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By B. D. Cullity

INTRODUCTION THIS investigation of bismuth-selenium alloys was made in an attempt to find a suitable material for use in thermoelectric generators. These devices are simply thermocouple circuits designed for the efficient production of electrical energy from thermal energy, which may in turn be derived directly from solar radiation or from the combustion of fuels. The requirements of a material for use in a thermoelectric generator are obviously quite different from those of a material used in a temperature-measuring thermocouple. Naturally, for power generating purposes, the thermoelectric power (voltage produced per degree difference in temperature between the junctions) must be as high as possible. Furthermore, in order to obtain reasonably high power outputs, the materials used in the generator must have an electrical conductivity which is as high as possible. Finally, in order to minimize heat lost by conduction to the cold junction, the thermal conductivity must be as low as possible. The relation between these several factors and the efficiency of conversion of thermal into electrical energy-the thermoelectric efficiency-has been discussed by Telkes1 in a recent review of the subject. She gives the thermoelectric efficiency as: [ ] For many materials, some of the desired properties (for example, high electrical and low thermal conductivity) are almost mutually exclusive; the problem thus becomes one of finding a material which has the optimum combination of properties. BISMUTH-SELENIUM ALLOYS Work on the equilibrium diagram of the bismuth-selenium alloys has been reviewed by Hanson,2 who gives the diagram reproduced in Fig I. There are two intermediate phases in this system, BiSe and Bi2Se3. The existence of an alpha and beta modification of BiSe has not been demonstrated satisfactorily and the writer found no evidence of it in the present work. BiSe and Bi2Se3 have, like bismuth, a rhombohedral crystal

Jan 1, 1948

By Gherman Pavlovich Nikonov

Results of preliminary research on the use of small diameter water jets at high pressure for cutting rocks has demonstrated the possibility of effective cutting of anthracite. Detailed research has, therefore, been conducted at the Skotchinsky Institute of Mining to study the dynamics and structure of the small water jets and the mechanism by which they cut coal. One of the objects of this research was to obtain data for the design of a machine for cutting rock, based on the same principles as that for cutting coal. The productivity of water jet mining machines depends on the hydro- dynamic parameters of the jet. Therefore, the research on small diameter water jets was directed, initially to a study of the nature of the variation of these parameters, and to obtain a profile of dynamic pressure distribution over the section of the jet. As has been confirmed previously, the required jet pressure (to cut coal) lies in the range of 100 to 500 atmospheres. These pressures were utilized for the research. The diameter of the nozzle was changed as ~follows; 0.97; 1.24; 1.5; 2.17; 2.87; and 3.57 mm. Graphs showing dynamic pressures for each nozzle diameter and varied axial dynamic pressure were obtained over distances ranging from 2 to 70 cm from the nozzle. One of the most important hydrodynamic parameters of a jet, closely related to the dynamics of jet disturbance in air, is the magnitude of the axial dynhmic pressure. A study of the variation in this pressure with increasing distance from the nozzle led to the separation of the jet into three specific parts, which differ from each other not only in the nature of the change in dynamic pressure, but also in structural properties.

Jan 1, 1971

By R. T. Torgerson, W. A. Baginski

Alloying studies were conducted on modifications of Cb-10W-1OHf (C-129) alloy as part of a cooperative alloy development effort between The Boeing Co. and the Wah Chang Corp. The purpose of these studies was to develop a fabricable, high- strength columbium alloy with superior melding properties. The initial investigations of alloy modifications were conducted using laboratory-melted button ingots. An alloy with the composition exhibited excellent veld ductility, elevated-ternpevature strength, and fabricability. The yttrium-modified alloy was desigrzated C-129Y and was selected for further developrnetzt. Three prodziction heats of C-129Y weve processed into sheet. Welding, forming, and tensile proper-lies are presented for this material. Tungsten-are welds of. C-129Y exhibited a minimum bend radius of 1/2T in the as-welded conditioti compared to 8T for C-129 alloy. An investigation was conducted on Disil coating of C-129Y and test data are presented on oxidation resistance and effects of re-entry environments. The excellent combination of strength, fabricability, weldability, and low transition temperature of C-129Y alloy offers potential design advantages for use of this alloy in structures of aerospace vehicles. It is atiticipated that C-129Y will rapidly supplant C-129 and similar alloys clue to the versatility provided by its impvoved welditzg properties. COLUMBIUM alloys with improved properties are required to achieve better performance and efficiency of radiation-cooled structures for re-entry vehicles and recoverable launch systems. Cooperative work by The Boeing Co. and the Wah Chang Corp. resulted in the development several years ago of C-129 alloy, a high-strength Cb-W-Hf alloy.' This alloy has received favorable consideration for many advanced designs of high-temperature structures due to its excellent combination of properties. However, this alloy exhibits low weld ductility unless given a high-temperature stress-relief treatment. For this reason the development effort was directed towards modification of the C-129 alloy composition (Cb-1OW-1OHf) to eliminate the need for post-weld heat treatment. This paper describes the successful development of an alloy meeting this requirement. This new alloy was designated C-129Y and has a nominal composition of EXPERIMENTAL PROCEDURES Alloying Studies. Various Cb-W-Hf compositions were investigated using are-melted button ingots. These buttons were hot-forged using a protective glass coating and rolled into sheet specimens. Metal-lographic examination: tensile testing, and welding studies were conducted to evaluate properties of the experimental alloys. Sheet Fabrication. Three pilot production heats of C-129Y were fabricated into sheet to establish processing techniques and to determine sheet properties. The three heats consisted of 6-in.-diam ingots weighing from 140 to 250 lb. The ingots were prepared by electron-be am melting followed by vacuum-arc melting. The hafnium and yttrium additions were made during the are-melting operation by tack welding alloy strip additions to the Cb-W master-alloy electrode. The final ingots were machined into billets with samples of the machine turnings collected for chemical analysis. Ingot breakdown methods for the three heats are as follows: Ingot Ingot Heat Size Weiaht___Breakdown Method A 6 in. 250 lb Hot extrusion B 6 in. 140 lb Hot forging C 6 in. 250 lb Hot extrusion Sheet bars from the extrusion and forging operations were conditioned, recrystallized, and rolled into sheet. Initial rolling was conducted at elevated temperatures and final rolling was conducted at room temperature.

