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By C. M. McKinney

Sulfur content data from Bureau of Mines routine analyses of 1,060 United States crude oils were used with crude oil production data for the years 1956-66 to prepare tables and charts that illustrate the volume and percentage distribution according to sulfur content of crude oil produced in 10 geographical areas of the United States. Similar relationships for foreign crude oils based on analyses of 201 crude oils and production during 1966 are illustrated for Africa, Canada, Middle East, and South America. Tables are included giving field name, sulfur content, geologic name and age of producing formation, depth of producing formation, and production during 1966 for 882 United States crude oils and 201 .foreign crude oils. Between 1955 and 1966 the average sulfur content of crude oils produced in the United States decreased from 0.73 to 0.67 percent.

Jan 1, 1967

By C. Q. Cupps

n view of increased interest in secondary recovery of oil in the Cut Bank field, Montana, a review has been made of unpublished data obtained during a 1943-44 study of reservoir oil characteristics in this field. Considerable uncertainty was attached to interpretations of subsurface oil sample analyses from six Cut Bank zone wells, one Lander sand well, and one Moulton sand well, because of adverse sampling conditions and wide range in the data. Much of this uncertainty has been removed by this review which has shown two of the Cut Bank zone samples and the Moulton sand sample to be representative of the reservoir oils. Estimates of original reservoir oil characteristics derived from differential-liberation analyses of these samples show that the oil in the Cut Bank zone was initially saturated at the gas-oil contact pres-sure, 750 psia, and the oil in the Moulton sand was undersaturated with a saturation pressure of only 380 psia. The rest of the samples were indicated to be nonrepresentative of the reservoir oils because of a disproportional vaporization of heavier components of the solution gas. The vaporization of these components is believed to be a cumulative effect of contact of the oil with bypassing, light-gravity gas which had been liberated at higher pressures from solution in oil farther back in the formation, or which had come from the gas cap, rather than from the singular effect of gas evolution caused by excessively low bottom-hole pressures. Change of oil composition caused by the latter was found to conform closely to that occurring during a differential liberation of gas in the laboratory.

Jan 1, 1967

By Klaus Schwerdtfeger

The rate of formation of silicon monoxide from silica spheres has been measured at 1500°C in H2, H2-H2O, H2-He, H2-Ar, and CO-CO2 gas mixtures. Indications are that in the hydrogen-containing gases the reaction rate is mainly determined by convective diffz~sion. In the CO-CO2 mixtures the rate approches a constant value which is independent of sphere diometer (and gas velocity). This suggests that a surface reaction becomes rate controlling in CO-CO2 gas. WHENEVER silica is exposed at elevated temperature to a strongly reducing atmosphere there occurs, inevitably, a volatilization of silica by the formation of gaseous silicon monoxide. Because of the importance of this reaction in metallurgical processes and laboratory experiments, its kinetics were studied in the present work. EXPERIMENTAL The spheres made of vitreous silica were suspended by a molybdenum wire in the hot zone of a gas-tight high-purity recrystallized alumina furnace tube of 3.1 cm internal diam and 100 cm length. Molybdenum wire resistance heating was used. A purified H2, H2-H2O, H2-He, H2-Ar, or CO-CO2 gas mixture was passed through the tube, from top to bottom. The amount of silicon monoxide formed was determined by weighing the silica balls before and after the experiments. The silica balls were made from commercially available translucent fused quartz glass. In experiments with hydrogen-containing gases the silica stayed vitreous during the experiment, whereas in experiments with CO-CO2 mixtures, which were performed over longer times, the balls were always crystallized to cristobalite (as determined by X-ray examination) at the surface. Constant-pressure head capillary flowmeters were used to control the composition of H2-He, H2-Ar, and CO-CO2 gas mixtures. The oxygen and water vapor were removed from the gases containing hydrogen by passage through columns containing platinized asbestos (450°C) and an-hydrone. The CO was purified from O2 and CO2 by passing it through activated copper (200°C) and through ascarite. The H2-H2O gas mixtures were prepared by passing purified Hz through a mixture of oxalic acid dihydrate and anhydrous oxalic acid held at a constant temperature in a water bath. The equilibrium water vapor pressures of oxalic acid dihydrate-anhydrous oxalic acid mixtures were taken from the available data.1 The furnace system was checked for sufficient gas tightness at regular intervals. As an additional check, the H2O and CO2 contents were measured in the exit gas and were found to agree closely with the metered contents when H2-H2O or CO-CO2 mixtures were used. When purified H2 was used, H2O pressures found in the exit gas were always below 0.1 mm Hg. These contents originate either from an incomplete reoxidation of silicon monoxide in the cold part of the furnace or from small leaks which cannot be avoided. If the latter is the case, such small uncontrolled H2O contents decrease the partial pressure of SiO in equilibrium with SiO2 by less than about 7 pct, which is considered small in comparison to other experimental uncertainties. The temperature of the furnace was controlled automatically in the usual manner. The reported temperature was measured with a Pl-Pt/l0pct Rh thermocouple and was accurate to ± 5°C. TRANSPORT-CONTROL LED RATE OF REDUCTION The gaseous convective diffusion from the surface of a sphere can be predicted from the semiempirical relationship obtained by Ranz and Marshall2 in a study of the evaporation of water and benzene drops in air. The following equation applies:

