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By F. R. Scauzillo

Equilibrium data which should be useful in the design and/or evaluation of glycol dehydration units were prepared from an analysis of various published data and the correlation of these data by the use of the thermo-dynamic equilibrium ratio. The equilibrium ratios of water are used to solve the glycol absorber problem; such solutions are necessary to define the number of trays and the glycol circulation rate needed to meet drying requirements. Activity coefficients were obtained which relate directly to the equilibrium ratios of water in the water-TEG-natural gas system. These activity coefficients have been used to calculate the equilibrium dew points for aqueous TEG concentrations of 60 to 99.9 weight per cent for the temperature range of 40° to 120° F. They also provide a means of calculating equilibrium ratios for water in the water-TEG-natural gas system; this applies to any desired TEG concentration and to the temperature range from 40° to 120°F. INTRODUCTION During the last several years, the drying of natural gas with aqueous triethylene-glycol (TEG) solutions has become very prominent. Most users of TEG as a drying agent have been satisfied with the performance of TEG solutions at the conditions used; however, there always has been some discussion of the drying ability of TEG solutions at conditions not commonly encountered such as temperatures below 50° or 60°F, but more particularly temperatures above 100°F, and pressures above 1,000 psia. Today, when higher wellhead temperatures such as 120°F are more commonly encountered many are skeptical of TEG's ability to dry sufficiently well to provide dew points around 32°F, which is generally the maximum tolerable when attempting to dry a gas to contract specifications of 7 Ib/MMscf. These views probably have evolved to some extent from the days when suppliers would not guarantee dew-point depressions in excess of 65° to 75 °OF. Also, the feelings about TEG drying may have arisen from the lack of information about the equilibrium relation of water in the drying operations. Porter and Reid' have reported equilibrium data for a 95 per cent TEG solution, while Townsend2 reported equilibrium data for 95, 98 and 100 per cent TEG solutions. Townsend also presented a calculational method which obtains activity coefficients in the liquid phase and, subsequently, the equilibrium water content of a saturated gas over glycol from published3 atmospheric dew points. Wise, Puck and Failey' presented activity data for the water-TEG system at atmospheric pressure. In the past, the equilibrium ratios published for water in a 95 per cent by weight aqueous TEG solution have been used indiscriminately by many for all concentrations of TEG encountered in gas drying operations. Since essentially all such gas operations require the use of more concentrated TEG solutions, a study was undertaken to correlate the existing equilibrium data for aqueous TEG and gas systems and to provide some means of calculating the equilibrium ratio of water in the natural gas-water-TEG system where TEG concentrations were other than 95 per cent. The data presented herein consider only the equilibrium drying ability of the TEG solutions and do not consider the effect of temperature and pressure on the tray eficiency of contactors. In other words, this paper is concerned primarily with the development of the equilibrium relationship between water in the dried natural gas and the water in the lean TEG entering the top tray of the absorber. BASIC EQUILIBRIUM RELATIONS A relationship which relates the K value of water in the natural gas-water-TEG system to the vapor pressure of water at the system temperature, the total pressure of the system and the activities of the liquid and gas phases has been evaluated. It is well known that, for any component of a mixture at equilibrium between a gas phase and a liquid phase,

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young's modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young's modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman' noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig' observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity' or the paramagnetic susceptibility.' Likewise, no one has noted a change in crystal symmetry. In the present investigation Young's modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,' and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.' The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder' the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young's Modulus: For measurement of Young's modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young's modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young's modulus at 25°C, Fig. la, is 28.2~10" dynes per cm' (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;' the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By I. Iwasaki, K. A. Nataratjan

In a previous paper, ozone was shown to remove residual xanthates in flotation pulp solutions as well as to destroy the xanthate coating on bulk copper-nickel sulfide concentrates before differential flotation (Iwasaki and Malicsi, 1985). The oxidation and decom- position mechanisms of xanthate solutions in the presence of commonly used oxidants such as oxygen, chlorine, hypochlorite, bromine, iodine, and hydrogen peroxide at different pH levels have been reported in the past (Rao, 1971). Most of these studies have been restricted to xanthate solutions of pH less than 10. Very few references are available on xanthate decomposition in highly alkaline (pH > 12) solutions (Jones and Woodcock, 1983; Philipp and Fichte, 1960; Tipman and Leja, 1975). No systematic study of xanthate oxidation by ozone has been reported, although its use in flotation has been recognized of late (Allegrini et al., IWO; Ishii et al., 1970; Matsubara et al., 1978). To improve the efficiency of ozone use in flotation, it is essential to understand the mechanisms involved in the decomposition of xanthates with ozone, more specifically, to establish the stoichiometry and decomposition rate. In the present work, a preliminary attempt was made to investigate the effect of pH on xanthate decomposition, and probable mechanisms of xanthate oxidation with ozone.

