On the other hand, the study of inter crystalline fracture surfaces has been limited. Perryman, in a recently published paper on the inter crystalline fracture of ß-brasses,' found that a thin layer of heavily deformed metal was invariably associated with these surfaces. Furthermore, the thickness of this layer was found to depend on the orientation of the grain boundary surface with respect to the applied stress. The mechanisms of grain boundary sliding and intercrystalline fracture have been presented in two previous papers,which described certain aspects of the deformation of a 20 pct Zn-A1 alloy. It is the purpose of this paper to present some observations on the structure of intercrystalline fracture surfaces and to correlate the structure of such surfaces with the mechanism of intercrystalline fracture. Experimental Techniques—The high purity 20 pct Zn-Al alloy was generously supplied by the Research Laboratories of the Aluminum Co. of America. Two sizes of specimen were used; the first had two parallel flat surfaces of dimensions 1x0.17x0.09 in. and the second was round with a 0.25 in. diam. A grain diameter of 1 to 3 mm was obtained by annealing the specimens at 1000°F for 24 hr. The specimens were then air cooled. The specimens were subjected to creep at 500°F and 2300 psi. The rupture times ranged from % to 3 hr, with one room temperature tensile test. It has been mentioned previous1y" that the intercrystalline fracture surfaces of this alloy, when tested under the conditions given above, are sharply defined. In the optical examination of the fracture surfaces, whenever possible, magnifications of at least X250 were used. The locations of the regions examined, both optically and by X-rays, were selected to give several fracture surface orientations with respect to the stress axis and to the specimen surfaces. This was possible for the X-ray studies since the grain diameters were large compared to the X-ray beam. A film to specimen distance of 3 cm, a 1 mm pinhole and Cr radiation were used for the Laue back reflection pictures.

Jan 1, 1957

By J. M. Toguri, K. Grjotheim

It is known 1,2 that the equilibrium between titanium metal, TiCl2 , and TiCl3, in a solvent of molten metal chlorides, is influenced both by the total amount of dissolved titanium and by the type of solvent. Assuming that the trivalent titanium forms the complex ion Ti111 Cl4, the equilibrium reaction may be expressed by the following equation, (Me) TiIII cl4+ 1/2 Ti = 3/2 TiII cl2+ (Me) Cl The ideal ionic equilibrium constant for this reaction is, Where the N's are the molar ionic fractions in the equilibrium melt, and (Me) the different types of cations present in the equilibrium mixture. The following thermodynamic relation is derived between Kand the concentration of cations in the equilibrium melt, mix The N"S are the equivalent ionic fractions, and so forth are constants corresponding to the standard changes in free energy for reactions in melts where only the cation indicated is present, and f (y1) is a function of the activity coefficients in the equilibrium mixture. When this term vanishes, a simplified linear relationship between In Kideal and the concentration is obtained. The simplified relationship has been applied with satisfactory results to the experimental data of Mellgren and pie,' and Kreye and Kellogg.2 MANY existing methods for the production of light metals involve the reduction of their respective metal halides in the presence of salt melts composed of alkali or alkaline earth chlorides. In such a solution phase, the light-metal halide may undergo stepwise reduction from a higher, to a lower valence, and finally to a zero valent state. In this connection, the disproportionation equilibrium is of great interest. In the case where the higher valence is three and the lower valence is two, the disproportionation equilibrium may be written as follows, 3 Me11 = 2 Me111 + Me [I] If this equilibrium occurs in a salt melt containing a large excess of alkali chlorides, a typical ionic melt is obtained. It is then possible to formulate the cation equilibrium: 2 Me+h' + Me = 3 Me++ [II] Reaction [11] is analogous to a cation exchange reaction. It has been shown thermodynamically that the equilibrium constant for such a reaction in 2

