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By A. Lubinski, J. L. Logan, W. S. Althouse

A4ost gas twells and flowing oil wells are completed and treated through a string of tubing and a packer. Changes in temperature and in pressure inside or outside the tubing will: (I) if free motion of the tubing inside the packer is permitted, increase or decrease the length of the rubing; or (2) if free motion is prevented, induce forces in the tubing and on the packer. If pressure inside the tubing is greater than outside, the tubing may buckle helically even in the presence of a packer-to-tubing tension. The tubing will always buckle, and much more severely, if free motion is permitted. The buckling may be prevented by pulling the tubing in sufficient tension. The prediction of these forces and tubing movement has here to fore been based upon calculations that did not inciude helical buckling. This paper preseitts means with which these length or force changes can be calculated while taking into account the effect of helical buckling. To avoid damaging formations, failure of remedial operations, or damage to the tubing or packer, application is made to practical problems involving calculations of the required length of seals, amount of sluckoff or tension, and prevention of permanent corkscrewing. INTRODUCTION Leakage of a packer may result in costly failures of such operations as squeeze cementing, hydraulic fracturing, etc. To avoid such failures, the authors are often asked questions pertaining to the length of necessary seals, the amount of necessary slackoff, etc. Published work' does not take into account helical buckling of tubing. Investigation of helical buckling was prompted by the fact that allowance must be made for this phenomenon in order to provide relevant answers. In the past, theoretical work on helical buckling was confined to conditions for which such buckling does not The mathematical treatment of behavior in a buckled condition, given in the Appendix, is novel. Assumptions upon which this investigation is based are listed and discussed in a special section. The following are a few of the many kinds of problems which may be solved with this paper. 1. Consider a packer in which tubing may move. Such movement will occur after pressures and temperature are changed. The paper provides means for: (a) calculating the amount of such movement and, therefore. the required length of seals; and (b) calculating the necessary amount of initial slackoff, for which there is no danger of unsealing the packer, if the length of seals is given. Such calculations, as well as those which follow, tully take into account the fact that part of the movement ib due to elastic helical buckling of the lower part of the string. This buckling may occur even in tubing under tension. Insufficient initial slackoff for a given length of seals, or insufficient length of seals for a given slackoff, may result in costly failures. A field case of such a failure will be given further in this paper. 2. In the case in which tubing cannot move in the packer, changes of pressure and temperature result in tubing-to-packer forces and forces in the tubing above the packer, both of which may be calculated. This knowledge is important because, if these forces are too large, the) could damage the packer or the tubing. 3. For wells in which wireline tools are to be run through the tubing, the paper provides means to keep the tubing from buckling, thereby permitting free passage of tools. 4. In deep wells, mainly in the presence of large casing, tubing may become "corkscrewed", i.e., take a permanent helical set. A field case is described further in the text. Using this paper, one may calculate in advance conditions under which permanent corkscrewing would occur, and then take preventive steps. HELICAL BUCKLING Consider a string of tubing, freely suspended in the absence of any fluid inside casing, as shown in Fig. I(a). Now consider an upward force F applied at the lower end of this tubing. This force compresses the string; and if the compression is large enough (which is always the case in actual problems), the lower portion of the string will buckle into a helix, as shown in Fig. 1 (b). The lower end of the tubing is subjected to a compression F. This compression decreases with the distance from the bottom and becomes nil (neither compression nor ten-