Jan 1, 1967

By K. Leutwyler

The key to realistic casing stress analysis in thermal recovery installations is accurate knowledge of the temperatures involved. Much information leading to prediction of heat losses from tubing string to wellbore has been published. This .same information permits calculation of casing temperature under certain conditions. This paper reviews the basis for most of the published work, the line source solution to the diflusivity equation and examines some of its application criteria in the light of unsteady-state conditions. An alternate finite differences method is presented for correlation, and experimental data pertaining to the heat transfer mechanism in the annulus is reported. In the light of the information presented in the paper, it appears that the assumption of a line source for the tubing-wellbore system is valid even for reasonably short periods of heat flow, .such as "steam soak" operations. The empirically modified equation presented earlier matches computer derived results of the finite differences approach lor periods as short as 50 hours. Previously predicted cas ing temperatures and the associated stress levels are thus verified based on these correlative computations and the reported experimental information. Fall out from the computer output resulting in some studies of the influence of insulating cement properties on casing temperature, and experimentally studied effects of nitrogen placed in the annulus at various pressures., are described. INTRODUCTION Generally speaking, predictions of average casing temperatures have been based on an idealized model involving a centralized tubing string at uniform constant temperature radiating energy towards the casing under steady-state conditions.'. ' Heat is transferred away from the casing to the formation by unsteady-state conduction across thermal barriers consisting of cement and the mud sheath. Heat balances written on the casing permit prediction of instantaneous casing temperatures. During early periods of injection, casing temperature varies appreciably as a function of time; however, for long injection times this variation decays as heat flow from the wellbore to the formation stabilizes, and it becomes virtually negligible as conditions surrounding the wellbore become quasi-steady-state (Fig. 1). Carslaw and Jaeger -escribe a solution to the diffusivity equation for a line source (Fig. 2). A constant supply of heat is introduced into the medium from the line placed into the origin of the x-y coordinate system and parallel to the z-axis. Heat spreads outward in the infinite cylindrical solid and the temperature increase on a line going through point (x, y) parallel to the z-axis at a distance r can be predicted by: The following criterion must be considered: the Carslaw and Jaeger equation is obtained on the basis of a large

Jan 1, 1967

By D. W. Peaceman

In previous papers by this author on numerical calculations of multidimensional miscible displacement, some simplifying assumptions were made in writing the dispersion term of the differential equation. It was assumed that the flow vectors were essentially parallel to the x-axis. However, in most multidimensional miscible displacements, the flow vectors are not so simply oriented with respect to the coordinate axes. This paper derives the correct dispersion term /or the more general case; gives a difference approximation /or the dispersion tern; and derives the stability criterion for the corresponding explicit difference eguation.

Jan 1, 1967

An attempt was made to determine the lateral extent of analcite in the Newcastle Coal Measure sediments of the Sydney Basin. From an examination of the cores of eleven bores it was concluded that the mineral is concentrated in the western sector of the original Newcastle Basin and this presumably was the region of greatest sodium concentration and aridity. The distribution of the analcite is such that it appears to have little correlative value.