Jan 1, 1960

By J. C. Martin

Stmplified equations are developed for the flow of fluids in gas drive reservoirs in which the effects of gravity can be neglected. The results show that the pressure distribution is governed by a nonlinear heat flow type of equation, and the saturation distributions are related to the pressure by the same equations QS those developed by Muskat for the average pressure and saturations in gas drive reservoirs. Unrler certain conditions the equation for the pressure can be approximated by the linear form of the heat flow equatlon. This equation tk analogous to the equation for the pressure in single-phase compressible flow The analysis reveals that the equation for the pressure in n~ultiphase flows can be obtained directly from the equation for the pressure in slngle-phase flows by simply replacing the single-phase compressibility by the total compressibility and the single-phase mobility by the sum of the mobilities of all the fluids present. Perrine's method of pressure buildup analysis for multiphme flows is based on these same substitutions. Thus, the development presented in this paper constitutes a theoretical justification for Perrine's method of pressure buildup analysis. One of the most difficult problems associated with the production of oil is the determination of the flow of the fluids within the reservoirs. One purpose of this paper is to present the development of simplified equations for the flow in gas drive reservoirs. The other purpose is to present some of the needed theoretical foundation for the methods currently being used in the analysis of multiphase pressure buildup data. The analysis presented in this paper makes use of a partial linearization of the equations governing multiphase flows. It is felt that the process of linearizing or partially linearizing the nonlinear equations of multiphase flows can lead to useful results since this process has proved extremely valuable in the study of other fields of science and engineering where nonlinear equations are encountered. Pressure buildup data of shut-in wells have been used for many years to estimate the static reservoir pressure. These data have also been used in studying the aver- age permeability both away from and close to the well-bores. The majority of the buildup data are obtained from wells producing two or three fluids. As yet the theoretical foundations for the methods of buildup analysis used in connection with rnultiphase buildup data have not been established. A number of methods of analysis of pressure buildup data have been developed." Most of these methods apply only to single-phase flows, and almost all of the theoretical analysis is confined to single-phase flows. Perrine' developed a method of analysis for rnultiphase flows from the method for single-phase flows of Miller, Dyes, and Hutchinson.' He did this by simply replacing the single-phase compressibility by the multiphase compressibility and replacing the single-phase mobility by the sum of the mobilities of the fluids in the rnultiphase flows. Obviously, such a procedure lacks a certain amount of theoretical justification, and such practices can lead to erroneous results. Fortunately, Perrine's results have a theoretical justification, and this justification is presented in the following discussion. It is assumed that gravitational effects and the cornpressibility of the rock can be neglected. Under these assumptions the equations governing the simultaneous flow of gas, oil and water in porous media areo* The preceding equations can be expanded into the following expressions.

By Robert G. Nisle

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

By O. G. Lellep

Modern shaft kilns in Europe are fully mechanized and burn cement of acceptable quality at 700,000 Btu per bbl and lime at 3.2 million Btu per net ton. Rotary kilns for cement have increased in thermal efficiency by using exit gas heat for preheating incoming raw material and by recovering heat from outgoing clinker in air-quench coolers. The dry process Lepol or ACL kiln has the lowest fuel consumption, 580,000 to 630,000 Btu per bbl, and very low dust loss, about 1 pct weight of clinker. The Holdebank-Gygi system reaches 720,000 Btu per bbl. The calcinator kiln for the wet process consumes 1.1 million Btu per bbl. IN every country economic circumstances prescribe the method used to produce a commodity at lowest cost. In Pennsvlvania a man's wages for working 4 hr buys a ton of coal wholesale; in Germany a laborer must work 40 hr, or ten times as long. In western Europe, therefore, conservation of fuel is of primary importance, and recent practices of burning lime and cement differ from those employed in the United States. 'This Paper presents data collected during a trip through western Europe in 1953. Considered uneconomical, shaft kilns for burning

Jan 1, 1955

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By R. G. Turner, M. G. Hubbard, A. E. Dukler