Jan 1, 1986

By K. M. Busen, J. Lindmayer

A heterojunction model is suggested for descrihzng the electronic conditions at oxide -semiconductor interfaces. Detailed study of the silicon oxide-silicon interface shows that the heterojunction model explains many experimental facts; however, it is necessary to assume that a transition layer exists at the interface. It will he demonstrated that ionic contrbution way also he present. Extended low-temperature heating stabilizes the oxide to a charge carrier density in the order of 10' cln-: determined by the heterojuncton model. OXIDIZED semiconductor surfaces are widely used, since they offer technological advantages and "passivate" the surfaces of semiconductor devices. However, it has been recognized that there are always n-type inversion layers formed in the silicon oxide-silicon system, which must be regarded as a definite disadvantage. An added complication is the "instability" of these inversion layers;' the inversion layer appears to vary with the processing and they change at temperatures as low as 100" to 200°C This paper will point out that the inversion layer is a result of the dissimilarity of the contacting materials and therefore must always be present. The dissimilarity is the essence of the heterojunction or electronic model and involves directly the structure of the materials involved. In addition, one finds the contribution from ions; this disturbance, however. can be eliminated for the case of silicon oxide-silicon interface. The strength of the inversion layer or channel will be expressed in terms of the density of elementary charges per square centimeter, N*, maintaining the channel. The next section contains the formulation of the heterojunction model by assuming a contact between two homogeneous materials. This calculation should not imply that silicon oxide is homogeneous; it serves only to point out the general properties of the electronic model. Following the electronic model, the practical case of the silicon oxide-silicon interface will be discussed. I) THE HETEROJUNCTION MODEL Contacting an oxide with a semiconductor, a work-function difference must be accommodated. Fig. 1 represents the oxide and the semiconductor before and after contact. When the contact has been made, one finds that qVi + qV, = A@; i.e., the work-function difference is distributed between the oxide and the semiconductor. Normally, the work-function difference appears on the wide-bandgap material, but in the present case the oxide is thin and far from being a single crystal. Accordingly, a significant fraction of the work-function difference must appear on the semiconductor. The work function of silicon2 is about 4.8 ev, but we shall not assign any particular work function for the oxide as it may vary. However, oxides usually have lower work functions and therefore the potentials must build up in the manner shown in Fig. 1. Such an argument predicts that the inversion layer must be n type, as opposed to the clean surface which is p type. Another important factor to be considered is that the oxide is disorderly and therefore contains many trapping levels. As a result, the charges in the oxide arise primarily from the change in trap occupation, while on the semiconductor side the space charge is composed of mobile free electrons. The consequence of this fact is that a change to another thermal equilibrium will require some time, dictated by the traps in the oxide. The conditions can easily be calculated on the semiconductor side. Assuming an intrinsic semiconductor, Poisson's equation is

Jan 1, 1965

By I. Iwasaki, K. A. Smith

A chlorination process for treating metal sulfide flotation concentrates is described. The process involves low temperature chlorination combined with sulfur chloride conversion and selective oxidation to produce nonferrous metal chlorides, elemental sulfur, and ferric oxide in a three-stage fluidized bed reactor. The nonferrous metal chlorides may then be water leached, separated, purified, and electrolyzed to recover copper and nickel metals and to regenerate chlorine for recycling.

