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By G. Krauss, W. Pitsch

The fine structure of the bcc martensite formed in an Fe-33 wt pct ATi single crystal of arrstenite is sho~on by transmission electron microscoPy to consist of combinations of transformation twins, stacking faults, deformation twins, and regular arrays of parallel screw dislocations. These structures constitute evidence for the multiple lattice-invariant deformations which operating during the formation of martensite could produce the real habit-plane scatter measured by a two-surface analysis of the plates formed in the single crystal of this investigation and reported in the literature for other Fe-Ni rnartensites. CRYSTALLOGRAPHIC theories1,2 of martensitic transformation show that the habit plane of martensite in a parent lattice is dependent in part upon an inhomogeneous distortion or lattice-invariant deformation which takes place on a fine scale within a martensite plate during its formation. Several recent theoretical papers3,4 have addressed themselves to an analysis of a wide variety of conceivable lat-tice-invarient deformations and the habit planes which they produce, while experimental investigation have been concerned with either the measurement of habit planes or the description and identification of the martensitic fine structure which reflects the nature of the lattice-invariant deformation operating during transformation. In Fe-Ni alloys with subzero Ms temperatures, the group of alloys with which this paper concerns itself, habit planes have often been found to scatter an amount greater than might be expected from possible experimental errors,5-7 and fine twinning has been identified as a major constituent of the fine structure of martensite.8-11 It has been suggested3,4 that more than one type of invariant shear occurs during martensitic transformation. This possibility has been experimentally supported12,13 by the observation of both dislocation configurations and twinning in a single martensite plate. The purpose of this paper is to report additional evidence for multiple lattice-invariant deformations in martensite and so to account for the real scatter in the habit planes of the martensite plates formed in Fe-Ni alloys. EXPERIMENTAL PROCEDURE The Fe-Ni single crystal was produced by pulling a high-purity iron and nickel charge through a single-crystal vacuum furnace in an alumina crucible. The crystal was double-melted to promote homogeneity and to increase its size by further additions on the second pass. In its final form the crystal was 4 cm in diam and 5 cm long. The nickel and carbon contents were analyzed at 32.9 and 0.006 wt pct, respectively. The austenite of this alloy first transformed to martensite by bursts at about -120°C, and, to preserve as much of the austenite as possible, all transformation was performed just below -120°C. Some observations were made on transformed samples which had been heated for 2 min at 340°C. It is assumed that the features of the martensite of these samples, Figs. 1 and 4, are the same as those of the as-quenched martensite. Orientation of the crystal by X-ray diffraction established 10.735 0.609 0.3161? as the axis of the crystal, an orientation that was checked within 2 deg by neutron diffraction. Further checks by electron diffraction of samples cut normal to the axis confirmed this orientation within the larger limits of error inherent in electron diffraction of thin foils. The X-ray orientation was the one used for the two-surface analysis of the martensite habit planes. A two-surface analysis was performed on the quadrant of the single crystal which had been oriented by both X-ray and neutron-diffraction techniques. Photomicrographs at X50 were made on two surfaces along an edge 2 cm long. Fiducial marks and the fact that many of the plates were almost completely surrounded by retained austenite made good matching of individual plates on two surfaces possible. The habit-plane trace on a surface was taken as the best line parallel to the long axis of a plate. A measure of the accuracy afforded by this criterion was provided by a family of very large plates which appeared at intervals along the entire 2 cm length of the edge. The plates all had habit-plane traces within 2 deg of one another. Many of the plates did not show midribs and, therefore, the use of midribs7 to represent habit-plane traces was not feasible in this investigation. The over-all experimental accuracy is estimated to be better than ±2 deg. Samples for transmission examination in a Siemens Elmiskop I at 100 kv were prepared by cutting 2-mm-thick discs from the single crystal, removing about 0.5 mm by chemical polishing,14 trans-

Jan 1, 1965

By A. T. Harris

Ground quartzite, known in the industry as amorphous silica, is produced from a quartzite deposit near Honey Brook, Pa., by George F. Pettinos, Inc., of Bala-Cynwyd, Pa. The quartzite is mined by the open pit method and processed in a mill at the mine. The operation regularly produces five standard grades of sand and one grade of crushed stone; however, the company accepts special orders and will produce material to meet the customer's specifications. Beneficiation (chiefly crushing and screening) is controlled by laboratory screen tests on samples taken during preparation of the sand. The chief uses of the sand are for foundry operations, furnace lining, concrete aggregate, and other specialized uses. The quartzite in this deposit is of uniform composition and does not require control by chemical analysis. However, for special purposes, analysis will be furnished.