Jan 1, 1967

By C. D. Tedmon, D. P. Ferriss

THE yield stress, o of low-carbon steel has been shown to vary with the average grain diameter, d, according to the relation1-3 where o is taken to be the lower yield-point stress Of is the friction stress on an unlocked dislocation, and ky is a constant. The interpretation2,4 of ky in terms of dislocation theory relates this constant to the stress to unlock a source across a grain boundary. cottrel14 predicted that ky would increase with decreasing temperature. This was observed to be the case by Adams and coworkers5 in their investigation of niobium (columbium). However, petch6 and Backofen: both working with low-carbon steel, found ky insensitive to temperature. In his work with high-purity niobium, Johnson' found ky equal to zero. Evansg showed that k, was essentially zero for niobium containing nitrogen in an appreciable concentration range. The present experiments were designed to check this apparent anomaly in the value of ky in another Group V metal. Yield points were determined as a function of grain size at several temperatures for tantalum and a tantalum-tungsten alloy. The material used was double are-melted tantalum and a double are-melted alloy of 90 pct Ta and 10 pct tungsten (by weight), both obtained as unannealed, swaged rod. The impurity content of the materials is given in Table I. The tantalum was annealed at 1325"C. in a vacuum resistance furnace using a tantalum boat. The alloy was similarly annealed at 1660°C. Annealing times varied from 15 min to 2 hr, depending on the desired grain size. Nominal pressure in the furnace was 3 X 10~4 mm of Kg. Metallographic examination showed that the annealing treatment produced grain sizes ranging frorn 0.021 to 0.200 mm in the tantalum, and 0.060 to 0.160 mm in the alloy. Tensile bars were made by centerless grinding the annealed specimen;, and then electropolishing to remove all grinding marks. The specimens were than pulled :it 2 1/2 pct per rnin in an Instron testing machine. The tantalum specimens were tested at 77", 195", and 300°K. The alloy was tested at 300°K only. All specimens exhibited a yield-point phenomenon at all temperatures. Typical load-elongation curves at the three test temperatures are shown in Fig. 1. The lower yield stress is plotted as a function of (grain size) in Figs. 2 and 3 for tantalum and the 90 pct Ta-10 pct W alloy, respectfully. The position and slope of the curves was determined by least-

Jan 1, 1962

By W. R. Foster, J. M. McMillen, A. S. Odeh

The complete equations of average linear momentum balance for a single-phase fluid in an incompreisible, homogeneous, porous medium are derived. The derivation begins with Euler's equation of motion for a continuum and uses an integral transform recently developed by Slattery. 7 For steady flow of a compressible, Newtonian fluid, the usual equations of motion result. For transient flow, the space-time description of the pressure is determined in the lowest approximation by the telegrapher's equation. From the analysis a new phenomenological coefficient results which connects the viscous traction to the deriv ative of the linear momentum density. The magnitude of this coefficient determines the velocity of sound through the pore structure in this approximation to the pressure field. INTRODUCTION The modification of Darcy's law of momentum balance for steady, single-phase flow through porous media has been discussed for many years. The first modification was suggested by Forcheimerl who added terms of higher order in the velocity. These can be expected to appear because the underlying microscopic equations of momentum balance are themselves nonlinear in the point velocity field. The Reynolds tensor pvv, which represents the convective flux of momentum density, appears in the momentum balance equation. Only in rectilinear flow (parallel stream lines) does the divergence of this tensor vanish. Since the steady flow stream lines in most porous media are not parallel, nonlinear dependence of the pressure gradient on the velocity should naturally appear. This nonlinearity has nothing to do with turbulence in the ordinary sense of random fluctuations in the pressure and velocity fields. It arises simply because the stream lines converge and diverge, even for steady flows. Klinkenberg2 demonstrated that the permeability coefficient in Darcy's law depends on the absolute pressure or, alternatively, on the density field. However, because he neglected inertial terms of the Forcheimer type, his correction coefficient could not be represented by a constant but tended toward a constant as the velocity decreased. Forcheimer's and Klinkenberg's modifications can be combined in a rigorous way to account for both inertia and slip during steady flow. This will be shown in a future paper. The transient change of pressure in porous media has been described by the diffusion equation.3 This form results from eliminating the velocity and density fields from a combination of the equations of motion in the form of Darcy's law, the continuity equation and an equation of state. Fatt4 suggested that the cause of deviations from the prediction of the diffusion equation for pressure transients lies not in the choice of Darcy's law as the equation of motion but on the existence of dead-end pores which might invalidate the averaged equation of continuity. On the other hand, Oroveanu and Pascal5 noted chat the time derivative of the momentum density must be included in the equations of motion since this measures the local rate of change of momentum density. Their differential equation for pressure is the telegrapher's equation (neglecting gravity). However, their form of this equation predicts that the speed of pressure propagation through the pore structure is the same as that through the bulk fluid. M. K. Hubbert6 attempted a derivation of Darcy's law by volume averaging the Navier-Stokes equations. Since these equations represent momentum balance at a point within an open set of points containing the fluid itself, Hubbert's volume averaging cannot lead to tenns involving transfer of momentum between the fluid and the walls of the pores. Once these viscous tractions are lost by choosing a control volume containing only fluid, they cannot

