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By A. Cochardt, D. H. Feisel

HE success of the sintered aluminum powder material (SAP)' in raising the maximum useful temperature of aluminum alloys has stimulated effort in investigating similar systems in which the metallic matrixes have higher melting points. Examples of such systems which have been studied are nickel-alumina,2, 3copper-silica,4 copper-alumina,4 titanium-cerium oxide,5 and 80/20 nickel-chromium,8 cobalt,= and molybdenum7 matrixes with various hardeners. Conventional precipitation-hardened high-temperature alloys are often thermally unstable in service. The original fine particles that are responsible for good strength properties grow in size at elevated operating temperatures, a process termed "over-aging." This growth of precipitated particles causes a gradual loss in strength properties. A previous paperb describes the factors that govern the process of overaging, and estimates the time required for overaging of a nickel-alloy matrix dispersion-hardened by various precipitates such as are found in current high-temperature alloys, and by alumina. These calculations indicate that nickel-base alloys hardened with Ni3Al, Tic, or TiN are quite unstable at 1340" F (727°F). Such alloys should overage within a few hours at that temperature. A nickel-base alloy hardened with alumina, on the other hand, should behave differently. It should not overage appreciably within a thousand years. It was further shown8 that the thermal stability of the oxide-hardened alloy is mainly due to the low solubility of oxygen in equilibrium with alumina in the nickel-base matrix. Since the oxygen solubility is small, little oxygen can diffuse, and structural changes require very long times. This paper illustrates the effects of time and temperature on the structural stability of nickel alloy matrixes hardened by dispersions of Ni3A1, Ni3Ti, Tic, and alumina, and of nickel-chromium matrixes hardened by alumina. Hardness measurements and metallography have been used as a measure of structural stability. EXPERIMENTAL PROCEDURE Using the best information from published phase diagrams,'-l4 compositions of the Ni-Al, Ni-Ti, and Ni-Ti-C alloys were determined so as to have 5 vol pct of precipitate at 1350° F(732°C), the temperature selected to illustrate the effect of time on structural stability. Table I lists the chemical compositions of these alloys. Standard laboratory melting and alloying techniques were used in preparing ingots of the F-Series of alloys. The cast ingots, 1 3/4 in. in diam, were forged to 3/8-in. diam rods.

Jan 1, 1960

By H. J. O’Donnell, B. C. Parks

IN 1930 the late Dr. Reinhardt Thiessen set up a method of microscopic analysis and type classification of coal that has since been followed as standard practice in the coal-petrography laboratory of the Bureau of Mines. Thiessen's terminology which designated the constituent parts of coal in terms of botanical origin was introduced in 1920.l The technique, however, of preparing a completely representative series of thin sections from a column sample of coal for use in making quantitative determinations of coal components with a microscope was developed about 10 years later by Thiessen and coworkers G. C. Sprunk and H. J. O'Donnell.2 Complete thin-section analyses subsequently have been made of 126 column samples of various ranks and types of American coals. The data and information were assembled from these thin-section studies and published in a large number of reports dealing chiefly with investigations of the coking and hydrogenation properties of certain American coals. In the years following adoption of Thiessen's method, a considerable amount of work was done in collecting column samples of many coals, making routine thin-section analyses of these, interpreting the results, and finding practical application for the information in other fields of coal research. The many reports and papers covering the work in coal petrography, however, offer very little discussion that can be considered as critical appraisal of the technique. Criticism outside the Bureau most often has voiced questioning opinions concerning the accuracy of the method used of measuring coal components microscopically and classifying the coal into arbitrary types on the basis of the quantitative determinations. The principal purpose of this paper is to discuss in some detail and present data showing the results of certain investigative work done in the petrography laboratory on the accuracy of the Bureau's method of microscopic measurement of components in coal thin sections. Data from microscopic analyses on file made by G. C. Sprunk and H. J. O'Donnell were freely used in the investigation, and a table of columnar analyses from an unpublished manuscript by Sprunk is included in this paper for reference. In the course of the experimental work a method was developed for measuring instrumentally with a planimeter the components shown in micrographs of selected thin sections. Measuring coal components with a planimeter furnished useful information for studying the accuracy of microscopically measuring the same components in thin sections. PETROGRAPHIC COMPONENTS AND TYPE CLASSIFICATION OF COAL Thiessen considered coal to be composed of two visibly different major components present in various types of coal in greatly varying proportions. He named