By W. T. Weller

In Part I, a study of pressure build-up curves calculated for conditions under which both oil and gas flow led to the conclusion that the presence of a dispersed free gas phase in an oil reservoir must be taken into consideration to estimate accurately average reservoir pressure and permeability from build-up curves. Familiar methods based on the assumption of no free gas can be extended to the two-phase case by using total compressibility and mobility in place of single-fluid compressibility and mobility. These methods give correct values for average pressure and permeability when gas saturation is small. Errors become larger as the gas saturation increases. However, for the use to which the results will be put, the methods are satisfactory for reservoir engineering purposes. An improved method of calculating the performance of depletion-type reservoirs is presented in Part 2. Because the mathematical relationships describing simultaneous flow of oil and gas are quite involved. simplifying assumptions are made to provide means of obtaining approximate solutions of reasonable accuracy. One such approximate method now in use is the constant-GOR solution. It involves the assumption that at any instant, the ratio of total gas flow rate (both free and disolved) to oil flow rate is the same at all points in the reservoir. The approach is not applicable unless the free gar saturation in the reservoir is everywhere greater than the critical gas saturation. This paper presents a modification which, by avoiding the constant-GOR assumption, makes the method applicable to all reservoir conditions, and so far appears to be more accurate than the constant-GOR solution and to he comparable in required compuctation time. PART I— BUILD-UP CURVE ANALYSIS INTRODUCTION Pressure build-up characteristics of shut-in wells have been used for many years by engineers to evaluate average reservoir pressure, effective permeability thickness of the pay section, effectiveness of well completion (skin effect) and reservoir size. A number of methods of analysis have appeared from time to time."" Without exception, these methods are based on the assumption that the reservoir contains but one fluid of constant small compressibility and constant mobility. It has been suggesteda" hat these single-fluid methods may be applied to data from reservoirs containing both oil and gas by substitution of some effective total properties of the multiphase system in place of the corresponding single-phase properties. The present investigation was undertaken primarily to evaluate this approach. METHOD A number of theoretical build-up curves were calculated for conditions of two-phase flow, under the assumption of certain reservoir and fluid properties, and were analyzed by single-fluid methods with appropriate total compressibility and total mobility values for the corresponding single-fluid properties. Results of the analyses were compared with the assumed conditions. The theoretical build-up curves were completed by procedures similar to those of West, Garvin and Sheldon." Since these calculations require a considerable amount of computer time, an attempt was made to derive an approximate calculation method. The attempt was unsuccessful for calculating build-up curves, but the effort did result in a new approximate method of calculating the performance of solution gas drive reservoirs, which appears to be an improvement over the constant-GOR method" used previously (see Part 2). The West, Garvin and Sheldon calculations involved the following assumptions: (1) the reservoir is circular and completely bounded, with a completely penetrating well at its center; (2) the porous medium is uniform and iso-tropic, with a constant water saturation at all points; (3) gravity effects can be neglected; (4) compressibility of rock and water can be neglected; (5) the composition and equilibrium are constant for oil and gas; (6) the same pressure exists in both the oil phase and the gas phase; and (7) no afterproduction occurs, i.e., the well is shut in at the sand face for build-up. These assumptions make it possible to describe two-phase flow of oil and gas by the partial differential equations:

Jan 1, 1967

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By M. M. Rao, P. G. Winchell, R. J. Russell

A detailed analysis has been used to correlate the avalable thermodynami c da In on iron-ric11 Fe-Ni (41loys in the body-centered a, and the face-centered y phases. The inp ut injovrt~ation required by the a am lysis consists of tile heat of the a, to y transformation at 1123°K, the heat of mixing of y at 1123°K, tile specific heats of both a, and y (decomposed into Debye, electronic, and magnelic contributions), and the positional and magnetic entropies of both a, and y. PYLrrzary oirt.bul of the analysis is the free energy of each phase as a Junction of temperature and composition. FOr Fe-Ni alloys the adjustment of twenty-one parunletevs allows the accurate reproduction of enthalpy data for both phases, the heat of mixing- for y, the a/y equilibrinm compositions in the Fe-Ni phase diagram, and the usually accepted enthalpy and entropy of a and y iron. Also obtaitzed are fuirly accurate reproductions of electronic specific heat coefficients predicted from electron- to-atom ratio interpolations and To temperatuves eslimanted from transformation studies. Also considered in the calculation are the elastic constants, Curie temperatures, saturation magnlelizalion values, and indications of short- range order. The measnred activity coefficient of iron in anstetnite could not be accurately matched. The major source of uncertainty in the model is thought to be the magnetic contribution to the entropy of austenite. Calcrclations were extended to Fe-ni-C alloys using available carbon-acliuity data. The free energy of transformation from martensile to r at fixed composition was obtained as a function of nickel and carbon contetzt, and binary thetal-carbon phase diagrams Were estimaled as a function of nickel contenl. We needed thermodynamic information for Fe-Ni and Fe-Ni-C alloys at temperatures between 400" and 800°K in order to interpret the results of several phase-transformation studies. The most recent theoretical analysis of the thermodynamics of Fe-Nialloysl was based on a lumped-parameter, regular-solution model and used the Fe-Ni phase diagram available at that time.' Because significant difficulties were encountered in attempting to extend this analysis to Fe-Ni-C alloys, and because more experimental data has become available recently, we decided to attempt a new correlation. The analysis used here allows the extrapolation of measured and calculated thermodynamic values to lower temperatures and the extension of the thermodynamic analysis to Fe-Ni-C alloys. The structure of this correlation consists of expressions containing a total of twenty-one adjustable parameters. The forms of these expressions are discussed in the next section; however, a less formal summary is presented now to provide a physical overview of the model and to indicate its connections to prior work. Primary input information for this correlation is described below. The measured values of the specific heat of iron3 and its analysis475 and theoretical estimates of the specific heat of y* iron at low tempera- loys at 1123°K has been measured by solution calori-metry.7 The enthalpies of both a, and y have been measured most recently by Scheil and Saftig,B who used a dry-ice calorimeter. These data are used to formulate expressions for the heat of mixing of y and the heat of transformation of a, to y both at 1123°K. The a and y solubility limits in the Fe-Ni phase diagram have been redetermined recently9 by methods which assure a close approach to equilibrium. The a to y transformation can occur without change in nickel content or free energy at a temperature called TO; TO temperatures for various nickel contents have been estimated from transformation studies. The computed free-energy functions are adjusted by means of the parameters to fit both the phase diagram and the TO temperatures. Primary emphasis is placed on the phase diagram fit. Iron activities have been measured in Fe-Ni austenite10 between 973" and 1173°K. These activity data, which cannot be fitted accurately with our model, indicate that iron is substantially ideal in iron-rich austenite. Secondary, but helpful, information for the present correlation is provided by neutron diffraction and saturation magnetization measurements on both body-centered and face-centered Fe-Ni alloys."-'3 These results were interpreted11 in terms of composition-insensitive, localized magnetic moments on both iron