Jan 1, 1965

By d&apos, Kathleen J. Amico

THIS SUMMARY appears in Minerals Yearbook volumes I and III, which cover mineral production in the United States, its island possessions, the Canal Zone, and the Commonwealth of Puerto Rico, as well as the principal minerals imported into and exported from the United States. The several commodity and area chapters contain further details on production. A summary table comparing world and U.S. mineral production also is included. Mineral production may be measured at any of several stages of extraction and processing. The stage of measurement used in the chapter is normally what is termed ?mine output." It usually refers to minerals in the form in which they are first extracted from the ground, but customarily includes for some minerals the product of auxiliary processing operations at or near mines.

Jan 1, 1965

By Hyung Sup Choi

The preparation of high-purity zirconyl compounds was studied in order to develop an economical process for obtaining pure zirconium via the caustic fritting of zircon sand. The direct dissolution of caustic frits with concentrated hydrochloric or nitric acid at 80c. followed by the addition of a small amount of acidified gelatin, gave high-purity zirconyl chloride or nitrate. The addition of a small amount of gelatin caused a mutual flocculation between colloidal silica and gelatin. The precipitation of this silica floc markedly lowered the content of silica in the product. The silica content of the compounds (or solution) so produced, generally less than 100 ppm., was sufficiently low for tributyl phosphate extraction for nitrate solutions. It was found that the degree of purification de-pends not only on the procedures employed but also on the nature of the frit itself. Silica was more effectively eliminated from the fritted product produced at higher temperatures, and less silica was present in the com-pound prepared from the frit produced in a shorter heating time. In order to ascertain the nature of the

Jan 1, 1965

By R. J. Leary

Oxidation testing of copper-clad steel strip was performed in a muffle furnace to determine whether copper in contact with steel scrap could be removed by oxidation in an airstream at high temperatures. Substantially all of the copper was oxidized before any significant iron oxidation occurred. The rate of copper oxidation was not affected by contact with iron. Copper oxide scale separated spontaneously from the underlying metal during cooling. Results indicate the possibility of removing light-gage copper coatings and components from ferrous scrap by oxidation in an incineration process.

Jan 1, 1965

By B. Paul, C. C. Fu

Experiments indicate that the fatigue limit of various drill steels becomes vanishingly small in the presence of water and other corrosive liquids. Therefore one must generally expect fatigue failures of drill steels in a great many field operations. However, it is theoretically possible to so choose the hammer impact speed of a percussion drill in order to maximize the total length of hole drilled before failure occurs. In this paper the existence of an optimum speed is demonstrated and it is shown to be comparable to presently used piston speeds. The influence on drilling speed and hole length of a number of other pertinent design features, such as bit geometry, hammer geometry and steel properties is also established. Although machinery should be designed to obtain optimum performance, it is not always clear just what performance characteristic is to be optimized. For example in a rock drill it would be desirable to optimize all of the following characteristics: drilling speed, bit life, steel life, total length of hole drilled before failure, and efficiency of energy conversion. The word failure could signify excessive bit wear, bit fracture, steel fracture, or some other type of component failure. It is not possible in general to optimize all performance criteria simultaneously. For example, one could achieve fantastically large drilling rates at the expense of bit or steel life, energy requirements and physical size of system. It therefore becomes necessary to compromise requirements in order to achieve a well-balanced albeit non-optimum design. It is, however, extremely useful to explore the interrelationships between the different performance characteristics. Such a procedure would help to establish theoretical limits of performance within the framework of existing knowledge and also serve as a practical design procedure for special applications where a particular performance characteristic is of greatest concern to the user (e.g., steel breakage might be especially undesirable in certain locations). It is the purpose of this paper to examine the problem of how one may drill the deepest possible hole before breakage of the drill steel occurs. Of course the problem is almost trivial if a well defined fatigue limit (endurance limit) exists for the drill steel. In such cases one merely keeps the piston impact speed sufficiently low to insure that the stresses in the steel never exceed the fatigue limit, thereby achieving an infinite life. If, however, no definite fatigue limit exists, as seems to be the case in the presence of even mildly corrosive agents such as water (see later discussion), then a finite life is inescapable and one can at best hope to maximize the useful life of the system. Indeed it will be shown that the system life is related to drilling speed in the manner shown schematically in Fig. 1-a. Even if a definite fatigue