Jan 1, 1948

By H. K. Shearer

There were no important developments in the oil and gas industry in South Arkansas during 1935. Oil production, totaling 11,138,340 bbl., continued the decline that has been normal since 1925, but the decline from 1934 was only 278,600 bbl., or 2.5 per cent. The principal decline was in the Smackover field, while only the Champagnolle and Garland City fields showed notable increases. More wells were drilled than in any recent year, with a total of 123 completions. There were 44 oil wells, with a total reported initial daily production of 10,013 bbl., or an average of 227 bbl. per well. Two small gas wells were completed in Union County, where the gas is used locally for pumping and field operations. There were 77 dry holes, of which 28 were in or near oil fields and 49 were wildcats. Active drilling oper-at'ions declined from 65 at the beginning of 1935 to 41 at the end. Most of the drilling was done during the first part of the year, espr-chially (luring the flurry caused by the discovery late in 1934 of the "Taylor" sand production in the Champagnolle field, but the producing area was soon outlined. In November, 1935, the J. E. Crosbie, Inc., NO. 1 Sullivant in sec. 12, 17s. 14W., producing 560 bbl. per day at 3175 ft., opened a new sand lens in the eastern part of the field. The Camden "oil field," discovered in the last week of 1934, remained a one-well field, although four offset tests were drilled, besides a number of others in the immediate vicinity. Several interesting deep tests were drilled during the year, which added a great deal to the general knowledge of the subsurface formations and the structure of south Arkansas, but were not particularly encouraging as to prospects for the very deep production. First, the H. L. Hunt, No. 15 E. F. Gregory well in sec. 10, 17S., 14\W., in the Champagnolle field, was drilled to a depth of 6911 ft. It pene-trated red beds for 2982 ft., from 2943 to 5925 ft., mostly if riot entirely of Lower Cretaceous age. There was some anhydrite in the last 135 ft. of red beds. This was followed by 890 ft. of limestone, probahly Permian, and the rock salt was struck at 6815 ft. The salt is now generally conceded to be of Permian age. Finding salt in this well strongly indicates

Jan 1, 1936

By H. K. Shearer

There were no important developments in the oil and gas industry in South Arkansas during 1935. Oil production, totaling 11,138,340 bbl., continued the decline that has been normal since 1925, but the decline from 1934 was only 278,600 bbl., or 2.5 per cent. The principal decline was in the Smackover field, while only the Champagnolle and Garland City fields showed notable increases. More wells were drilled than in any recent year, with a total of 123 completions. There were 44 oil wells, with a total reported initial daily production of 10,013 bbl., or an average of 227 bbl. per well. Two small gas wells were completed in Union County, where the gas is used locally for pumping and field operations. There were 77 dry holes, of which 28 were in or near oil fields and 49 were wildcats. Active drilling oper-at'ions declined from 65 at the beginning of 1935 to 41 at the end. Most of the drilling was done during the first part of the year, espr-chially (luring the flurry caused by the discovery late in 1934 of the "Taylor" sand production in the Champagnolle field, but the producing area was soon outlined. In November, 1935, the J. E. Crosbie, Inc., NO. 1 Sullivant in sec. 12, 17s. 14W., producing 560 bbl. per day at 3175 ft., opened a new sand lens in the eastern part of the field. The Camden "oil field," discovered in the last week of 1934, remained a one-well field, although four offset tests were drilled, besides a number of others in the immediate vicinity. Several interesting deep tests were drilled during the year, which added a great deal to the general knowledge of the subsurface formations and the structure of south Arkansas, but were not particularly encouraging as to prospects for the very deep production. First, the H. L. Hunt, No. 15 E. F. Gregory well in sec. 10, 17S., 14\W., in the Champagnolle field, was drilled to a depth of 6911 ft. It pene-trated red beds for 2982 ft., from 2943 to 5925 ft., mostly if riot entirely of Lower Cretaceous age. There was some anhydrite in the last 135 ft. of red beds. This was followed by 890 ft. of limestone, probahly Permian, and the rock salt was struck at 6815 ft. The salt is now generally conceded to be of Permian age. Finding salt in this well strongly indicates

Jan 1, 1936

By Carl F. Floe, John Chipman

A YEAR ago the authors published a paper on the solubility of sulphur dioxide in molten copper.1 The data in that paper agreed closely with that obtained by previous investigators, which, however, did not agree with the theoretical predictions for solubility of triatomic gases of this type. It has generally been assumed that the reaction of solution is: [ ] Neglecting the slight change in copper concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume of gas absorbed, it follows that this volume should be proportional to the cube root of the pressure. It was found that a plot of the volume absorbed versus the cube root of the pressure gave a straight line, but that this line did not pass through the origin. Calculations of the equilibrium constant for the reaction showed that it was fairly constant for pressures above l00 mm. but that actually it approached zero at lower pressures. The conclusion was made therefore that the solubility as determined could not be expressed by Eq. I or by any other simple equation, particularly at low pressures. Other investigators have concluded that the solubility of sulphur dioxide in copper as well as in several copper alloys is more nearly proportional to the square root of the pressure.* Such a conclusion, however, does not satisfactorily account for the results, even when rather complicated mechanisms for the solution are assumed. The highly improbable speculations of Lepp2 and of Schneider and Esch3 based upon hypothetical dissociation pressures of Cu20 and (a; 2S dissolved in copper illustrate the type of reasoning that has been used to account for the discrepancy. In the discussion of the previous paper, the authors pointed out that the discrepancy might possibly be due to impurities in the copper, although the purest form available was used. Further consideration of the problem suggested that the impurities likely to have the greatest effect on the solubility of SO2 in copper were oxygen, sulphur and carbon. Accordingly, further experiments have been made to show the effects of these elements. EXPERIMENTAL METHODS The apparatus used for measuring solubility was essentially the same as that shown in the previous paper. However, since it was desired to make measurements at low pressures, a McLeod gauge was added and 6-mm. glass tubing was substituted for the capillary. This increased the "hot volume" considerably but was necessary in order to obtain good vacuums in a reasonable length of time. A mercury diffusion pump was also installed.

