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By Charles L. Mantell, P. P. Napolitano

High-purity tellurium oJ semiconductor grade may be prepared by a combination of electrowinning from tellurium oxide, electrorefining and controlled atmosphere melting, as detailed in the paper. SEMICONDUCTOR devices such as transistors and rectifiers depend upon extremely pure forms of silicon, germanium, and selenium. Although tellurium is chemically related to these elements, it has not been studied as a semiconductor because commercial forms are too impure. Highly purified tellurium would be an interesting starting point for a study of its solid-state characteristics. Tellurium shows a greater electrical conductivity in the direction of the helices or chains forming the crystals than at right angles to the chains, and thus is a semiconductor. Unlike selenium, the conductivity is only slightly increased by exposure to light. Impurities such as Ag, Cu, Au, Fe, Sn, As, Sb, Bi, Br, and I provide accepters and make extrinsic tellurium of the P type. So far, however, no elements have been found which, when introduced, would act as donors. Small amounts of tellurium dioxide enormously increase the thermoelectric power. Many extremely pure metals have been made by electrolytic refining or electrowinning procedures. Tellurium forms compounds in a number of valences, as indicated in Table I. The physical properties given in Table II do not show any unusual conditions which would interfere with the formation of elec- trodes, or the deposition of the metal on a cathode. Tellurium dioxide could be obtained in relatively high purities of 98 pct TeO2 or better at reasonable prices. Tellurium dioxide is soluble in caustic to form tellurites, which are conductive, ionizable, and from which tellurium metal may be deposited at a cathode. Preliminary solubility tests to saturation of tellurium dioxide in approximately 10 pct sodium hydroxide gave the results of Table III. The temperature range is a practical one for electroplating. Electrochemical test facilities were set up and these met the operating conditions of Table IV. For a determination of purity of deposits, there was available a Jarrell Ash Co. quantitative emission

Jan 1, 1964

By R. P. Rothwell

Jan 1, 1885

GENTLEMEN : Herewith are submitted reports for the calendar year 1933 of your Treasurer and the Chairmen of the following standing committees: Finance, Admissions, Membership, Papers and Publications, Library, and MINING AND METALLURGY. TO these reports you are referred for additional details of the year's activity. Finances.-Income for 1933 from all sources totaled $121,690 com- pared with $138,331 in 1932. Incidentally, this exceeded the income as estimated in the budget by $7,190; the largest item being a "surplus" of $3,316 over the budget expectancy as to member dues. As compared with 1932 the most important items of shrinkage in income were $9,000 from dues and initiation fees; $5,500 from the magazine, MINING AND METALLURGY; and $2,500 from sales of publications other than the magazine.

Jan 1, 1934

By Klaus Schwerdtfeger, Leo Zwell

The equilibrium between Ir-Fe or Rh-Fe alloys, iron oxide (wüstite or magnetite), and CO2-CO atmospheres has been determined at 1200°C. The data are used to derive the activities in these binary solid solutions. Both systems show negative deviations from Raoult's law. The lattice parameters are given for the investigated Ir-Fe and Rh-Fe alloys. IRIDIUM and iron form a continuous series of fcc solid solutions at elevated temperatures.' Rhodium-rich Rh- Fe alloys have fcc structure.' In the medium concentration range an ordered bcc phase is stable at temperatures up to about 1300°C. Phase relations in iron-rich alloys are not well-known. No thermody-namic data are available for these alloys. EXPERIMENTAL METHOD The experimental method used was to measure the equilibria between a gas phase of known CO2/C0 ratio, the alloy, and iron oxide (wüstite or magnetite). In one series of experiments the alloys of known composition were heated in CO 2-CO gas mixtures. After treatment (usually 1 day) the sample was quenched to room temperature and its surface examined visually to determine whether an oxide tarnish had formed. The procedure was repeated at slightly higher CO 2/CO ratios until the CO 2/CO ratio of incipient oxidation was found. Subsequently, the CO 2/C0 ratio was lowered again in small increments until the tarnish was reduced. In other experiments mixtures of alloy and iron oxide powders were pressed into pellets and equilibrated with the CO2-CO gas phase. In order to ensure that equilibrium was attained, two specimens with different starting iron content were heated side by side; in most cases, equilibrium was approached in one pellet by reduction of iron oxide and in the other pellet by oxidation of metallic iron. The sample was quenched to room temperature, and the composition of the equilibrated alloy was determined by X-ray measurements of lattice parameters and comparison of these values with calibration curves obtained from alloys of known composition. The oxides present in the specimens were identified by comparison of their diffraction patterns with those in the ASTM Card File. It may be expected from the noble character of iridium and rhodium that no appreciable amount of iridium or rhodium is dissolved in wiistite and magnetite under the present experimental conditions. The activity of iron in the alloy is then equal to that established in the iron oxide by the COrCO atmosphere. The activities of iron in wüstite and magnetite, as a function of oxygen pressure, were taken from the work of Darken and Gurry,