Jan 1, 1965

By N. A. D. Parlee, I. D. Shah, W. C. Phelps

THIS note reports on a continuation of a program on the thermodynamics of Fe-S-X systems in the "steel-burning" temperature range begun by Bock, Barloga, and parlee.' Small coils of 0.039-in.-diameter pure iron (Ferrovac-E) wire were equilibrated with Fe-S-0 melts in ingot iron crucibles under argon at 1324°C in the assembly shown in Fig. 1, the lower part of which was heated in a large Globar furnace. Fig. 1 shows (R) the coiled iron wire sample, (M) the Fe-S-0 melt prepared from desired proportions of ferrous sulfide and ferric oxide, (K) the iron crucible, (I) a mullite guide tube, (J) an alumina crucible, (L) alundum sand, (N) crushed mullite, (Q) hollow cylinders of K30 brick, (C) a steel rod, (B), (El, (F), (G), (P), and (O), details of brass water-cooled head, and (H) a mullite tube 2-3/4 in. ID and 26 in. long. The rod (C) bearing the sample could be removed at will and be replaced by a tube for sampling the melt, or by a thermocouple for comparing the melt temperature with a control thermocouple not far from the 2-3/4-in. mullite tube. After equilibration the iron coils were treated with acid to remove the outer layer of metal and then they were analyzed for sulfur by a standard combustion method. The melt samples were analyzed for oxygen by a variation of Lander's2 hydrogen-reduction method for mattes, and for sulfur by the ASTM combustion-iodometric method NO. E 30-47. When the results of some forty-two runs were examined it was found that the sulfur and oxygen contents of the equilibrated melts showed good consistency, in that the plotted compositions fell along the smooth curve shown in Fig. 2. The points on this curve represent the experimental compositions of melts in equilibrium with ?-iron (Fe-S-0) solid solutions. These solid solutions are saturated with sulfur and oxygen with respect to the melt and therefore have the same sulfur and oxygen activities as the melt. The curve drawn through the points therefore delineates the ? liquidus. It falls in such a position as to roughly confirm the liquidus curves of Hilty and crafts3 at 1200" and 1300°C which are

Jan 1, 1965

By A. Gillis

"In order to obtain the equipment necessary to automate the equipment it was decided that the Department of Mines and Milltronics would jointly survey the circuit. This survey involved a metallurgical study by the Department of Mines and Milltronics took sound recordings during manual operation, checking in circuit bottle necks and determining the number of sensors that could be applied.The conveyer is driven by 2 PIV drives, each has a variable speed of 3/ 1. The cross conveyer that feeds directly into the rod mill feed chute will contain an automatic sampler and will eliminate the necessity of stopping the belt feeders to take samples. At present, hourly samples are taken from this point and the circuit is upset and cycling results.The Adequate scale is very close to the rod mill to totalize and thereby give a continuous indication and the second purpose is to take a signal from it and control the solution addition to the rod mill.A pneumatic positioner was obtained and put on the scale which produces a 3 tp 15 psi signal which is proportional to the actual tonnage going across the scale. This signal was fed to a bias loader which was mounted on the control panel. From there the operator can set the amount of solution that is wanted by the rod mill. No matter what the feed rate is, the signal coming from the bias loader will follow it automatically. This in turn goes to the pneumatic solution valve (1 ½” ) and the solution goes in with the feed to the rod mill. This is only part of the solution required for dilution since the rest of it is used as a force jet for the feed to the rod mill."