By P. J. Soltis

Direct as well as indirect evidence of a-phase ordering was found in a "near-a" type titanium alloy, Ti-8Al-1Mo-1V. The annealed alloy showed an anomalous decrease in second-stage creep rate at 950°F (510°C) and 47,500 psi. Anomalous increases were noted in initial yield stress after 500 hr creep exposure and in tensile strength after 1100 hr creep exposure. Debye-Scherrer X-ray diffraction patterns obtained on fine-grained polycrystalline speci-ment showed much line broadening and development of superlattice lines after 500 hr at 510° C. Examination with the light and electron microscopes failed to reveal phase changes in thermally exposed material, but detailed metallography is presented illustrating the plastic and fracture characteristics of the alloy. Electron-metallographic evidence is presented, however, which shows the nature of the nucleation and growth of ordered regions from the disordered a in annealed material. In the original phase diagram of the binary Ti-Al system constructed by Ogden et al.1 aluminum was shown to be soluble in a titanium over a wide temperature range at concentrations up to about 30 pct. Subsequently, a number of papers2-7 have appeared which indicate the existence of either intermetallic compounds and/or ordered phases in the a field up to 25 pct Al. In the most recent of these, Goldak and Gordon paw7 have determined unequivocally the ordered hexagonal D019 structure for Ti3Al in a 25 pct Al alloy. No superlattice lines were observed above 1112°F (600°C). Previously, the embrittle-ment encountered by Crossley and Carew4 in low- temperature heat treatments of binary Ti-Al alloys low in aluminum had been attributed to the appearance of a new phase in light micrographs. In the present work, direct as well as indirect evidence is presented showing the existence of a-phase ordering in what is essentially the binary Ti-8A1 alloy containing small percentages of the ß stabilizers molybdenum and vanadium, i.e., the "near-a" Ti-8Al-1Mo-1V alloy. Although Bohanek and Kessler8 have shown that this alloy has good stability at temperatures up to 1100°F (593°C), the present work shows instability at 950°F (510°C) where long exposure times were used. Light and electron microscopy proved very useful in revealing the mechanical behavior of ordered a and led to the conviction that ordered "near-a" alloys may have remarkably good properties and useful engineering applications.

Jan 1, 1965

By D. W. Philips

The problem of strata control has of necessity been prominent in mining, and accounts of individual experience and research abound in the literature of most mining countries. Organized rescarch began in Britain by the formation of a committee, upon the recommendation of the Safety in Mines Research Board in 1923, to investigate methods of reducing accidents from falls of roof in coal mines. This committee examined current practice in supporting underground workings in the principal coal fields, and its findings have been published in the Board's publications.' - Toward the end of these investigations it was suggested by the Chief Inspector of Mines that committees of the several mining institutes be formed to examine the problem in their respective districts. The formation of these committees marked a new phase in research on strata control. The work, though being done in the separate coal fields, followed a scheme outlined by the chief Mining Engineer of the Research Board, and was coordinated by his office. FACTORS INVOLVED The subject is being considered in Britain from two aspects: 1. To provide. by supports, means to prevent falls of fractured ground. 2. TO develop methods whereby the strata can be maintained in the least broken condition and thus make falls less likely. The first aspect is the one that will most likely lead to immediate results from the accident standpoint. It depends largely upon the assimilation of already acquired knowledge regarding the properties of supports and their correct application. The second aspect is perhaps more fundamental, and involves also the properties of the strata and their behavior under the influence of the forces induced by mining. The problem involves many natural factors that cannot be controlled, such as depth, inclination and thickness of seam and nature of the rocks. Other factors, which may be considered to a certain extent controllable, cannot be varied readily and with sufficient frequency to facilitate easy investigation; some of these are: rate of advance of the working face, length of face, direction of the face with regard to cleat and inclination, system and arrangements of rock packing behind longwall faces. In any given case the very many factors present have a mutual influence upon the effects produced in the mine. For example, a study of the effects of rate of advance cannot be done without considering the effects of other factors such as nature of strata, direction of face and quality and arrangement of supports. Conversely, the length and direction of a working face