Jan 1, 1986

By GLENVILTE A. COLLINS

(Presented at a Meeting of the Spokane Local Section of the Institute, Feb. 17, 1912, and accepted for publication in the Bulletin. ) WHILE I am not at the present time engaged in active mine-management, my duties permit of extensive study and examination of many mines, mills, and reduction-works in various places throughout the United States. Being much interested in efficiency-work in general, and an ardent reader of writings on this subject by Frederick W. Taylor and others, as applied to manufacturing-plants, and having served my apprenticeship from mucking to the engineering design of ore-dressing and underground plants, I hope that this paper will lead others to investigate the field more fully, to the improvement of general mine- and mill-operations, as well as the advancement, intellectually, physically, and financially, of the employee and his relations with the employer. If a man who is prepared to look closely and observe broadly starts in Canada and zig-zags from camp to camp to southern Mexico, taking time casually to inspect mines, mills, and smelters, he will be pitifully impressed by the great difference in customs, and the general waste of labor, time, and money throughout the country. He will so seldom observe a dollar's worth of results given in exchange for a dollar spent that he will form a poor opinion of operating-efficiency and management. This highly-scientific department, requiring an amount of skill and executive ability equaled in few, if any, of the professions, certainly falls short of the standard established in our greater manufacturing industries. It is easily said that this is due to the diversity of conditions in mining, milling, and smelting. But on second view it must be admitted that there is room for tremendous improvements in nearly every mining-organization. The proposal of such improvements is often met by the argument that any mine

Sep 1, 1912

Members whose deaths were reported from Apr. 5, 1920, to Apr. 9, 1921. Elected Died 1916 ALLAN, FERGUS L 1920 1916 ATKINSON, CHESTER 1921 1920 BARBERENA, RAUL R 1920 1918 BARKER, F. L 1920 1914 BELL, D. A. S 1920 1920 BREWSTER, GEORGE AUGUSTUS 1920 1917 BRIGHAM, EDMUND D 1921 1915 CARROLL, D. J 1920 1897 CHAPMAN, ROBERT H 1920 1919 COOPER, W. G 1920 1918 CRITCHLOW, EDWARD B 1920 1917 CURTIS, WILLIAM L 1920 1893 DARSIE, JAMES 1920 1892 DELANO, WARREN 1920 1877 DEWEY, FREDERIC P 1921 1917 ENEBO, BENJAMIN A 1920 1896 FAWCETT, JAMES H 1920 1906 FRASER, A LEXANDER J . 1920 1889 GARLICHS, HERMAN 1921 1893 GILLET, LORENZO M 1920 1886 HALDEMAN, HORACE L 1920 1914 HALL, HARRY E 1919 1905 CHART, C. R 1920 1906 HART, PHILIP E 1920 1877 HARTRANFT, SAMUEL S 1921 1914 HICKMAN, E C 1920 1919 || INMAN, WILLIAM ELLIOTT 1921 1920 JETER, J. TINSLEY 1920 1918 JOHNSON, CHARLES W 1920 1916 JOHNSON, FRANK E 1920 1913 KING, FREDERICK G 1921 1887 KNAPP, GEORGE F 1920 1902 LAMB, RICHARD 1920 1880 LANE, J. S 1920 1920 LECKIE, WILLIAM 1920 1887 LEVAT, DAVID 1921 1882 LAWRENCE, BENJAMIN B 1918 1916 LEYNER, J GEORGE 1920 1871 LYMAN, BENJAMIN S 1920 1903 MCCHRYSTAL, JOHN H1920

Jan 1, 1923

By L. K. Eigenbrod, F. Notaro

Enactment of Public Law 91-173 (Federal Coal Mine Health and Safety Act of 1969) has placed new responsibilities on the mining industry. The new law, aimed at eventually solving the problem of pneumoconiosis, sets new respirable dust standards at 2 mg per cu m. Techniques employed to date have been shown to lack total effectiveness in meeting the prescribed standards. Since it is possible that even the new standards will eventually have to be lowered to effectively attack the medical problem, the need for new and more reliable methods of assuring clean respirable air will intensity. This paper presents, in a preliminary manner, both the present technical capability and growth potential of cryogenic technology for supplying miners with clean breathing air. Work with two sizes of prototype supplied-air (cryogenic-liquid) respiratiors in Union Carbide's Fawn Coal mine, will be described. Other potentially fabricable systems will be discussed and a preliminary assessment made of the potential cost of introducing cryogenic air breathing systems in coal mine service.

