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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 George S. Rice

GROUND movement from mining, whether it be for coal, metal, industrial minerals, or .oil, will always present many difficult problems. These are especially serious when valuable surface improvements may be badly damaged. The mine itself, if mining methods are not suitable to the formation, is subject to heavy falls of the main roof in the working places; and with certain structural conditions the movements may cause in coal mines disastrous bumps and outbursts of gas, and in deep metal mines rock bursts. In open-cut work rock and earth slides may result. Absolute prevention of ground movement from mining is impossible unless large pillars are left unmined,

Jan 1, 1937

By D. R. Knowlton

IF I were a minister, and this were a sermon, and such a passage appeared in the Bible, I would choose for my text: "From whence cometh the oil for our war?" And no preacher was ever more serious than I am. You petroleum engineers recognize that the producing branch of the industry is passing through an era of plenty and inflated potentials into an era of scarcity and unmet allowables. Not too long ago the oil operators of Kansas, California, and Texas were appearing before operators' meetings and regulatory authorities asserting that these States were capable of producing at rates far in excess of what the demand at that time would absorb. Today every oil-producing area in the United States except the Texas Gulf Coast and West Texas is producing close to or in excess of its maximum efficient rate.

Jan 1, 1943

By W. A. Backofen, N. E. Paton

DEFORMATION twinning contributes to the plasticity of titanium and has been reported on {10i2}, {1121},{11221}, {1123}, and {1124} planes.' Twinning on {1011} has also been reported in commercially pure titanium as a result of quenching from 1000', but no reports of such twins occurring as a result of deformation alone are known to the authors. In this study single crystals grown from iodide titanium were compressed parallel to the c axis over the temperature range 25 to 800°C. From it has come evidence that (10il) deformation twins are the most common type between 400" and 800°C. Crystals about 6 mm high with a rectangular cross section measuring about 3 by 4 mm were used in the tests. Chemical analyses showed them to contain 220 to 250 ppm 0 arid 10 to 15 ppm N. The long axes of the crystals were made parallel to the c axis while the sides were parallel to (i100) and (1120), as shown in Fig. 1. The crystals were compressed between polished alumina platens with no lubrication, in a vacuum of 2 x lom5 torr. Between 25' and 300°C the predominant twinning mode was (11221, which is to be expected for this stress state. There was an abrupt change at 400°C, however, and from that temperature up to 800°C twinning took place almost entirely on (10i1 ). Twin planes were determined by the two-surface rnethd. Measurement of the crystal orientation within several (10i1) twins by means of polarized-light4 and transmission electron microscopy showed that the lattice reorientations were the same as those previously reported for the (10i l ) twinning in magnesium.' This reorientation is consistent with The calculated (10il ) twinning shear for titanium is 0.10, while that measured from surface offsets on a (1150) face, which is parallel to the shear direction, was about 0.15. Slip within the twins, or in the matrix adjacent to the twins, probably accounts for the larger measurement. Slip in both locations was judged to have occurred from observations on foils in the electron microscope.

Jan 1, 1970

By G. F. Jenkins

The word asbestos is a broad term that has been accepted and applied to a number of fibrous mineral silicates found in nature. They are incombustible and can be separated by mechanical means into fibers of various lengths and thicknesses, but differ in chemical composition and other properties. It is generally recognized that there are six varieties of asbestos; the finely fibrous form of serpentine known as chrysotile, and five minerals of the amphibole group, i.e., amosite (not fully recognized as a mineral species name but accepted in asbestos terminology), anthophyllite, crocidolite, tremolite and actinolite. (Figs 1-4.) Physical and Other Properties The structures of asbestos fibers have been studied intensely in recent years. X-ray diffraction patterns 1 to 15 have been used as a means of identification and classification. The amphibole group structures have been fairly well established while the serpentine group has been the subject of many investigations during the past six years. Low-angle X-ray scattering techniques5 have shown that the chrysotile fibrils are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 180Å* units to 300Å units, while the amphibole fibers are many times larger in cross section. The electron micrographs of chrysotile asbestos (Figs 1-4) have also indicated that the fibrils might be in the form of a hollow tube. This point has been the subject of considerable controversy by a number of investigators.7 to 16 Density measurements17 made on a sample of high quality Arizona fiber did not indicate that the fiber had a hollow tube structure; however, the so-called "sheet structure" of the fibril could be distorted in such a way that it gives the appearance of a hollow tube in the electron microscope. It is of interest to quote one investigator, F. L. Pundsack,17 in this connection: Although the empirical composition of chrysotile is 3MgO.2SiO2.2H20, the true unit cell[#] composition is best represented as Mg12(OH)16Si8O20. This cell has dimensions of a= 5.3Å, b = 9.2 Å, and c = 14.6 Å where the "a" direction is the fiber axis. The calculated density of this unit is 2.56 g/cc, a value in close agreement with experimentally determined density values for chrysotile. The exact manner in which the unit cells of asbestos are stacked together to build up a single fiber of chrysotile is not known, but from various