Jan 1, 1965

By T. E. Sterner

The Bureau of Mines investigated the use of a chromatographic gas analyzer in determining the concentration of combustion products in gas produced during field and laboratory thermal oil-recovery tests. Several parameters (carrier-gas flow, cell current, sample size, and temperature) known to affect quantitative analyses were studied using a commercially available dual-column, dual-detector chromatographic gas analyzer which had been modified to provide close control of these variables. The apparatus made possible a much closer control of air-and gas-injection rates and provided adequate data for performing material-balance calculations and for determining oxygen utilization during the laboratory and field combustion tests. The chromatographic analysis also aided materially in evaluating and measuring bypassing and gas travel times and in detecting high-permeability zones that were present in the reservoir.

Jan 1, 1965

By C J. Coveney

This paper, after a brief introduction to the mineralization and structure in the mine area, outlines the methods now being employed for grade control at Bethlehem Copper Corporation. Sampling, subgrade drilling, blasting and the actual outlining of the ore are among the topics covered. The paper concludes with a summary of the results obtained, showing a reduction in dilution and an improvement in the grade of the copper ore going to the mill. Introduction T HE Bethlehem property is located in southern British Columbia in the Highland Valley about 30 miles southeast of the town of Ashcroft. The property is located within the Guichon batholith. The rock comprising the batholith is a massive, coarse-textured diorite, which, at Bethlehem, has been intruded by a younger quartz diorite, porphyries and breccia, referred to as the "Younger Complex." Mineralization, consisting of chalcopyrite and bornite with minor pyrite and molybdenite, occurs as disseminations, fracture fillings and coarse blebs. The ore zone lies close to the Guichon -Younger Complex contact where, prior to the development of the breccia, the rocks were shattered and jointed. Subsequent mineral

Jan 1, 1965

By Haydn H. Murray

Kaolin is an important industrial mineral because it exhibits desirable properties in many applications and because of its relatively low cost, Approximately 2,000,000 tons of kaolin from Georgia and South Carolina are processed and used commercially in the United States each year. Strictly defined, the name kaolin is applied to a group of hydrous aluminum silicates of which the mineral kaolinite is the most common. Kaolinite has such desirable properties as natural whiteness, chernical stability, non- abrasiveness, and very fine particle size. Kaolinite particles are characteristically thin, flat, and hexagonal in outline. The particles range in size from submicron to as much as 40 microns (equivalent spherical diameter). In addition to the general properties mentioned in the first paragraph, it is soft, has low viscosity at high solids content in many systems, is readily wet and dispersed in water and some organic systems, and can be produced with a controlled particle size distribution. Some of the important physical constants of kaolin are: specific gravity, 2.60; index of refraction, 1.56; hardness (Mohs scale), 2; fusion temperature, 1850°C; dry brightness, 78-92 percent.1