Jan 1, 1972

By P. E. Arnold, G. S. Ansell

RELAXATION in metals has been studied in detail by many workers in recent years.1-5 These studies have shown that there is an energy-loss peak observed in a metal placed in mechanical resonance at low frequencies which may be correlated with various metallurgical processes. These experiments have been largely used to study single-phase materials. In order to study the effect of a finely dispersed second phase in a metal matrix upon this phenomenon, the relaxation behavior of an aluminum-aluminum oxide SAP-Type alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions was investigated by the use of internal-friction measurements. The alloys studied, designated MD 2100, consist of a matrix of commercial-purity aluminum containing a finely dispersed second phase of aluminum oxide. The aluminum oxide is present in this alloy in the form of fine platelets approximately 130A units thick and several microns on edge. The mean free path betwen dispersed platelets is approximately 0.5 p. The grain size of this alloy is extremely stable at temperatures as high as the melting temperature of the aluminum matrix. In the as-extruded condition the grain diameter is several microns, while in the recrystallized condition it is several millimeters in diameter. The damping characteristics of the alloy samples were determined using a torsional-pendulum device. The internal-friction constant was determined for this alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions over the temperature range from 343" to 923°K at frequencies of 0.9, 1.3, and 1.8 cycles per sec. An internal-friction peak was observed in testing the fine-grained alloys which was not observed for the coarse-grained alloys. This peak, which might be associated with a type of grain-boundary relaxation, was observed at each of the three different test frequencies for the fine-grained sample. The temperature at which the relaxation peak occurred for each of the three different frequencies is shown in Table I. From these data an activation energy of relaxation for each pair of frequencies was determined by comparing the temperature shift of the relaxation peak with frequency between each of the test frequencies, assuming that an Arrhenius-type rate equation is applicable. The activation energy of relaxation determined from these data is also shown in Table I. The mean value of the activation energy was about 6 kcal per mole. The activation energy for the relaxation process determined in this investigation indicates that the relaxation associated with the grain boundaries in this aluminum-aluminum oxide SAP-Type alloy is quite a different process than grain boundary relaxation in single-phase aluminum alloys. In these latter alloys, the activation energy for relaxation has been found to be the activation energy for self-diffusion, approximately 36 kcal per mole1,2 Where the activation energy is the same as the activation energy for self diffusion, it has been proposed that the relaxation phenomena is dependent upon vacancy formation and motion. It is apparent therefore, that, in this aluminum-aluminum oxide SAP-Type alloy, the relaxation must be due to another type of atom transport. It has been shown previously in studies of the high-temperature, low-stress, steady-state creep behavior of as-extruded aluminum SAP-Type alloys, that the activation energy for steady-state creep is one that may be characterized by the nucleation of dislocations from the grain boundaries. It is proposed that the relaxation behavior observed here is due to a similar effect. In this case, the internal-friction peak is a resonance behavior due to the time-dependent nucleation of dislocations from grain boundaries in the sample. A process of this type would have an activation energy which is undoubtedly stress-dependent and of the form Q = Q, + (dQ/du)u

Jan 1, 1962

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By J. D. A. Morrow

This discussion relates to the distribution of coal under the di , of the U. S. Fuel Administration beginning Apr. 1, 1918. At t' L a definite method of controlling and directing distribution was put int effect. Prior thereto, although some of the machinery utilized was in operation, especially in the few weeks immediately preceding' Apr. 1, distribution had not been effectively and comprehensively organized. The writer was called to the Fuel Administration by Dr. Garfield about the first of February, 1918, to assume general direction of the distribution of coal for the Fuel Administration, to develop the general plans, and to obtain practical men to assist in this work and in carrying through the program finally devised. A study of the situation and conferences with the Fuel Administrator and leading men in the business made it plain that it would be necessary to begin at the bottom, measure the undertaking, develop plans to meet the need thus shown, and build an organization to effect the distribution required. This work had to be done under war pressure in the midst of a bad coal shortage. The successful performance of such a task is always primarily a matter of putting competent men in the right places and giving them the power and opportunity to function properly together. In the Distribution Division of the U. S. Fuel Administration, the men who were chiefly responsible for whipping plans into practical form and then for carrying out these plans were A. W. Calloway, of Baltimore, President of the Davis Coal & Coke Co., who served as the Director of Bituminous Coal Distribution; S. Lovell Yerkes, of Birmingham, Alabama, Secretary of the Grider Coal Sales Agency, who assumed general charge of distribution while the new plans and organization were being perfected and then became the Assistant Director of Bituminous Coal Distribution; Warren S. Blauvelt, of Detroit, who was Director of Coke Distri. bution; A. S. Learoyd of New York, Director of Anthracite Distribution, in connection with the Anthracite Committee, consisting of Joseph P. Dickson, President of Dickson & Eddy, Chairman; S. D. Warriner, President of the Lehigh Coal & Navigation Co., and W. H. Richards,