Jan 1, 1960

By Joseph M. Jacisin

Fatigue tests were conducted on 2017-T4 alumium in alloy in an u1lrcthig.h vacuum of 2 x 10-lo Torr and in air. The vatio of vacuum-to-air faligue life for this ~malerial varied Jrom 3.5:1 at a strain of 2.5 X 1O-3 ill. pegr in. to 8:l at a strum of 3.3 x X ill. per 171. Sotlze pvelivtlinary data were also obtained on the faligue life of the alumirnum alloy in a dvy-nitrogen atmosphere. A dark deposit observed on the fracture surfaces of the aiv-tested specimens was identified as oxides of tr~angarzese and magnesium This observalion, and the close correlalion betaveen results obtained in vaCuum and dry-nitrogen environtments, tend to confirm that air stvongly influences the fatigue mechanism by a covrosion process. THE fatigue life of certain metals is known to increase when the atmospheric pressure is reduced. Gough and Sopwith1-2 postulated that this is due to a joint chemical and mechanical process operating in air at the surface of the metal with oxygen and water vapor playing significant roles. Wadsworth and Hutchings3 observed that aluminum is mainly affected by the presence of water vapor. Very little information is available on the fatigue properties of structural aluminum alloys in a vacuum environment. This report describes work performed on 2017-T4 aluminum alloy in an ultrahigh vacuum (2 x 10-loTorr) and in air. Some preliminary data are also presented on the fatigue life of the alloy in a dry-nitrogen environment. 1) EXPERIMENT 1.1) Test Material. The material tested was commerciaT 2017-T4 aluminum alloy which, in addition to aluminum, has an approximate composition of 4 pct Cu, 1 pct Fe, 0.8 pct Si, 0.5 pct Mg, 0.5 pct Mn, plus smaller amounts of other elements.* Some typical naturally age to a substantially stable condition. Specimens were then machined from these rods and ground to a No. 8 microfinish. In order to minimize variation in material characteristics, specimens were made from rods procured from the same lot. 1.2) Apparatus. The apparatus and test specimen used in the fatigue tests are shown in Fig. 1. The device utilized a single-cantilever beam with rotating-bending loading. Bending stress was applied to the fatigue test specimen by placing a spacer beneath the bearing support, thereby providing a constant deflec-

Jan 1, 1968

By Arno C. Fieldner

METALLURGICAL coke and the by-products of the carbonization of coal continue in strong demand. Nearly 500 new by-product ovens were constructed in 1943. Output of by-product coke in the first ten months of the year was about 2 1/2 percent higher than in the corresponding period of 1942, but beehive production remained on approximately the same level as last year and constituted about 11 per cent of the total coke output.

Jan 1, 1944

By Benjamin F. Tillson

THE past seven years, and 1937 in particular, have witnessed the return of New Jersey iron mining to a place of importance. Following the World War period, little mining was done for several reasons. The properties were operated by small merchant furnaces whose demand was not sufficiently large to warrant large-scale methods with their attendant low operating costs. Under those conditions, the ore produced could not compete with that from the Great Lakes. However, when on Nov. 1, 1.929, the Alan Wood Steel Co., of Conshohocken, Pa., leased the Scrub Oak and Washington properties at Mine Hill and Oxford respectively, they made radical changes in the mining and milling processes which greatly reduced the cost of production and pointed the way to a renewed interest in mining in New Jersey. The following factors have been advanced as influencing the reopening of New Jersey mines:

Jan 1, 1938

By W. M. Baldwin, C. R. Johns

Cobalt is reported1,2 to scale in accordance with the Pilling and Bed-worth3 parabolic law: where w = weight increase per unit surface area K = constant l = time The reported values of the parabolic oxidation constant, K, in the temperature range 600 to 1100°C follow an Arrhenius type of equation as inspection of Fig 1 shows. According to Valensi's theory5 on the scaling of metals where multiple-layered scales (for example, MeX, MeX2, and others) are possible, this fact could be construed as indicating that a single oxide only is formed on cobalt in this temperature range. Since the single straight line extends above 920°C where only CoO is stable in air (see Fig 2) it might be inferred that this is the only oxide formed on scaling. Arkharov and Voroshilova10 have studied the scales formed when cobalt is heated in air in the temperature range 385 to 800°C and report that CoO is indeed found in the scale but that CoO4 is also found as an overlay and in increasing amounts in the lower temperature ranges. No quantitative data regarding the relative proportions of the two oxides were reported. Again in the light of Valensi's theory this would indicate that the straight line in Fig 1 would be expected to undergo an inflection at some point in the temperature range 385 to 800°C. Chauvenet2 has studied the oxidation rates of CoO to Co3O4 and has found this reaction to proceed parabolically with time but reports parabolic scaling rates which are considerably (about ten times) larger than the scaling rates of cobalt metal itself. This is difficult to explain in terms of Valensi's theory although a full discussion of the possible discrepancy cannot be made in view of the lack of sufficient data. These points made an investigation of the scaling behavior of cobalt in air an attractive study. Discussion of Results Relatively large (approximately 95 sq cm of surface area) samples of 0.020 in. thick electrolytic cobalt strip,* sanded with 2/0 paper, were heated in air in a cyclone type furnace. The samples were weighed before and after the scaling treatment. The weight increases so observed obeyed the Pilling and Bedworth parabolic law at all temperatures studied. The parabolic scaling constants when plotted on a logarithmic scale as a function of absolute temperature are reproduced

Jan 1, 1950

By C. A. Hartnagel, D. H. Newland

Detailed production statistics listing the operations according to producing sands, districts, etc., are not available for New York State and are scarcely obtainable without extraordinary effort and expense, hardly warranted by the current rate of developments. The oil industry is practically stabilized, so far as exploration for new sources of supply are concerned; no new pools have been tapped in the last 25 or 30 years. There is little prospect of extending the boundary of the oil fields beyond their present limits, though possibly some additional reserves may be found below the present productive sands. Natural gas, on the other hand, is not restricted to such confined areas. Drilling for gas has been fairly active, under the stimulation of some important finds in formations that previously were overlooked. The year's field operations will be covered somewhat fully. Oil production, which has been steadily advancing for a number of years, showed a further moderate gain in 1936. The output for 11 months (figures for December are not yet available) was 4,217,000 bbl., indicating a total for the year of around 4,600,000 bbl. The increase was about 10 per cent, a rate maintained for some time. Prices were more satisfactory than in the preceding five years, with an advance to $2.57 a barrel before the year's close. New York State yield is all paraffin-base, in the same class with high-grade Pennsylvania oil. Most of the output is now obtained by the water drive, which has given a new lease of life to the fields and promises to bring the total to about 200,000,000 bbl. before the known acreage has been exhausted by this method. Before its introduction the annual production was under 1,000,000 bbl. a year. The fields cover an aggrcgate area of 55,000 acres, with some 17,000 wells in operation. Development Exploring for natural gas in New York in 1936 outside of the old established pools continued actively, as in the previous year. There was an increase in total initial production. Operations were conducted in nine counties of the central and western parts of the state, and 43 wells

Jan 1, 1937

Truman H. Aldrich W. Lawrence Austin W. S. Ayres John Henry Banks Wrn de L Benedict Andrew A Blair Walter M. Brodie H. H. Burden Charles Butters

Jan 1, 1932

Truman H. Aldrich John H. Allen W. Lawrence Austin W. S. Ayres John Henry Banks Wm de L. Benedict Robert Bentley Andrew A Blair Walter M. Brodie

Jan 1, 1934

Truman H. Aldrich John H. Allen W. Lawrence Austin W. S. Ayres John Henry Banks Wm de L. Benedict Robert Bentley Andrew A Blair Walter M. Brodie