Gas phase hydrocarbons produced from underground reservoirs will, in many instances, have liquid phase material associated with them, the presence of which can affect the flowing characteristics of the well. Liquids can come from condensation of hydrocarbon gas (condensate) or from interstitial water in the reservoir matrix. In either case, the higher density liquid phase, being essentially discontinuous, must be transported to the surface by the gas. In the event the gas phase does not provide sufficient transport energy to lift the liquids out of the well, the liquids will accumulate in the wellbore. The accumulation of the liquid will impose an additional back pressure on the formation that can significantly affect the production capacity of the well. In low pressure wells the liquid may completely kill the well; and in the higher pressure wells there can occur a variable degree of slugging or churning of the liquids, which can affect calculations used in routine well tests. Specifically, the calculated bottom-hole pressures used in multirate backpressure tests will be erroneous if the well is not removing liquids on a continuous basis, and gas:liquid ratios observed during such a test may not be correct. Several authors1,3,8,14 have suggested methods to determine if the flow rate of a well is sufficient to remove liquid phase material. Vitter14 and Duggan' proposed that wellhead velocities observed in the field would be adequate for keeping wells unloaded. Jones8 and Dukler3 presented analytical treatments resulting in equations for calculating, from physical properties, the minimum necessary flow rate. An analysis of these studies indicates the existence of two proposed physical models for the removal of gas well liquids: (1) liquid film movement along the walls of the pipe and (2) liquid droplets entrained in the high velocity gas core. Although there probably is a continuous exchange of liquid between the gas core and the film, they will be treated separately for the purposes of this study. The development and comparison of these separate models with experimental data will permit the determination of which, if either, is the controlling mechanism for the removal of liquids from gas wells. The Continuous Film Model Liquid phase accumulation on the walls of a conduit during two-phase gas/liquid flow is inevitable due to the impingement of entrained liquid drops and the condensation of vapors. The movement of the liquid on the wall is therefore of interest in the analysis of liquid removal from gas wells. If the annular liquid film must be moved upward along the walls in order to keep a gas well from loading up, then the minimum gas flow rate necessary to accomplish this is of primary interest. The analysis technique used follows Dukler2 and Hewitt5 and involves describing the profile of the velocity of a liquid film moving upward on the inside of a tube. The minimum rate of gas flow required to move the film upward is then calculated.

Jan 1, 1970

By Peter F. Weiss, H. Riedler, I. M. Moschitz, A. Olsacher, G. B. Fettweis

CONTENTS : 1. NATURAL FACTORS Geology Petrography and Rock Mechanics Mining System Orientation Rock Bolting System Movability of the Ore Grain Size Distribution Permeability Contamination Value of the Ore Hydrology 2. TECHNICAL FACTORS Height Length and Width Drawing Areas Time Factor Water Predrainage Surf ace Draining Underground Draining Advancing Slitting Sequence of Development Initiation of the Caving Process Drawing Rate 3. SPECIFIC MINING RULES Advancing Development Drawing Rate Interruption of Drawing (Water Distribution, Concentration of Mud, Dilution) Blasting 4. CONTROLS Safety Controls for Operation Computerised Drawing Control Structure of the Computer Program Hard Ware Print Outs 5. SUMMARY 6. ACKNOWLEDGEMENTS 7. REFERENCES Under the heading "Development System for Block Caving under Severe Conditions" a report was presented to this congress regarding a magnesite mine using block caving for several years. On account of the experience gathered in this mine and the results of far reaching exchange of experience, as well as under due consideration of the international literature it is tried to systematically list and briefly discuss the following factors that have to be considered for development and draw control of block caving. 1. NATURAL FACTORS It is self evident that this implies all those circumstances given by nature and which cannot be altered by man. Any mining activity is subjected to those and the success is depending on how far technology can be adjusted to those conditions. Geology Deposits of considerable thickness with rather steeply inclined flat-faced contacts are optimal for block caving. While vertically there is practically no limitation- for the deposit, theoretically, the smallest horizontal basis apt for operating block caving is the minimum area necessary to get the rock to completely cave in by undercutting and drawing. Practically, only consider- ably bigger main dimensions are found, mainly because of technical factors (machinery and equipment) and economic factors (cost ratio of exploration vs. development, danger of contamination).