Jan 1, 1947

By D. W. Philips

The problem of strata control has of necessity been prominent in mining, and accounts of individual experience and research abound in the literature of most mining countries. Organized rescarch began in Britain by the formation of a committee, upon the recommendation of the Safety in Mines Research Board in 1923, to investigate methods of reducing accidents from falls of roof in coal mines. This committee examined current practice in supporting underground workings in the principal coal fields, and its findings have been published in the Board's publications.' - Toward the end of these investigations it was suggested by the Chief Inspector of Mines that committees of the several mining institutes be formed to examine the problem in their respective districts. The formation of these committees marked a new phase in research on strata control. The work, though being done in the separate coal fields, followed a scheme outlined by the chief Mining Engineer of the Research Board, and was coordinated by his office. FACTORS INVOLVED The subject is being considered in Britain from two aspects: 1. To provide. by supports, means to prevent falls of fractured ground. 2. TO develop methods whereby the strata can be maintained in the least broken condition and thus make falls less likely. The first aspect is the one that will most likely lead to immediate results from the accident standpoint. It depends largely upon the assimilation of already acquired knowledge regarding the properties of supports and their correct application. The second aspect is perhaps more fundamental, and involves also the properties of the strata and their behavior under the influence of the forces induced by mining. The problem involves many natural factors that cannot be controlled, such as depth, inclination and thickness of seam and nature of the rocks. Other factors, which may be considered to a certain extent controllable, cannot be varied readily and with sufficient frequency to facilitate easy investigation; some of these are: rate of advance of the working face, length of face, direction of the face with regard to cleat and inclination, system and arrangements of rock packing behind longwall faces. In any given case the very many factors present have a mutual influence upon the effects produced in the mine. For example, a study of the effects of rate of advance cannot be done without considering the effects of other factors such as nature of strata, direction of face and quality and arrangement of supports. Conversely, the length and direction of a working face

Jan 1, 1947

By D. W. Philips

THE problem of strata control has of necessity been prominent in mining, and accounts of individual experience and research abound in the literature of most mining countries. Organized research began in Britain by the formation of a committee, upon the recommendation of the Safety in Mines Research Board in 1923, to investigate methods of reducing accidents from falls of roof in coal mines. This committee examined current practice in supporting underground workings in the principal coal fields, and its findings have been published in the Board's publications. Toward the end of these investigations it was suggested by the Chief Inspector of Mines that committees of the several mining institutes be formed to examine the problem in their respective districts. The formation of these committees marked a new phase in research on strata control. The work, though being done in the separate coal fields, followed a scheme outlined by the Chief Mining Engineer of the Research Board, and was coordi¬nated by his office. FACTORS INVOLVED The subject is being considered in Britain from two aspects: I. To provide, by supports, means to prevent falls of fractured ground. 2. To develop methods whereby the strata can be maintained in the least broken condition and thus make falls less likely. The first aspect is the one that will most likely lead to immediate results from the accident standpoint. It depends largely upon the assimilation of already acquired knowledge regarding the proper¬ties of supports and their correct applica¬tion. The second aspect is perhaps more fundamental, and involves also the proper¬ties of the strata and their behavior under the influence of the forces induced by mining. The problem involves many natural factors that cannot be controlled, such as depth, inclination and thickness of seam and nature of the rocks. Other factors, which may be considered to a certain extent controllable, cannot be varied readily and with sufficient fre¬quency to facilitate easy investigation; some of these are: rate of advance of the working face, length of face, direction of the face with regard to cleat and inclination, system and arrangements of rock packing behind longwall faces. In any given case the very many factors present have a mutual influence upon the effects produced in the mine. For example, a study of the effects of rate of advance cannot be done without considering the effects of other factors such as nature of strata, direction of face and quality and arrangement of supports. Conversely, the length and direction of a working face

Jan 1, 1946

By D. O. Hobson

Zirconium single crystals of various specific orientations were fabricated by rolling or drawing. The resulting textures were determined and are discussed with respect to the deformation modes that produced them. The crystals deformed in a predictable manner by combinations of up to third-order twinning with three twinning modes and by slip. Twinning was found to play a major role in initial texture formation. Texture changes produced by slip occurred only at the higher reductions. The twinning sequences that produced each intensity peak during the initial reductions could be identified. Schmid factor criteria were found useful in predicting which deformation modes to expect for each crystal orientation and fabrication procedure. The possible application of these data to poly-crystalline material is discussed. PREFERRED orientation or texture has a significant effect on the properties of most materials, causing anisotropy in fabricated cubic metals and enhancing the natural anisotropy of noncubic metals. This study evaluates the effects of several fabrication methods on the textures formed from specific starting orientations of zirconium single crystals and, it is hoped, gives an insight into the effects of the same operations on poly-crystalline material. BACKGROUND In fcc and bcc metals, texture changes take place by gradual lattice rotations caused by the operation of one or more slip systems. Deformation twinning plays an insignificant role in the deformation of such metals. In zirconium and its alloys, however, and in many other hep metals the ability to twin allows very rapid texture changes to be made with very small amounts of deformation. The deformation systems found in zirconium and its alloys are prism slip and three twinning modes.1 Slip occurs on the {1010}< 1120) system. There is little or no appreciable basal slip in zirconium. The twinning planes, illustrated in Fig. 1, are {1012}, {ll2l}, and {1122}. Two twinning modes, the {1012} and the {ll2l} operate for a tensile stress along the basal pole. A compressive stress parallel to the basal pole is required for {ll22} twinning. These twinning operations cause a 35- to 85-deg reorientation of the basal pole. The {1012} twin is the predominant tensile twin at room temperature. The twinning shears, S, are shown in the figure. A criterion for predicting which deformation system will operate when a grain is subjected to a known stress state is the Schmid (orientation) factor. This factor gives the fraction of the applied stress that computer program was written2 to calculate the Schmid factors for the four deformation modes in zirconium. It assumed three orthogonal stress axes and considered ninety-one different orientations of the basal pole in one octant of this stress space. At each basal pole position the Schmid factors were calculated for seven positions of rotation at 10-deg increments of the unit cell about the basal pole. Schmid factors were determined for a total of 637 orientations and for twenty-four deformation systems in each orientation. The program listed the Schmid factors for uniaxial stress parallel to each axis and, to approximate rolling, or-thonormal biaxial stress was also considered. Fig. 2 shows the range of orientations over which the various types of deformation would tend to predominate in biaxial plane strain with the stresses, equal magnitude. The exact boundary position between regions of different deformation modes depends, however, on the relative values of the critical shear stress for each deformation mode. Fig. 2 is drawn on the assumption that they are equal and it therefore may be only approximately correct. It is also recognized that the biaxial stress analysis may not be applicable in certain crystal orientations. EXPERIMENTAL PROCEDURE Single crystals of zone-refined zirconium, produced by Wilson of this Laboratory,3 were electrical-discharge-machined to form specimens for rolling, tube-drawing, and rod-drawing studies. Specimens were rolled at room temperature on 2-|--in.-diam hand-powered rolls from three different starting orientations: 1) the basal plane parallel to the rolling plane and the [1120] in the rolling direction, (0001)[ll20]; 2) the (1120) plane parallel to the rolling plane and the basal pole in the rolling direction, (1120)[0001]; and 3)_the (1120) plane parallel to the rolling plane and the [1100] in the rolling direction, (1120)[ll00]. Drawing specimens were cut with the [0001] direction as the drawing direction in the tube blank and [1120] as the drawing direction in the rod specimen. The drawing