Jan 1, 1920

By R. W. Raymond

(Chattanooga Meeting, October, 1908.) THE immense commercial value of the Gayley dry-blast process has been established beyond controversy. The testimony of practical blast-furnace managers, on both sides of the Atlantic, agrees that it reduces the cost of pig-iron about $1 per ton; but from the same testimony it appears that this direct economy does not by any means cover its commercial advantages-in fact, that under conditions frequently encountered in practice, it presents other benefits of even greater immediate financial importance. To this point I shall recur in a later part of the present paper. The history of the reception given to this invention, especially on the other side of the Atlantic, has repeated an experience familiar to American engineers. First, the reports of our practice were rejected as theoretically impossible, according to generally accepted notions and formulas; then the figures were reluctantly accepted ; and finally the attempt has been made to explain how they could have been obtained. As to the Gayley dry blast, we Americans have been for several years in the last stage of the discussion, and the rest of the professional world is rapidly coming to it. Meanwhile, the remark has been repeatedly made that, whatever Mr. Gayley's process may turn out to be worth, it was not an invention on his part, but simply the energetic and persevering execution of a procedure already proposed by others. This question I wish to discuss first in the present paper. I. WHAT DID MR. GAYLEY INVENT Realizing that this is not the place for detailed argument on an issue of patent law, I shall not undertake to quote and criticise the publications prior to Mr. Gayley's first patents. It may be admitted, without such critical analysis, that the possi-

Jan 1, 1909

By CHARLES SIMENSTAD

COAL preparation, or coal washing, is not a new subject to the Pacific Northwest. Most of the coals mined in this state smaller than lump, and nearly all such sizes mined on the Pacific slope of the Cascade mountains, require washing before marketing. A large proportion is being put through some washing process, but coal washing in this state, has not reached the efficiency it is practicable to obtain. In fields where the coal, as mined, contains less impurities, where working conditions make it practicable to eliminate some of these impurities under- ground, or where a large proportion of the run-of-mine coal is lump, coal preparation does not present the problem it does in our local field. Here the coal is associated with considerable impurities and the slack, or steam sizes, aggregate about 80 per cent. of the output. Therefore, approximately 80 per cent. of the coal mined must be washed to become a valuable fuel. Washing then becomes a major operation, as hand picking of the 20 per cent. of lump is a standard and comparatively simple operation. Some coal beds here are so interstratified with bone, of a more or less massive nature, that hand picking of lump is not economically efficient. In such cases the coal must be crushed fine enough for it to be freed from the bone, so that the two may be separated. Coal cleaning in this field, therefore, must receive skilled attention to purify this fuel and raise its stand- ard. Without greater efficiency in cleaning, the importation of coal from outside the state will be even greater than in the past.

Jan 1, 1926

By T. D. Mueller, F. C. Miller, Jr. Earlougher R. C.

In analyzing pressure buildup tests for field wells producing both oil and gas, the common practice is to use a modification of single-phase flow theory. Validity of such an approximation has been demonstrated for single-well solution-gas-drive systems. This paper indicates that such approximations are also valid for two-well solution-gas'-drive systems. From this it is inferred that the technique can be used for multiple-well systems. A computer was used to simulate the behavior of a two-well solution-gas-drive reservoir to test the validity of the above type of analysis. Simulation results indicate that pressure buildup tests in such a system can be analyzed within engineering accuracy for formation permeability and pressure. A rule of thumb is given for estimating the length of time a well must be shut in for the pressure in a nearby producing well to increase significantly. To observe such an increase, the shut-in well would have to be left shut in much longer than normal. INTRODUCTION An important technique for obtaining data concerning a producing petroleum reservoir is the pressure buildup test. Such a test, when properly conducted and analyzed, provides information on the average reservoir pressure and the permeability in the major drainage area of a well. The theory upon which the analysis of a pressure buildup test is based assumes that the behavior of the fluid in the reservoir is adequately described by the diffusivity equation.1 Use of the diffusivity equation implies that a single fluid of small and constant compressibility is flowing. To analyze a pressure buildup test in situations which involve more than one fluid phase, the single-fluid analysis is extended. This paper verifies the extension of pressure buildup analyses to two-phase, two-well systems. Miller, Dyes and Hutchinson1 have presented a technique for analyzing pressure buildup tests in circular bounded reservoirs. Their method requires that the reservoir be producing at pseudo-steady state (constant pressure gradients) prior to shut-in. An alternate reservoir model, presented by Horner,2 assumes that the reservoir is infinite. The Homer model does not assume a Pseudo-steady state prior to shut-in, but the assumption that the reservoir is infinite implies that the average pressure can be determined only if the total production prior to shut-in is small compared to the total fluid originally present. Limitations imposed by the pseudo-steady state and infinite reservoir assumptions are avoided by the technique proposed by Matthews, Brons and Hazebroek.3 Their method can be used to calculate both the Permeability and the average pressure in bounded single-well systems which are not necessarily at steady state. They also suggested determining the average pressure of a multi-well reservoir producing from pseudo-steady state by volumetrically averaging the static pressures of the individual wells. Matthews and Lefkovits4 used numerical simulation techniques to verify that this method does produce adequate results for single-phase, multiple-well systems. Perrine5 proposed modifications to the single-phase theory so that pressure buildup tests in multiple-phase systems could be analyzed. He suggested replacing the single-phase mobility (k/µ) by the sum of the mobilities of the individual phases, and replacing the fluid compressibility by an average compressibility weighted by the saturations of the separate phases. By using numerical techniques to solve the two-phase flow problem for a single-well system, he concluded that this approximation gives results within engineering accuracy. More recently, Weller6 has shown that, for a gas-oil system with a single well at the center of a circular reservoir, pressure buildup tests can be analyzed adequately by using the modification proposed by Perrine. Feller's results also indicate that, as the gas saturation increases, this analysis becomes less accurate. To date, no evidence is available to show that the Perrine approximations can be combined with the Matthews-Brons-Hazebroek technique to calculate the average pressure of a multi-well,

