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By R. E. Goodman, M. A. Mahtab

The, state of stress around a vertical wellbore in rock following nonlinear stress-strain laws is examined by means of finite element analysis. The wellbore, is considered an axisymmetrier body with axisymmetric loading. The initial vertcal and borizontal stresses are "locked" in the rock elements around the wellbore and a new state of stress is generated by the displacements which occur around the borehole. A point-uise variation of the elastic moduli is made on the basis of the new stress state and the triaxial data. The initial stresses tire now reintroduced along with tile changed moduli and original boundary constraints. This procedure is repeatrd until convergent stresses are reached. The effect of nonlinearity on streases is examined for a 6,000-ft wellbore in a scbistose gnezss and Berea sandstone using results of laborratory triaxial compression tests. The results sbou that the effect is restrited to one well radius from the bottom periphery of the bole. Beyond a distance of one-quarter radius, the elfect of nonlinearity on stresscs IS almost always less than percent for the cases conszdered, The consideration of a static pressure inside the well does not magnify the effect of monlinearity on borehole stresscs. INTRODUCTION The terms " wellbore" and "borehole" here designate cylindrical openings in the ground with vertical axis and a circular cross-section. A knowledge of the stress redistribution that occurs on excavating a wellbore is important in understanding (1) the behavior of the lined or unlined hole, (2) hydraulic fracture response, and (3) the effect of stress redistribution on drillability; also it is important in predicting initial stresses in the virgin ground, and in analyzing the response of measuring instruments placed in the borehole. Our knowledge of the state of stress around a wellbore has been restricted to homogeneous, isotropic, elastic material and derives chiefly from the analysis by Miles and Toppingl and the photoelastic work of Galle and Wilhoit2 and Word and Wilhoit.3 In this investigation the state of stress is examined for a nonlinear elastic material by means of finite element analysis. Many rocks possess stress-strain curves that depart notably from straight lines in their initial or final portions. While the literature contains abundant stress-strain data from triaxial tests (axisymmetric loading) on cylindrical rock specimens, there is little information on rock deformability under nonaxisymmetric loading conditions such as occur at each point around the bottom of a wellbore. Although there is some knowledge of the effect of intermediate principal stress on rock strength, there is virtually nothing known about its effect on rock deformability; therefore, we have assumed here that the effect of intermediate principal stress can be ignored. A schistose gneiss4 and Berea sandstone5 were selected as representative rocks for this analysis. The traditional graphs of deviator stress (ol -o3) vs axial strain were reworked to give the tangent modulus as a function of the deviator stress for varying values of the minor principal stress. The result is a nesting family of skewed, bell-shaped curves for tile gneiss (Fig. 1A) and the sandstone (Fig. 2A). A similar replotting of the lateral strain data defines the variation of Poisson's ratio (v) with the deviator stress and confining pressure. These curves, shown in Fig. 1B for the gneiss and in Fig. 2B for the sandstone, are not so well ordered as the tangent modulus curves. However, all of these display an increase of v with deviator stress application, but the rate of increase diminishes with confinement. The ET and v curves for the two rock types are tabulated in Tables 1A and 1A for use in a digital computer so that material properties corresponding to a given state of stress can be assigned by interpolation. STATEMENT OF THE PROBLEM Given a state of stress in the ground prior to drilling a hole (initial stresses), we assume that

Jan 1, 1969

By S. B. Twiss, P. R. Basford

The relationship between areas of iron powders, briquettes, and sintered compacts and tensile strength has been determined. It has been found necessary to distinguish between two types of areas which exist in such powders—a macroscopic area due to the shape and size of particles and a microscopic area due to pores and cracks in the surface. Only the macroscopic area, specifically the area due to particle irregularity, contributes to tensile strength; the microscopic area cannot be forced into contact with adjacent particles ond does not participate in bond formation. Of the two methods of area measurement employed in this study—permeability to liquids and gas-phase adsorption—only the former is useful for determining the roughness factor. A measure of this roughness, (area measured by permeability to liquid) -f- (orea of powder with the same size distribution, but made up of spherical particles), is shown to be uniquely related to tensile strength at constant density. The other important factors in determining the strength of sintered-metal compacts are the density and presence or absence of surface oxide. THE manufacture of metal parts by the process of powder metallurgy is an important and rapidly growing industry. Progress has been rapid and continuous, largely because of the excellent research in the field. Nevertheless, the process remains inherently complex and empirical. Several investigators have shown that the properties of the final compact must depend on many variables; namely, shape,' size distribution,"-" nd compositiona of the original particles, the pressure necessary to compress to the desired density, the density of the compact, the time and temperature of sintering, and so on. Through the application of some new techniques to the study of powders and compacts, and the correlation of a number of observations of known variables, the present paper attempts to clarify and simplify the underlying theory of the powder-metallurgy process. Any theory must start with the obvious fact that the strength of a compact, its most useful property, is due to the formation of welded areas between adjacent particles, and attempt to deduce what effect other variables will have on (a) the area and (b) the intrinsic strength of these welds. Such welded areas can be demonstrated by electron micrographs, as in Fig. 1. It was believed that (a) could be most directly studied by means of surface-area measurements on the original powders and on the compacts made from them; the area decrease should be related closely to the welded area. A representative group of eleven iron powders from commercial sources, and made by a variety of processes, was chosen for this study. In addition to the surface-area measurements, correlations were established between the tensile strength and all the known variables which might possibly affect it. The results are quite unexpected. They indicate that the situation is much simpler than the authors had anticipated. The strength of the sintered compact is determined, indeed, by no more than three variables; viz., the irregularity of the original particles, the density of the compact and, in exceptional cases, the amount of surface oxide. All three had been recognized previously as having some effect on the tensile strength, but in the absence of the special techniques and interpretations to be developed here, there could be no suspicion that they were the only relevant variables. Materials and Methods Material—All the iron powders were commercial products obtained from the Amplex Division of Chrysler Corporation. Powders A, B, C, and J were very pure electrolytic iron. Powder D was made from oxidized scrap reduced by heating with an excess of cast iron. Powder E was a high-grade iron ore reduced by hydrogen. Powder I was prepared by atomizing molten cast iron in an air blast, quenching the droplets in cold water, and crushing the coarse powder. Mill scale (oxide) is added and the mixture heated to reduce the high carbon content. The other powders were all prepared by reduction of iron oxides, such as mill scale. They