Jan 1, 1981

By John R. Eckel

A Iaboratory drilling rig has been devised and placed in operation which permits the application of hydrostatic, terrastatic, and formation pore pressures to a rock sample for drilling under controlled conditions. Calibrated rests of this equipment in-dicate qualitative agreerment with field results on the effect of weight on bit, rotary speed, and rate of circ~~lation on drilling rate. Tests under pressure, using water and air as the drilling fluids, indicate that when drilling saturated limestone samples, a pressure differential between hydrostatic and formation pressure is the only pressure which affects drilling rate. A differential in either direction causes a reduction in rate, but the same diflerential from the wellbore into the formation causes the greater reduction. Also, in lime.stone, air favorably affected drilling rote only when compared to water at high hydrostatic pressurre, all other conditions remaining constant. Large increases in drilling rate with air could be obtained in the laboratory only while drilling a shale, which offered a limited permeability to nitrogen and which could be drilled with a differential from the formation into the wellbore. In general, the magnitude of the changes due to the pressure effect were small compared to changes in drilling rate obtainable by changing either bit weight or rotary speed. INTRODUCTION In the course of Humble's drilling research program, the desirability of investigating several factors which lend themselves to laboratory rather than field study became obvious. Principal reasons for this are the expense involved in field studies and the difficulty of exercising the required degree of control. Of primary importance are investigations of the effect of fluid pressure on rock rate, the effect of pressure on rock drillability, and a study of the fundamental mechanics of rock failure and chip generation. Several years ago some work in the laboratory on the effect of mud properties on drilling rate was re- ported to the API', but the completion of this work and the investigation of the other variables affecting drilling rate required equipment somewhat more elaborate than that used on these earlier tests. This equipment has been assembled to form Humble's Drilling Engineering laboratory. To date only the effect of pressure on rock drillability while using water and air has been investigated, and this work is not yet complete. Facilities are available to investigate the effect of fluid properties on rate of penetration, and information is being assembled on a current basis on the mechanics of drilling. The sequence of presentation in this progress report is somewhat different from that in which the data were obtained since the order of ex-

By Douglas D. Donald

The New Jersey Zinc Co. successfully holed through a 2 1/2-mile haulage tunnel connecting its new Ivanhoe shaft with the Van Mater Shaft at Austinville, Va. This 8x 10-ft cross-section tunnel was driven from both ends and met at a point approximately a mile from one shaft and a mile and a half from the other. In order to make certain that the faces met accurately on line and grade it was necessary to refine conventional mine surveying practices. The mines that are serviced by these shafts are located in the southwestern part of Virginia approximately midway between Roanoke and Bristol at the west foot of the Blue Ridge. While the presence of lead-zinc sulfide ores has been known in this area for more than 200 years, it was in 1902 that New Jersey Zinc Co. acquired the Austinville property, which has been in constant operation since that time. About ten years ago the company undertook an extensive diamond drilling program at Ivanhoe several miles to the southwest. This program was successful in locating sufficient ore to justify the purchase of a number of the properties in this area and plans were made to develop the new orebodies. The discovery of this ore as well as substantial addi- tional reserves at Austinville resulted in a decision by the company to increase its daily milling capacity to 3000 tons, of which about 1000 tons would be supplied from the Ivanhoe mine. After careful consideration of all possible methods of transporting this volume of ore from Ivanhoe to the mill, it became evident that diesel locomotive haulage through a 2½-mile tunnel between the two mines would best suit prevailing conditions. Since the lowest operating level, known as the 1100 level, of each mine would be at approximately the same elevation, it was obvious that such a tunnel should be driven on this level. Not only would this tunnel facilitate feeding Ivanhoe ore into the underground crusher and skip loading installation at Austinville, but it would also open up a known orebody 5000 ft southwest of the Van Mater shaft. In addition it would provide a valuable diamond drilling base from which a large and a potentially favorable but untested block of ground might be explored. In order to hasten the completion of the tunnel, it was felt that it should be driven from both ends. ENGINEERING CONTROL PROCEDURES It was vital that the tunnel junction be made accurately on line and grade; thus it was felt that engineering control of an unusually high degree of reliability was required to prevent an accumulation

Jan 1, 1959

By L. W. Berger, and R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were stzdied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.' This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

By H. H. Dreissen, F. J. Fontein

The operating principle of the classifying cyclone has been described often but some special aspects of the cyclone receive further clarification here. In addition, several uses of the classifiers are summarized and made clear by means of practical examples. In coal and ore washeries, the washing cyclone is widely used for the separation by specific gravity of sizes up to about 12 mm. This application has lately been extended to the separation by specific gravity of particles up to about 50 mm. This use makes special demands on the construction and wear resistance of the cyclone. The sieve bend, a development of the Dutch State Mines which is less well known than the hydrocy-clone, is dealt with at some length. The sieve bend is an apparatus designed for wet screening. Attention is given to the variables influencing the performance of the sieve bend. Hydrocyclones are now so widely applied that it would be difficult to find an industry not, directly or indirectly, using them or knowing how to use them since publications on this subject abound.1-3,5,9-11,13-15 However, because of the large number of variables influencing the operation of classifying cyclones, it is not entirely possible to calculate the results of this type of cyclone. Therefore, a number of lesser known variables will be discussed here along with some special applications of the classifying cyclone. FACTORS INFLUENCING CYCLONE CLASSIFICATION Shape of Particles: The shape of particles may cause a much coarser classification than the one expected, considering the sieve analysis and the cyclone dimensions chosen. This was clearly shown by feeding a mixture of spheres and disks in water into a cyclone. The spheres were 0.36 mm diam and the disks, 3 mm diam and 0.03 mm thick. These dimensions were chosen in order that the disks and spheres might have the same rates of fall under gravity. Both spheres and disks had a specific gravity of 1.05. The results obtained with these particles in a cyclone are summarized in Table I. Test No. 2 shows that the catch of spheres was