Jan 1, 1967

By R. J. Brown

Design of a submarine pipeline system is governed by many factors, one of which is the effect of transverse horizontal currents on the pipeline structure itself Although this feature alone can be of utmost importance to the life span and stability of the underwater pipeline, it is usually the least recognized, with these hydro-dynamic forces being either completely overlooked or grossly underestimated. In an attempt to supply the methods and means for stabilization of sub-marine pipelines, much capital has been spent by pipeline companies. Design criteria incorporated by these organizations extend over a broad spectrum of engineering with bases varying from pure theory to cut and dry methods. A history of numerous failures has substantiated the postulate that many of these submarine pipelines have been underdesigned from the stability standpoint. By the same token, equally as many have been excessively overdesigned with resultant excess expenditures. An attempt has been made in this paper to establish the magnitudes of these hydrodynamic forces by measuring the lateral current-induced differential pressure distribution around the periphery of the submarine pipeline. INTRODUCTION The expenditure of money for research by corporations obviously requires beneficial results to justify the investment. One of the functions of the engineer is first to make the problem known and then to provide a means of solution at the least possible cost. The initial procedure is to investigate all pertinent published technical articles on the subject to determine if this problem has been previously solved. If resolution of this problem is not obtainable, the next course of action is to evaluate through experiments these forces and their magnitudes. On the specific subject of drag and lift, the accumulation of data is provided from three separate and distinct sources: from experience, from theoreticians and through experimental observations. The experience source has proved costly with money wasted either because of underdesign and failure or excessive expenditures for overdesign, and has not been sufficient to form a definite conclusion on these hydrodynamic forces. The pure theoretician is often not completely cognizant of the situation and his works bear little adaptation to the real problem. The experimentalist has his own problems with regard to obtaining results from small-scaled models and successfully adapting them to the larger prototypes. Each method has its own advocates who diligently adhere to their own separate routes as being the only means of resolving this problem. However, a review of the various methods of analysis leads one to the conclusion that if the advantages of all three are combined, a reasonable solution to this problem can be reached. Briefly then, the problem is to obtain the magnitudes of the forces on the submarine pipeline subjected to a lateral current by investigations of previous design considerations, by a study of existing theoretica1 data and by appropriate experimentation. This paper deals mainly with obtaining experimental data and the interweaving of theoretical and experience factors for resolution of these forces. APPARATUS AND PROCEDURE These tests were performed in 1961 at Collins Construction Co.'s main office near Port Lavaca, Tex. Test equipment consisted of a steel tank 3 ft high by 4 ft wide by 40 ft long, with several pumps circulating the water through the tank via suction lines from the downstream portion of the tank and discharging from the pumps directly into the upstream end of the tank. For reduction of turbulence, a wire section was constmcted in the upstream portion and straightening vanes in the form of pipes, screens, etc., were used to reduce the vortex and eddy action in the tank (Fig. 1). A venturi was built at the test specimen for obtaining velocity sufficient to simulate actual conditions. This full-scale test was initiated to eliminate the error introduced in modeling and obtain a truer picture of forces actually encountered. Six- and 10-in. specimens were prepared by

Jan 1, 1967

By George A. Roberts

The development of an alloy system, high-speed steel, is used as an example of the progress of physical metallurgy. Tracing the history of men and their thoughts as they studied and invented and modified these materials, the story of high-speed steel since the 1890's is seen to be a long, slow, but steady progression of achievements. Today's multiplicity of high-speed steels are the result. Data are presented on quantitative metallography of carbides in high-speed steel with high vanadium content using the QTM instrument. Grindability as well as mechanical properties are related to the content of excess MC and M6C carbides in a series of high-speed steels and the newer matrix steels. These emphasize the present state of knowledge and show the current stages of thought that may affect the development in succeeding years. It is a great thrill for me, an ex-research metallurgist and ex-practicing metallurgical engineer, to speak to an audience currently engaged in both pursuits on the occasion of the 43rd Howe Memorial Lecture before the Iron and Steel Division of the AIME. I shall not review Henry Marion Howe's distinguished career, so adequately reviewed in Maxwell Gensamer's contribution in the 1965 AIME History of Metallurgy, except to point out that, while leading the life of an intellectual, he worked as a practicing research metallurgist and a practicing metallurgical engineer for significant periods of time and contributed greatly in both areas. For those of you who believe, as I do, that in the intellectual activity of metallurgy we are blessed with an intimate mixture of science and engineering (see Mehl's 1960 Howe Lecture), we might recall that Howe, while pursuing a life of writing and teaching in later years, served as the first Chairman of the Division of Engineering of the National Academy of Sciences. That metallurgists were called upon then to lead an engineering recognition movement is perhaps related to the strong part played by the AIME and its members in the recent establishment of a National Academy of Engineering and to the fact that a metallurgist is its head, 47 years after Howe served. I stress these engineering aspects for I wish to talk about a metallurgical engineering subject today. Alloy systems, physical metallurgy, and steel blended with an historical perspective and a report on new techniques to improve the old will, I trust, be of sufficient interest to bring these lectures back to the physical-metallurgy banner from which they have departed for 4 years. Those process metallurgists, open-hearth fiends, and physical chemists among you will just have to be patient. The development of an alloy system is the engineering application of scientific thought and fact. There are many interesting alloy systems, developed to a high degree of technology and sophistication over the past 40 to 70 years. These systems are bound together and related by a similar set of characteristics. For example, stainless steels are a system in which the members are related by a high chromium content which gives a corrosion-resistant characteristic. A subfamily in this system would be austenitic steels