Jan 1, 1969

By M. Cross

INTRODUCTION The results of the Japanese dissective investigations have [l-4] transformed our understanding of how the blast furnace operates. These studies revealed an internal structure of the furnace burden with five main zones, as illustrated in Figure 1. In the granular zone the charged material retains its structure whereas in the cohesive zone the iron ore particles are at advanced stages of reduction and form a semi-molten mass with a relatively high flow resistance. In the active coke zone molten iron and slag flow through a matrix of loosely packed coke. The raceway is a relatively small void space generated by displacement of coke due to the hot blast momentum, whilst the hearth is packed with coke, slag and molten iron. [ ] It is now well appreciated that furnace control is largely achieved and maintained by using the burden charge distribution to determine the gas glow distribution within the furnace and, hence, the shape and extent of the cohesive zone. In fact, Wakayama et a1 [5] of Nippon Steel Corporation state that optimum furnace operation is synonomous with the formation of a desirable cohesive zone shape, which in turn is almost solely determined by the burden charge distribution and its mechanical properties [6]. Much of the development work on operating furnaces since the dissective investigations has been oriented towards the identification of external furnace measures which reliably predict the shape of the cohesive zone. Currently the most popular measures are top gas temperature, velocity and CO/CO, ratio profiles [5]. More recently pressure distributions as evaluated from a series of wall measurements down the height of the furnace are also being utilised [7] to identify the position and shape of the cohesive zone. A great deal of emphasis has been placed upon achieving a consistent quality in the burden charge materials, establishing a suitable set of operating conditions and only making changes when forced to, ie., the operation for some reason moves outside a desired operating range or the production requirements change. Operational control schemes based upon this philosophy (eg., Kawasaki's GO-STOP system [8]) have been remarkably successful at achieving both high production rates and relatively low fuel costs. Mathematical models have long been used as tools to assist in the analysis of the blast furnace process. Although, the models have been useful in post-operative analysis and for identifying trends, etc., they have not proved reliable for detailed design criteria or as the basis for effective control schemes. Such mathematical models have moved from simple statistical correlation, through overall and stagewise heat-and-mass balance calcu-

Jan 1, 1984

By A. M. Gaudin

This year the American Institute of Mining, Metallurgical and Petroleum Engineers has chosen to give me its Robert H. Richards Award, a distinction which is widely regarded as the highest honor in the field of mineral engineering. I am deeply moved by this tribute, which suggests not only regard for my service to the profession but also the affectionate esteem of my fellow mineral engineers. You have made me happy at the prospect of the permanent association of my name with that of Robert Hallowell Richards and of the distinguished recipients of the award, Arthur Fay Taggart, Frank R. Milliken, John F. Myers, Edward William Englemann, C. Harry Benedict, Edward W. Davis and Arthur W. Fahrenwald. I wish to thank you all for an honor so generously bestowed. Professor Richards is known to us all as a legendary figure, and we can read about him in the Richards Memorial Volume of our Transactions. Some of us have even had the good fortune of knowing him. I count myself among those lucky few. In its intangible attributes the Award recalls those things for which Professor Richards stood: for Science in Art, for thoroughness, for meticulous accuracy, for bold imaginativeness, most of all for professional integrity. Now, as in his day, these attributes are central to an engineer's creed. They are appropriately needed in a formulation of a definition of the mineral engineering profession.

Jan 6, 1957

By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF'-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By George A. Laird

THIs old and once famous district played, through its enormous production of silver and gold, an important part in the history of the State of San Luis Potosi. According to a pamphlet prepared under the direction of the Governor of the State, Sr. Don Blas Escontria, and presented to the visiting members of the Institute during the Mexican meeting of 1901, this district is situated 20 km. east of the city of San Luis Potosi, in a range of mountains of moderate height, extending 135 km. N. and S., and 16 km. E. and W.; and the mineralized area hitherto developed is about 600,000 sq. m. The history of the district, as given by the record dated 1778, and formerly kept in the Sail Francisco convent, says that it was discovered in 1575 by Sr. Don Pedro Irarte, and adds that the city of San Luis Rey de Francisco de1 Potosi received its name (in allusion to the famous Potosi mines in Bolivia) by reason of the remarkable productiveness of its gold- and silver-mines in the first period of their exploration, during which they paid to the Crown, as quintos (the fifth part of the product), $97,000,000, as appears from the accounts of the royal treasury. The amount of the quintos paid during the " bonanza period " of 80 years was $72,000,000. The larger sum first mentioned probably represents a longer series of years. But either will suffice to indicate the great wealth of the mines. In 1663, the decadence of the industry began with the caving-in of several mines, concerning which the record of 1778, already cited, says, in substance, that on Good Friday one of the owners in the enterprise, in view of the unfavorable prospect of a lawsuit in which he was engaged, set fire to the timbers supporting the underground galleries and workings of the Sail

Jan 1, 1905

[For the year ending February, 1936 PRESIDENT AND DIRECTOR HENBY A. BUEHLER3 ROLLA, Mo. PAST PRESIDENTS AND DIRECTORS FREDERICK M. BECKET1 NEW YORK, N. Y. HOWARD N. EAVENSON2 PITTSBURGH, PA.]