Jan 1, 1969

By J. N. Hobstetter, J. J. Becker

Deformed copper single crystals exhibited, upon annealing, a recrystallized twinned grain with a twin plane parallel to an active deformation plane, rotated approximately 22" about its pole, or else did not recrystallize at all. If extraneous deformation was not carefully removed, no simple orientation relationship was found. RECRYSTALLIZATION textures have been a subject of practical interest for many years, but any real understanding of their formation will have to start with a study of the recrystallization of carefully deformed single crystals. Some efforts have been made in this direction,&apos;-&apos; but much more experimental information is needed before a satisfactory picture of the crystallography of recrystallization can be formed. This paper reports a few results in copper single crystals. The crystals studied in this investigation were grown by the Bridgman method," and their orientations determined by the back-reflection Laue technique." Some specimens were simply deformed in compression, others were sheared, and still others tested in a rotating-grip device, in attempts to remove end constraints. The details of their deformation behavior are described elsewhere.&apos; The deformed specimens were annealed and the orientations of the recrystallized grains were determined optically, as described by Barrett and Levenson.8 Compressed Specimens Specimen 17-A, whose orientation is given in Fig. 1, was compressed to a total of 19 pct. As observed before,&apos; increasing deformation took place by increasing density of slip lines in initially formed clusters, with little if any formation of new slip clusters in unslipped areas. The specimen was then etched in nitric acid until its length had been reduced from 0.766 to 0.735 in. It was annealed at 1000°C, in increments of a few minutes. After 63 min, two small grains had appeared in the center, Fig. 2. They were found to be twinned with respect to each other (AB, Fig. 4). After 30 min more, the specimen was completely recrystallized. A typical view of it is given in Fig. 3. A summary of all orientations found is given in Fig. 4, in which the prominent grain G is in (001) standard projection, and the poles of the active slip planes after deformation are indicated by SP (primary slip plane), CrSP (cross-slip plane), and CnSP (conjugate slip plane). All the orientations found were related through seven orders of twinning. A "family tree" of these twins is given in Fig. 5. Furthermore, the BG twin composition plane lies close to the cross-slip plane

Jan 1, 1954

[E. E. SCHUMACHER, Chairman ARTHUR PHILLIPS, Past-Chairman L W. KEMPF, Senior Vice-Chairman E. A. ANDERSON, Vice-Chairman H. A. MALONEY, Treasurer FRANK T..SISCO. Secretary 29 West 39th Street, New York 18, N. Y.]

Jan 1, 1946

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria &apos;Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By L. Guttman

THE equilibrium diagram of the indium-thallium system was of interest to us in connection with a study of the superconducting properties of metallic solid solutions in progress at this Institute. For this purpose, a series of alloys was prepared covering the range from pure indium to 75 atomic pet TI, and X-ray diffraction patterns were obtained. Roughly speaking, the results indicated a region of continuous decrease in the axial ratio of the face-centered tetragonal structure from the value ca. 1.08 in pure indium to unity at about 23 atomic pct TI. From this concentration to the solubility limit, the structure was face-centered cubic, a form not reported by Hansen.1 At this point we became aware of the work of Valentiner,2 who had found the same structures at room temperature but had not investigated further the relationship between them. To study the transformation f.c.c.??f.c.t., and to clarify the phase diagram, we undertook the work reported in this paper and that which follows." Preparation of Alloys Pure indium and thallium* (both about 99.9 pct, as estimated from spectroscopic analyses) were weighed out in quantities sufficient to prepare 10 to 25 g of alloy of the desired concentration. (Occasionally indium was mixed with a previously pre- pared solution.) The metals were melted over a flame, in an open graphite crucible, stirred with a graphite rod, and poured into a graphite trough. The rough slug was hammered and swaged into a rod of 2 to 3 mm diam, and annealed in a drying oven at about 125°C for 1 to 2 days. Samples were taken from the rod for analysis, as well as for diffraction and other measurements. The thallium was determined by electrometric titration, using a modification of the method of Beale and co-workers.&apos; The precision of analysis was generally about 2 0.2 pct of the thallium content. The rods were sometimes found to vary in thallium content as much as 1.5 pct from end to end, but since analyses were also made close to the segments used in the various studies, the composition was usually known as accurately as the analyses could be made. Where one less significant figure is given, the error is estimated to be ±0.4 pct of the thallium content. X-Ray Diffraction Measurements Three different cameras were used: (1) A 7 cm Debye camera, with oscillating specimen (manufactured by the Picker X-ray Corp., Cleveland, Ohio); (2) a 9 cm diam Debye camera of the type designed by Bradley;" (3) a 10 cm diam symmetrical focusing back-reflection camera (manufactured by Geo. C. Wyland, Ramsay, N. J.). Samples were prepared from the homogenized rods, either by filing under liquid nitrogen, or more often, in the form of wires or foils made by working at room temperature or liquid nitrogen temperature. Sharp patterns were obtained from specimens annealed at room temperature, although higher annealing temperatures were also used (cf. below). Generally, copper radiation was used; a few patterns were obtained with