By K. A. Natarajan, I. Iwasaki

The effect of poisoning on the behavior of platinum electrodes in redox potential measurements in metallurgical systems was studied in the presence of such inorganic surfactants as cyanide and sulfide and such organic surfactants as dodecylammonium acetate, trimethyldodecylammonium chloride, potassium ethyl xanthate, and potassium diethyl dithiophosphate (Aerofloat®). These chemical species represent, more or less, typical constituents encountered in leaching, flotation, and sewage treatment systems. Triangular wave voltammetry was used as the experimental technique to study the nature of poisoned surfaces. Among the species studied hydrogen sulfide and dodecylamine were found to form a resistant surface film affecting charge transfer. Platinum electrodes appeared to have a weaker tendency to adsorb sulfide species in alkaline pH ranges, while cyanide, xanthate, and dithiophosphate affected the normal electrode behavior differently. Possible methods of reactivation of a poisoned electrode by mechanical cleaning are suggested.

Jan 1, 1974

By G. W. Toop

In a recent publication,31 Darken has derived an equation to describe thermodynamic behavior in ternary metallic solutions with compositions near pure component 1: Eq. [I] is understood to be a general equation, consistent with the ternary Gibbs-Duhem equation, which is proposed as a logical formalism in view of observed behavior in some binary metallic solutions31'32 rich In Eq. and am are constants obtainable from the 1-2 and 1-3 binaries. The parameter 023 may be determined from measurements on the ternary The purpose of this discussion is to compare Eq. [I) or [3] with other ternary formulations involving binary terms, within the regions of validity of Eqs. [I], [2], and [3]. First, the ternary point is considered to be at the intersection of two composition paths, one with constant N1 and another with constant N2/N3 as shown in Fig. 10. The terms in Eq. [3] may be related to the binary points shown by multiplying the first term on the right-hand side of Eq. [3] by N2 (1) /l -N1, the second term by the third term by and the fourth term by each multiplier being unity: It should be noted here that no suggestion has been made that either the binary or the ternary systems form regular solutions. However, Eq. [5] and hence Eq. [3] shows that the contribution made to the ternary excess free energy from the 1-2 and 1-3 binaries has the same form as for a regular ternary system.1 Before considering the term a23 for the above case, a second geometrical relationship is examined with the ternary point at the intersect ion of three composition paths with constant N1/N2, N2/N3, and Nl/N3, respectively, as shown in Fig. 11. For this geometry, ternary values of NZ and N3 in terms of the binary values shown may be substituted into Eq. [I]. Then by making use of identities of the form Eq. [6] contains terms that are similar to those in a ternary regular solution formulation34 based on the geometry shown in Fig. 11. Although at finite concentrations, unless the 1-2 and 1-3 binaries form