Jan 1, 1936

By P. E. Baker

The commercial neutron-gamma log measures the intensity of gamma-rays produced by the interaction of neutrons with nuclei in the formation and in the bore hole. This measurement gives information concerning the distribution of neutrons around the neutron source, and in particular gives information on porosity or fluid content. Another type of information is contained in the frequency or energy spectrum of the neutron capture gamma-rays. The capture gamma-rays of each element, in fact of each isotope, have only those energies characteristic of that isotope.'" The neutron capture gamma-ray spectrum, if obtainable, would permit the identification of the elements producing the spectrum. Such information would have considerable value in oilfield exploration work if it could be applied practically in well logging. Experiments have been carried out at the La Habra Laboratory of California Research Cop. to determine the feasibility of a method of well logging in which neutron capture gamma-ray spectra are measured down hole. In these experiments, spectra were obtained for artificial formations under simulated borehole conditions, using actual borehole geometry. This paper will describe the experimental apparatus and methods and will present the spectrum curves for several formations. THEORY Basic Formulas The neutron capture cross section of an element is a measure of its tendency to capture neutrons. The macroscopic cross section, or cross section per cubic centimeter, of a material composed of several elements is the sum of the cross sections of the nuclei making up 1 cc of the material. This is expressed in the equation SB = Sn1s2, ..........(1) where SB is the macroscopic cross section, s, is the cross section of a nucleus of type i, and ni is the number of nuclei of type i/cu cm. If N is the number of neutrons absorbed per second by the composite material, then the number captured by element j is Ni = N nisi/SB = N nisi/Si ni si ......(2) When the nucleus captures a neutron, a new nucleus is formed, which is usually in an excited state and falls to its ground or unexcited state by emitting one or more gamma-ray quanta.* The emission spectrum has been measured for many elements (see Table 1). The intensity of gamma-rays produced by an element is proportional to the number of neutrons captured per unit time by the element, which in turn depends on the capture cross section of that element and the capture cross sections of the other elements present which are competing with the first element for thermal neutrons. In a small sample of material the number of neutrons, N, captured per second is N = ?SB, ..........(3) where $ is the thermal neutron flux and SB is the macro-scopic cross section defined above. The number of neutrons captured by element j is N1 = ?ni si = N ni si/SB . ......(4) The number of gamma-ray quanta of energy, E, pro-duced per unit time by element, j, is I(E)=Nni si/SB P(E) .......(5) where P(E) is the emission probability of element, j, for this gamma-ray energy. Borehole Effects The capture gamma-ray spectra of many elements have been measured accurately in academic and government laboratories. These measurements are made on small samples, and from these measurements the emission spectra of the elements are obtained.

Jan 1, 1958

By Grover J. Holt

IN order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.o.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the "straight wash" ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces-namely, low price of product and minimum amount of fines-iron-ore concentration has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. [ ] Table I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1943