Jan 1, 1967

The Kalkadoon Granite is regarded as composite in character with at least two different phases. The older phase is considered older than the sediments of the Western Geosyncline, and the younger phase is considered younger than the sediments of the Western Geosyncline.Consequently, the older phase could be a time equivalent of the Ewen Granite, whereas the younger phase could not. An age of 1760 million years seems plausible for the older phase, and an age of 1540 millionyears seems appropriate for the younger phase.

Jan 1, 1967

By C. M. Wayman, M. Miyagi

COMPARED to many of the binary alloys of iron, Fe-Ir alloys have received very little tud.'' Virtually nothing is known about the Fe-Ir equilibrium diagram' except for a few details concerning the liquidus-solidus positions for dilute iron-based alloys. It is reported1 that the y to a transformation temperature in Fe-Ir alloys (up to 40 wt pct Ir) is composition-dependent, varying from -900°C for pure iron to 0" to 100°C for Fe-40 pct Ir in an almost linear manner. The y to a transformation appears to be reversible,' the transformation hysteresis width increasing with increasing iridium content. In a qualitative way, the composition dependence of the y to a (and vice versa) transformations appears similar to those in the widely studied Fe-Ni system. In that the y phase (in Fe-40 pct Ir) can transform at -1000C, it

Jan 1, 1967

By F. W. Hoertel

Near-optimum parameters were determined by the Bureau of Mines for vapor deposition of rhenium on heated copper substrates by hydrogen reduction of rhenium hexafluoride (ReF6). High-purity deposits of nearly 90-percent theo¬retical density were obtained with the reaction chamber at 250° C, with an H2 to ReF6 volume ratio of 25 to 1, and with an ReF6 flow rate of 5 grams per hour. Some rhenium deposited as a loose, black powder. When the established near-optimum parameters were carefully followed, this could be minimized but never completely avoided. Varying the reaction chamber pressure, both above and below atmospheric, yielded excessive quantities of rhenium powder. Deposition efficiencies, based on only the coherent metal, ranged between 70 and 75 percent. Massive deposits contained only spectrographic traces of impurities. The average microhardness (Knoop, 100-gram load) of vapor-deposited rhenium was 907. Limited research on the deposition of rhenium-tungsten alloys by reduction of the mixed hexafluorides produced deposits in which linear composition gradients were pronounced; this nonhomogeneity was attributed to the wide variation in optimum hydrogen-reduction temperatures of the two hexafluorides (250° C for ReF6 and 550° C for WF6). Using deposition temperatures between 250° and 550° C did not eliminate the composition variations.