Jan 1, 1934

By R. J. Blackwell, J. R. Rayne, W. M. Terry

This paper presents results of an experimental investigation of factors that control the efficiency with which oil is displaced from porous media by a miscible fluid. The study was made to elucidate the relevant processes both on microscopic level (within individual or between neighboring pore spaces) and on macroscopic level (within a large sand body). Mixing of miscible fluids on the microscopic level was studied in sand-packed tubes. It was found that molecular diffusion is the dominant dispersion mechanism for reservoir conditions of rate, length and pore sizes. Macroscopic channeling was studied for various mobility ratios in reservoir mode1s scaled to relate viscous, gravitational, and diffusional forces. The formation of channels was due to viscous firzgering, gravity segregation and variations in permeability. With adverse mobility ratios, it was found for reservoirs of realistic widths that diffusion will not be effective in preventing the formation and growth of fingers, even in homogeneous sands. At sufficiently low rates channeling was eliminated by gravity segregation in tilted reservoirs. The dependence of recovery on mobility ratio, length-to-width ratio, flow rate and angle of dip is presented. INTRODUCTION Oil recovery by solvent flooding is finding increasing application in the field. While the process promises high recoveries from the region swept by solvent, under adverse conditions only a small fraction of the reservoir volume may be swept at the time solvent breaks through to the producing well. Further, the high cost of the solvent encourages its use only as a bank whose size must be kept at a minimum. Thus, two important questions arise: (1) what fraction of the reservoir can be swept, practically, by solvent? and (2) what is the minimum size solvent bank that can be used to carry out the displacement? The answers to these questions require knowledge of both macroscopic channeling processes and microscopic mixing processes. The studies described here were carried out to gain this knowledge. Microscopic mechanisms which cause mixing will be discussed first, because an understanding of these mechanisms is necessary for proper interpretation of the experimental work on channeling described later. INVESTIGATION OF MICROSCOPIC DISPLACEMENT PHENOMENA FOR MISCIBLE FLUIDS The questions to be resolved concerning microscopic displacement behavior are: (1) how much mixing occurs between oil and solvent in the direction of flow? and (2) does the solvent completely flush the oil from the pore spaces in the region invaded by solvent? The classic work of Sir Geoffrey Taylor' and its extension by Aris2 have shown that it is possible from theory to describe the amount of mixing in single straight capillaries when solvent displaces a fluid of equal viscosity and equal density. Aris showed that the lengths of the mixing zones, 81, corresponding to the 10 per cent and 90 per cent concentration levels of the solvent can be calculated from the formula, 81 = 3.62 \/Kt, .........(1) where 8l is the length of the mixing zone, cm; t is the time, sec; and K is the effective dispersion coefficient, cm2/sec, given by K/D = 1 + (1/48) (au/D)2......(2) where a is the radius of the capillary, cm; D is the molecular diffusivity, cm2/sec; u is the average velocity

By Roy Moore

THE Tom Reed Extension and Big Jim mines of United Eastern Mining Co. are situated in the Oatman district, Mohave County, Ariz., about 28 miles southwest of Kingman, the nearest railway point. Articles descriptive of the mine surface plant, mill construction, and plant operations have been written by Otto Wartenweiler1, the designing engineer; Wheeler 0. North,2 when he was assistant general manager for the company, and Earle M. Bagley, mill superintendent.3 The last article covers average costs for the full time the mill was operated. The geology of the mines is described by F. L. Ransome4 of the United States Geological Survey. Production was started in January,. 1917, and the known orebodies were exhausted in May, 1925, showing a life of seven years and five months. On account of the comparatively short life and the fact that stoping operations were confined to two orebodies, little experimenting was done with mining methods. The two orebodies were in what is generally called the Tom Reed-United Eastern vein, which occupies a fault fissure having a normal displacement of several hundred feet. Seven or eight very productive ore shoots were mined along this vein in a distance of 1 ½ miles, the two worked by the United Eastern being 1 mile apart. The maximum dimensions of the Tom Reed Extension ore shoot were height, 750. ft.; length, 950 ft.; thickness, 48 ft. The vein structure varied from a solid quartz-calcite filling to a series of parallel stringers separated by andesite. From this body, 511,976 tons of ore were mined. (Fig. 1.)