By R. L. Fullman

IN the investigation of metallurgical transformations and the relationships between microstructure and properties of metals, it frequently is desirable to obtain a measurement of the relative amounts of the various phases present and of the mean size of particles into which each phase is dispersed. The relative amounts of the phases can be measured by the classical methods of area, lineal, and point analysis,1-5 in accordance with the principle that the volume fraction of a phase, the fraction of a polished cross section occupied by the phase, the fraction of a random line occupied by the phase, and the fraction of randomly arrayed points occupied by the phase are all equal. The validity of this relationship depends only on the attainment of a truly random sample of area, length, or points, and not on the size, shape, or distribution of the particles constituting the phase. Smith and Guttman8 have derived a relationship between the interface area per unit volume S, and the measurable quantities L., the interface length per unit area on a cross section, and NL, the number of interfaces per unit length intersected by a random line. Their equation, Sv = — L8 = 2NL is also valid regardless of the distribution of particle sizes and shapes. In contrast to the situation concerning measurement of relative fractions of phases and of interface area, the measurement of particle sizes in opaque samples has not been subjected to a complete analysis. It has been common to measure some lineal or area dimension of particles on a polished cross section and to use the mean value as a qualitative measure of particle size. In the present paper, quantitative relationships are established among the various mean dimensions on a polished cross section and the actual dimensions of the particles present. Particles of Uniform Size Spheres: If a metal sample contains particles of a phase a dispersed in the form of spheres of uniform size, a polished cross section through the sample will reveal circular areas of phase a with radii from 0 to ?, the radius of the spheres. Consider a cube of unit dimensions to be cut from the sample. If a cross section parallel to one of the cube faces is examined, the average number of particles per unit area (N,) equals the number of particles per unit volume (Nv) times the probability p1 that the plane would intersect a single sphere positioned at random within the unit cube. Since, of the various possible positions for the cross-sectional plane over the unit length from top to bottom of the cube, only those positions existing over the length 2r would lead to the plane intersecting the sphere, the probability of intersecting a single sphere is just 2r. N8= Nvp1 = Nd-2r [1] Applying the equality of area and volume fractions, the relationship is found between sphere size and average area s of uniform spheres intersected by a random cross section, 4 - f = NV V = Nr . — pra = N s = Nd . 2rs S = —pr2 [2] A similar analysis reveals the average traverse length across spheres of uniform size when random lines are passed through the sample. If a randomly oriented unit cube is cut from the sample and a randomly positioned line is passed through the cube parallel to a cube edge, the number of spheres intersected by the line (Nl) equals the number of spheres per unit volume times the probability p1 of the line hitting a single randomly placed sphere in the cube. Since possible positions of the line occupy unit area, and possible positions for which it will pass through the sphere occupy an area of pr2, the probability of the line hitting a randomly placed single sphere is pr2. NL = Nv p1 = Nvpr2 [3] Combining this relationship with the equality of volume and lineal fraction, the desired relationship is obtained between radius and mean lineal traverse length -i, for spheres of uniform size. 4 - - 3 l=4/3r [4] Circular Plates: Consider a sample containing particles of a phase a in the form of circular plates of uniform radius r and thickness t, where r >> t. If the plates are randomly oriented, as in a sufficiently large sample of a fine grained polycrystalline material, area and lineal analysis may be carried out with parallel cross-sectional planes and lineal traverses. If the plates are not randomly oriented, it is necessary to randomize the orientation of the cross-sectional planes and traverse directions. Let a unit cube be cut from the sample, and a cross-section plane be passed through the cube parallel to one of the cube faces. The number of plates cut by the cross-sectional plane per unit area is equal to the number of plates per unit volume times the probability of a plate intersecting a single randomly positioned and randomly oriented plate in the cube. If J is the component of the plate diameter in the direction normal to the cross-sectional planes, the probability of a plane cutting a single randomly oriented plate is equal to J, the mean value of J for all possible orientations of the plate. Let 4 be the dihedral angle between a plate and the cross-sectional plane, and let p?, d? be the probability that a plate makes an angle between 4 and ? + d? with the cross-sectional plane. Then for ran-

Jan 1, 1954

By John C. Calhoun, Frank T. Bethel

The application of a method for analyzing pressure build-up curves to determine the effective permeability in the Spraberry is presented. Sixteen upper Spraberry wells of the Driver area arc analyzed and show variations in the in-place effective permeability of 2 to 183 md. Since these value- are much larger than the .5 md. or less reported for the matrix rock. a large part of the vertical fractures noted in Spraberry cores- must be considered native to the formation. The effectiveness of the well fracture treatment in connecting the well bore to the native fracture system is analyzed by comparison of the effective permeability as determined from the PI test to that obtained from a pressure build-up curve. These results show that the fracture treatment is sufficiently effective in connecting tile well bore to the native fractrure system to yield a flow capacity within about 50 per cent of that dictated by the native fracture system About two-thirds of the wells show some degree of local blockage. INTRODUCTION Fractured reservoirs have been known in the past.' However, during the past two years the Spraberry formation has directed the attention of the petroleum industry to a study of the performance of a fractured reservoir. The large variation in the number of fractures noted in Spraberry cores rile large variation in the producing ability of offset well.. the dramatic effect of well treatment on well ,productivity. the unknown quantity of oil stored in the fractures and matrix rock. and the unknown oil to be recovered were part of the initial Spraberry puzzle. In this type reservoir where the well treatment is an important factor in determining the productivity. it i- particularly desirable to determine the in-place flow capacity of the drainage area at distance* far removed from the well bore. This value. when compared to the flow capacity obtained from a PI measurement, will show the effectiveness of the well treatment (completion. fracture treatment, acidization. etc. in establishing a flow capacity in the vicinity of the well bore equal to that in the more remote region. The object of this paper i.; to show the application of a method of pressure build-up analysis for this purpose in studying the Upper Spraberry formation in the Driver area. STATEMENT OF THEORY The theoretical basis for the application of a pressure buildup curve to show the effective permeability of the rock at distances far removed from the well bore has been presented in detail in earlier publications.', in the previous development it was shown that pressure build-up behavior of all wells could be reduced to the same dimensionless build-up curve of Fig. 1. This mean.; that the bottom hole pressure of a well after hut-in will rise in such a manner that a plot of pressure against the logaritllm of time yields a straight line. The slope of this linp can be rlzed to calculate the effective permeability as expressed by the following equation: where: effective oil permeability md oil production rate prior to shnt in. STB/I) In practice the flow which occurs into the well bore after shut in and the variation in flow capacity in the immediate vicinity of the well bore usually cause the early part of the build-up curve to be unsatisfactory in the determination of permeability. In general the effect of these factors on the straight line section will become negligible after a time when the of the following equation is equal to 0.1. and the preferred section Of the curve for use in defining the slope lie-