Jan 1, 1951

By L. W. Fagg

The purpose of this paper is to present in a convenient form data and examples necessary in making dynamometer card analyses; also to outline a procedure of well weighing. Many articles and papers have been written delving into the mathematical considerations relative to the shape and characteristics of dynamometer cards. However. it is recognized that there are too many unknown factors involved in such calculations to assure a workable degree of accuracy. For this reason the accepted procedure is to take dynamometer cards on wells in question rather than try to calculate the load curve. The polished rod dynamometer is now recognized as a necessary tool for measuring loads, torque, and horsepower. It is also used to determine pump action and trouble-shoot for any seemingly abnormal pumping condition. The apparently infinite variety of a = maximum load (height x scale constant) b = minimum load. Range of load is difference between maximum and minimum load speed—taken with stop watch stroke —measured at polished rod c = beginning of down stroke in direction of arrow. (End of up stroke) d = beginning of up stroke. (End of down stroke). Polished Rod Horsepower = (Area of card) x Scale const. x Stroke x Length x spm (Length of card) 33000x 12 1.35 1.35------x5300x 24 x 12 2.53 --------------------------= 2.06 23000x12 Appraximate Peak Torque: Upstroke = (2390) (12) (1) = 28,700 in. Ib Downstroke = (1 860) (12) (.866) = 19,300 in. Ib Counterbalance should be increased to make up stroke and down stroke peak torque equal. FIG. 1 dynamometer cards that can be obtained is one reason for the general lack of usage of the dynamometer as a control instrument rather than a means for making routine measurements of leads and horsepower. When it is considered that the dynamometer card is a record of the resultant of all forces acting on the polished rod at any particular instant during the pumping stroke. the problem is then one of breaking down this resultant into its various components. As a means of a quick review we shall consider the examples shown in Figs. 1 to 9: and Tables I and II and then proceed to the interpretation of variously shaped cards caused by some abnormal operating condition. In Table 11, when we were considering the factors involved in calculating the peak polished rod load, it can be seen that the factors involved greatly oversimplify the problem. Certain assumptions are made which may or may not he even close to the actual field conditions, such as the specific gravity of the fluid generally considered as one; that the crank has constant angular velocity; that the down-hole friction is zero; and that the fluid lift is from the pump. In the following examples we shall see what a variation in fluid weight and friction can do to the general shape and magnitude of the dynamometer card. (Figs. 10 to 22.) MAKING THE WELL STUDY It is obvious that it would be impractical to consider in detail all of these factors each time a well study is made, inasmuch as each well study job could conceivably be extended into a research project rather than serve the practical requirements of finding the answer to a specific problem. For this reason it is important that some objective be established previous to the time the well study is made. Load at TU = 3070 Ib Crank angle when polished rod is at position TU = ? ? = 30° Maximum counterbalance effect at polished rod = 2760 Ib Torque at TU = (Load at TU — Max. counterbalance effect-lbs) sin 0 x Length of Stroke 2 = (3070-2760) .5 x 24 = 1860 in. 15 2 Torque at TD = (Load at TD — Max. counterbalance effect-lbs) sin ? x Length of Stroke 2 = (530 - 2760) sin 330&apos; x 24 = 13,400 in. Ib 2 Note: sin 0 from c to d on UPSTROKE will be positive value. sin 0 from c to d on DOWNSTROKE will be negative value Torque at c and d is zero because 0 is zero. FIG. 2 —APPROXIMATE METHOD FOR CALCUlATlNG TORQUE