Jan 1, 1963

By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

By L. W. Berger, R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were studied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.' This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

By L. D. Jaffe

IN previous metallographic work on titanium and its alloys, difficulty has been encountered in distinguishing spheroidal particles of titanium hydride, dispersed in a-titanium, from other phases that may be present, such as p-titanium. This problem is common in examination of commercial unalloyed titanium.' In the course of an investigation of the Ti-H phase diagram, it was noted that titanium hydride, dispersed in a matrix of a-titanium, showed strong optical anisotropy when examined under polarized light. With sensitive tint illumination, particles of the hydride, when the stage is rotated, changed from bright yellow to bright blue in color. Since P-titanium is cubic, it showed no color change on rotation, remaining dark gray or blue-gray. Although a-titanium is hexagonal, it showed only a minor color change, going from pale pinkish-blue to pale purplish-blue. These colors could be modified somewhat by adjustment of the illumination. They were observed in specimens mechanically polished, both without etching and after etching with hydrofluoric acid-nitric acid mixtures in either water or glycerine. The strong color change of the hydride seems to offer a simple method for its metallographic identification. Optical anisotropy of titanium hydride is inconsistent with its accepted face-centered-cubic structure.' Samples of iodide titanium containing 6 to 40 atomic pct deuterium were prepared for diffraction studies. After deuterating and slow cooling' the samples were held 21 % hr at 400 °C, water quenched, held 61 hr at 100°C and quenched, then held 64% hr at 255 C and quenched. Debye ex-posures with MoKa X-rays and 1.111A neutrons were made at room temperature of samples as-deuterated and after the 100" and 255°C treatments. Table I shows the lines observed, in addition to those attributable to a-titanium. These data show that the hydride phase was not cubic, but probably tetragonal. The titanium atoms appeared to form a body-centered-tetragonal lattice complex, two titanium atoms per cell, with approximate dimensions: a = 3.12A, c = 4.18A, and c/a =1.34A. This is equivalent to a face-centered-tetragonal complex, four titanium atoms per cell, with approximate dimensions: a = 4.42A, c = 4.18A, and c/a - 0.946A. The presence of the 2.98 and 1.81A neutron lines indicates that the true Bravais lattice is not identical with this lattice complex, but may be primitive tetragonal with dimensions some multiple of those of the complex. The relative intensities of the hydride and a-titanium X-ray lines as functions of overall composition indicated that the hydride, presumably in equilibrium with the a at 100" to 255"C, contained more than 62 atomic pct H. Acknowledgments The experimental work covered in this report was done at Brookhaven National Laboratory, through the courtesy of D. Gurinsky. The cooperation of J. Sadofsky, 0. Kammerer, A. McReynolds, and A. Cendrowski is gratefully acknowledged.