Jan 1, 1965

By D. R. Hay, E. Scala

Electrotransport has been superimposed on the rate-limiling- step in zone refining which is the impurity diffusion through the liquid at the solid/liquid interface. The efficiency of zone refining is increased and relative resistivity ratios (P300°k/P4 2°K) he increased by 50 pel in tungsten for a given number of posses using- the electrotransport field-aided method. The effiect of zotze refining in the presence of an electric field on the relative resistivity ratio is examined as a function of its intensity and polarity. THE effect of electrodiffusion on the effective distribution coefficient of zone refining has been discussed by Pfann and Wagner.' Control of the distribution coefficient in zone refining is of twofold interest. A distribution coefficient of unity can be increased or decreased, making possible the transfer of some previously inseparable solutes. The general efficiency of zone refining can also be increased. In the conventional zone-refining process impurities are removed by their retention in the molten zone and subsequent deposition at the end of the rod after a complete passage of the zone. In higher-melting-point systems a second mechanism may also operate, the volatilization of impurities from the molten zone. It has been suggested by schadler2 that, in refractory metals, vacuum distillation plays the predominant role in purification. In Koo's results,3 the resistivity ratio decreased beyond a zone-refined length of 6 in. from the starting end, indicating that some purification does in fact occur by true zone-refining action. Hay and scala4 showed that the degree of purity as measured by the relative resistivity ratio method depends on the square root of time in the molten zone (number of passes) and thus appears to be limited by diffusion in the boundary layer at the solidifying interface assuming good mixing in the body of the molten zone where a linear rate would prevail. The final concentration of impurities in electron-beam floating-zone purification depends very much on the operating conditions and results obtained by various investigators2,3,5 are difficult to correlate. The diameter of the starting material, operating vacuum, and rate of traverse are among the factors to be considered. There are, nevertheless, some general observations to be obtained from the literature. Lawley5 reviewed the literature up to 1962 and concluded that the major contaminants generally remaining in tungsten after electron-beam zone refining are molybdenum and carbon. Molybdenum due to its high melting point and distribution coefficient of nearly unity would be expected to be difficult to remove by either volatilization or zone refining. Carbon is not only a common contaminant in vacuum systems, but is also very difficult to remove by conventional vacuum melting. even with vacuums of 10-7 mm Hg. For each of those impurities removed by zone refining the equation of Pfann and Wagner may be applied: It relates the effective distribution coefficient k to a superimposed driving force which accelerates the solute away from the interface with a terminal velocity L" and to the more conventional zone-refining parameters; v = rate of traverse, t = thickness of the diffusion layer at the solidifying interface, D = diffusivity of the solute in the molten zone, and ko = equilibrium distribution coefficient of the impurity.

Jan 1, 1965

By A. H. Daane, W. J. Wunderlin, B. J. Beaudry

In an earlier study at this laboratory,' the authors investigated the solid solubility of holmium in copper, silver, and gold, and also the melting point of the first eutectic on the noble-metal-rich side in these systems. In a more recent study of the solubility of rare-earth metals in gold at this laboratory. Rider, Gschneidner, and McMasters2 noted that the reported eutectic temperature in the Ho-Au system was lower than the corresponding eutectics in systems of dysprosium and erbium with gold. A redetermination of the eutectic temperature in the Ho-Au system with the same alloy used in the original study showed the eutectic temperature to be 810°C instead of 778°C as originally reported. (The eutectic temperatures in the Ho-Ag and Ho-Cu systems were also redetermined and were found to be 795" and 864°C compared to 787° and 868°C, respectively, which were reported originally.) Since this large change in eutectic temperature made the solubility data appear questionable, new alloys were prepared, heat-treated, and examined metallographically. The procedure of sample preparation and heat treatment used in the original work' was followed except longer heat treatments were used ranging from 7 days at 600°C to 6 hr at 900°C. The results obtained are shown in Fig. 1. There is good agreement between the two studies in the maximum solubility of holmium in gold. Since the slope of the solvus is less pronounced in the present study, the extrapolation to 550°C shows a solubility of 1.6 wt pct Ho in gold compared with 1.0 wt pct in the original work. Since additional data were obtained and longer heat treatments were used in the present study, the larger value is believed to be more accurate. The authors wish to express their appreciation to P. Rider and K. A. Gschneidner. Jr., for bringing this discrepancy to their attention, and also to D. Thompson for assisting in the present study.