Jan 1, 1959

By Henry Leidheiser, Melvin C. Jr. Hobson

The rate of formation of the intermetallic compound, indium antimonide, at the interface between iudium and antimony at 100°C is greatly increased when a composite electrode of indium electrode -posited on antimony is made the cathode in an electrolytic cell. The amount of indium antimonide formed during electrolytic treatment at constant potential appeared to he proportional to the square root of time, but the scatter of the data, particularly at long times, makes it impossible to state this conclzlsi1:ely. The rate constant for the electrochemical synthesis was estimated to he 1.5 x 10-12 sq cm per sec. A similar- set of experiments was conducted in the absence of an applied potential but under otherwise similar conditions. The rate constant lor the thermal synthesis was less than 2 x 10-14 sq cm per, sec, at least two orders of magnitude less than obtained during electrolytic treatment. In a series of electrochemical studies it was observed that intermetallic compounds formed on the surface of polarized electrodes.1'2 The possibility of using this technique for the electrochemical preparation of intermetallic compounds was investigated and subsequently applied to the synthesis of the semiconducting III-V compounds. Gallium antimonide, indium arsenide. indium antimonide, and indium bismuthide were successfully formed by electrodepositing the Group III element from a boiling acid solution onto an electrode made of the Group V element. The following kinetic studies were undertaken on indium antimonide to obtain quantitative information on the rate of formation of this representative III-V compound under a potential gradient. EXPERIMENTAL The electrolytic cell for these experiments was a modified, three-neck, round-bottom, 500-ml distillation flask. Sealed into the side of the flask was a Luggin probe which monitored the surface of the working electrode and extended out of the flask to a small reservoir containing a saturated calomel electrode. The counter electrode was platinum. The three electrodes were connected to a Wenking po-tentiostat which maintained a preselected constant potential near the surface of the working electrode with reference to a saturated calomel electrode. All potentials noted in this paper are with reference to a saturated calomel electrode at 45° ± 5°C. The potential and the current were both monitored using Sargent Model MR recorders. The antimony electrodes were cast in graphite molds to form spheres about 15 mm in diameter with a shank 6 mm in diameter and 10 mm long. A heavy copper wire (12B & S gage) was soldered to this shank. Collodion was applied for protection to the shank and the connecting part of the copper lead. A snug-fitting O-ring was slipped over the shank and the electrode was then fitted into a teflon holder such that only the spherical portion was exposed. The electrode surfaces were cleaned and chemically polished prior to assembly and introduction into the electrolyte by etching in a modified CP-4 solution (50 parts glacial acetic acid, 10 parts concentrated nitric acid, 2 parts 48 pct hydrofluoric acid). The electrolyte was 10-2 M In+3 in 1 MH2So4 and its temperature was held constant by refluxing. The reflux condenser was open to the atmosphere and no temperature correction was made for changes in barometric pressure. The indium concentration in the electrolyte was checked from time to time by the analytical method outlined below for the determination of the amount of indium antimonide formed electrochemically. A schematic of the recorded potential is shown in Fig. 1. At point A the antimony electrode was introduced into the cell and the open-circuit potential recorded. At point B the potentiostat, preset at the desired potential, was switched on. It was switched off at point C and the potential fell to the open-circuit value of the electrodeposited indium. The

Jan 1, 1965

By Robert A. Jankowski, Charles D. Taylor

The objective of this program was to conduct dust surveys at six longwall sections having double-drum shearers, that were regularly in compliance, and to identify the dust control techniques that were the most effective. As each of the mines selected had a record of regular compliance with the Federal Dust Standard, all sampling was "short-term" (often less than 30 minutes) and no attempt was made to relate the survey results to dust-sampling results obtained by the companies for compliance purposes. The sampling procedures (1) used during this survey were developed jointly by the Bureau of Mines and Foster-Miller Associates, Inc. In addition to monitoring dust levels, measurements were also taken throughout the shift to monitor airflow along the face and water usage on the shearer. This program was a cooperative effort of the Bureau of Mines and the Mine Safety and Health Administration (MSHA). The following MSHA health specialists contributed to its successful completion: Paul Lenyo, CMS&H, Dist. 2; Ellis Mitchell, CMS&H, Dist. 3; Carl Jenkins, CMS&H, Dist. 4; David Stritzel, CMS&H, Dist. 8; and John Prelc, CMS&H, Dist. 9. RESULTS CUTTING SEQUENCE - WORK LOCATION At all mines surveyed, an important factor in controlling dust exposure at the shearer is the design of the cutting sequence so as to allow the shearer operator to work most of the time on the intake-air side of the lead drum. It is generally accepted that most of the dust generated by a double-drum shearer comes from the lead drum, which in the raised position normally takes a full sump. Because the position of the drum that is in the raised position determines the horizon control, the operator must be close enough to carefully monitor its operation. Therefore, his position relative to the lead drum has a significant effect on his dust exposure. Dust profiles, such as those constructed from data collected at Mines A and B (Figure 1), show the large gradient in dust concentrations that can exist between the intake and return air side of the lead drum. When the primary cut is taken head to tail, the lead drum is downwind and dust levels can be maintained at a low level until air has passed the shearer (Mine A). Thus, shearer operators can stay in relatively uncontaminated air. When the primary cut is taken tail to head, the lead drum is upwind of the shearer controls, resulting in higher dust concentrations at the shearer operator's work location (Mine B). At the mines where this cutting sequence was used, it was company policy for the shearer operators to walk on the intake side of the lead drum, returning to the controls only to adjust the height of the lead drum. DIRECTED WATER SPRAYS AND PASSIVE BARRIERS It is not always possible to keep the shearer operator on the intake air side of the lead drum. Various techniques have been tried to keep the dust generated by the shearer away from the machine operators when they work adjacent to the shearer. At all mines visited, the external water spray nozzles were directed so that dust from the shearer was directed downwind and toward the face, and away from the shearer operators. The effectiveness of using external water sprays to keep dusty air close to the face was noted during Bureau of Mines efforts to develop improved water spray systems (2). Laboratory and underground tests showed that water sprays located properly and directed downwind can create aiflow patterns that move dust generated by the shearer toward the face and away from the shearer operators. Sprays directed upwind, into the airflow, can actually move dust away from the face