Jan 1, 1968

By Richard H. Bube

Photoelectronic radiation detectors may be conveniently classified as homogeneous intrinsic, homogeneom extrinsic, or junction type. Highly photosensitive homogeneous intrinsic photodetectors may be prepared from a number of different II-VI, III-V, or IV materials. Such materials require the presence of specific imperfections that can act as sensitizing centers to provide long majority carrier lifetime. Homogeneous extrinsic photodetectors are of interest primarity for infrared detection, and consist principully of germaniuim and silicon with suitable inpurities. A vaviety of junction photodetectors exist, with silicon us the most common material for them all. The following extrema in performance are found: 1) highest photoconductivity gain in homogeneous intrinsic photodetectors; 2) smallest response time (highest frequency response) in p-i-n junctions; 3) largest gain-bandwidth product in avalanche diodes. ALTHOUGH the total number of materials exhibiting photoconductivity effects is very large, only a relatively few of these have appropriate properties for a practical photoelectronic radiation detector. In fact if one surveys the commercial detectors currently available, one finds that the field is dominated by some ten or fewer materials. These are summarized in Table 1 in terms of the other important variable in detector fabrication, the structure of the material, i.e., whether the material is used as a single crystal or in polycrystalline form, and whether the material is used as a homogeneous detector or whether the detector depends upon the existence of a junction or barrier in the material. The principal wavelength range for each type of material is also shown, together with an indication of the utilization of intrinsic or extrinsic excitation. For the purposes of the present comparison of various detectors, it will be convenient to discuss two main topics: homogeneous photodetectors and junction photodetectors. The performance of a photoelectronic radiation detector is measured in terms of two parameters: the photoconductivity gain, and the response time of the detector. A convenient figure-of-merit is given by the ratio of gain to response time, often called the gain-bandwidth product. The photoconductivity gain is a device parameter since it varies in many cases with the applied voltage and the detector geometry, and should be distinguished from the actual photosensitivity of the material involved. This photosensitivity can be conveniently given as the product of free carrier lifetime and mobility in the material. The photoconductivity gain is defined as the number of charge carriers which pass between the electrodes per second for each photon absorbed per second, where G is the photoconductivity gain, is the pho-tocurrent in amperes, e is the electronic charge in coulombs, and F is the total number of electron-hole pairs created in the photo conductor per second by the absorption of light. The gain may also be expressed as the ratio of the lifetime of a free carrier to the transit time for that carrier, i.e., the time required for the carrier to move between the electrodes. For a material in which one-carrier conductivity dominates, where T is the lifetime of a free carrier, ttr is the transit time for this carrier, p is the carrier mobil-ity, V is the applied voltage, and L is the electrode spacing. From Eq. [2] it follows that the photoconductivity gain is proportional to the photosensitivity of the material (tP), the proportionality constant being The photosensitivity of a material, and hence the photoconductivity gain of a device utilizing the material, depends on the lifetime of the free carriers as a critical parameter. In a homogeneous material this lifetime is determined by the nature of imperfections in the material, and in an inhomogeneous material the lifetime is determined by the specific junction structure. The speed of response, the other basic photodetec-tor parameter, is determined by factors quite similar to those important for photoconductivity gain. Imperfections are of primary importance in homogeneous materials, and the structure of the junction is a determining factor in junction devices. For infrared detectors it has become common to define another quantity designed to indicate directly how effective the detector is in distinguishing between a small photoconductivity signal and random noise due to the detector and its environment. The detectivity D* is given by