Jan 1, 1942

By B. Post, F. W. Glaser

Three borides of zirconium have been reported: ZrB,l ZrB2,2,3 and ZrB12, 4 The phase relationships, ranges of stability, and some physical properties of these compounds are described. THE zirconium borides differ considerably from one another, particularly with respect to their relative stabilities at high temperatures in the presence of carbon.4,5 ZrB2 is extremelv stable at all temperatures (to the melting point) in contact with carbon. Both ZrB and ZrB12 tend to decompose at elevated temperatures when carbon is present in excess of about 0.5 pct. ZrB forms ZrB2 and ZrC, and ZrB12 decomposes to form ZrB2 and a boron-carbide phase. In the ZrB12 preparation, boron present in excess of that needed to form ZrB2 reacts with carbon, if present, to form carbides, in preference to forming the higher boride. Similar instability of borides, other than diborides of the transition metals of the 4th and 5th groups of the periodic table, has been reported.5,6 special precautions had, therefore, to be taken to minimize carbon contamination in the preparation of ZrB and ZrB12. Reactions below 1400°C were carried out by heating powdered mixtures of zirconium hydride and boron in quartz tubes in a hydrogen atmosphere. For temperatures above 1400°C, reactions were carried out in graphite molds. Carbon contamination from the molds was minimized by employing extremely rapid heating rates to reduce carbon diffusion into the body of the specimen, and by subsequent "shaving" of sample surfaces that had been in contact with the graphite dies. A heating rate of about 2000°C per min was obtained by heating the dies (by direct conduction), using a current of 40,000 amp. Although this type of heating cycle apparently allowed little time for "homogenization," close approximations to equilibrium conditions were usually obtained as a result of the very strongly exothermic reactions between zirconium hydride and boron at elevated temperatures. Reproducibility of results in repeated runs under varying conditions was taken as a reasonable indication that equilibrium conditions had been effectively achieved. Quenching was accomplished by rapidly immersing the entire die, containing the reaction products, in water. Specimens could also be cooled at controlled rates by adjustment of the rate of flow of water through the water-cooled copper electrodes in contact with the graphite dies.

Jan 1, 1954

ONE of the features of the annual meeting was a round table conference on carbon in pig iron, on Feb. 16. This was presided over by R. H. Sweetser, and the discussion, which was so interesting as to require holding an additional session in the after-noon, ranged over such a wide field that only a brief outline of it will be attempted here. The full discus-sion together with the papers will be printed later. The first paper was one on the need for research in foundry pig iron (1648-C) by Richard Moldenke, who pointed out the trend in present practice of attaining low cost in pig iron production by hotter blast, addi-tion of. scrap to the blast furnace, and. the enormous increase in the output per furnace day. He pointed out that remelting processes are oxidizing processes, to some degree at least, and the metal cannot be given the deoxidizing finish which is characteristic of the steel-making process. The trend today is toward specifying total carbon content in foundry pig irons, and since the carbon content depends on a variety of factors, he suggested that the blast-furnace men and the foundry men study the question and agree on a minimum of total carbon for the given silicon ranges. The discussion of this paper was participated in by E. J. Lowry, Robert Jones, T. L. Joseph,. R. H. Sweet-ser, J. G. Ferguson, W. B. Coleman, E. P. Ross and D. J. Demorest and ranged from a comparison of the total carbon used in making a ton of pig iron in charcoal practice versus coke practice to a discussion of the bad effects observable from the use of scrap This paper was followed by one on carbon character-istics of copper-bearing pig iron by W.. B. Coleman. In view of the belief in many foundries that copper-bear-ing pig iron made trouble in the foundry, experiments were made by adding copper in various amounts up to 1 per cent and with the cooperation of the Robesonia Iron Co. a large number of tests were made over a run of foundry iron. The final conclusion was that the ad-dition of less than 1 per cent metallic copper did not seem to alter the physical properties and that a blast furnace using copper-bearing ore can produce pig iron suitable for making small castings, showing low-Brinell hardness test, good transverse and deflection tests, and high-total carbon.