Jan 1, 1953

By Michael Hoch, Walter C. Wyder

The isothermul section of the Nb-Ti-Zr-O system at 1500°C was investigated using X-ray dzffraction and metallographic techniques. UP to 66.7 at. pct 0, the system contains nine four-phase regions. Tsopleths at 10, 20, 30, 40, 50, and 55 at. pct 0 weye constructed. The purpose of this investigation was to determine the general shape of the quaternary equilibrium phase diagram of niobium, titanium, zirconium, and oxygen at 1500°C. The system was truncated at 66.7 at. pct. O., PREVIOUS INVESTIGATIONS The Ti-Zr-O system was investigated in this laboratory.' The binary systems of interest have been compiled and discussed by anssen2 and Levin, McMurdie, and Ha11. Elliott4 has determined the Nb-O system by metallographic and X-ray diffraction techniques. He shows the existence of three oxides, namely NbO, NbO2, and Nb2O5. At 1500°C the solubility of oxygen in niobium is about 4 at. pct. No solid solubility region is shown for either NbO or NbO2. EQUIPMENT The same equipment as that for the study of the Ti-Zr-O system was used. The X-ray diffraction patterns were analyzed with the help of the ASTM card set5 and NBS circulars.6 MATERIALS The niobium powder (99 pct pure), the titanium powder (99.6 pct pure), the niobium pentoxide, and the zirconium dioxide used in this study were purchased from the Fairmount Chemical Co., Newark, N.J. The zirconium powder (99.4 pct pure) was obtained from the Charles Hardy Co., Inc., N.Y. Reagent-grade titanium dioxide was purchased from the Matheson Co., Inc., Norwood, Ohio. The oxides were dried in air at 700°C for 24 hr before use. Though the materials used were not "hyper-pure," the impurities present do not affect the results (lattice parameters, phase boundaries), within the experimental accuracy. PROCEDURE Samples of the desired compositions were made up, in mole pct, from the materials listed above. In some cases the intermediate binary compounds, such as NbO and TiZrO4 were prepared beforehand and used in the preparation of the samples. This technique enabled equilibrium to be reached from two sides. The components of each sample were mechanically mixed in a mortar and pestle and pressed into 3/16-in. diam pellets. The pressures used in compacting were of the order of 50 to 100 x 103 psi. Sintering was accomplished by heating the samples in a tungsten crucible (3/4-in. high, %-in. diam, 1/8-in. wall, lid with XB-in. hole). The pellets were separated from each other and from the crucible by means of small spiral coils of tungsten wire placed between the stacked pellets and on the bottom of the crucible. The sintering time was from 4 to 12 hr at 1500°C under a vacuum of 6 x 101-5 to 1 x 10-6 mm of Hg. All samples were reground after the first or second heating repressed, and reheated. In most cases: equilibrium was obtained after the first heating, as the X-ray diffraction pictures after each heating remained unchanged. Quenching of the samples from 1500°C was at first only possible by allowing the crucible and its contents to lose heat by radiation. The temperature dropped from 1500° to 900°c in approximately 1 1/2 min, which was considered adequate when compared to the times used by other investigators to reach equilibrium in the temperature range of 1000°c and lower. Later, a new technique for faster quenching of the samples was cleveloped. This technique involved the removal of the samples from the crucible, whereupon they were quenched by coming in contact with the water-cooled copper base of the furnace. This manipulation was performed without breaking the vacuum. The sample pellets were placed on a tungsten wire rack inside the crucible. The wire rack passed through the hole in the crucible lid, where it was connected to a small nonmagnetic chain. The chain was fed to the side of the furnace by means of a brass rack which fitted between the body and lid of the furnace. Suspended at the end of the chain, near the furnace wall, were three magnetic washers. With the use of a strong