Jan 1, 1968

By K. Harms, T. D. Jones

TO unload large tonnages of lead bullion cast in 100-lb. bars is a problem which has confronted the lead refineries for many years. The bars, on arrival, must be restacked for unloading by truck or hand-charged to charging machines. Selected crews of labor, capable of working at sustained speeds for five- or six-hour periods, are required for this exhausting task. Due to the fatigue involved crew personnel changes rapidly. During the war it became increasingly difficult to maintain crews, especially in critical labor areas, so that the development of casting and shipping ten-ton lead blocks from the smelters to the refineries became a must in our operating program. For many years lead refineries, when making interdepartment or intradepartment transfers, have cast lead blocks weighing five or ten tons which are easily handled by crane by merely attaching the crane hook to a steel anchor embedded in the frozen lead blocks. In previous years, the practice was to use regular smelter slag pots which, due to their rounded shape, produced what were called "buttons" by the refinery personnel. The button-type blocks were unsafe as they rolled and tipped easily and were unsatisfactory for stacking since no piling pattern could be followed. To remedy this situation, flat-bottom molds came into general use and later the bottoms were made concave to prevent slipping.

Jan 1, 1946

By Walter S. Weeks

CONFUSION appears to exist in the discussions of fan testing because engineers do not agree on what energy should be credited to the fan in certain cases, and because certain terms that are used in the discussions seem to have double meanings. The purpose of this paper, therefore, is to discuss the useful energy that should be credited to the fan and the methods of determining this energy, and to suggest changes in nomenclature for the sake of clearness. The instruments commonly used in the measurement of fan pressures are the manometer, the static tube, and the impact tube. The static tube is a tube with small pinholes in it. When connected to one leg of the manometer and placed in the air current with the holes facing at right angles to the direction of the current, this tube causes the manometer to register the static pressure, unaffected by the impact of the air. The impact tube is a tube with an opening that faces the air current. When connected to one leg of the manometer, this tube causes the manometer to register a pressure which is the static pressure modified by the impact of the flowing' air on the end of the tube. If the static tube is connected to one leg of the manometer and the impact tube to the other leg, and both instruments are inserted close together in the air current, the static pressure is eliminated and the manometer registers the impact pressure. The efficiency of a fan is the percentage of the expended power utilized in useful work. The items to be included as useful work are a matter of convention, and as the conventions are not universal I feel that the matter is open to discussion.

Jan 1, 1929

By M. T. Hepworth, T. P. Papazoglou

Hydrogen diffusion in hcp and bcc titanium in the temperature range 610° to 900°C was measured by reacting cylindrical specimens of high-purity titanium at constant temperature with small constant pressures of hydrogen of the order of a few Torr. In the range 0 to 6.7 at. pct H in hcp titanium, the diffusion coefficient D in sq cm per sec is given by: where T is in °K and R in cal per g-atom OK. Only three measurements of diffusivity in bcc titanium were made: at 900' : the diffusivity in ß titanium was found to be 1.8 x 10-4 sq crn per sec. McQUILLAN1 has studied the constitution of the Ti-H system and reported the concentration of hydrogen as a function of pressure of hydrogen and temperature. He found hydrogen absorption was reversible and rapid at temperatures above 500°C in both crystallographic modifications, the a (hcp) phase and the ß (bcc) phase, with the latter phase stabilized by hydrogen additions. Wasilewski and Kehl 2 measured the diffusivity of hydrogen in hcp and bcc Ti-H alloys. For bcc alloys, they reacted cylindrical specimens of titanium with hydrogen gas at 1 atm pressure. They measured the rate of absorption of hydrogen isothermally on specimens ranging from zero hydrogen content when above the transformation temperature to hydrogen contents sufficient to stabilize the bcc phase when below the transformation temperature. By integrating Fick's second law for a cylindrical geometry, assuming a diffusion coefficient independent of composition, they calculated diffusivities as a function of temperature. In the range 650" to 1000°C their results in bcc titanium yielded the expression: where D is in sq cm per sec, T in OK, and R the gas constant in cal per g-atom-OK. Their studies on the hcp a phase were conducted by exposing long cylindrical titanium specimens to hydrogen at a sufficiently high pressure to establish a surface layer of fl phase 80 to 120 u thick for the duration of an isothermal experiment. Concentration profiles were then determined by hydrogen analysis from chips obtained upon machining quenched specimens. The diffusivity of hydrogen was then calculated yielding the expression: The present investigation was undertaken principally to redetermine the diffusivity data on a titanium by a direct absorption from the gas phase at sufficiently low hydrogen pressures to avoid the presence of a surface bcc phase and also to check the diffusivity data at low hydrogen concentrations in the bcc stmcture. EXPERIMENTAL PROCEDURE High-purity electrolytic sponge titanium (99.9 pct) of BHN 91 was arc-melted, forged, rolled, and machined into cylinders of final hardness, upon annealing, of BHN 92. Cylindrical specimens of two sets of dimensions were used: 1.524 by 2.931 cm and 1.905 by 3.663 cm diam and length, respectively. The experimental apparatus used for annealing specimens and for admitting known amounts of hydrogen at constant pressure is shown in Fig. 1. In a typical experiment, a specimen was lightly abraded with fine-grain silicon carbide, washed with water and detergent, and then thoroughly degreased with reagent-grade tri-chlorethylene and acetone. The specimen was suspended by a Chrome1 wire in the center of a quartz furnace tube, without contact with the tube, and heated to 925°C (as measured by a thermocouple adjacent to the specimen, outside the tube) for a period of at least 4 hr under a vacuum of from 10-6 to -7 Torr as measured by an ionization gage. The furnace temperature was then adjusted to the temperature chosen for the particular diffusion study and the specimen allowed to equilibrate thermally. Hydrogen was then ad-