Jan 1, 1957

By E. P. Abrahamson II

The effect of transition elements which form binary solid solution upon the recrystallization temperature of zirconium has been investigated. All additions raised the recrystallization temperature. A correlation is obtained between the logarithm of the rate of change of recrystallization temperature with atomic percent solute and the free atom ground state electron configuration of the solute element. ThE work of Abrahamson, et al., on dilute binary solid-solution alloys indicated a correlation between the free-atom ground state electron configuration of the solute and either the brittle-ductile transition or recrystallization temperature. These studies were carried out on bcc base materials. The implication is that the outer s and d electrons of the solute are the prime determinant of the absolute rate of change of recrystallization or transition temperature. Furthermore, the limit of linearity has been shown to be a function of solute electron configuration for recrystallization in iron and vanadium. To date no Complete systematic recrystallization study of dilute binary zirconium base alloys has been made. It is the purpose of this study to note whether the change in solvent structure from bcc to hcp will influence the correlation. It was also desired to learn more of the role of the electron configuration of the solvent on recrystallization temperature. PROCEDURE All alloys were made using 99.87 pct Zr with 0.01 Cr, 0.04 Fe, 0.006 Hf, 0.003 Mg, 0.003 Mn, 0.003 N, and 0.080 0 (132 BHN). The solute elements were 99.9 pct pure. According to the published binary phase diagrams6 and metallographic examinations at X750, all alloys used were solid solutions. The alloys were arc melted and remelted six times in the form of cubic 200-g buttons under an argon atmosphere. They were then hot pressed at 950°C to 0.450 in., upset pressed to 0.350 in., and annealed at 800°C for 1 hr. The specimens were then Blanchard ground to 0.250 in., removing 0.050 in. from each side. The grain size of the material at this stage was found to be 8000 100 grains per sq mm. The specimens were then cold rolled to 0.130 in. and cold pressed to 0.125 in., yielding 50 1 pct cold work. All alloys were then chemically analyzed for the principal addition. The interstitial contents remained at the values of the starting material when checked on random alloy specimens. The rolled sheet was cut into 6.75 by 0.25-in. lengths and heat treated in a gradient furnace for 1 hr. The gradient was 250o to 900°C over the 6-in. length, recorded continuously by six thermocouples resting on each specimen. Control was 3oC, accomplished at the hot end. The recrystallization temperature was determined metallographically using polarized light. The criterion chosen was the point on the specimen showing the first recrystallized grain at a constant magnification, X200. Specimens were repeated, and the agreement was found to be 3°C. RESULTS Three different pure zirconium specimens were tested, and the recrystallization temperature was

Jan 1, 1962

By K. Takahashi, I. Iwasaki

it is well known1 that racemic mixtures of optical isomers can be separated by passing their solutions through a column packed with r- or 1-quartz powder so that one of the isomers becomes adsorbed selectively on the asymmetric quartz surfaces. Although the natural occurrence of r- and 1-quartz is more or less equally distributed, some localities show enough deviations toward a higher proportion of l-quartz2 to suggest that optical isomerism might influence quartz flotation. Beta-amines have an asymmetric carbon atom, and therefore optical activity may be expected. Beta-amines are reported to behave quite differently from alpha-amines in the flotation upgrading of certain oxidized iron ores.3 It is of interest, for both practical and theoretical reasons, to determine whether or not optical isomerism plays a role in the amine flotation of quartz. In this article the results of Hallimond tube flotation tests and of adsorption measurements using d-beta-phenylisopropylamine on both r- and 1-quartz are compared. D-beta-phenylisopropylamine was chosen for the tests because it is commercially available in optical isomers. MATERIALS AND METHODS Brazilian quartz crystals were hand-sorted according to the difference in trigonal trapezohedral faces, and each crystal was further checked by the Airy's spiral.4 The respective crystals were then crushed, and the -150 + 200-mesh fractions were screened out for the Hallimond tube tests. The samples were cleaned by brief leaching with warm, dilute hydrochloric acid, and then by repeated rinsing with distilled water. In preparation for the adsorption measurements, they were then dry-ground in a pebble mill for several hours, washed a few times with distilled water, and finally dried in a vacuum desiccator. By means of the Krypton gas adsorption method, the specific surfaces of r- and 1-quartz samples were determined to be 27,700 and 19,800 sq cm per gm respectively, the difference being due mainly to the decantation procedure rather than to the inherent difference in their grindability. D-beta-phenylisopropylamine was the only collector used in the study. It was solubilized by neutralizing with 110% of the stoichiometric requirement of 0.1 N hydrochloric acid. The specific rotation of the d-beta-phenylisopropylamine was determined with a polari-meter using sodium D line to be, Although the d-beta-phenylis~prop~lamine showed absorption maxima in the wave length region of 250 to 270 millimicrons, due presumably to the phenyl group, these peaks were too sensitive to be used for colorimetric determination of the residual concentration in the adsorption measurements. The amine-picrate method, used in the colorimetric analysis of dodecylammonium chloride,' was found to work satisfactorily for the d-beta-phenylisopropylamine. The adsorption densities were thus determined after equilibrating 40 gm of the ground quartz sample with 300 ml of solution by tumbling in separate glass-stoppered Erlenmeyer flasks for one hour. EXPERIMENTAL RESULTS Fig. 1 presents the adsorption densities of d-beta-phenylisopropylamine on the r- and 1-quarts in the pH range of 6 to 7.5. In agreement with data reported in the literature, the adsorption density of d-beta-phenylisopropylamine was slightly higher on the r-quartz than on the 1-quartz, although the difference was not as pronounced as one might expect from the capacity of r-quartz and 1-quartz to separate racemic