Jan 3, 1927

By R. W. Smashey, B. J. Piearcey

The structure, composition, and morphology of the carbide phases present in the nickel-base superalloy, Mar-M200, hare been determined and three carbide phases observed. The MC carbide is a solidification product, and the M23 Co and M6C carbides are both prod~icts of solid-state precipitation. The identity of each phase usas determined by both X-ray and electron-diffraction techn~ques. Compositions of all three carbides were studied using the electron beam micro-probe analyzer and by unalyszs of electrolytically extracted residues. Optical and electron microscopy were employed in order that the time/temperature -dependent behavior of the carbides might be observed. Supplementary studies were completed on thin foils and oriented single crystals to determine the mor-phology and orientation relationship of each phase with that of the matrix. MAR-M~OO* is a high-temperature, creep-resistant superalloy designed for use in the as-cast condition. The "as-cast" microstructure consists of a solid-solution matrix, referred to as gamma (y), which contains a general, coherent precipitate of the inter-metallic Ni3(A1,Ti) referred to as gamma prime (?). As a result of dendritic segregation during solidification, a degenerate, spherulitic ? -?' eutectic constituent is present at the grain boundaries and the in-terdendritic regions, which is nucleated by the y on the dendrite tips. A primary carbide phase, a solidification product, is also present at the grain boundaries and in the interdendritic areas, and an additional carbide appears at the grain boundaries as a fine discontinuous precipitate. The alloy is particularly susceptible to heat treatment. For example, the mechanical properties of the columnar grained mater- ial are substantially improved by solution heat treatment, followed by an intermediate temperature age. Metallographic examination of heat-treated material reveals, however, that exposure to elevated temperatures has a marked effect on the microstructure of the alloy; in particular, it is observed that precipitation of considerable amounts of various carbide phases occur. The following investigation was carried out to determine the morphology, composition, and behavior of the carbides in Mar-Ma00 as an aid to the determination of their effect on the mechanical properties and stability of the alloy. THE PRIMARY MC CARBIDE The MC carbide phase appears in the interdendritic interstices and the grain boundaries. In directionally solidified Mar-M200 the carbide appears as very small particles in the chilled region, Fig. l(a), whereas in material less affected by the chill, it becomes larger and develops a dendritic morphology, Fig. 1(b). Step polishing of metallographic specimens from this region shows that in directionally solidified material the individual carbide dendrites are connected in a dendritic network within the metallic interdendritic interstices, whereas in material from the chilled region and in conventional Mar-M200 they are discontinuous, isolated dendrites. No orientation relationship exists between the primary carbide and the matrix.

Jan 1, 1968

By J. H. Carpenter

LMENITE, rutile, zircon, and other heavy minerals are found in small amounts in the sand that covers most of Florida. Small enriched deposits occur on the beaches and coastal dunes. One beach deposit east of Jacksonville was worked during World War I and another near Vero Beach during World War 11. Both ceased operation when the resumption of imports reduced prices. Early in World War II reduction of rutile imports made a domestic source of the mineral necessary to maintain the expansion of armaments. Explorations made near Jacksonville discovered a relatively large body of low-grade ore about 10 miles inland from the beaches. A plant installed by Rutile Mining Co. of Florida using both flotation and tables encountered difficulties because of low plant capacity and organic slimes in the ore. In 1944 Humphreys Gold Corp. solved the problem of concentrating the low-grade ore by using the newly developed Humphreys spiral concentrator and by mining with a hydraulic dredge. This combination of low cost mining and concentration permitted the plant to continue operation in competition with foreign ores when imports were resumed following the war. The success of the Jacksonville operation renewed interest in Florida as a source of titanium. An extensive survey of the state was made by E. I. du Pont de Nemours and Co., Inc., under the direction of J. L. Gillson in 1945 to 1946. Sampling was carried on by drive pipe drilling to depths of 20 to 25 ft. Encouraging values were discovered near the location of the present Trail Ridge mine, 50 miles southwest of Jacksonville, near the town of Starke. The United States Bureau of Mines was interested in exploring for heavy minerals in Florida, and on the recommendation of both the state geologist of Florida and of Du Pont geologists, drilled deeper where marginal indications were found on Trail Ridge. In 1947 it was discovered that sufficiently higher values occurred at depth to make the deposit commercial. The orebody at Trail Ridge is a long sand deposit averaging about 1 mile in width and 35 ft in depth. It is approximately 1 1/2 miles wide at the north end of the portion now being worked, tapering to a blunt point 3 miles to the south. The ore reaches a maximum depth of 65 ft near the center and feathers out into barren sand at the edges. The ground surface is relatively flat and is covered with vegetation including pine, scrub oak, palmetto, and occasionally in swampy areas, cypress. The remain of a dense woody growth underlies and marks the bottom of the Ore 'One. It is difficult to drill through this layer, but in some cases where it is less than 5 ft thick it has been possible to drive through the wood. Sand lying below is coarser than that in the ore zone and contains no values. The wood layer consists of unconsolidated carbonized fragments of branches and other forest trash associated with a considerable amount of ar-