Jan 1, 1982

By J. D. Sudbury, J. E. Landers, D. A. Shock

The external corrosion of casing is one of the most important problems facing the present day production man. A 1953 NACE report' estimated the annual cost of casing corrosion at $2,200,000 in 22 fields studied. The fields represented only 10 per cent of the wells in the United States. It was significant that 77 per cent of the failures reported were due to external corrosion. A variety of means for combatting the casing corrosion problem have been discussed in papers such as the NACE survey' mentioned previously. No attempt to revicw these will be made in this paper. Thc scope of this paper has been limited to a discussion of the following major items: (I) an instrument for studying external electrolytic corrosion; (2) use of this instrument to determine the quantity of protective current required to prevent corrosion of casing; and (3) problem of accelerated external corrosion of the oil string at the base of the surface string. ELECTROCHEMICAL MECHANISM OF CORROSION It IS gcncrally belleved that one major cause of external corrosion is the existence of electrolytic cells operating between various formation waters. A theoretical discussion of the role of earth potentials in casing corrosion has been presented by L. de Witte and F. J. Radd.2 A brief picture of the electrolytic corrosion action between two differcnt formations (A and B) is presented in Fig. I. This picture is a review to many but is given to insure clarity. In the anode area, oxidation takes place as iron ions go into solution in formation A as a product of corrosion. In the cathode area. reduction takes place and hydrogen atoms are formed at the boundary between the pipe and formation B. The flow of electrons. as indicated. is into the pipe at the anode or corroding area and out of the pipe into the formation at the cathode. In order to conform with regulations of this journal, the flow of a conventional current (I! is also indicated in this sketch. All subsequent references will be to this so-called conventional current flow and will be indicated by the symbol (I). As this action takes place the layer of hydrogen developed on the cathode offers a resistance to the flow of current in the cell. It is said (hat the cathode has been polarized. This polarizing film can be rcmoved by addition of a so-called dcpolarizing agent which reacts with and removes this hydrogen film. Such an agent must be present in ordcr for this corrosion reaction to go at a rate sufficient to cause a severe corrosion problem. The two common depolarizing agents are: (I) oxy-sen. which readily reacts with hydro gen to form water, and (2) certain bacteria which use atomic hydrogen as part of their life process. It is not difficult to explain the presence of these agents. Oxygen may be present in some very shallow formations. Sulfate reducing bacteria are found to exist in nearly any ground where mud pits might be dug. THE CASING POTENTIAl-PROFILE Instrumentation A sketch of the equipment* uscd in determining casing potential profiles is shown in Fig. 2. The tool is run in the hole using a hoist truck with a three-conductor cable. This tool must be run with tubing and rods out of the hole and should be run with the flow line disconnected. By proper choice of electrode size it can be run in any size casing. The electrodes must be run in an open hole or a hole filled with oil. Measurements cannot be made while immersed in water. The tungsten carbide-tipped knives serve as the electrical robes and arc spaced 25 ft apart. The potential difference along a 25-ft section of casing is measured with a potentinmeter to an accuracy of about 5 mv. Current flowing in the pipe can then

Jan 1, 1956

By R. I. Jaff, H. R. Ogden, D. J. Maykuth

A phase diagram for alloys containing from 0 to 66.9 pct Mn was determined. Two compounds, tentatively labeled 6 and y, were found in this range. The 6 compound is located at about 66.9 pct Mn and melts congruently at 1330°C. The ? compound has a composition near 53 pct Mn and originates in a peritectic reaction at 1200°C between liquid and 6. ß and Y enter into a eutectic reaction at 1175°C. The ß phase field terminates in a very sluggish eutectoid reaction between a and ? at 550°C. MANGANESE is one of the important alloying addition elements to titanium. As a ß-stabiliz-ing addition for a-ß and ß alloys, it provides high strength with adequate ductility.' Two of the earliest commercial alloys contain manganese as a major alloying component.' The earliest published data on the constitution of Ti-Mn alloys was that of Wallbaum,~ who reported the existence of the compound TiMn2. The transformation range of commercial-purity Ti-Mn alloys was investigated by Craighead, Simmons, and Eastwood' who found limited a solubility and a lowering of the ß transus to about 790°C at 7 pct Mn. Preliminary work by the authors of this paper, using high-purity titanium, confirmed the ß-stabilizing action of manganese and showed the existence of several intermediate phases in the Ti-Mn system." More recently, McQuillan3 determined the ß transus temperatures for high-purity Ti-base alloys containing up through 4.4 pct Mn. These data are given in Fig. 1. The present investigation covered alloys made with a high-purity base. The constitution of titanium-rich alloys made with commercial titanium has been reported4," by Holladay, Kura, and Jackson. The alloy range covered in the present investigation was from 0 to 69.5 pct Mn. This alloy range extends slightly beyond the composition of the first congruent-melting compound encountered on proceeding from the titanium end of the system. A description of the materials and methods used in the determination of the diagram is given in the Appendix. The partial phase diagram determined for the Ti-Mn system is shown in Fig. 2. Details on equilibria in the titanium-rich alloys are given in Fig. 3. Liquid-Solid Relationships Observations on the cast structures of the arc-melted ingots showed that the terminal solid solution of manganese in ß titanium enters into a eutectic reaction with an intermetallic compound labeled ?. As will be shown later, this compound has a composition around 53 pct Mn. The eutectic reaction temperature was determined as 1175°C by thermal analysis which also showed that the ? phase originates in a peritectic reaction at 1200°C. Fig. 4 shows typical eutectic structures for alloy compositions on both sides of the eutectic composition which is located at 42.5 pct Mn. In alloys over the range of 45.4 through 69.5 pct Mn, a second intermetallic compound, labeled 6, was identifield as the primary phase. This phase consistently increased in amount as the manganese content approached 66.9 pct, and, as shown in Fig. 5, an alloy structure containing 66.9 pct Mn consisted essentially of the 6 compound. Thermal-analysis data indicate a melting point of about 1330°C for the 6 intermediate phase. At 67.0 pct Mn, small quantities of a new, higher manganese-content phase were observed in the form of Chinese-script eutectic particles. Comparison of Fig. 6a and b shows an increasing quantity of this phase as the composition was increased to 69.5 pct Mn. The formation of peritectic ? in arc-melted alloys containing 45.4 pct Mn and above appears to be almost entirely suppressed, as shown in Fig. 7a and b. This is because of the narrow freezing range available for its formation by peritectic reaction and because of the very high cooling rates obtained in