Jan 1, 1969

By R. M. Goldhoff, J. W. Spretnak, R. Speiser

IT has been observed by Grange and Garvey' that the homogenization of boron-treated steels could lead to complete elimination of the hardenability effect caused by boron. The experimental conditions leading to this conclusion involved the heating of steel specimens with and without boron at 2350°F for 24 hr. To prevent oxidation and decarburization, the specimens were encapsulated under vacuum in silica tubes. This observation of permanent deterioration of boron effect was noted in both a 0.63 pct plain carbon steel and a 0.25 pct C low alloy steel, both of which had been treated with ferroboron and homogenized at 2350°F for 24 hr. In another series of boron-treated steels which had been homogenized for shorter times, the effect was to reduce, but not completely eliminate, the boron effect. Under these circumstances, it was presumed that longer heating times would cause permanent deterioration of the boron effect in this series of steels also. Since the characteristic grain boundary constituent could not be formed in any of these steels after homogenization, it was concluded that possibly boron was being converted into an ineffective form through chemical combination resulting from prolonged heating at high temperatures. Assuming the validity of this observation, a series of experiments to establish the relationship between temperature of homogenization and kinetics of deterioration was contemplated. Initially an attempt was made to reproduce the results just described. For this purpose commercial lots of AISI 8640 and AISI 86B40 steels were used. The analyses of these steels appear in Table I. Hardenability evaluation was on the basis of the hardness of normalized sections. Grange and Garvey' pointed out that these steels are air hardening to some extent and such a technique can be used. For these tests the specimens were held for 20 min in a salt bath at 1600°F and then cooled in still air. Several evacuated silica capsules containing pairs of the test steels were made up and heated for 24 hr at 2350°F. A number of failures occurred among these capsules, but evaluation of the specimens successfully treated indicated a complete deterioration of the boron effect. However, examination of the surface of the treated specimens showed that some reaction, probably with the silica tube, had taken place, since none of the specimens was bright. One further test was made at 2350°F for 12 hr, using a pair of specimens wrapped in tantalum foil prior to encapsulation. These specimens appeared bright after treatment, and their hardenability evaluation showed that no deterioration had taken place. Since these steels are extremely sensitive to de-boronization at high temperatures and particularly at long times of holding, the experimental observations raised some doubt as to the real occurrence of the permanent deterioration effect. To resolve this question an experiment was undertaken in which the high temperature portion of the treatment was completed in vacuum. For this purpose a molybdenum wound resistance furnace capable of maintaining good vacuum was used. All the pertinent accessories to this furnace were machined from molybdenum stock in order to withstand the high temperature involved in the experiment. With this equipment a temperature of 2400 °F was obtained and held under a pressure of 5x10-" mm Hg for 24 hr. A specimen of each of the two test steels was suspended in the furnace and both were heated simultaneously. Temperature was measured with a standardized Pt—Pt-13 pct Rh thermocouple, whose millivoltage at 2400°F was extrapolated from the standardization equation, good up to 2200°F. The complete evaluation of these specimens is shown in Table 11. The hardness values attained by each steel after normalizing, both before and after the prolonged high temperature treatment, remain the same. A microscopic study of the decomposition products present in the microstructures of specimens at various points in the heat treatment correlated with the hardness values observed. It seems that no permanent loss of boron hardenability effect occurs, at least in these Grainal-treated steels, when deboronization is circumvented. Acknowledgments This work was conducted under the sponsorship of the Aeronautical Research Laboratory, Wright Air Development Center, under Contract No. AF 18(600)-94, and their support and permission to publish is gratefully acknowledged. A note of thanks is also extended to the Republic Steel Corp. for supplying the materials used in the work. References ' R. A. Grange and T. M. Garvey: Factors Affecting the Harden-ability of Boron Treated Steels. Tro.ns. ASM, 1946, vol. 37, p. 136.

Jan 1, 1957