Jan 1, 1967

By F. A. Crossley

The titanium-rich end of the Ti-A1 system has been investigated up to 35 at. pct A1 (23 wt pet). One conzpound Ti3Al was found to occur between primary a and TiAl. It is ordered hcp with DO19 structure, it has virtually no solid-solubility range, and it has a closed maximum at about 875°C. OIL either side of the compound are a +Ti3Al two-phase fields. The limiting a1uminum solubility in primary a at the titanium-rich end is indicated to be 7.5 at. pct A1 (4.4 wt pet) at 550°C and about 6.8 at. pct Al fl wt pct) at 500°C. Quenching alloys from above the a + Ti3Al two-phase field produces the following structures with respect to alloy composition: Up to 13 at. pct A1 (7.8 wt pet), a solid solution; from 15 to 18 at. pct A1 (9 to 11 wt pct), shear transformation product or martensite; from 19 to approximately 30 at. pct (11 to 19 wt pet), submicro-scopic coherent Ti3Al in an a malvix. The twin hcp phase fields reported in the literature are the result of nonequilibrium corzdztions. Ti-A1 alloys, once partitioned by dwelling- in the a + ß phase field during either hot working or heat treatment, are extremely difjicult to homogenize at temperatures below 1000°C. Such partitioned alloys exhibit the characteristics or symptoms of two-phase materials, and may be said to suffer the "twin-phase syndrome". THE earliest investigations of the Ti-A1 system by Ogden et al.1 and Bumps et al.2 reported wide solubility of the primary solid solutions. Aluminum was reported soluble in the low-temperature allomorph to the extent of 37 at. pct (25 wt pct), and the first intermediate phase was reportedly TiA1. Somewhat later Kornilov et al.3 reported a similar diagram with phase boundaries displaced towards lower aluminum contents and higher temperatures. Beginning about this time (1956) reports in the literature made it very clear that one or more intermediate phases occurred at lower aluminum contents than TiAl.4-17 These reports included five major investigations of the titanium-rich end of the Ti-A1 diagram.4,12,14,16,17 Three of these diagrams show two two-phase fields below 37 at. pct Al, while two of them show a single two-phase field. The existence of the phase Ti3A1 is firmly established and is included in each of the diagrams, except one—that of Sato and Huang.12 The new phases are reportedly hcp and differ from primary a only slightly when disordered, and when ordered the "a" parameter is approximately one,4,12,15 two, 6-10,13,14 or four14 times that for primary a. Beyond this, however, the diagrams are remarkable for their lack of agreement. Two tacit assumptions are usually made in phase-diagram determinations of metal systems. These are: 1) equilibrium anneals bring the alloy to equilibrium or to indistinguishable closeness to it, and 2) equilibrium conditions established at elevated temperatures are either "frozen" by rapid quenching for evaluation at room temperature, or quench-transformation products are recognized as such. In the current investigation evidence was obtained that over substantial composition ranges neither of these two conditions was met in any of the more recent major investigations. I) MATERIALS, METHODS, AND TECHNIQUES The alloys of this investigation were prepared by nonc on sum able electrode arc melting. Materials used in the preparation of the alloys are summarized in Table I. The investigative tools employed were: optical and electron microscopy, differential thermal analysis (DTA), disatometry, X-ray diffraction, electron diffraction, and resistometry. Alloys for microscopic and X-ray investigations were prepared as 15-g melts. Alloys containing from 7 through 11 at. pct A1 were hot-rolled out of a furnace at 900°C, from 12 through 15 at. pct out of a furnace at 1000°C, and from 16 through 18 at. pct out of a furnace at 1125°C. Alloys containing more than 18 at. pct A1 could not be hot-rolled. The ingots were covered with Markal coating prior to hot rolling to minimize atmospheric contamination. After hot rolling, alloys containing up to 15 at. pct A1 were ground and pickled to remove 7 mils from each surface; alloys containing 16 and 18 at. pct A1 were skinned to a