Jan 1, 1954

By E. P. Sadowski, L. P. Trudeau, C. R. Cupp

The apparent high radiation resistance of two varieties of maraging steel is described and an indication is given of some phenomena that require further study. Two aspects were included in this work: a) effects of neutron irradiation on the room-ternperature tensile properties of 18 Ni (250) maraging steel; b) effects of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5pct Cr-3 pct Mo maraging steel. Subsize tensile and impact test specimens were used. The 18 pct Ni steel was irradiated to a neutron fluence of 3.3 x 10 n per sq cm (>1 mev). The 12-5-3 variety was irradiated to two neutron fluence levels: 1) 1.5 x 10 per sq CTTL (>I mev) 2) 3.1 x 10'9nper sq cm (>1 mev) In all respects both varieties showed unusually high resistance to change in strength and ductility after neutron irradiation. There was no noteuorthy over-aging in fully aged specimens. The aged 18 pct Ni variety showed a 4 pct drop in yield strength upon irradiation with little or no decrease in ductility. The aged 12-5-3 variety showed a 5 pct increase in yield strength on irradiation with a very slight decrease in ductility. The impact transition of the 12-5-3 variety only increased 35 to 45 Co upon irradiation, and the shear energy fracture value for the subsized specimens decreased only half as much as expected frorn experience with conventional steels. THE development of new reactor concepts and nuclear technology now depends to a large extent on the availability of new alloys capable of operating in stringent reactor environments. One of the most important new types of metallurgical material that has been developed in recent years is the maraging steels. This type of alloy is notable for its remarkable retention of toughness at high strength levels. In the course of a research program which incorporated ambient temperature radiation effects studies to determine the mechanisms of strengthening of 18 pct nickel maraging steel,' it became evident that the resistance of the alloy to neutron-induced changes in mechanical properties should be studied. This paper is to present evidence for the apparent high radiation resistance of maraging steel. The experimental program was in two parts: a) Effect of neutron irradiation on the room-temperature tensile properties of 18 Ni (250) maraging steel. b) Effect of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5 pct Cr-3 pct Mo maraging steel, a cobalt-free alloy. EXPERIMENTAL PROCEDURE 18 Ni (250) Maraging Steel. Tensile test specimens were machined to the dimensions shown in Fig. 1 from $-in.-diam hot-rolled bar of the composition shown in Table I. All specimens were austenitized for 1 hr at 1500°F (815°C) in argon and water-quenched. Half of the specimens were then mar aged for 3 hr at 900° F (482°C) in argon. The specimens were irradiated in a fast neutron transformer rod at approximately 120°F (50°C) to a neutron fluence of 3.3 x 10 10 n per sq cm (>1 mev). The irradiation was performed in the NRX reactor of Atomic Energy of Canada, Ltd., at Chalk River, Ontario, Canada. In all cases, the thermal neutron flux was three times as high as the reported (> 1 mev) fluxes. The room-temperature tensile tests were performed with an Instron tensile testing machine operating at a crosshead speed of 0.05 in. per min. The loading frame of the machine, mounted in a hot cell, was remotely controlled. The specimens were tested either

Jan 1, 1968

By G. H. Kesler, C. E. Dryden, J. H. Oxley

Rates of heat- and mass-transfer from rods to recirculating air were determined within a one-quarter-scale model of a metals deposition bulb. The dependence of local and averaged rates of transfer upon outlet geometry, number of rods, position upon a rod, and airflow rate was established for flow patterns created by radial and tangential air inlets. The results are given a qualitative interpretation in terms of rates and distribution of metal deposition in a prototype deposition bulb. IT is well known that a number of metals can be prepared from volatile compounds containing them by causing dissociation of their compounds to occur at heated surfaces. Examples of such metals include silicon, titanium, zirconium, and aluminum, which can be prepared from their halides. While the ability to prepare high-purity metals by this technique is of importance in itself, the rate of deposition of metal also is important in considering the commercial potential of such a process. If the over-all process of deposition is broken down into separate steps of transport of materials to and from the heated deposition surface and establishment of chemical equilibrium at the surface, as was described in a recent paper,1 then since surface temperatures are usually high and surface equilibrium is attained very rapidly, the rate-controlling step can be considered as either that of transport of reactants to the surface or of transport of products other than deposited metal away from the surface. These two transport steps are related through the reaction stoichiometry. It can be shown1 that the rate and distribution of metal in such a transport-controlled process are determined by the over-all and local mass-transfer coefficients in conjunction with the equilibrium conversions at the hot surfaces. The rate relationship is: w = [KA(y a-y s)] B.E where the bracketed group is the rate of arrival of the reactant at the surface of area A as determined by the mole fraction driving force (y a - y s) and the convective transport constant K. The factor B is the weight fraction of metal in the reactant, and E is the equilibrium fractional conversion to metal. Numerical values of y, and y, are fixed by the vapor composition and the equilibrium compositim of reactant at the surface; and E can be determined by thermodynamic calculations or by experiment. However, values for the convective coefficient K are available generally only for systems of simple geometry, such as cross-flow past a rod or sphere or parallel flow past a flat plate or through a tube. Often it is necessary to work with systems of more complex geometry and in which the vapor flow may not be uniform or exactly parallel or perpendicular to the surface. It is possible, of course, to establish working correlations for these more complex systems by direct experiment; but the experiments usually are costly in both time and money. To circumvent this objection and to aid in arriving at an understanding of the relationships and interactions of the process variables, it is helpful to construct a model of the flow system in which air, water, or other convenient fluids can be substituted for the process vapors and with which mass-transfer measurements or analogous he at-transfer measurements can be made upon a simulated deposition surface. By this means, a large number of measurements can be made in a reasonable time, and the correlation of these results can be applied to the prototype system. Examples of the application of these techniques are to be found in the literature (e.g., Ref. 2). It is the purpose of this paper to illustrate these techniques by description of a model study which was done at Battelle Memorial Institute. The work to be described was of a preliminary nature; the investigation subsequently was extended to develop quantitative relationships among the significant dimensionless transport, geometric, and flow parameters. This more detailed study will be the subject of a future paper.