Jan 1, 1954

By C. B. Dudley

bas shown us that the railroads of this country can save several milt liohs a par by adopting uniform rail sections, and as unfortunately for him, he cannot patent his idea, it only remains for the railroads to adopt it, and to thank him for his payer. Dr. C. B. Dudley, Altoona, Pa. : 111 rising to close this interestin~ discussion, I want, in the first place, to thank every one who has contributed to it for his full and open criticism. The work tvhich has been done on steel rails, and which has been diwu&e,l here Juring thee two days, was not done to establish any pet theories, nor to make out that any person was great or any person small, but with a sincere desire to get at what is the truth in regard to the wedring capacity of steel rails. There are enormous commercial coneiderations invoIved in this question, and, as I look at the matter, the more honest criticism and fair discussion there is, the Inore likely it is that the truth will appear. Ad first I would like to say that it seems to me very little has been said here upon the main conclusion of the paper, namely, that the softer rails give the better wear. All sorts of side issues have been discussed; but this poiat, which is really the principal one at issue, has been largely ignored, aid I cannot But feel that it still remains unshaken. Witb regard to ohemists end chemical work, there has been considerable said tending to throw discredib on chemists and their work; and while I believe that there have been in the past, are now, and may be in the futnre, a good many poor chemical analyses made, X also believe that chemists are, as a rule, as honest and competent as gentlemen who belong to other professiomc. There are chemisb who are chemists, and who are not chemists. The determination of -manganese has bee* called in question. Now I think the chemist at almost every steel works in the country will tell you that, in his experience, the manganese diffe1.s in different parts of the same ingot. Mr. T. T. Morrell, chemist of the Camhria Iron Company, whom I believe to be s thoroughly competent and hone6t chemist, tells me that he has often found different amounts of manganese in different parts of the same ingot. Come with me to Altoona, and I will take you into the machine shop where steel is king cut aud shaped, and I will show you that it is often necessary to stop the lathe or planer and take a cold chisel to cut oat a hard spot, or else ntn the risk of breaking the tool. This hard spot is simply a pttrt of the syiegel which was not thoraughiy mixed with the ma

Jan 1, 1881

By R. G. Vardiman, M. R. Achter

THERE has been interest recently in the conditions under which dislocation pipe diffusion may be observed. In order to extend the measurements to temperatures below Tm/2, where pipe diffusion becomes more important, a chemical sectioning technique was developed for silver single crystals which makes possible the removal of layers of 100A or less. The procedure is briefly as follows. Silver single crystals of 99.995 pct purity were cut in the form of discs t by 4 in., electropolished, and electropolated with Ag110 to about 1000A thickness. The thickness was determined by calibrating the activity with the weight of heavier platings, up to 10,000A. Both diffused and undiffused samples were sectioned in a two-step process. Reaction with a solution of iodine in alcohol formed a thin, even layer of AgI, which was then dissolved in a KCN solution. The reaction rate of the iodine solution varied slightly over a period of time, so that the thickness of the stripped layers, while quite even and regular for a given specimen, ranged from 65 to l00W for different specimens. This variation was checked by using a thickly plated standard with each run. Layer thickness was determined from undiffused samples by the point where the layer activity drops to half the maximum. This maximum intensity also provides, with appropriate corrections, the initial concentration per layer co. Because of the small penetration distances, it is necessary to use the exact solution of Fick's law for a source of finite thickness.' For a plating of thick- where c is the concentration at depth x. flj the error function, D the apparent diffusion coefficient, and t the time. The diffusion coefficient was obtained from the concentration-penetration data by extrapolating to x = 0 where c/co = erf h/2(Dt)1/2 Enough points were taken to impart confidence in the accuracy of the intersection, generally about ten layers. Four temperatures were used as in Table I. For best accuracy, t and h were chosen to give values of the parameter (Dt)1/2/h between 1.0 and 1.7. A typical concentration-penetration curve is shown in Fig. 1. The diffusion coefficients calculated from Eq. [I] are plotted in Fig. 2. For comparison, the high-temperature data of Tomizuka and sonder 2 which go down to 630°C are plotted as the solid line 2(a) from their expression D = 0.40 exp (-44,090/RT). Also for comparison, the lowest temperature point of Hoffman and Tumbull3 is plotted. It is apparent that our data diverge appreciably from the high-temperature extrapolation by 373°C. A better straight line fit for the low-temperature portion is obtained by subtracting the extrapolated volume diffusion coefficient from the apparent. or measured coefficient, and plotting the difference, curve (h) of