Jan 1, 1967

By R. F. Hehemann, Darrell W. Smith

The kinetics of alloying- in W-5 rot pct Re powder compacts were investigated at temperature about the upper limit for the formation of the x phase, such that a single intermediate phase was involved in the process. The rates and directions of motion of the a-o and o-b interface were assessed as functions of tinze at the sintering teri7peraticve by quantitative izetallog-ralhic techtziques. The iiotion 01 these interjuces could be specified approxitnate1.y by u Parabolic )-ate law and deviations from this ,rate law were attribuled to a complex interaction between surface dif'fusion and volume diffusion during the initial stages of sintering. WHEN binary or more complex alloys are produced by sintering compacted blends of elemental powders, a complication is encountered which does not arise in the sintering of pure metals. In addition to concern for grain size and densification, the rate of inter diffusion of the component elements must be considered. The general problem of alloying during sintering has been treated by numerous investigators.'-7 These investigations have been concerned only with systems that form continuous series of solid solutions and a concentric-sphere diffusion model4 provides a useful description of homogenization in these stems.' Some controversy remains, however, over the contribution of surface and grain boundary diffusion to the homogenization process. Heckel% ePorts that homogenization can be described by volume diffusion at all temperatures, whereas other invetiators'' recognize the importance of surface and grain boundary diffusion, particularly at lower temperatures. Analysis of the homogenization process in partially miscible systems is complicated by the motion of the interfaces separating the individual phases. A simple analytical solution does not exist for such finite systems with spherical symmetry. It was the purpose of this work to examine the kinetics of the formation and dissolution of an intermediate phase in a binary system through an assessment of the motion of the interfaces separating this phase from the terminal solid solutions. PROCEDURE The W-Re system is an example of a partially miscible binary system and was selected for study because of its current importance in refractory-metal technology. The equilibrium phase diagram, Fig. 1, shows that the o phase will be formed by interdiffu-sion between tungsten and rhenium. At temperatures between approximately 2125" and 282O°C, the o phase will appear as the only intermediate phase in the diffusion system. In this work, a mixture of elemental powders containing 5 pct Re was employed. In such a mixture, the rhenium particles will be distributed randomly in a tungsten matrix. During sintering, a o-phase layer will form at the W-Re interface. The development and subsequent disappearance of the o phase are controlled by the relative rates and directions of motion of the 0-0 and a-p interfaces. The motion of these interfaces can be inferred from quantitative metallographic measurements of the average radii of the o shells surrounding rhenium particles. Elemental tungsten and rhenium powders of commercial purity were employed in these investigations. The rhenium powder was spheroidized from +200 mesh agglomerates by plasma-arc spraying and was then classified to yield a powder composed of essentially

Jan 1, 1967

By R. S. Wagner, R. G. Treuting, W. C. Ellis

Use of the Weisseizbevg goniometer for the study of the morphology of whisker crystals and transfer of the results to a stereograplzic projection are described. While in almost all instances a complete and rapid solution is obtained with a purely gaphical treatment, an absolute analytical treatment applicable to difficult cases is given. Examples are given for determination of growth direction and external features of a crystal, for detection of 'twintzittg, and for establislting the orientation relntionships in a kinked whisker crystal. We give here a method for the use of the Weissen-berg goniometerl" in the study of orientation relationships in "whisker" (micro) crystals3-8 and direct transference of the data to the stereographic projection. The operations are straightforward and require no involved calculations: in almost all cases solely graphical treatment is adequate. In a few complex instances, a more exact analytic method may be required. In the method, not only are equatorial reflections of an oscillation photograph used, but also those on higher layer lines, or those not occurring on a recognized layer line. Such reflections off the zero level are often essentialy to detect the presence of twinning. The method is particularly suitable for examination of whisker crystals since the axial or growth direction is almost always one of high symmetry, permitting a more restricted oscillation range to obtain the necessary reflections and an accordingly shorter exposure time. The method is also applicable when there is no lattice-related external symmetry, and is as well able to identify external crystal surfaces, when such exist, with the aid of an optical beam. Thus growth direction, identification of lateral faces, twinning, and orientation relationships in a kinked crystal can be established. A test for the Eshelby twist6-8 can readily be made. The method can be used for orientation, for structure analysis, and as an aid in the identification of an unknown crystal. Moving-film techniques have previously been employed variously for crystal-orientation studies.1,2,9-13 In particular, use of the Weissenberg method for orientation determination has been reported by Wooster and wooster.14 While their method derives the same data as here described, it differs in depending on the tracing of constant p streaks, a less than dependable phenomenon with small specimens, a few microns or less in cross section. The Laue method can and has been used for orientation studies of microcrystals,15 e.g., 2 p in cross section, but requires the extreme intensity and concentration from a microfocus tube to obtain reasonable exposure time. PRINCIPLES OF THE PRESENT METHOD Consider a crystal of random orientation with respect to the oscillation axis in a Weissenberg goniometer. Its diffraction pattern need not necessarily result in recognizable layer lines. In Fig. 1, a stereo-graphic projection of the reference sphere is given with the equatorial plane XZ normal to the oscillation axis Y, and the X-ray beam directed from X towards 2. The great circle ZZ is then normal to the beam, and the axes are right-handed. Thus the reflected X-ray beam lies at the intersection R of small circle ARB of radius 28 from 2, and of small circle RE of radius a from the rotation axis Y. a is the conventional semiapex angle of a cone of diffracted rays from the atoms aligned in the direction