Jan 1, 1950

By T. Yamasaki, S. Usu

Adsorption of potassium dodecyl xanthate from aqueous solutions on artificial and natural zinc sul-fides was studied by means of infrared absorption spectroscopy. The adsorption species and their stabilities varied depending upon the conditions of the surfaces of the zinc sulfides. Adsorption products were analyzed after they had been removed from the surface with pyridine. Zinc dodecyl xanthate was confirmed for surfaces covered with oxidized products while dodecyl alcohol and carbon disulfide were detected on purified or weakly oxidized surfaces. It is of great significance to study the adsorbed species of collectors on the surface of sulfide minerals with a view of increasing our understanding of the mechanism of flotation. Compared with other methods, infrared spectroscopy promises to be of particular value in determining the nature of the species adsorbed at the mineral/solution interface since it gives direct identification of the adsorption products; and, furthermore, it has an advantage over the electron diffraction technique which has been employed in similar problems in that infrared spectroscopy utilizes radiation of very low energy so that the probability of changing the unstable surface films during examination should be correspondingly decreased. Infrared spectroscopic studies concerned with sulfide mineral flotation have already been reported by several investigators on zinc sulfide-hexanthi01&apos; and lead sulfide-xanthate2,3 systems. The purpose of the present study was to investigate the adsorption of potassium dodecyl xanthate (KDX) at the zinc sulfide-aqueous solution interface by means of infrared spectroscopy. Rarely is the pure zinc sulfide-xanthate system encountered in practical flotation since zinc sulfide is usually activated with small amounts of certain metallic ions, such as copper ion. However, investigation of the pure zinc sulfide-xanthate system appeared promising for studying the fundamental mechanism of the adsorption of xanthate on the sulfide minerals. Although there are few cases where xanthates having an alkyl radical higher than hexyl are employed in practical operations, KDX was used in this study since it was reported that the adsorbability of xanthate on zinc sulfide was increased with an increasing number of carbon atoms of the alkyl radicals.4 EXPERIMENTAL Samples: Experiments were made on artificial zinc sulfide and natural sphalerite. The artificial zinc sulfide was obtained commercially from Dainihon Toryo Co. as a fluorescent pigment of the purest grade A. Considering the fact that there are often cases where the surface of sulfide minerals are apt to be oxidized so that the adsorption of xanthate at sulfide mineral/solution interfaces may be substantially affected, two different procedures were employed in preparing the samples of the artificial zinc sulfide. 1) The zinc sulfide was washed with hot concentrated ammonium chloride solution (300 g per liter) to remove surface oxidation products and followed by washing with deoxygenated hot distilled water by centrifugation until the constant electric conductivity of the solution was reached (Sample I) (specific conductivity of the solution = 8.6 x l0-5 ohm-&apos; cm-&apos;). 2) Sample I in a suspension of 5% by weight was oxidized with a 1.5% aqueous hydrogen peroxide solution for about one hour, and then was washed with distilled water as mentioned in the preparation of Sample I (Sample 11) (specific conductivity of the solution = 1.0 x 10"4 ohm-&apos; cm-&apos;). Both Samples I and II were dried under vacuum and stored in a vacuum desiccator. The specific surface areas of the samples determined by the BET method using carbon dioxide gas were 19 x l04 cm2 per g for Sample I and 35 x l04 cm2 per g for Sample 11. In addition, a sample which was derived from Sample I was also prepared. In 40 ml of 3 x 10-2 M zinc sulfate solution was placed 2 g of Sample I for 2 hours, washed with distilled water by successive centrifugation until no sulfate ion could be detected and dried under vacuum (Sample 111). The purpose of this treatment will be described later. Natural sphalerite was carefully selected by hand, ground in a mechanical agate mortar for about 40

Jan 1, 1965

By H. T. Sumsion, A. U. Seybolt

The results of an investigation of vanadium-rich V-O solid solutions are presented, indicating the structure and lattice parameters of two solutions, a and ß, and their approximate temperature-composition existence. The a solution is the terminal body-centered cubic one, and contains up to 3.2 atomic pct 0. The ß solution has an ordered body-centered tetragonal structure, is formed at 1270°C, and exists from about 15 to 22 atomic pct 0. From the evidence available, the various phase boundaries have no appreciable temperature dependence. Evidence has been found for a polymorphic transformation in pure vanadium at 1550°C. IN an earlier investigation&apos; dealing with the preparation of pure vanadium by calcium reduction of the oxide, it was found that small amounts of oxygen drastically reduced the ductility of the metal. Because this effect was so marked, it was decided to make a study of the solubility of oxygen in solid vanadium. This report deals principally with this solubility and the nature of the phase relationships in the vanadium-rich region, particularly at temperatures below 1300 °C. However, during the investigation enough data on the V-0 system were obtained to make it appear worthwhile to present a tentative phase diagram up to the composition VO. The only significant prior work found on this system are the contributions of Klemm and Grimm,&apos; and Mathewson et al.3 Klemm and Grimm prepared a wide range of V-O compositions by powder techniques including the compositions VO.l, VO.2, VO.3 and VO4 (9.1, 16.8, 23, and 28.6 atomic pct 0, respectively). The first three compositions were found to consist of a body-centered tetragonal solid solution, while the last also showed lines of VO (NaCl structure). They found that the parameter c, increased and the parameter a, decreased with increasing concentration of oxygen. For their composition VO.27, or about 16.8 atomic pct O, they cite the values a, = 2.948A, c, = 3.53A, and c/a = 1.2. Klemm and Grimm made no attempt to determine the solid solubility limit nor to construct a phase diagram. They did, however, give some data on the homogeneity range of VO, and they proposed a structure for the body-centered tetragonal solid solution; these points will be taken up later. Materials and Preparation of Samples The vanadium used in this investigation was prepared in the laboratory by the method previously mentioned.&apos; A typical analysis is as follows: Fe, 0.007 pct; Si, 0.02; Ca, 0.06; C, 0.224; O2, 0.044; N,, 0.0017; H2, 0.003; and V, 99.34 ±0.3 (assay). The vanadium assay is probably low by about the error given. The impurities total about 0.36 which, if subtracted from 100, gives a purity of about 99.6. At the time material was being prepared for this work no suitable technique was available for melting vanadium without appreciable contamination. The procedure adopted therefore was to cut the calcium-reduced regulii into slices which were then rolled to strip about 0.025 in. thick for oxygen diffusion. Pieces of rolled vanadium of approximately 0.025xY4xl in. and weighing about 0.3 g were suspended in a vertical fused-silica tube which was part of an ordinary gas absorption apparatus. The silica tube was heated by an electric resistance-tube furnace which could be raised around the silica tube or lowered away from it as desired. This apparatus had no novel features which require detailed description. Other than the silica tube and furnace, it consisted of a glass system evacuated by a liquid nitrogen trapped mercury diffusion pump, a mercury-operated gas burette, a McLeod and a Pirani gage, and a mercury manometer. It was also equipped with suitably located stopcocks for isolating various parts of the system; the vacuum ordinarily attained was between 10" and 10-6 mm of mercury. Oxygen generated by decomposing MnO2 was passed through anhydrous magnesium perchlo-rate before introducing it into the gas burette and thence to the absorption chamber.