Jan 1, 1970

By W. D. Potter, E. T. Peters

Single-crystal films of boron have been prepared by thermal reduction of purified BCl3 with subsequent deposition of boron onto oriented silicon substrates. The structural properties of films prepared under various experimental conditions have been determined by light microscopy and "grazing-" angle electron-diffraction analysis. An orientation relationship is proposed for silicon and a-rhombo-heclral boron which can be described as: (111)Si (112)B; [110]Si [110]B ElEMENTAL boron is known to have a high energy gap* and consequently has potential value as a high- *Energy gaps of 1.35 to 1.55 ev1-3 and 2.0 ev4 are reported for ß-rhombohedra1 and a-rhombohedra1 boron, respectively. temperature semiconductor.5 Exploitation of this property, however, has been hampered by the unavailability of pure, single-crystal boron. Two recent symposia6,7 have treated the subjects of purification, crystallization, crystal structure, and properties of boron and provide a foundation for further investigation in these areas. The structure, lattice constants, and observed ranges of stability for four reported polymorphs of boron8°12 are listed in Table I. The rhombohedral structures are generally accepted as true polymorphs whereas the tetragonal structures are believed to be transient. Most currently available single crystals of boron are grown by Czochralski and floating-zone methods. Unfortunately, these crystals generally contain numerous defects and are highly strained as a result of the polymorphic transformations and thermal contractions which accompany cooling. Recently, Armington, Potter, and Tanner13 have reported the formation of single-crystal films of boron on silicon single-crystal substrates through thermal reduction of BC13 by hydrogen. Boron E. T. PETERS, Junior Member AIME, is Senior Scientist, ManLabs, Inc., Cambridge, Mass., and W. D. POTTER is Research Chemist, Air Force Cambridge Research Loboratories, L. G. Hanscom Field, Bedford, Mass. formed at temperatures near 1000°C was identified as the a-rhombohedra1 form, consistent with expectation. The present paper describes a continuation of this work with specific reference to characterization of the structural features of the deposited boron films. The ultimate goal of this program is to produce large-area single-crystal films of a-rhombohedra1 boron to be used for electrical and optical studies by other workers. PREPARATION OF BORON FILMS The experimental procedure of preparing thin films is similar to that described by Theuerer14 for the epitaxial growth of silicon by thermal reduction of SiC14 and has already been described as applied to the preparation of boron thin films.13 Briefly, a mixture of BCl3 vapor and dry hydrogen is passed over a heated silicon substrate. Thermal reduction of the BC13 allows deposition of boron on the substrate. The substrates were {111}-oriented, single-crystal silicon. Square specimens 0.63 cm on an edge by 0.1 to 3.0 mm thickness were prepared by

Jan 1, 1965

By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By D. B. Robinson, J. Lukacs

A knowledge of the equilibrium water content of hydrocarbon systems under pressure is important to the natural gas industry. The information available on the solubility of water in hydrocarbon, hydrogen sulfide, and carbon dioxide systems is reviewed in this paper and the influence of the more important variables such as temperature, pressure and molecular structure on solubility in liquids and gases is discussed. A suitable cbromatographic technique has been developed for determining low concentrations of water. Tailing of the water peaks has been elim inated by adding water to the carrier gas stream The method is applicable for both gas or liquid samples and is effective in the presence of hydrogen sulfide. The experimental study of water solubility in methane-hydrogen sulfide systems at a temperature of 16oF has shown that the presence of hydrogen sulfide causes only a modest increase in water content at pressures up to 1,400 psia. Theoretical considerations and data on pure hydrogen sulfide and carbon dioxide suggest that the effect of both these compounds will be greater at higher pressures and in the liquid phase. INTRODUCTION Before transporting or processing natural gases and gas condensates, it is usually necessary to dry them using suitable dehydration equipment. The design and operation of this equipment requires a knowledge of the amount of water present in the fluid at the reservoir and operating conditions. This is influenced by temperature, pressure and composition, particular1y when certain non-hydrocarbon components are present. Field experience indicates that hydrogen sulfide and carbon dioxide, for example, alter the usual water solubility relationships appreciably. However, an extensive search of the literature does not reveal any quantitative data on such systems. For sweet natural gases, generalized empirical correlations such as the one proposed by Katz, et al,6 can be used to predict water solubility with confidence at most temperatures and pressures of interest. However, existing theoretical relationships do not permit a calculation of the deviation from these curves when polar substances like hydrogen sulfide are present in the system. Thus one must resort to an experimental approach to obtain the necessary information. The fact that laboratory experimental methods frequently involve the use of mercury which reacts with hydrogen sulfide in the presence of water, and that hydrogen sulfide interferes with many chemical reactions specific for water has contributed to the difficulty of studying water solubility in systems containing hydrogen sulfide. In this investigation the water content of a limited member of methane-hydrogen sulfide mixtures was determined using a special technique with gas chromatography. REVIEW OF PUBLISHED DATA Experimentally determined water solubility data have been reported for methane, 14 ethane, 15 propane, 9 n-butane, 16 1-butene, 11 hydrogen sulfide 18 and carbon dioxide. 19 These studies report the effect of pressure, temperature and molecular structure on water solubility in single component gases and liquids. Fig. 1 compares experimentally determined water solubilities in several hydrocarbons, carbon dioxide and hydrogen sulfide at l00F as taken from this