Jan 1, 1962

By David J. Mack, Dennis R. O’Boyle

The mechanical properties of three polycrystalline intermediale Phases that have the y bvass structure were measured in compression between 400° and 900°K. At the lower testing temperatures— termed Region I— no plaslic deformalion occurred prior to brittle fracture. A1 higher temperatuves— lermed Region III—the three phases deformted plaslically for all strain rules from 1.5 to 36.0 x 10-4 sec-1. The homologous temperature for the inilialion of plaslic flow increased in the same order as tile atomic size difference between atoms in each plmse (0.50Tmp for y AgZn, 0.62Tmp for y CuZn, and 0.76 Tmp for y CuCd). The increased flow resistance oj. y CuCd above 0.50Tmp is explaitzed in terms of the more random arrangement of copper and cadmiwn atoms on the laltice sites of&apos; the y bvass slrilctlire. Plaslic deformation of the three intevmiediate phases in the smooth plaslic flow region appears to be controlled by oacancy-induced dislocation climb. RESULTS are reported in this paper on the mechanical properties of three binary intermediate phases having the complex cubic y brass structure (D82, 143m) containing fifty-two atoms in the unit cell. The structure of the prototype y brass phase, y CuZn, was first analyzed by Bradley and Thewlis&apos; based on the X-ray work of Westgren and Phragmen.2 The y brass structure can be visualized as an arrangement of twenty-seven body centered cubes (3 by 3 by 3) into a unit cell containing fifty-four atoms. From this cell the center atom and the four corner atoms are removed and the remaining fifty-two atoms are slightly displaced, resulting in the y brass structure. Approximately thirty-five binary intermediate phases that have an electron to atom ratio of 21:13 have been reported to form the y brass structure. The three y brass intermediate phases selected for this study are formed from elements in groups IB and IIB of the first and second long period. Each compound exists over a composition range that includes the stoi-chiometric composition A5BB (Cu5Zn8, Ag5Zn8, Cu5Cd8). y CuZn (a0 = 9.944A) has solubility limits extending from 57 to 67 at. pct Zn at 500°C apd melts peritecti-cally at 834°C; y AgZn (a0 = 9.326A) has a solubility range from 58 to 63 at. pct Za and melts peritectically at 661°C. y CuCd (a, = 9.596A) melts congruently at 563°C and has a maximum range of solubility extending from 58 to 64 at. pct Cd. In order to minimize coring and microporosity during solidification, the composi- tion of the compounds that form peritectically (y CuZn and y AgZn) was chosen so that the temperature difference between the liquidus and the solidus is only a few degrees centigrade. In selecting y brass compounds for this study, phases were avoided that contained a transition element or that had an electron to atom ratio greater than 1.70. Hume-Rothery et a1.3 has observed that, when the electron to atom ratio of y brass intermediate phases exceeds 1.70, atoms begin to drop out of the unit cell to maintain a constant electron to unit cell ratio. EXPERIMENTAL PROCEDURE Each of the three intermediate phases was prepared from elements having a purity >99.999 pct. Only trace quantities of impurities (<0.0001 pct) were detected by spectrographic analysis of the four elements. A master alloy of each compound weighing approximately 130 g was prepared by melting the elements in evacuated sealed quartz tubes heated in an electric furnace. Specimens having the desired diameter for the mechanical property measurements were obtained by remelting the master alloy in a Vycor tube under argon and drawing specimens from the melt into 4-mm-diam quartz tubes. To obtain a smooth surface on specimens drawn from the melt, the inside of the quartz tube was coated with a thin layer of graphite formed by thermally decompositing acetone. All specimens were imbedded in sealing wax and cut to the proper length with a diamond-impregnated cut-off wheel. The individual specimens (4 mm diam by 8 mm long) were then sealed in evacuated Pyrex tubes and homogenized at 500°C for 72 hr. Chemical composition, variations over the length of the rod (10 cm long) were generally less than 0.2 pct and the analyzed composition differed from the desired composition by less than 0.5 pct.4 Metallographic evaluation of the specimens after homogenization showed no evidence of a second phase in any of the compounds. The average grain size of the specimens after homogenization was 1 to 2 mm. All mechanical property measurements were carried out in an argon atmosphere using a compression apparatus described previously.5 Prior to applying the load to the specimen, the test apparatus was evacuated, back-filled with argon, and heated to the test temperature for 20 min to establish thermal equilibrium. EXPERIMENTAL RESULTS Mechanical properties measured as a function of temperature and strain rate for each of the three y brass phases were similar. From room temperature to the ductile-to-brittle transition temperature, only elastic deformation was observed prior to fracture.