Jan 1, 1969

By R. M. Rose, D. P. Ferriss, J. Wulff

Single crystals of tantalum, tungsten, and the binary alloys thereof were grown by electron-beam zone melting and tested in tension between 77° and 373°K. The ductile-to-brittle transition temperature increased sharply with solute concentration, for both tungsten-rich and tantalum-rich alloys; apparently, the maximum transition temperature exists near the 50 pet concentration. Twinning was observed to be a consequence of cleavage-crack propagation. Cleavage occurred on(100)planes, and extensive tearing and "river markings" were present. The onset of brittleness could not be associated with any change in deformation mode, the yield point phenomenon, or the large rise in yield stress with decreasing temperature. Cleavage was observed to initiate at either the specimen surface, or subgrain boundaries. The observation was made that the grain boundaries of Polycrystalline materials are probably even better as nucleation sites for fracture, and are responsible for brittleness at high temperatures and lower solute concentrations than those of the corresponding single crystals. TUNGSTEN and tantalum, the two high-melting neighbors in the third transition period of the periodic table, present striking contrasts. Although both are bee, tungsten has far higher elastic moduli, and the highest ductile-to-brittle transition (DBT) of all the pure metals.' Tantalum, however, is ductile at liquid helium temperatures. Large strain aging and yield point phenomena are observed in tantalum,2,3 but only to a lesser extent in tungsten.4 Tungsten work-hardens at a high rate,5 whereas this effect is negligible in tantalum.' Since the mutual solid solubility of these two metals is complete,7 and no ordering has yet been reported in the binary system, the possibility of depressing tungsten's DBT by tantalum additions was considered. Also, tungsten additions to tantalum could produce hard, high-melting alloys which might be ductile at room temperature. Such alloys offered excellent bases for complex alloy development, particularly with regard to the effect of rhenium on Group VI metals.8"10 In addition, there was the opportunity to examine flow and fracture modes in the vicinity of the DBT, with particular emphasis on the correlation between brittleness and fundamental deformation mechanisms. Myers11 has reported that recrystallized alloys with up to 10 pet W in tantalum are ductile at room temperature, but alloys with 20 pct W could not be swaged at temperatures as high as 500°C. The whole spectrum of Ta-W alloys has been surveyed by Braun, Sedlatschek, and Kiefferl2 using sintered powder compacts. In addition to some physical properties they reported a maximum hardness at about 50 at. pet W, dropping to much lower hardness levels for the pure components. They were able to cold work tantalum-base alloys with as much as 30 pet W and to warm work tungsten-base alloys with up to 20 pet Ta by procedures similar to those used for pure tungsten. EXPERIMENTAL In order to study deformation modes and to keep the impurity concentrations at a minimum, electron-beam zone melting was used to prepare single crystals of high purity. The electron-beam zone melting apparatus is similar to that described by Calverley, Davis, and ever" and incorporates a grid control rectifier to maintain control of emission current. Pure metals were refined by making three zone passes at 4 mm per min up the rod. Alloys were prepared by melting together wire of one constituent on a previously melted rod of the major constituent. Subsequently, two zone passes were made in opposite directions to level the composition after the manner suggested by pfann.14 Purification of the starting materials was accomplished by evaporation of the several impurities, and the degree to which this was accomplished is indicated in the chemical analyses of Table I. The uniformity of composition along a zone levelled rod was within the i 1 pet accuracy of the fluorescent X-ray technique used to determine composition. Crystallographic orientation of the

Jan 1, 1962