By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By G. F. Comstock

These notes should be considered as a further discussion of Mr. S. W. Miller's paper on "Some Structures in Steel Fusion Welds."l In that paper and the resulting discussion, several conflicting opinions were expressed as to the identity of the needles or small crystals present in oxyacetylene and electric welds. An interesting specimen of an electric weld examined by the writer seems to afford new evidence regarding the needles, that may be worth presenting at this time. The specimen consisted of a piece of 3/8-in. (9.5-mm.) steel plate, about 21/4 by 13/4 in. (5.7 by 4.5 cm.) in size, on which some iron had been deposited by arc-welding to a depth of about 3/16 in. (4.7 mm.). The weld appeared to be a very good one, with no noticeable break or boundary between the plate and the deposited iron. Sections for microscopic examination were cut in three planes at right angles to each other through the deposited metal, two of these sections also extended through the steel base. After polishing in the usual way, the microscope showed that the deposited metal was full of very small, round, gray, oxide spots, while the steel plate contained quite a number of alumina inclusions and a little slag. The sections were etched with nitric acid in ordinary alcohol, and structures similar to those described by Mr. Miller were then displayed. Fig. 1 shows the typical appearance of the deposited metal, which was quite uniform in all three of the planes examined. The round dark-gray spots are oxides, and the pale angular crystals are evidently what Mr. Miller called cem-entite and Mr. Jeffries martensite, while Mr. Ruder and Professor Boyls-ton think that they might be nitride. The boundary between this structure and the steel base was sharply defined under the microscope. Fig. 2 shows the structure of the plate just under the weld; this is almost martensitic and resembles a coarse-grained casting. This coarse cast structure soon became finer as the distance from the weld increased, finally becoming very fine, with numerous small particles of sorbite. This very fine structure, shown in Pig. 3, became coarser in turn and finally merged into the original normal structure of the steel plate, shown

Jan 1, 1920

By Abram S. Hewitt

GENTLEMEN : If my first words were other than those of thanks for the high honor of being called to preside over the American Institute of Mining Engineers, I should do injustice alike to you and to my own sense of the obligation, under which I have been placed by your voluntary choice. When the position was first suggested to me, I resolutely declined to allow the use of my name, on the ground that, by training and occupation, I was not entitled to this honor, which, it then seemed to me, should be conferred only on a professional engineer. In fact, the history of the Institute, which had honored itself, as well as my distinguished predecessors, David Thomas, Rossiter W. Raymond, and Alexander L. Holley, by elevating them to its highest office, seemed to indicate the line and the limit of safe precedent, in which I did not then see how I could be included. But my scruples were finally removed by the consideration that, as in the course of human industry, the pioneer, of whom Mr. Thomas was so marked a type, must precede the mining engineer, so fitly personified in Dr. Raymond, and be followed by the mechanical engineer, whose incarnation we behold in Mr. Holley; so all these must be supplemented by the man of affairs and finance, in order that "enterprises of great pith and moment" may be prosecuted to a successful issue. I felt, therefore, that I had no longer any right to resist your preference, or to deprive myself of what I must regard as the crowning honor of an active career. On an occasion like the present it seems appropriate to review the history in this country, during the last hundred years, of those industries which the Institute of Mining Engineers specially represents. There is much in the story with which other members of this body are more familiarly acquainted than myself; yet I fancy that to all of them, and not less to our distinguished and most heartily welcome guests from abroad, a comprehensive outline of the progress of mining and metallurgy in the United States will prove interesting. I ask your attention, therefore, to a condensed account of that subject, embracing a statement of the beginnings of the industry on our shores, of the notable events attending its increase, and of its present

Jan 1, 1877

By Hon. Abrams S. Hewitt

Gentlemen : If my first words were other than those of thanks for the high honor of being called to preside over the American Institute of Mining Engineers, I should do injustice alike to you and to my own sense of the obligation, under which I have been placed by your voluntary choice. When the position was first suggested to me, I resolutely declined to allow the use of my name, on the ground that, by training and occopation, I was not entitled to this honor, which, it then seemed to me, should be conferred only on a professional engineer. In fact, the history of the Institute, which had honored itself, as well as my distinguished predecessors, David Thomas, Rossiter W. Raymond, and Alexander L. Holley, by elevating then] to its highest office, seemed to indicate the line and the limit of safe precedent, in which I did not then see how I could be included. But my scruples were finally removed by the consideration that, as in the course of human industry, the pioneer, of whom Mr. Thomas was so marked a type, must precede the mining engineer, so fitly personified in Dr. Raymond, and be followed by the mechanical engineer, whose incarnation we behold in Mr. Holley; so all these must be supplemented by the man of affairs and finance, in order that "enterprises of great pith and moment" may be prosecuted to a successful issue. I felt, therefore, that I had no longer any right to resist your preference, or to deprive myself of what I must regard as the crowning honor of an active career. On an occasion like the present it seems appropriate to review the history in this country, during the last hundred years, of those industries which the Institute of Mining Engineers specially represents. There is much in the story with which other members of this body are more familiarly acquainted than myself; yet I fancy that to all of them, and not less to our distinguished and most heartily welcome gnests from abroad, a comprehensive outline of the progress of mining and metallurgy in the United States mill prove interesting. I ask your attention, therefore, to a condensed account of that subject, embracing a statement of the beginnings of the industry on our shores, of the notable events attending its increase, and of its present