Jan 1, 1928

By Edward Keller

Although the subject matter contained in this paper is presented under a new title, its writing was induced by the work of S. Skowronski and K. W. McComas.' A discussion of the latter is here combined with the presentation of new and independent data. The' physical constants quoted by the authors of that paper, such as melting and boiling points, as also the chemical reactions of the substances involved, are so well established that the numerous confirmatory experiments and their application to metallurgical conditions leave little or no room for criticisms. On the contrary, they will greatly aid to dispel any lingering skepticism as to possible considerable losses of copper accruing when the metal is melted in the presence of its own and, probably, other chlorides and when no provision is made for the recovery of volatile products. Exception may be taken, to some degree, to that part of the work under the caption Melting Drillings of Copper Mixed with Sodium Chloride. These experiments should have been extended in order to make the implied reactions clear and the results convincing. The latter are stated to be, "that when sodium chloride is present above certain minimum quantity relative to copper some of it is found to volatilize in the melt while another part reacts with the metallic copper to produce the volatile cuprous chloride, and that when smaller quantities of sodium chloride are present the reaction is complete and all chlorine is found to have volatilized as cuprous chloride." Metallic copper and sodium chloride are mentioned as the sole reagents in this chemical process, acting, according to the authors, in a neutral atmosphere of carbon dioxide. The chemist, quite naturally, wi11 inquire into the formula according to which that reaction takes place and will find that it presents itself as follows: 2Cu + 2NaCl = 2Na + Cu2Cl2 It would appear that the truth of this formula will be challenged and a more rational explanation of the reaction sought. Apparently, carbon dioxide is neutral relative to metallic copper in its molten state; whether it remains neutral in the presence of sodium chloride is quite another

Jan 1, 1921

By I. A. Ettlinger

DEPRECIATION allowances have become firmly rooted in our income tax structure both by legislation and by court decisions. Secretary of the Treasury Morgenthau has recently stated before the Ways and Means Committee of the House: A taxpayer who did not provide for depreciation of assets used in his business could not long remain in business and the income tax should be levied on the assumption that he will provide for such depreciation. The 1934 Revenue Act has now been enacted, the depreciation provisions of the 1932 Revenue Act having been carried forward without change. However, there has arisen, in connection with the preparation of this new Revenue Act, a determination by the Treasury Department to make certain changes in the future administration of the depreciation allowances that will affect all corporations, and mining companies in particular.

Jan 1, 1934

By Tracy Jarrett

In 14-karat gold alloys, as in 10-karat gold alloys,3 the addition of such metals as zinc, nickel, copper and silver produces a wide range of physical and chemical proper-ties such as color, hardness, corrosion resist-ance and melting points. These important factors made gold alloys desirable in the optical work and for jewelry. In 14-karat gold alloys, as well as in 10-karat or 12-karat, it is possible to have two golds of the same color, one of which will corrode more than the other, although it may be harder. Some of these alloys have been investigated by F. E. Carter,1 E. M. Wise,5 and L. Sterner Rainer.4 In this group of alloys the gold content of 58.3 per cent (14-karat) was held constant, while the copper varied from 36 to 24 per cent. The balance of the alloy consisted of one, two, or three of the metals silver, zinc, and nickel. All the alloys were melted in an induction furnace and cast into an ingot that meas-ured 3 by 1/4 by 3/4 in. The method of determining the melting points, color deter-minations and acid test have been discussed in previous papers by the author.2,3 It is necessary to use small test bars (Fig. r). The tensile bars were annealed at 1300°F. for 20 min. and then air-cooled. There being a very marked drop when the yield point was reached, "the drop of the beam" method was used in determining the yield point.

Jan 1, 1940

By F. Keller

SOME PHRASEMAKER has aptly said that nature made aluminum light but research made it strong. Research has been a vital element in the past progress of the aluminum industry and its future growth likewise depends upon the application of the results of research. The role of aluminum products in World War II is well known and this metal will certainly be increasingly important in the postwar world. Some of the principal developments in the war years were in the field of high-strength aluminum alloys. New and stronger alloys were developed which enabled designers to get increased speed and performance in our fighter planes and bombers. The aircraft industry will continue to use these new materials for peacetime passenger and cargo airplanes. High-strength alloys will also find structural applications in trucks, buses, trains, ships, and bridges.

Jan 1, 1946

By Lucien Eaton

INCREASED mining activity during the past year has brought to light changes in mining practice and advances in technique, born and incubated in the period of depression from which the mining industry is now emerging. Although the tendency toward large output from individual mines has continued, a salutary trend is evident toward greater efficiency at small mines, in which the gold mines of Canada have led the way. Improvement in excavating machinery and washing plants for small placers has continued, and knowledge of the possibilities and limitations of this kind of equipment has increased. Greater portability through sectionalization has been the keynote. Power, shovels and draglines mounted on caterpillar treads move from one deposit to another under their own power, and floating washing plants mounted on pontoons can be taken down, moved, and set up again by a small crew of men in only a few days.

Jan 1, 1937