Jan 1, 1962

By W. C. Ellis

IN an ingot of germanium solidified progressively from the bottom by a method' devised by J. H. Scaff and H. C. Theuerer, examination discloses ex- IH. C. Torrey and C. A. Whitmer, Crystal Rectifiers. p. 364. 1948. New York. McGraw-Hill Pub. Co. tensive twin relationships. A slice taken about midway in a cylindrical ingot approximately 3/4 in. in diameter and 1 1/2 in. in length, after etching and polishing to delineate different orientations, is shown in fig. la. The orientations of the regions designated with letters were determined by Laue X-ray back-reflection methods and plotted on stereograms. The orientation relationships of the designated components were determined by comparing the values for the nine angles between the three respective cube poles of each orientation with the values calculated in a formal treatment of octahedral multiple twinning in cubic crystals. Germanium, diamond cubic in structure, has the octahedral twinning habit. I am indebted to K. H. Storks for the calculation of the angular relationships of cube poles in octahedral twinning to four orders. The set of values for the nine angles is distinctive of the order of twinning. Confirmation for a multiple twin relationship is obtained from the determined indices of the mirror planes. These exist for all orders of twinning through the third and for some of the fourth." If the orientations are not those for twinning, then the nine angles for the cube poles do not correspond in value and distribution to those formally calculated. Since all nine angles must correspond in values and distribution of values to the calculated ones, the Laue method with a precision of one or two degrees is adequate to establish or deny with confidence the existence of multiple twins. Regions of the same orientation can also frequently be identified by the optical reflections. For example, the narrow twin bands in A at 2: 00 o'clock have orientation B1. The interesting twin relationships shown schematically in fig. lb were found for the section in fig. la. Most of this slice was made up of orientation, A, appearing in widely separated regions. Of the four possible first order twins of A, three were present in this slice and are designated by B with subscripts. Four second order twins of A are designated by C with subscripts. It is worth emphasizing that two of these, C, and C,, are second orders of A through the first order missing in this section. Two regions, designated by D with subscripts are third order twins of A. D2 is a sixth order twin of D,. All orientations found were ascribable to multiple twinning, as if the orientations in this section originated earlier in solidification from a single nucleus. The presence of extensive multiple twinning to- gether with the absence of other orientations appears to be a characteristic result in many instances of solidification of germanium. Fertile conditions for twinning probably exist in the array of atoms in the diamond cubic structure. The high order twins in the section shown, it is reasonable to presume, are the result of progressive octahedral twinning through several generations in the material freezing earlier. Some of these generations do not appear in this section, it is suggested, because their orientations with respect to the growth direction were unfavorable for survival. The extensive twinning is probably promoted during solidification by constraint imposed by volume increase, and to an irregular growth front. Twinning may also be due, in part, to the attempt of the solidifying region to attain the orientation most favorable to the growth direction (maximum thermal gradient). The nucleus for a twinned orientation could have its origin in a "stacking fault" on the close-packed octahedral plane. Further work is being done in which the course of twinning throughout an ingot is being studied. The results appear to be important in the general theory of solidification.

Jan 1, 1951

By R. F. Mitchell, G. F. Dillon, A. F. Armington

In this paper the present methods of boron preparation are discussed with emphasis on the iodide intermediate. Several methods of boron triiodide preparation were investigated, the most satisfactory method being the preparation from the elements. A yield of 60 pct based on iodine is found for this method. Zone-refining, sublinzation, distillation, and fractional-recrystallization results are given for the boron triiodide, with distillation producing the best results. Several methods of decomposition are also discussed. The purity of the resulting iodide boron approximates the puritjl of the best available bromide boron, ELEMENTAL boron has been suggested as a possible high-temperature semiconductor by several workers,' but has never been exploited as a device material. The principal difficulty with boron is the unavailability of pure crystalline material from which accurate information on electrical properties could be obtained. Most boron crystals presently produced are very imperfect in structure and of questionable purity, particularly in relation to carbon content. Several methods of boron purification have been reported in the past few years, all of which produce material with a purity better than 99.0 pct. Most of these methods have been the subject of a recent review by Starks' and will not be elaborated upon in this report. However, of all the purification methods reported, only those using halide intermediates produce a purity approaching that usually required for electronic applications. The bromide intermediate has been most used for the preparation of high-purity boron.'y3 This material is easily prepared from the elements and can be effectively purified by distillation and decomposed by hydrogen reduction. The resulting product contains a trace of silicon, and an uncertain amount of carbon, believed to be approximately 100 ppm. It has been recently reported by Russian workers that high-purity boron can be produced using an iodide intermediate.' In the work cited, boron is reported free of spectro-scopically determined impurities, but the reported detection limits are quite high (- 100 ppm). In addition, no data is given on the carbon content of the product. In the present paper, boron triiodide was chosen as the intermediate for several reasons. First, carbon tetraiodide, which could be a major impurity, is reported to be unstable above 200" and hence could be easily separated from the boron triiodide by its decomposition, since temperatures greater than this are attained during the purification process. The low melting point (45°C) and boiling point (20B°C) and the relatively high vapor pressure of boron triiodide should allow the application of any physical purification technique to the material. The possibility of a lower decomposition temperature than that used for the bromide process is another advantage which might cut down extraneous contamination. The iodide, however, does have certain disadvantages when compared with the bromide, the production cost being the most significant. This is the result of a higher halide-to-boron weight ratio, which means more intermediate must be employed. The cost of the starting material is also greater for the iodide. This cost could be considerably reduced however, by recycling the iodine byproduct. Epitaxial growth of boron, which is probably the best method of producing junctions, should be possible with either the bromide or the iodide as the intermediate. However, this has been attempted only on a limited scale up to the present time because of the unavailability of good crystals. The authors have been relatively successful in laying down a heterotaxy of boron on silicon, however. This will be reported at a later date. Several crystalline modifications have been reported for boron, four of which are now believed to be real.' These are the a! and 0 rhombohedral and the a, and 0 tetragonal. In general, the a! rhombohedral is the low-temperature form and the B rhombohedral is the high-temperature form. The tetragonal structures are detected between 1000"