Jan 1, 1967

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By Sarkis G. Ampian

Extraction of alumina was correlated with the sinter and leach products from the lime soda sinter process for anorthosite. The effect of composition and grain size of reactants, time and temperature of sintering, and techniques of sample preparation were investigated. Greater than 90 percent Al2O3 extractions were obtained from dry-mixed minus 200-mesh anorthosite sinter mixes having mole ratios of CaO/SiO2 = 1.8 and Na2O/Al2O3 = 0.8. These sinter mixes were briquetted at 15,000 psi and fired between 1,200° C and 1,320° C for 20 to 60 minutes. The sinter phases that contribute to low alumina recovery were determined by X-ray diffractometry, optical microscopy, and electron probe X-ray spectrography. The mechanism of the sintering reaction was investigated by high-temperature X-ray diffractometry. The contrast in the lime soda sinter process for clays and for anorthosites are discussed. Explanations and suggested solutions are presented for problems such as gelation and variable alumina recovery encountered by previous investigations.

Jan 1, 1967

By Jr. Koch

As a means of investigating the distribution and variability of gold in ore from the Homestake mine, Lead, S. Dak., the Bureau of Mines performed a designed sampling experiment, and assay results were statistically interpreted. Fifty-six feet of diamond-drill core from five boreholes was sawed into l-inch-long cylinders, which were sampled randomly and were assayed. Analyses of variance of the assay results were used to compare and assess the different types of variation: within drill holes, among paired drill holes, among unpaired drill holes, and among furnace runs. The extreme variability in gold mineralization found is the natural variability on the smallest scale that can be detected by fire assay; most of the variability is associated with among-feet rather than within-feet sample intervals. Because of the extreme variability, one-half of the gold is in 3 percent of the samples.

Jan 1, 1967

By R. L. Loofbourow

Reasons for reexamining underground mining include: 1. The assurance that more deep deposits of useful minerals will be found. 2. The existence of deeply covered deposits of industrial minerals near large markets where quarries are becoming depleted or are lacking. 3. Surface property values, zoning and other limitations on open pit mining. 4. Expectation that underground space will be increasingly used for transportation, power plants, storage and similar purposes. 5. The improvements which have been made in underground mining. During the last three or four decades many changes and improvements have been made underground. All underground construction and mining has benefitted to some extent but the effect on the productivity of labor employed with some methods- has changed little and the use of these methods has declined. Productivity of labor in other methods has increased substantially. The relative usefulness of mining methods has changed and a vital industry, bituminous coal, has been returned to health. In this paper, consideration is limited to nine methods used with high productivity during the period under review. These methods are not necessarily better than others but they may be considered the prime methods in the sense that, in our economy, many, low grade ores, coal and the principal industrial minerals could hardly be produced by less productive means.2 Although most of the examples cited are from mining as such., the first four methods discussed can be used for the construction of stable excavations of various' shapes in sound rock.

Jan 1, 1967

By Roger L. Williams

The Bureau of Mines investigated northern New Jersey as a potential future source of yttrium and the rare-earth elements. The studies, consisting of geophysical surveying, sampling, and exploratory drilling, began in the spring of 1959. A total of three and one-half months were spent in the field collecting data. Thirty-three deposits were investigated, of which five demonstrated some potential resources of yttrium and rare-earth minerals. Results indicate that the deposits examined do not contain quantities of yttrium and the rare-earth elements recoverable under present economic conditions. Detailed studies conducted at the Scrub Oaks mine, near Dover, N. J., delineated a yttrium and rare-earth-bearing zone within the magnetite-hematite ore body that represents a potential low-grade deposit. Beneficiation studies on this deposit indicate that a final product, averaging 31.3 percent rare-earth oxides including yttrium, could be produced through amine and fatty acid flotation procedures with 77 percent recovery. Two hundred and eighty-five feet of diamond drill core was obtained from exploration studies conducted at the Bemco prospect in Sussex County. The deposit averages 2.30 percent rare-earth oxides (including yttrium), 0.45 percent uranium and 0.24 percent thorium. Low-grade deposits were identified at the Canfield phosphat2 mine and the Tanners Brook Monazite placers in Morris County, and the Marble Mountain prospect in Warren County.