Jan 1, 1954

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965

By D. H. Turner, F. A. Crossley

The titanium-rich corner of the system Ti-Al-Si has been studied to determine the phase relationships in the temperature interval 600° to 1200°C. Metallographic examination of long time isothermally annealed specimens was the means of investigation. PART of a program on phase relations and transformation processes of titanium alloy systems included the study of the titanium-rich corner of the Ti-Al-Si system. The investigation covered ternary compositions in the range 2 to 8 pet A1 and 0.1 to 2 pet Si and binary compositions in the range 0.2 to 2 pet Si. Temperatures were in the range of 600" to 1200°C. Alloys containing 6 pet A1-0.1 to 0.5 pet Si were investigated down to 400°C. Partial vertical sections are presented for 2, 4, 6, and 8 pet Al. The Ti-Si system has been reported by Hansen et al.&apos; It is characterized by a eutectoid decomposition, ß = ± a + Ti3Si3, at 860°C. The maximum solubility of silicon in a is reported to be about 0.5 pet at the eutectoid temperature. The solubility of silicon in 0 increases from 0.9 pet at the eutectoid temperature to approximately 3 pet at the eutectic temperature, 1330°C. Several investigations in the composition range of interest have been reported for the Ti-A1 system."&apos; These investigations are in agreement on the phase fields, but differ to small extents on boundary positions. However, very recent, and as yet unpublished, findings" " indicate that there are perhaps two phases which occur at lower aluminum contents than the ? (TiA1) phase, and that the solubility of aluminum in a titanium is less than 6 pet. In the present investigation phase relations found are in agreement with the published literature exemplified by the work of Bumps et al.3 Therefore, it is probable that the partial system reported herein is metastable and does not represent true equilibrium. Experimental Procedure High purity Bureau of Mines titanium sponge of 103 Bhn hardness, granulated aluminum shot of 99.7 pet purity, and silicon powder of 99.8 pet purity were used in making the alloys. For the work in the range from 600" to 1200°C, 100 g ingots were prepared by arc melting. Melting losses were negligible and spot checks by chemical analysis showed good agreement between nominal and analyzed results. Nominal compositions are used throughout this paper. Ingots were forged to 3/8 in. rounds and cut into specimens for heat treatment. Isothermal anneals in the range from 600" to 900°C were preceded by solution treatment at 1000°C for 1 hr, followed by furnace cooling to the annealing temperature. Samples were sealed in evacuated Vycor bulbs for heat treatments up to 1000°C. Higher temperature anneals were done with the samples sealed in quartz bulbs under a partial pressure of argon.

Jan 1, 1959

By M. H. Cullender

The performance characteristics 01 gas wells producing from formations which fail to stabilize within a relatively short period of time are obscured by the interrelation of the coefficient (C) and the slope "n" of the conventional back-pressure curve q = C(P2 f- p2s)n An empirical method is presented whereby the characteristic or true slope (11) of the back-pressure curve may be determined for a particular gas well. For those gas wells which do not stabilize within a relatively short period of time, the coefficient (C) is considered as a variable with respect to time and as a constant only with respect to a specific time. Thus, the back-presrure performance of such a well is presented as a series of parallel curve5, each curve representing the performance of the well at the end of a given time interval. Through use of the method presented, a simple presture gradient is developed and maintained within the drainage area around a producing gas well during the test period in order that the variation of the coefficient (C) with respect to time does not obscure the true value of the lope. INTRODUCTION The back-pressure method of testing gas wells as set forth by Schellhardt and Rawlins1 is dependent upon the requirement that a series of flow rates and corresponding pressure data be obtained under stabilized conditions. These data arc then plotted on logarithmic coordinates of flow rate (Q) vs difference in squared pressures (P2f — P2s) in order to determine the constants (C) and (n) for Equation 1. With respect to this method of presenting the performance characteristics of a gas well, it should be pointed out that although Equation 1 is an empirical relationship, the form of the equation was justified to a considerable extent by an independent development by Muskat and Botset.2 This development was theoretical in nature; however, certain assumptions with respect to the type of flow existing (viscous vs non-viscous) were madc which may or may not be correct. As the use of the method presented by Schellhardt and Rawlins spread through the industry, it became evident that the method of testing was applicable for those wells which approached stabilized prbducing conditions within a relatively short period of time. Performance characteristics could not be determined by this method, however, for wells which approached stabilized protlucing conditions slowly over a considerable period of time. This characteristic of "slow stabilization" has generally been associated with gas wells producing frorn reservoirs of low permeability. As the demand for natural gas continued to grow through the years, a great number of wells were completed in reservoirs of low permeability which exhibited "slow stabiliz:~tion" characteristics. Consequently, the problem of determining the true performancc characteristics of these wells became more apparent. It is with this problem in mind that the isochronal performance method of determining the flow characteristics of gas wells is presented.

Jan 1, 1956