Jan 1, 1965

By A. J. Forney

Recent experiments used catalysts of plate assemblies in synthesizing high-Btu gas and gasoline indirectly from coal. A gas with a heating value of 925 to 943 Bt-: per cubic foot has been prod u la the hot-gas-recycle pilot plant from synthesis gas (3H2+100) with lathe turnings used as catalyst in the first reactor, and assemblies of parallel sprayed plats of nickel in the second. Solid plates made of Raney nickel, and steel and aluminum plates sprayed with Raney nickel or nickel oxide were tested. Those catalysts had very low resistance to gas flow; 90 percent lower than nickel granules used in previous experiments. In a single stage of synthesis thee nickel plates were only partially successful. Although the heating values of the product gas ranged from 856 to 941 Btu per cubic foot, the carbon monoxide content of he gas was above 0.1 percent. Both steel and wrought turnings were tested in single-stage synthesis, but the conversion of hydrogen and carbon monoxide was too low to attain the desired heating value of 900 Btu per cubic foot in the product gas. Assemblies of plates thermally sprayed with fusel iron were tried in an experiment to make gasoline. A gasoline yield of 52 percent (of the hydro¬carbons produced) was obtained using a 1H2-10O feed These sprayed assemblies were in service for 1,500 hours, the longest that this type of catalyst has been used. When a second reactor containing Raney nickel catalyst was added in series with the first reactor, complete utilization of the feed gas was obtained because in addition to the liquid product, a high-Btu gas with a heating value of 800 Btu per cubic foot was made.

Jan 1, 1965

By B. E. Eakin, A. L. Lee

Atmospheric pressure viscosity values For light hydrocarbons were calculated by a simple mixing rule based on the Sutherland constants for pure components. This method was further extended so that the atmospheric pressure viscosity of a mixture may be calculated based on the molecular weight information only. INTRODUCTION A proven method for estimating the gas-phase viscosity of a mixture is the one by Herning and zipperer.l This mixing rule has the following form: One method for calculating the pure component viscosity i is the Sutherland equation,2 which has the following form: The Sutherland constants B and S are determined from experimental data. A set of Sutherland constants for light hydrocarbons based on the data of several investigators3-5 is presented in Table 1. APPLICATION The Herning-Zipperer equation and the Sutherland equation were used to obtain an equation for calculating the gas-phase viscosity of light hydrocarbons. This equation has the form, Eq. 3 was used successfully in the study of methane-n-butane mixtures.6 Further analysis indicated that the Sutherland constants are a function of molecular weight.7 The gas-phase viscosity may be calculated based on molecular weight information only. The following equation was developed: The atmospheric pressure viscosity of ethane, propane, n-butaneand four methane-propane mixtures calculated on the basis of Eq. 6 are compared with the data of other investigators in Tables 2, 3, 4 and 5, respectively. A plot of atmospheric pressure viscosity vs molecular weight based on Eq. 6 is presented in Fig. 1.

Jan 1, 1965

By Richard L. Ash

In many instances, blasting exerts the dominant control over the economics and safety of excavation, where the materials involved are too hard and tough to be fragmented efficiently by other means. However, associated with the fragmentation process other effects very often result that are not desirable and may even be hazardous, such as fly rock, air blast, excessive overbreak, and damaging ground virbrations. It has always been the desire of those concerned with blasting to better control the forces involved so as to improve the breakage of materials, but at the same time reduce, or eliminate if possible, the unwanted side effects. Until the last decade or two, little was known of the phenomena concerned with blasting. However, since that time many investigators have studied blast mechanisms produced from both chemical and nuclear explosions, with the result that general concepts of the principles have been developed. But, in general, it is assumed that the energy from the explosion would be propagated spherically throughout the material, the latter of which for convenience of analyses is considered homogeneous and isotropic, i.e., the properties are the same in all directions, However, rocks are not isotropic as a rule, and evidence clearly indicates blasting forces rarely function uniformly or in spherical form as theorized.

Jan 1, 1965

By Roger N. Dokken

It is well-known1-4 that Fe-Si alloys from approximately 9 to 27 at. pct Si show an ordered structure of the Fe3Si type at room temperature. Recently Meinhardt and Krisement,' through an investigation of Fe-Si alloys at room temperature by neutron diffraction, discovered that at 10.8 at. pct Si ordering of the FeSi type occurs while above this composition the normal Fe3Si-type superstructure appears. This FeSi type of ordering was also found by Davies8 as indicated by X-ray diffraction measurements on an Fe-8.7 at. pct Si alloy. Meinhardt and Krisement7 extended their neutron-diffraction work and determined the phase-boundary temperatures for both FeSi- and Fe3Si-type ordering. Ordering phenomena can also be studied by resistance measurements.4,8-11 Krivoglas and Maty-sina" carried out a theoretical development of the