Jan 1, 1968

By I. Mihajlovic

This paper investigates a potential method for arsenic removal from copper concentrates using hypochlorite leaching. The problems concerning pyrometallurgical processing of copper concentrates with high arsenic contents are discussed. A possible solution to the problem by leaching of natural enargite crystals with sodium hypochlorite under alkaline oxidizing conditions, with enargite converted into crystalline CuO and the soluble arsenic forming AsO43-, was experimentally investigated and results are presented. Kinetic parameters were calculated for enargite leaching, using a model-free approach. Advanced isoconversional methods were used to investigate the dependence of activation energy (Ea) on reaction rate (a). Keywords Enargite, copper concentrate, isoconversional method, kinetics, activation energy.

Jan 1, 2011

By D. K. Bose, R. H. Rakhasia, V. D. Shah, J. C. Sehra

A series of experiments was conducted to determine the effects of roasting temperature, soaking period and quantity of soda ash added. At a laboratory scale, under optimum conditions of roasting at 873 K for 2 700 s with soda ash 10 wt% in excess of stoichiometric, molybdenum recovery was 99%. The investigations indicate the technical feasibility of producing high-purity MoO3 by combining the roasting process with carbon adsorption/desorption. The process uses low-cost chemicals, can be scaled up readily and is free of the SO2 pollution generated by conventional roasting, as the sulphur content of the concentrate is converted to sodium sulphate

Jun 18, 1905

By Antonio De Biase

In October 2006, a 7m Double Shield TBM, boring through very poor volcanic formations, was pushed back by fluid mud, which presence had not been detected during previous field investigations, due to the high covers characterizing the majority of the tunnel axis. The present work describes the investigations made to gain better knowledge of the conditions in front and all around the TBM, the special measures implemented, the exploratory and bypass tunnels excavated, the extraordinary occurrences came true during the execution of these tunnels, the drainage campaigns, the design of the chamber excavated to free the TBM, the dismounting and restarting of the TBM.