(Separates of all the Pamphlets published within the last three years (starting with No. 1469) are available, with few exceptions, at Institute headquarters. Separates of all the Technical Publications are also available. All the papers are on file in public, university and technical libraries, and when so indicated in the list, may be found either in the TRANSACTIONS or in the special volumes issued by the Institute.] METAL MINING TRANS. PAMPHLET VOLUME NUMBER TITLE AUTHOR MEETING AND PAGE'S 1033 Relation of Air Pressure to Drilling H. W. Seamon New York 66, 743, 756 Speeds of Hammer Drills Feb., 1921 1034 Time Factor in Depletion of Mines J. W. Roberts New York 66,711 Feb., 1921 1035 Calculation of Ore Tonnage and Grade J. E. Harding New York 66, 117, 122 from Drill-hole Samples Feb., 1921 1038 Discussion of Papers Presented in 1920 1041 Run-off and Mine Drainage H. N. Eavenson New York 66, 624,630 Feb., 1921 1043 The Health of the Underground Worker A. J. Lanza New York Feb., 1021 1045 Dust-ventilation Studies in Metal D. Harrington New York 66, 272, 289Mines Feb., 1921 1046 Discussion of Papers Presented at New York Meeting, 1021 1072 Breakage and Heat Treatment of Rock- B. F. Tillson New York 66,1758 drill Steel Feb., 1921 1073 Discussion of Papers Presented at New York Meeting, 1921 1076-M Analysis of Some Drill-steel Testa F. B. Foley New York 66, 789 Feb., 1921 1077-M Application of Magnetic. Analysis to C. W. Burrows New York 66, 796 Rock Drills Feb. 1921 1078-M Heat Treatment of Rock-drill Steel G.H. Gilman New York 66, 779_ Feb., 1921 1080 What is the Ideal Drill Steel? F. H. Kingdon New York 66,807 Feb., 1921 1051 Rock Drill Steels, etc. - W. T. Ober New York 66,814 Feb., 1921 1082-C Underground Mine Development, Its J. B. Dilworth Wilkes-Barre 66,715, 7.21 Definition and Valuation Sept., 1921 1084 Drill Steel from Hollow Ingots P. A. E. Armstrong New York, 66, 809 Feb., 1921 1088 Authors' Replies to Recent Discussion 1092 Heat Treatment of Rock Drill Steel A. E. Perkins New York 66,811 Feb., 1921 1096-M Octagonal Ventilation Shaft. of Davis- J. L. Bruce Wilkes-Barre 66, 252, 268 Daly Copper Co. Sept., 1921 1100-C Determination of Electrical Equip- G. Bright Wilkes-Barre 66, 580, 605 ment for a Mine Hoist Sept. 1921

Jan 1, 1927

By J. R. Thoenen

The Bureau of Mines has used various sizes of core barrels above 2 in. and below 10 in. in diameter to core manganese, potash, coal, brown iron ore and bauxite. The paper describes in some detail the methods and types of equipment used to obtain maximum sampling accuracy. Introduction On December 11, 1946, R. D. Longyear, in his capacity as Chairman of the Subcommittee on Exploration Drilling, wrote the author requesting him to prepare a paper presenting the collective ideas of engineers in the Bureau of Mines on the design, standardization and application of core barrels using diamonds or other hard cutting media for drilling holes larger than two inches and less than ten inches in diameter. In subsequent correspondence it was indicated that similar papers covering the experience of other government agencies would be solicited and all such papers received would be combined in a symposium on the subject for discussion at the March 1947 meeting of the Mining Methods Committee AIME. In soliciting such information from other Bureau engineers, it developed that most Bureau experience had been confined to standard core size, two inches or less in diameter, and that larger sizes had been used only for special purposes. It is hoped the data contained herein will be of help to other operators in solving problems encountered in the field. Acknowledgments This paper was made possible by the request of Lowell B. Moon, Chief, Mining Division, Bureau of Mines, to all Division engineers to send to the author any data they had on the subject. Engineers of the Mining Division contributing were: M. H. Kline, Chief, Raleigh Branch. Paul T. Allsman, Chief, Salt Lake City Branch. J. H. Hedges, Chief, Tucson Branch. C. H. Johnson, Chief, Rolla Branch. A. M. Evans, Mining Engineer, College Park Branch. Wing Agnew, Engineer in charge, Mount Weather, Virginia. Andrew Brown, Mining Engineer, Tus-caloosa Branch. In addition Albert L. Toenges, Supervising Engineer, Bituminous Coal Mining Section, Pittsburgh, contributed his experience in coring coal beds. The author's experience in the use of cores within the limits stated has been confined to the brown iron-ore work described by Brown and coring bauxite and clay in Arkansas. Design and Standardization of Core Barrels Bureau engineers are primarily interested in obtaining core that will best represent

Jan 1, 1949