Jan 1, 1965

By C. E. Morris, S. R. Pollack

Current -vo1tage -temperature characteristics were studied for Al-A12O3-Al, Au structures. The oxide film was grown by gaseous oxidation in an 0, glow discharge. The electron-transfer mechanism was identified as tunneling and the barrier heights and thickness were determined. It was found that the barrier height at the parent aluminum-oxide interface is 1.5 ev and the built-in vloltage with an aluminum counter electrode is 0.35 v. The growth mechanism of the oxide is also discussed and it is suggested that Mott&apos;s theory is not applicable in describing the growth. Discrepancies were observed in the detailed comparison of tunneling theory, based on a trapezoidal model, with the data, and several possible explanations are discussed. THEORETICAL analyses of electron tunneling from one nonsuperconducting metal to another through an extremely thin insulating film have been presented.1-6 These calculations relate the current density, J, to the voltage, V, between the two metals, and to the temperature, T. The results of these calculations indicate that the magnitude of J and the detailed shape of the J-V characteristic will in general depend most strongly upon such properties of the insulating film as the thickness, the dielectric constant, and the structure of the electron energy barrier profile. The experimental results of many7-11 workers have corroborated the main features of these calcu- lations and have in fact been used to determine properties of the thin insulating film. It has been demonstrated, for example, that the tunneling current formulation of simmons4 is adequate to describe the observed J-V characteristic over approximately 10 orders of magnitude of current. Furthermore, from these observations and analyses, insight into the nature of the A1-A12O3 (thermally grown) interface region has been obtained.&apos;&apos; The temperature dependence of the tunnel current has also been studied and, although a self-consistent set of tunneling parameters can be chosen to describe these data at low voltages (i.e., <0.5 v), the tunneling parameters are different from those obtained from higher voltage (i.e., of the order of 1 to 5 v) measurements." We have measured the effect of temperature and voltage upon the tunnel current at higher applied voltages and find that the theory is inadequate to describe all of the effects reported here. A discussion of the origin of this inadequacy is presented following a description of the samples used for these experiments, and the experimental results. SAMPLE PREPARATION Metal-insulator-metal structures were fabricated in the following way. A 99.999 pct A1 charge was used to deposit, in vacuo, thirty films, 2000Å thick, onto a 1 by 2 in. glass substrate (7059 Corning glass). Prior to deposition the substrate was glow-discharged for final cleanup and then baked at 200°C for 2 hr at a pressure of 5 x 10-7 torr. The pressure during deposition of the metal films was 2 X 10-6 torr and the deposition rate was 50 to 100Å per