Jan 1, 1967

By M. Nicholas, D. M. Poole

The diameters of sessile drops have been found to increase linearly with time in five reacting binary metal systems. The spreading rates of the drops are markedly dependent on temperature and on prior alloying of the solid with the lower melting point metal, hut are independent of the drop volume, wetting atruosphere , solid-surface roughness, and prior alloying of the drop with the substrate metal. A mechanism has been suggested that relates the linear-spreading rate to lateral diffusion of the liquid-metal atoms into the solid at the drop edge. An Arrhenius- type equation has been derived that describes the temperature dependence 0) the spreading rate, and although the agreement between the actual and the predicted pre-exponen-tial terms is poor that between the activation energies is excellent and the variation in the spreading rate of copper on Ni-Cu alloys produced by different extents of alloying can be predicted with considerable accuracy. CHEMICAL interactions frequently change the wetting behavior of solid-liquid systems causing, for example, "secondary spreading1 of sessile drops beyond the size defined by the surface and interfacial tensions of the unreacted components. The kinetics of the contact-angle decreases associated with this spreading are similar for many systems, but few studies have been made with the objective of determining whether the similarities are a reflection of a common mechanism. Some workers2,3 have assumed the secondary spreading is controlled by changes in the liquid surface and liquid-solid interfacial tensions and hence by the composition of the liquid, and contact-angle changes measured by the vertical-plate technique have been used to follow the course of liquid-solid chemical reactions.4 Other processes that have been invoked to explain these time-dependent changes in specific systems include the removal of adsorbed gas from the liquid-solid interface.5 penetration of containment layers on the solid Surface,6 interdiffusion,1,7 reori-entation of the solid surface into a wettable configuration: vapor-phase transport of the liquid onto the solid in advance of the drop,9 and, from vertical-plate studies. capillary flow between oxide layers and the solid surface.10 One of the reasons for the profuseness of these suggestions may be the complexity of the contact-angle change kinetics. However, in an analysis of secondary spreading gold and copper on UC,11 it was found that the diameter of the contact area between the sessile drop and the solid surface showed a simple linear increase with time although contact-angle changes were more complex. To check whether the linearity was merely fortuitous! additional exploratory work was conducted with four reacting metal-metal systems: Au on Ni. Cu on Ni, Cu on Fe, and Ag on Au. Linear spreading was observed in every case even though the kinetics of the contact-angle changes were complex. A further detailed study of the kinetics of linear spreading of five reacting metal-metal systems has been made with the object of determining the mechanism involved. The influence of variables such as temperature, drop volume. and the initial composition of the drop on the linear-spreading rate has been measured and compared with those predicted by a number of possible mechanisms. The systems employed in this study (Cu and Au on Ni and Pt, and Ag on Au) were selected because of the availability of potentially relevant chemical and physical property data. the simplicity of their phase diagrams at the wetting temperatures, and the ease of experimentation. EXPERIMENTAL TECHNIQUES The purities of the metals used in the study were: copper, 99.9 pct; gold. 99.96 pct; nickel, 99.2 pct; platinum 99.99 pct; and silver, 99.999 pct. The wetting tests were performed in a split tantalum tube vacuum resistance furnace of a conventional design. The furnace element was held vertically and was 1 $ in. in diam and 6 in, long. Viewing ports were provided in the water-cooled chamber to enable the specimens to be observed in both the horizontal and vertical planes. The temperature in the hot zone of the furnace could be held at 1500" i 5°C for an indefinite time. The surfaces of the solid-plaque metals were ground flat on Microcut paper and both the sessile drop and substrate metals were ultrasonically cleaned in methyl alcohol prior to their insertion in the furnace. After loading, the furnace was pumped down to a pressure of 2 x 10-5 mm of mercury and degassed for 30 min at 900° to 950°C. The temperature was then increased at more than 100°C per min to that used in the wetting test. The vacuum at the wetting temperature was better than 5 x 10-5 mm of mercury. Dewetting and retraction of the drop on cooling did not occur and the contact-area diameters, therefore, were measured after solidification with a vernier traveling microscope. The diameters quoted later are arithmetic means of ten measurements. The standard error of the mean never exceeded 3 pct and was often less than 1 pct.

Jan 1, 1967