Jan 1, 1964

By S. S. Lisnyak, B. D. Lichter

An important question in the study of the "hot corrosion" phenomenon (i.e., accelerated oxidation of Ni-Cr-base and Co-Cr-base "superalloys" in the presence of sulfur) is the condition of formation and physico-chemical properties of different sulfides in the system Ni-Co-Cr-S. seyboltl has observed the presence of ((chromium-rich" sulfides of compositions M3S4, and M2S3 in the scales of superalloys after hot corrosion; however, as he points out, much confusion exists as to the identity of sulfides found on Ni-Cr and Co-Cr alloys. According to the literature,&apos; ternary sulfides, e.g., NiCr2S4, (monoclinic structure) and CoCr2S4 (spinel structure) exist in these systems. Therefore, it is likely that these compounds are found in the scale of alloys undergoing hot corrosion. At present this possibility has not been discussed in the literature. Accordingly, we have begun investigation on the properties of ternary sulfides and their mutual interaction. The magnetic and electrical properties of pure NiCr2S4 and pure CoCr2S2 have been previously determined."-&apos; In the present work we have studied the interaction between these sulfides at high temperatures by means of X-ray diffraction and magnetic susceptibility. The measurements were carried out at room temperature after appropriate thermai treatment of samples at high temperatures. For alloys containing the three elements nickel, chromium, and cobalt this interaction may be of importance in the study of the hot corrosion phenomenon. The compounds NiCr2S4 and CoCr2S4 were prepared from stoichiometric amounts of the elements and CoS in the case of CoCr2S4. Samples were mixed and sealed in evacuated silica tubes, slowly heated to 900&apos; to 100O°C, and held at temperature for a total of 120 hr (NiCr2S4) or 80 hr (CoCr2S4) with intermediate re-grinding~. X-ray diffraction showed a pure spinel structure for CoCr2S4 and a monoclinic structure for NiCr2S4. Samples of mixtures of the two ternary sulfides were prepared with different compositions, see Table I. Samples were heated for a total of 80 hr at 900&apos;C in evacuated silica tubes, with one intermediate regrind-ing. The capsules were slow-cooled to room temperature in the furnace. Samples for X-ray diffraction were prepared by placing powder on a glass slide with vaseline. Dif- fractometer traces were obtained on a G.E. XRD-5 diffractometer using a chromium tube and vanadium filter (40 kv and 31 ma). The size of the spinel unit cell was determined from the eight highest angle peaks (80 deg < 2b < 160 deg). Calculated lattice parameters were plotted vs cos B . ctn 0 and extrapolated to 6 = 90 deg. Measurements of the magnetic susceptibility were carried out at room temperature using the Faraday method in a magnetic field of 3000 G and using a Cahn RG automatic microbalance. The system was calibrated from the well-established susceptibilities of platinum and palladium: (Xpt = 0.968 x 10-6 g-1 and Xpd 7 5.04 x 10~6 g-1). The weight of samples were approximately 0.200 g. X-ray diffraction patterns for unsintered mixtures showed Bragg peaks from both the spinel (CoCr2S4) and monoclinic (NiCr2S4) structures. After sintering no monoclinic peaks were observed in samples containing up to 40 mol pct NiCr2S4. However, the spinel peaks were displaced to higher angles with increasing

Jan 1, 1970

By A. S. Yue

Small-angle tilt boundaries have been observed in a lamellar eutectic structure. These boundaries are morphologically similar to a theoretical till boundary originally proposed by Burgers. The production of a small-angle tilt boundary in the lamellar eutectic structure is attributed to the formation of an indentation on a planar solid-liquid interface during growth. Constitutional supercooling due to the accumulation of impurity atoms ahead of the interface is primarily responsible for the generation of an indentation. The distance between two faults of like sign, designated as lamellar fault distance, is calculated by the Burgers equation for small-angle boundaries. It was found that the lamellar fault distance decreases exponentially and the tilt angle increases exponentially with freezing rate. SMALL-ANGLE tilt boundaries have been observed in many crystals in the as-grown states by etching techniques. However, a detailed substantial proof for revealing the presence of dislocations in the form of etch-pits was recently accomplished by Vogel. These boundaries are described as an array of dislocations of like sign. The angle of tilt associated with a boundary is treated theoretically by Burgers3 and is given by 0 = b/D for small tilt-angle where b is the Burgers vector of the dislocations and D is their average spacing. During the course of experimentation on the solidi fication of the lamellar Mg-32 wt pct Al eutectic a microstructure which was strikingly similar to a dislocation tilt boundary was observed. An example of the type of microstructure is given in Fig. 1, which shows a combination of transverse and top sections of the lamellar eutectic structure. The lamellae of the top section on one side of the apparent tilt angle are not parallel with those on the other side. Consequently, some lamellae must be terminated somewhere. Fig. 1 shows that the termination of lamellae is analogous to a dislocation tilt boundary in a crystal lattice originally proposed by Burgers. This work represents a closer look at such structures. The factors governing the production of the small-angle tilt boundary are discussed in terms of the freezing condition and impurity distribution in the melt. The effect of freezing rate on the distance between two faults, designated as lamellar fault distance, and the tilt angle is also described. In addition, the lamellar fault distance is determined by means of the Burgers equation for small-angle tilt boundary. EXPERIMENTAL PROCEDURE The slightly impure Mg-32 wt pct Al eutectic rods, 5/8 in. in diam and 12 in. long, were made from 99.99 wt pct Al and 99.98 wt pct Mg and were cast in a high-purity graphite mold. Some of these rods were purified by zone-refining the eutectic using direct-radiation helical-coil furnaces5 A molten zone about 2 in. long was passed through the cast rods at a speed of 5.3 x 104 cm per sec for ten passes of the molten zone. Before the freezing experiment was begun, 2-1/2 in. of the material from the head and tail ends of the zone-refined eutectic were removed from the rod to eliminate any impurity. The freezing experiments were carried out under controlled conditions,8 using a protective atmosphere of purified argon. At the end of each run, observation of the tilt boundary was made throughout the entire length of the rod with a light microscope on the top, longitudinal, and transverse sections (three mutually perpendicular sections) of the lamellar eutectic solid. The experimental data used for the determination of interlamellar spacing and tilt angle were taken from the middle portion of