Jan 1, 1965

By F. W. Jessen, H. Kazemi

A washing technique has been developed to form a spherical cavity in massive salt. The technique is, basically, a process of controlling the fluid motion in the cavity, the concentration distribution of brine, the rate of dissolution at the walls of the cavity, and the particular settings of the wash pipe, or pipes (inlet and outlet pipe) employed. For a particular arrangement of tubing and casing, fresh water enters from the casing annulus at a position above the bottom of the tubing, and the dissolved material leaves the cavity through the tubing near the bottom of the projected hole. The initial configuration of the cavity is cylindrical, representing the drilled hole situated at the axis of the projected cavity. As washing progresses the original hole is enlarged radially (any direction perpendicular to the axis of the hole). An inert fluid (generally a hydrocarbon, natural gas, or air) which serves as a blanket is injected through the annular space between the original hole and the casing. The controlled downward motion of this blanket maintains the upper edge of the brine region that is expanding on the surface of the projected sphere. A large spherical glass container and a radial model were used to investigate the flow patterns and the concentration distribution of brine occurring during the progress of solution of the salt. Aluminum flakes and dye were injected and flow patterns were observed and recorded on motion picture film. Based on the results of these model studies and other work carried out in this laboratory, the controlled washing technique was formulated. INTRODUCTION Underground cavities leached in salt beds and salt domes have been used extensively for storing hydrocarbons. Little attention has been focused on the shape of the cavities as long as large volumes were obtained and the cavities were structurally stable. The general process involves circulating fresh water and removing brine. Two distinctly different circulating systems can be employed, each of which yields characteristically different shapes. By far the most generally accepted method of washing storage caverns in salt domes is the direct circulation system. Water is introduced through the innermost pipe of a concentric pipe system, and brine is withdrawn through the annulus. In the reverse-circulation method, water enters through the annulus and is discharged through the smallesc tubing string. The size of the operation, and hence the size of tubing and casing used, depends on such factors as cavity volume, length of hole, availability of water, disposal of brine and power requirements. Underground caverns are from 100 to 1,000 ft or more in length, and when completed vary from 40 to 100 ft in diameter, providing storage of 100,000 bbl or more. The volumes of water required per volume of salt removed vary from 6 to 7 for the reverse circulation method to 10 to 11 for the direct circulation method. Up to 80,000 BWPD are often circulated. In the direct circulation method, because water enters near the bottom of the projected cavity, solution of salt is greatest at this point, particularly in view of the fact that when the washing is begun turbulent flow undoubtedly exists in the immediate vicinity of the discharge of the inlet water. As the diameter of the hole increases, flow rates also are increased, so perhaps the condition of fluid turbulence is maintained for some time. During the later stages of leaching, when capacity of equipment may be the limiting factor in maintaining flow rates, there may still exist some turbulence adjacent to the point of influx; however, for the most part laminar flow conditions prevail. There appears, therefore, rather good evidence to indicate that the state of fluid motion is responsible for the typically shaped cavity which results from such washing — namely a cylindrical form, generally somewhat larger at the bottom than at the top. Depending on the number of so-called stages which might be employed, the walls or surfaces of the salt diminish rather uniformly from bottom to

Jan 1, 1965

By J. W. Taylor, E. G. Zukas

THE results of shock-loading studies on copper were reported several years ago by smith. In his experiments, Smith found that there was a correlation between the shock direction and the orientation of twins which the shock produced. By using free-surface-type shots in which the free surface of the specimen was not normal to the shock direction, he showed conclusively that twinning of copper in impulsive loading was caused by the rarefaction wave. Similar tests with iron, however, showed that it twinned during compression. More recent studies of iron2 and on Fe-Si single crystals3 have shown that twinning can be suppressed in these materials by shock loading at pressures high enough so that the velocity of the shock wave exceeds the elastic-wave velocity. From these observations, it appeared that twinning was caused by the shear stresses present in the zone undergoing adjustment from one-dimensional to three-dimensional loading. At high pressures, such a zone becomes so thin that there is insufficient time for the relatively ordered motion of atoms involved in twinning to occur. Twinning in copper, therefore, cannot be produced by a single compressive shock wave because resolved shear stress large enough to create twins exists only for a very short time (0.01 psec or less) before the pressure increases suddenly and loading becomes essentially hydrostatic. (A typical pressure vs time record for a copper shot, illustrating the short rise time of the compression wave, is shown in Fig. 1.) If, on the other hand, a second shock wave can be created in a precompressed sample, then the new elastic limit is several kilobars,4 and a resolved shear stress sufficient to cause twinning should be maintained for an adequate time period (0.1 psec or more). This experimental situation can, in fact, be realized. The experimental arrangement used to do so is shown in Fig. 2. By utilizing the pressure transformation in Fe-V alloys, it was possible to shock-load the copper in compression while the copper was already precompressed. In the first test, an 8 wt pct V-Fe sample was used as a driver for loading the copper, and the copper was exposed to the following series of compressive shocks: 1) an elastic wave of about 8 kbars, which is usually ignored in shock studies; 2) the pressure transformation wave for the driver of 200 kbars; and 3) the driving shock wave of 270 kbars pressure. Metallurgical determination of the angular twin distribution, shown in Fig. 3, with respect to the shock direction and the shock rarefaction direction (which was 23 deg from the shock direction) showed that twinning took place

Jan 1, 1965