Jan 1, 1968

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Extensive solid solubilities of CdTe (zincblende-type struckre) and InTe (B37 type) in each of the rock salt-type compounds, PbTe and SnTe, have been observed. Partial phase diagrams have been determined by thermal analysis and X-ray metallography. The limiting mol fraction. X,, of the solute in the rock salt-type a phase and the corresponding eutectic temperatures, T,, are: (PbTe)l-x(CdTe)x: X,- 0.2, T, =866°C; (PbTe),-,(lnTe),: X, - 0.35, T, = 646"C; (SnTe),-,(CdTe),:X,- 0.11, T, = 784 "C; (SnTe),-,(lnTe),: X,-0.53, T, = 630°C. The lattice parameters of the a phase decrease linearly with X, even in (PbTe),-,(CdTe),, where a, (CdTe) = 6.481A > %(PbTe) = 6.459A. This is taken as proof that the cadmium atom enters an octahedral interstice of the tellurium atom sublattice; i.e., the formation of the a phase entails the direct replacement of lead by cadmium. The a, us X curve extrapolates to 6.16A at X = 1, in agreement with the value predicted for an ionic crystal of CdTe; it is also consistent with the reported lattice parameter It is well-established that the compositions of intrinsic semiconducting and semimetallic compounds conform to normal valence rules.1"5 The apparent exceptions can be explained by taking account of anion-anion covalences, as in CdSb, or of multiple cation valences, as in In Te.&apos;This empirical generalization is the basis of the chemical approach to semiconductors2 by which the properties of an intrinsic semiconductor are rationalized in terms of the ionic-covalent bonds necessary to saturate the valence-electron complement of the anion sublattice. A fundamental shortcoming of this approach is its disregard of long-range crystal interactions. It cannot, accordingly, deal with the phenomenon of charge conduction except through the use of ad hoc postulates. As an example, a crystal of CdTe would, in the valence-bond picture: be described in terms of electron pairs, each with the same discrete energy, localized between every cadmium and tellurium atom. This is, of course, contrary to the Pauli of the high-pressure rock-salt form of CdTe, corrected for decompression from 36 kbar. The free energy of formation of the a phase of pure CdTe at room temperature is calculated from the phase diagram to be +10 kcal per g-atom, in accmd with the value calculated from the transformation pressure. The standard enthalpy is +13 kcal per g-atom, and the standard entropy is +9 eu. The latter value implies the formation of extra classical particles, such as vacancies, interstitials, or nondegenerate charge carriers, but these alternatives are not consistent with the semiconducting properties and the densities of the a phase. The extrapolated values of the lattice parameters of (PbTe),-,(lnTe), and Spectively, for the rock salt-type modification of InTe. The corresponding interatomic separation is intermediate between monovalent and trivalent indium. The qualitative implications of the results are considered from the viewpoints of both valence-band theory and energy-band theory. principle, and is corrected by methods of molecular-orbital theory in which bonds are replaced by bands of molecular orbitals whose energies, E, depend upon a crystal-momentum vector, k.7 Each band is derived from a linear combination of atomic orbitals with two electrons required to saturate each molecular orbital in the band. In a crystal of N atoms containing z atoms in its primitive unit cell, there are 2 N/z states per band which lie in a region of k space bound by the Brillouin zone. In an intrinsic semiconductor, the bands can be grouped into valence bands which are normally filled and conduction bands which are normally empty. If the highest valence band and the lowest conduction band overlap anywhere within the Brillouin zone, the material is rendered semimetallic. The quantity defines the effective mass, m*, of an electron in a conduction band (or of a hole, i.e., an electron deficiency, in the valence band) and leads directly to the concept of charge mobility through the relation \x = et/m*, where e is the electron charge and t is the lattice relaxation time.

Jan 1, 1964

Abramovits, Charles, Student, Case School of Applied Science Cleveland, Ohio. &apos;37 Abreu, Ovidio M., Student, Stanford Univ Stanford University. Calif. &apos;38 Adams, Albert, Student, New Mexico School of Mines Socorro, N. M. &apos;38 Adams, Benjamin C., Jr Address Wanted. &apos;36 Adams, George H 44S2 4th St., Riverside, Calif. &apos;36 Adams, Robert E., Student, Univ. of Wisconsin Madison, Wis. &apos;38 Adkisson, J. F., Jr., Student, Agricultural & Mech. College of Texas, Box 2044, College Station, Tex. &apos;38 Afshar, Hodji khan A., Amiranian Oil Co 10 Khiahan-i-Nusrat, Teheran, Iran. &apos;35 Agvas, Cesar G., Student, Adamson School of Industrial Chem. & EngrgManila, P. I. &apos;38 Ahlen, Louis S., Student, Univ. of North Dakota Univ. Sta., Grand Forks, N. D. &apos;37 Albers, Francis C., Student, Univ. of Wisconsin Madison, Wis. &apos;38 Alden, George P., Student, Univ. of Tulsa Tulsa, Okla. &apos;38 Alexander, Donald B... Student. Univ. of Oklahoma, Sigma Nu House Norman, Okla. &apos;37Alexander, Joe M., Student, Agricultural & Mech. College of Texas. Box 954. College Station. Tex. &apos;38