Jan 1, 1964

By J. H. Scaff, H. C. Theurer, E. E. Schumacher

The microwave region of the radio spectrum was effectively utilized in radar designs during the recent war and it has become of increasing interest in the field of communications. Work in this field has led to an important use for silicon—that of the point contact rectifiers†1 in the frequency converter of microwave (radar or radio) receivers—and has stimulated considerable interest in the electrical properties and preparation of silicon and its alloys. Silicon is an electronic semiconductor. Its conductivity at room temperature results principally from the presence of certain impurities. While for metals an increase in impurity content increases the resistivity, for semiconductors such as silicon the opposite occurs and, in general, the addition of impurities lowers the resistivity. Silicon materials may be classified into one of two groups depending upon the manner in which the impurities contribute to electrical properties. These have been termed for convenience p-type or n-type. P-type silicon develops a very large positive thermal emf against metals, has a Hall coefficient of positive sign and a low resistance direction in point contact rectification with the silicon positive with respect to the point. N-type silicon, on the other hand, develops a negative thermal emf against metals, has a Hall coefficient of negative sign and a low resistance direction in rectification with the silicon negative with respect to the point. Impurities which produce n-type silicon are called donors inasmuch as these elements contribute to electrical conductivity by donating electrons to an unfilled energy band in the silicon. On the other hand, elements which produce p-type silicon are known as acceptors as these impurities contribute to the electrical conductivity by accepting electrons from a filled energy band permitting what is known as conductivity by "holes" in which the sign of the carriers appears to be positive. A general treatment of the mechanism of conduction in semiconductors from the viewpoint of modern band theory has been given recently by Pearson,2 by Becker, Green and Pearson,3 and by Torrey and Whitmer.4 In this investigation boron and aluminum have been found to be acceptors, and phosphorus, arsenic, and antimony to be donors in silicon. Data on the effect of boron and phosphorus on the electrical properties, when present singly and in combination, have been acquired. These data are discussed in the present paper. Raw Materials Used and Methods for Adding Seeond Constituents Silicon from two sources was used in this work and these will be referred to as A and B respectively. Silicon A is a material of high purity supplied by the Electro Metallurgical Co. It is prepared by chemical purification of "commercial" silicon obtained from the arc furnace reduction of SiO2. It contains 99.8 pct silicon, minimum, with small amounts of calcium, iron, aluminum, boron, and phosphorus as the principal impurities. This material was extensively employed in these studies as well as in the commercial preparation of rectifier materials. Silicon B is a material of high purity from the du-Pont Co. It is prepared by a pyrolytic reduction of Sicl4 and is free of analytically detectable amounts of boron and phosphorus. Its use permitted study of the effect of boron and phosphorus individually on the properties. This material contains, however, spec-troscopic traees of a number of metals, some of which affect electrical and rectification properties. Typical analyses for the two grades of silicon are given in Table 1. To make controlled additions of boron to the charge it was necessary to employ a low boron content master alloy since the quantity of boron to be added was usually only a few thousandths of one percent. The alloy containing nominally one percent boron was prepared by melting chemically pure boron with silicon A using the melting techniques for 320 g silicon

Jan 1, 1950

By Sherwin F. Kelly

GEOPHYSICS may be considered a vice (albeit, I submit, a comparatively harmless one) whose career is aptly described by Pope&apos;s lines: Vice is a monster of so frightful mien, As to be hated needs but to be seen; Yet too oft, familiar with her face, We first endure, then pity, then embrace. Although there may be some that have not yet succeeded in emancipating themselves from the first stage of horrified contemplation, geophysicists may be duly thankful that there are mining men and geologists that have arrived at a state of apparently irretrievable damnation.

Jan 1, 1936

By George H. Deike

DURING the past year a survey was conducted by the Committee on the Promotion of Student Interest in Coal Mining to determine whether the program as laid down in past years was operating effectively. It is a source of satisfaction and pleasure to be able to report considerable headway among operating companies in putting cooperative scholarship plans into operation. In previous committee reports the pioneer work along this line by Eugene McAuliffe, president of the Union Pacific Coal Co., has been cited. That Company now has in its employ, in responsible positions, three men who received their education under such scholarship plans. One student under a similar plan is now studying at the Colorado School of Mines.

Jan 1, 1942

By A. B. Stickney

UPWARDS of 200,000 engineers in this country are sufficiently interested in engineering as a profession to have joined a society, but not over 10% of them belong to any one society. There is a widely-felt need of an over-all organization of all the societies to act as spokesman for all engineers on matters of common concern. On a local basis, over 100,000 engineers in 35 metropolitan areas have organized themselves into local councils, and are doing an effective job of intersocietal co-operation within their sphere of activity. In the last few years much has been said and written about a similar organization on a national scale. Everybody wants iteverybody is talking about it-it&apos;s in the air-it&apos;s coming-it&apos;s inevitable. Although it is no longer necessary to talk about why or whether there should be such an organization, there is no such unanimity about what it should be like. This paper outlines a proposed organization by answering four questions-who, how, what, and who will pay for it.

Jan 1, 1946

By Bernard Kopelman

THE particle size of tungsten metal powder used to make tungsten wire for use in radio tubes and incandescent lamps must be closely controlled if the highly desirable feature of nonsagging is to be achieved. Our knowledge of factors affecting the particle size of tungsten powder has been limited by lack of any extensive literature on the subject. There are no publications in the English language discussing this problem in any but the most general terms. In this paper the published experimental information on this subject is reviewed. Based on the published data and some experimental data obtained by the author, a general theory of factors affecting the particle size of tungsten metal powder obtained by reduction of the oxides in hydrogen is offered. The various forms of the tungsten oxides and tungsten metal used in the experiments described were those prepared by com¬mercial processes, so that the experimental results obtained on a laboratory scale would be more directly applicable to actual commercial reduction conditions. The effects of time of reduction, temperature, and concentration of water vapor in the hydrogen were observed by counting microscopically the particle distribution obtained. Such a method is very time-consuming, but the data obtained by this method are more reliable and more fundamental than those obtained by any of the several instruments available for measurement of particle size. REVIEW OF THE LITERATURE Until the year 1912, tungsten powder was prepared commercially by reducing tungstic oxide in the presence of carbon or one of its compounds (such as glycerin or ethylene glycol), usually by firing the mixture in a closed fire-clay crucible. The resultant powder contained about 95 per cent tungsten.1 When reduction of tungsten oxides by H2 was introduced commercially, 2.1 several investigators became concerned with the equilibria between tungsten metal and its several oxides in an atmosphere of hydrogen and water vapor.4-13 While these many investigations were in fair agreement on the equilibria there arose considerable controversy as to the chemical composition of the oxide between W03 and W02, because of very poor agreement on the equilibrium constant of this intermediate oxide reduction reaction. The controversy on this intermediate oxide has been in progress for more than 10o years. Thus Malguti,14 in 1835, decided it was W02.56. In 1857, Riche" proposed the formula W308. Usler,16 in 1865, confirmed the existence of W308 and further proposed W4O11. In 1897, Desi17 agreed upon W308 but also found W5014.