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

By M. D. Banus, M. B. Bever, A. K. Jena

The heals of formation at 78", 195, and 273°K of the ternary compound h3SbTe2 based on the elements and based on the binary compounds In Sb and [inTe have been measured. The heats of formation at these temperatlcres of the binary compounds In Sb and In Te based on the elements have also been determined. Heal contents and free energies of the three compounds have been calculated from 0° lo 80I)°K. The free energies of joyrrzalion, heats of formations, and entropies of formation at 298°K have also been calculated. The results shown that the tertnary compound is metastable with vespecl to InSh and ln Te below 696 °K. bul is slable above that temperature. The weaker bonding of results in a positice entropy of formation which with incrensirzg temperature makes increasing negative conlvihtclions to the free energy and above 696°K renders the compound slable. THE ternary compound In3SbTez occurring in the quasi-binary system In Sb- In Te' forms on cooling at 829°K by a peritectic reaction.' Observations at 673" and 573 K have shown that this ternary compound decomposes slowly into the binary compounds InSb and1n~e.l'' It has not been possible to analyze the metastable behavior of the ternary compound because up to the present time data on its thermodynamic properties have been lacking. Some information on the binary compounds, however, is available. The heat of formation of InTe at 273°K and its free energy at 673°K are kn~wn.~'~ The heats of formation of InSb at 78", 273', 298", and 723°K have been measured5-' and its heat capacity between approximately 12" and 300"Kg9l0 is also known. In the investigation reported here the heats of formation at 78% 195% and 273°K of the ternary compound In3SbTez have been measured. The heats of formation of the binary compounds InSb and InTe at these temperatures have been obtained by combining new calorimetric results with previously published data. The heat contents and free energies of the three compounds at various temperatures from 0" to 800°K have been calculated. Against the background of this information, the metastability of the ternary compound will be discussed. 1) EXPERIMENTAL 1.l) Preparation of Specimens. The materials used consisted of the elements indium, antimony, and tellurium, the binary compounds InSb and InTe, and the ternary compound In3SbTez. The elements, obtained from American Smelting and Refining Co., had a nominal purity of 99.999+ pct. The compound InSb was Cominco semiconductor grade; the compound InTe was prepared from the elements by melting under a vacuum of 10-h m Hg followed by slow cooling. Three batches of specimens of the compound In3SbTez were used. One batch was prepared by melting appropriate amounts of the elements in an evacuated and sealed Vycor tube. The melt was held at approximately 100°K above the liquidus for about 8 hr, shaken repeatedly, and quenched into a mixture of ice and water. The specimen was annealed in vacuum at 760°K for 4 weeks. In preparing a second batch, a mixture of the component elements was melted and quenched in water. The resulting ingot was powdered. The powder was pressed into pellets, which were annealed in vacuum at 748" to 773°K for 4 weeks. A third batch was prepared in the same manner as the second, except that the starting materials were InSb and InTe rather than the elements. Metallographic examination of samples of the three batches and X-ray diffraction examination of a sample of the second batch did not reveal evidence of microsegregation or a second phase. The results obtained with the three batches showed no systematic differences. 1.2) Calorimetry. The calorimetric method has been described in detail." Samples of the compound In3SbTez, mechanical mixtures of InSb and InTe in the proportion of 1:2, and mechanical mixtures of indium, antimony, and tellurium in the proportion of 3:1:2 were added to a bismuth-rich bath at 623°K in a metal-solution calorimeter. These additions were made from 78°K (liquid nitrogen), 195°K (dry ice and acetone), and 273°K (ice and water). The heat effects of the additions were measured. The difference in the heat effects of the additions of a compound and the additions of the mixtures of its constituents, adjusted for differences in the concentration of the bath, is the heat of formation of the compound. In the concentration range not exceeding 1.5 at. pct solute, the heat effect of the additions was a linear function of concentration. The heat of formation refers to the temperature from which the additions were made, namely, 78", 195", or 273°K. Several calibrating additions were made in each calorimetric run. The calculated heat capacity of the calorimeter and hence the calculated heat effects of the additions of samples depend upon the values adopted for the heat contents of the calibrating substance. In this investigation bismuth at 273°K was used and a value of 4.96 kcal per g-atom was taken for (HGZ3"k . 2) RESULTS AND DISCUSSION 2.l) Heats of Formation. The heats of formation of the ternary compound In~SbTez from the component elements indium, antimony, and tellurium and from

Jan 1, 1968

By S. Vivek

An atomic force microscope (AFM) was used to measure the surface forces between silica plate and glass sphere in sodium oleate solutions. Hydrophobic forces were observed when the two surfaces were activated by CaOH+ or MgOH+ ions. The force measurements conducted in the absence of the surfactant showed that the activated silica surfaces do not exhibit the primary hydration forces that have been observed between unactivated surfaces. The activation mechanism was studied by calculating the contributions from electrostatic and chemical interactions to the total free energy change. The results suggest that the adsorption of the hydroxo-complexes is controlled mainly by the lateral interactions between the adsorbed species on the silica surface.

Jan 1, 1999

By Wagner Viana Bielefeldt, Felipe Buboltz Ferreira, Antônio Cezar Faria Vilela

The continuous casting machine is one of the most important steel production steps in a melt shop. The tundish, a reservoir between the steelmaking ladle and the mold, has great influence over the steel cleanliness, along with the productivity bid. It must takes into account the quality of the metal and operational safety. Several different variables are related to the tundish process, of inclusionary cleanliness. Some of them are discussed in this paper: the free opening of ladle, tundish inertization, steel temperature in the reservoir and clogging formation, besides a brief topic about castability. Therefore, a critical analysis, with a review from some papers available in literature, is proposed in this study, with its focus on tundish.

Oct 1, 2019

By E. G. King

Strontium sulfide and barium sulfide occur as intermediates in commercial treatments of the impure natural sulfates to produce pure strontium and barium chemicals. Thermodynamic considerations involving these sulfides have been hampered by lack of basic data, such as the entropies at 298.15°K. This paper reports the results of heat capacity measurements of strontium sulfide and barium sulfide in the temperature range 50°-298°K. The entropies at 298.15°K. were derived from the heat capacity values. Free energies of formation at 298.15°k. were computed from the entropies and literature values of the heats of formation. Strontium sulfide and barium sulfide are thermo-dynamically less stable than calcium sulfide, but more stable than magnesium sulfide.