Jan 1, 1938

By William B. Phillips

It is proposed in this paper to discuss some of the chemical and physical principles involved in the manufacture and use of this important by-product obtained in the manufacture of steel by the basic process. The name, " phosphate slag," is adopted as a sort of compromise between "Thomas slag" and "tetrabasic phosphate." By the first of these latter names, viz., " Thomas slag," it is known in Germany, Austria, France, and the other continental countries, and in England, and is more easily apprehended by those who have no special Knowledge of chemistry, while the name " tetrabasic phosphate," being descriptive of the nature of the slag, is perhaps the best. It is but seldom that a discovery of such moment to two great industries is to be chronicled in the history of technical science. On the one hand, the manufacture of iron and steel has been greatly benefited, while on the other hand, the effects already noticed, and still to follow, to the agriculturalist, are of scarcely less conseqnence. The great majority of iron ores in the world, perhaps 90 per cent. of then), are now available for the steel manufacturer, while the manufacturer, and more especially the consumer, of artificial manures is relieved from the fear of the exhaustion of the crude phosphates. We have in phosphate slag, therefore, a product of the highest importance to those who make and we steel and fertilizers. Two great industries, which heretofore have had but little in common, are thus brought into close connection with each other, and the results sure to follow, if one may judge from the history of the past ten years, cannot fail to be of great and increasing value. These results may be compared with those which followed the introduction of the cupriferous Spanish pyrites into England for the manufacture of sulphuric acid. The copper extracted greatly reduced the cost of the acid, hence that of artificial manures. Cheap manures meant better farming and cheaper farm products, and these meant better and cheaper living to nearly all classes of society. The amount of fertilizers now manufactured in the United States

Jan 1, 1889

By E. A. Trager, A. W. McCoy, H. R. Shidel

Sampling of the fluid from oil wells for percentages of oil, emulsified oil, and water during the last two years has brought out some interesting facts concerning oil-water emulsion. This result led to a laboratory investigation of emulsion, which substantiated the conclusions made from the field observations. The purpose of this paper is to present the information collected, the laboratory experiments, and our interpretation of the same. In order to define emulsified .oil exactly, give its synthesis and origin, and to show how and when it is formed in the wells, the work was necessarily divided into two separate lines—laboratory work and field observations. It is hoped that this study may lead to a discussion of such points so that the petroleum engineer, geologist, or technologist may be benefited by its practical bearing on oil-field management. Special credit is due Mr. Everett Carpenter, chief geologist of the Empire Gas & Fuel Co., for his assistance and cooperation in this work. Labobatory Investigations on Emulsified Oil Laboratory investigations were conducted in an attempt to learn the composition and some of the properties of emulsified oil, or B. S., as it is more commonly called, also to demonstrate, by laboratory methods, how B. 5. may be formed under conditions similar to those existing at the time a well is being pumped, and how it may be broken down. Literature bearing on this subject is widely scattered and very limited in scope. Bacon and Hamor define B. S., or bottom settlings, as "earthy matter, inert organic matter, or, in the case of Pennsylvanian petroleum, an emulsion of paraffin wax and water, which accompanies crude oil." In this discussion we will limit the term B. S. to that heavy, dark-brown emulsion, composed of a physical mixture of water, oil, and air with some included inert matter, either organic or inorganic. Possibly the first step in a description of this product should be a description of its physical properties, but since most operators are quite

Jan 1, 1921

By E. C. Franz

IN an effort to understand high cycle fatigue, as well as to study the mechanism of fracture in general, a number of researches have been undertaken whereby the fracture properties of a metal have been determined under conditions of repeated cyclic prestsain employing high strains with relatively few cycles. Liu, Lynch, Ripling, and Sachs&apos; showed the effect of a definite strain history consisting of small increments of tensile or compressive prestrain upon the flow and fracture characteristics of metals after a limited number of repeated loadings. Liu and SachsW emonstrated by cyclic straining of the aluminum alloy 24s-T4 that the least reduction in ductility was obtained when the compressive stress was nearly equal to the tensile stress. Attempts have been made to correlate the reduction in ductility under such prestraining with conventional fatigue data, as was done by Liu and co-workers.&apos; The following research was conducted to determine if such reduction as has been noted could be correlated with conventional fatigue data or whether the effect resulted from causes extraneous to the basic mechanism of fatigue failure such as strain aging. It might be pointed out in this connection that the reduction in ductility has occurred in alloys that might be susceptible to strain aging or similar behavior, such as alloy 24s-T4. In the present investigation, the test specimens were prepared from the aluminum alloy 75s-T6 and annealed electrolytic copper. Alloy 75s-T6 is a complex precipitation hardenable alloy, whereas electrolytic copper would not be expected to exhibit strain aging effects, particularly at room temperature. The experimental procedure consisted of prestraining test specimens repeatedly by increasing tension in small increments to various total prestrain values, followed by testing to failure in a tension test. The prestraining as well as the final testing was performed on a tensile machine using special fixtures9 0 maintain concentricity of the specimens. After prestraining, the specimens were unloaded as rapidly as possible and immediately reloaded so that the total time lapse between strains was held to a few seconds. Logarithmic or true natural strain was used in all calculations. The results are presented in Figs. 1 and 2. In Fig. 1, the retained ductility, area after prestrain area at fracture is plotted against the tensile prestrain, initial area area after prestrain as abscissa with the number of stress reversals executed to attain the required prestrain plotted as parameter. Several specimens that fractured during

Jan 1, 1955