Jan 1, 1946

By W. N. Lacey, R. H. Olds, B. H. Sage

The volumetric behavior of five mixtures of black oil and natural gas and of two mixtures of condensate and natural gas from a field in the San Joaquin Valley was experimentally established. This work was carried out at roo°, I9o° and 250°F in the pressure interval between 400 and 5000 psi. The viscosity of the liquid phase of four mixtures of black oil and natural gas was experimentally measured in the above-indicated temperature and pressure intervals. The effect of methane upon the precipitation of bitumen from the black oil was studied at 230°F. Introduction The solution of a number of the economical and technological problems which arise in connection with petroleum production is dependent upon the availability of the necessary quantitative information covering the materials involved. This requires data concerning physical properties of naturally occurring hydrocarbon mixtures at the pressures and temperatures characteristic of underground petroleum reservoirs. The experimental determination of the desired data for each situation encountered is relatively time-consuming. However, it is considered to yield results sufficiently more reliable than those obtained from correlations to justify the effort. For these reasons there was undertaken a laboratory investigation of the viscosity of the liquid phase and the volu- metric and phase behavior of mixtures of oil and gas samples obtained from wells in a field located in the San Joaquin Valley. Terminology The nomenclature of petroleum engineering is not at present entirely standardized. Many commonly used technical terms are not everywhere given the same meanings. For the purposes of this paper the following definitions will be adopted: Black oil refers to the dark-colored, hydrocarbon liquid obtained when the producing horizon of the well lies partly in the condensed hydrocarbon phase of the reservoir. Condensate is the term applied to the relatively volatile, pale yellow or amber-colored hydrocarbon liquid that is often obtained from the surface separator system when the producing horizon of the well lies in the gas cap of the reservoir. The gas obtained from the surface separator system is called natural gas regardless of whether the well is producing black oil or condensate. As might be expected from the multi-component character of naturally occurring hydrocarbon materials, the compositions of black oil, condensate and natural gas are subject to considerable variation depending upon the temperatures and pressures prevailing in the surface separator system as well as upon the overall composition of the material produced from the reservoir. In order to obtain samples capable of reproducing the total hydrocarbon material produced by the well, all oil and gas mixtures used in this investigation were com-

Jan 1, 1949

By WILFRED SYKES

IT is with particular pleasure that I welcome the members of the Open-hearth Conference of the I American Institute of Mining and Metallurgical Engineers to this meeting, as I feel this is one of the most useful activities of the Institute in the field of ferrous metallurgy. For the information of our other members I might say the Open-hearth Conference was organized by Mr. Reynders when he was president, and is made up of open-hearth superintendents and metallurgists. All the plants are invited to send representatives, and practically all do, with the exception of the U. S. Steel Corporation. It meets twice a year to discuss various problems in connection with the manufacture of steel, and its minutes are published for the benefit of those attending, the expense being defrayed by the participating companies. This conference, .1 believe, should be a model for activities in the other branches of the work covered by this Institute. It works, not by reading formal papers, which we all know is not a very satisfactory method to bring out the experience of others, but rather by a round-table method of discussion. The spirit of the meetings is such that each member feels perfectly free to state his experience, and he gets as much as he gives. A series of topics for, discussion is brought to the attention of the chairman and after one is exhausted the next point is taken up. In this way there is a real interchange of ideas and experiences which cannot fail l to be of the greatest benefit to those attending. That these meetings are beneficial is evidenced by the "continued growing attendance and lively discussions at these half-yearly meetings.

Jan 1, 1930

By James Howe

EVERY engineer and user of wire rope is desirous of information that will enable him to determine whether the performance of any particular piece of rope is satisfactory, and what conditions can be changed so as to increase the life of a rope. In most cases, it is far from easy to analyze the conditions of service and tell which is the greatest factor in determining the life of wire rope. If we start on a layout for an entirely new rope system, the task of making conditions satisfactory is simplified so far as the engineering details are concerned; but if the plant requiring wire rope is in operation, any change is likely to involve the expenditure of consider-, able money to replace and change over machinery that must be kept in constant operation, because a large monetary loss will result from a shutdown for even a few days. Often wire rope is kept operating under bad conditions, as the user thinks that it is cheaper and quicker to replace the rope than to make alterations in the hoisting machinery. A typical case is a metal mine operating in what is now almost the center of a large mining city, where it owns a few acres of mineral rights. It was expected that the shaft would go to a depth of 1000 ft. (305 m.), so a moderate sized rope, about 1 ¼ in. (31.7 mm.), was used on a 6-ft. drum with a 7-ft. head-frame sheave and rather short lead from drum to head sheave. This mine has gone deeper each year until, it is now 2500 ft. deep and the rope speed has been increased from 1500 ft. per min. to over 3000 ft. The original rope just filled the drum in one layer, now it overwinds three layers. The original ropes were probably 6 X 19 crucible steel and lasted from 12 to 18 mo.; now, the highest grade plow steel is used, yet the average service is only about 6 mo. The cause is not hard to find. If the engineers had known at the outset what would be done with this hoist, the design would have been very different. Conditions at this mine, from a wire rope standpoint, have gradually become worse and it is difficult to see how rope service on this hoist can be com-pared with the service of previous years with any fairness to the wire-

Jan 2, 1922