Jan 1, 1960

By G. W. Birge

Twenty-eight samples, representing the Pittsburgh, Lower Kittanning, Stockton-Lewiston, Coalburg, Winifrede, Cedar Grove, Peerless, No. 2 Gas, Powellton, and Eagle beds, were carbonized by the Bureau of Mines--American Gas Association (BM-AGA) method, and yields of products and physical properties of cokes were determined. Expanding characteristics of 22 of the samples were determined in the Bureau of Mines sole-heated oven. The Kanawha County coals tested were high-volatile A bituminous in rank, with dry, mineral-matter- free fixed- carbon contents ranging from 53.9 to 66.3 percent. With few exceptions, they were chemically satisfactory for metallurgical use, and most of the coke-strength indexes were within the industrially accepted range for high-volatile blending coals.

Jan 1, 1963

By R. L. Grayson

Compliance standards for respirable dust which are reduced because of high quartz concentrations have become an industry-wide problem. Research on the physical and chemical character of quartz-classified particles in respirable coal mine dusts indicates that they may exist in intermixed layers or may be coated by clay or coal material. The relative amount of intermixing varies with the coal seam being mined. If most of the quartz particles of a mine dust are "pure," then the dust may have a high fibrogenic risk potential because of truly free silica and the compliance standard should be lowered. If, however, the quartz is locked inside another material matrix, or coated, a reduced compliance standard may not be appropriate.

Jan 1, 1990

By R. L. Soderberg

Large open stopes mined by vertical crater retreat or sublevel s are sometimes backfilled with uncemented sand to support the stope walls and alleviate rock bursts. The failure of bulkheads in two different mines prompted a research project at the Bureau of Mines to prevent a recurrence of these failures. A series of laboratory tests with drains and sand filters was conducted to measure the bulk-head pressures when adequate drainage was maintained. Results showed that bulkhead pressure was reduced to near zero while drains were in operation, as compared to full hydrostatic pressure when drains were blocked or drainage was restricted. A relatively simple, free-draining bulkhead was shown to be adequate.

Jan 1, 1985

By Alla D. Mah

No experimental heat-of-formation value has been reported in the literature for cerium sesquioxide. The heat of formation of bismuth sesquioxide has not been determined in recent years, and the older value was subject to large uncertainty. Accordingly, the heats of combustion of cerium sesquioxide and bismuth metal were measured by the Federal Bureau of Mines. The heats of formation were: ?H°298.15 = -427.01 ± 0.70 kcal. /mole for cerium sesquioxide and ?H°298.15 = -137.16 ± 0.30 kcal./mole for bismuth sesquioxide. The free energy of formation was estimated for cerium sesquioxide and accurately calculated for bismuth sesquioxide. The data were compared with values in the literature.

Jan 1, 1961

By P. R. Taylor

Titanium carbide and titanium diboride powders have been successfully synthesized by direct treatment of ilmenite concentrates in a non-transferred arc thermal plasma reactor. Methane gas was used as the reducing agent and boron oxide was used as the boron source in these processes. Free energy minimization plots were used to predict the behavior of each system under different molar ratios and operating conditions. Products were characterized by XRD, SEM and chemical analytical techniques. The average size of the ceramic product is in the submicron range. Metallic iron apparently is finely deposited on the surface of the titanium carbide or titanium diboride particles. Minor impurities such as silica, manganese and zircon were converted to the carbide form.

Jan 1, 1995

By Roy J. Helfinstine

One of the most urgent needs in the field of coal combustion is the ability to predict the performance of a coal from knowledge gained from small-scale tests. Numerous types of analyses and tests are conducted on coal, including the proximate and ultimate analyses, heating value, varieties of sulphur, ash analysis, ash fusion temperatures, free swelling index, petrographic analysis, and Gieseler plasticity. The Illinois Geological Survey has made an intensive study of the value of these tests for judging the performance characteristics of the coal as actually utilized. To date, three reports 1 2 3 have been is- sued, and another is being prepared. The present paper briefly summarizes some of the results found in the studies.

Jan 1, 1949

By M. R. Anderton

"A hierarchical four-character code designed for geological and allied data may be used to log exploration drill-holes and store the information on magnetic media. The code is intended for use in semi-free format and permits the collection of as much, or as little, data as the geologist may require for the purpose in hand. A method of data storage by variable length records is discussed.Information may be retrieved by means of a simple enquiry language. Optional output facilities could allow the retrieval of data in a form suitable for direct input to a contouring package. The enquiry parameters and interrogation program can thus provide the interface between the data bank and associated application systems."

Jan 1, 2014