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[Alphabetic Section (Page 689): The letter immediately following the member's name indicates grade: M-Member, A-Associate, J-Junior. The numerals following member's grade indicate year of election. The letter following year of election indicates primary Divisional affiliation: A-Mining & Exploration F-Coal B-Minerals Beneficiation G-Petroleum C-Iron and Steel H-Industrial Minerals D-Extractive Metallurgy J-Council o f Education E-Institute of Metals K-Council o f Economics]

Jan 1, 1961

By A. Satter

Studies of wellbore heat transtnission during the injection of a hot fluid, as either gas or liquid, have appeared in he literature. The present investigation takes into account the effect of condensation, which is of practical sig-nificance when considering steam injection operations. Calculation procedures are given for superheated and for saturated and undersaturated steam. Effects of injection rate, time, pressure, temperature and depth of a well on heat losses have been analyzed. The benefits of using a packer are discussed. Also presented are correlations for estimating heat losses involved during injection of saturated steam. INTRODUCTION Studies of wellbore heat losses during the injection of a hot fluid have appeared in the literature. Ramey' has presented a useful solution for calculating temperature of a heated gas as a function of depth and injection time. Ramey and others have also presented solutions for the hot liquid case.'. ' No method is available to take into account the effect of condensation, which is of practical significance when considering steam injection operations. This paper presents a method of estimating the quality of a condensing fluid as a function of depth and time. The approach is basically the same as that used by Ramey. The following injected fluids and conditions are considered in this study: 1. Injection of superheated steam A. Decrease in temperature until cooled to the saturated state B. Condensation until condensed completely into hot (saturated) water 2. Injection of saturated or undersaturated steam; condensation until condensed completely into hot (saturated) water. Although this investigation does not include cooling of water after steam is completely condensed, Ramey's solution for the hot liquid case can be used for this purpose. The effects of various process variables on heat losses During the injection of steam into a well are investigated. THEORY QUALITY OF CONDENSING STEAM Predicting the behavior of condensing steam flowing down the injection wellbore requires an estimate of the quality of steam, i.e., the mass fraction of vapor in the mixture. Let us divide the total depth of the injection well into several segments which might be, but do not have to be, of equal magnitude. Consider condensation within a given depth interval AZ, the bottom of which is located at a depth Z from the surface (Fig 1). The following equation, derived in the Appendix- relates the quality of steam at the bottom of an interval to that at the top of the interval:

Jan 1, 1966

[Alphabetic Section (Page 1): The letter immediately following the member's name indicates grade: M-Member, A-Associate, J-Junior. The numerals following member's grade indicate year of election. The letter following year of election indicates primary Divisional affiliation: A-Mining & Exploration F-Coal B-Minerals Beneficiation G-Petroleum C-Iron and Steel H-Industrial Minerals D-Extractive Metallurgy J-Council o f Education E-Institute o f Metals K-Council o f Economics]

Jan 1, 1961

By J. J. Frawley, W. J. Childs

The dynamic nucleation of supercooled bismuth and Bi-Sn alloys has been studied over a frequency range of 15 to 20,000 cps. For low-frequency vibration, a minimum vibrational energy was required for enhancement of nucleation. Above this critical energy, the dynamic supercooling was less than static supercooling showing that vibration promoted nucleation. The amount of dynamic supercooling continued to decrease with increasing vibrational energy until a minimum or threshold value was reached. This minimum value of supercooling for nucleation remained constant joy all further increases in vibrational energy. For higher frequencies, similar results were observed. This behavior has been related to the necessity of cavitation for dynamic nucleation. When a liquid is cooled to a temperature below its equilibrium melting point, the solid phase is more thermodynamically stable. However, for solidification to occur, a two-step process, nucleation and subsequent growth of the solid phase, must occur. When a liquid is supercooled, that is cooled below the equilibrium melting point, the controlling process for solidification to begin is the rate of nucleation. Once nucleation has occurred, the solidification process is controlled by the rate of growth. Nucleation can be induced by two factors: either by a catalyst or by the use of mechanical shock. Numerous investigators1-4 have studied the effect of nucleation catalysis but much less systematic study has been made of nucleation by mechanical shock waves. The influence of vibrations on grain size in castings and ingots has been studied by many authors but no clear understanding of the mechanism or accurate prediction of the effect has been presented.5 It would be intuitively expected that the further the departure from equilibrium (i.e., the greater the supercooling), the easier it would be to induce nucleation. This has been quantitatively demonstrated both by walker6 and later by Stuhr,7 that the greater the degree of supercooling the easier it is to nucleate by a shock wave. Stuhr also attempted to obtain the mechanical energy required for nucleation of bismuth as a function of supercooling. He vibrated a crucible containing supercooled metal at low frequencies and various amplitudes and noted the corresponding dynamic supercooling obtained. The amount of supercooling was inversely proportional to the mechanical energy applied. Limitation of his experiment was the problem of the confinement of the liquid in the crucible without splashing and minimizing other unwanted modes of vibration. Tiller et al.8,9 did similar work on tin and Sn-Pb alloys using an electromagnetic stirring device. Their conclusions were that the magnitude of the magnetic field strength did not affect the amount of undercooling at which nucleation was initiated. While conclusive experimental results have been lacking to explain this effect of mechanical vibration on inducing nucleation, a number of theories have been proposed. Two of these theories are discussed below. 1) The Change in Melting:- Point Locally Due to the Change in Pressure (Clapeyron Equation). According to Vonnegut10 the most plausible explanation for the nucleation of a supercooled melt by cavitation is the effect of changing the melting point by a change in pressure. For materials where the volume decreases on solidification, an increase in pressure raises the melting point; for materials which expand on solidification, the melting point is raised for a decrease in pressure, i.e., rarefaction. Using the Clapeyron equation, the melting point of a metal can be calculated as a function of pressure. If it is assumed that the equation can also be used to calculate the temperature of nucleation of a supercooled melt as a function of pressure (i.e., the temperature of heterogeneous nucleation will increase with pressure at the same rate as the melting point), the amount of supercooling required for nucleation will be constant at all pressures as shown in Fig. 1. It is obvious that an isothermal change which results in an increase in melting point results in an equal increase in supercooling. This increase in supercooling may now be sufficient for nucleation. A pressure of 80,000 atm was calculated, using the Clapeyron equation, as the pressure required to increase the temperature of nucleation of nickel by 200°C. According to Lord Rayleigh,11 this very large pressure could be generated for a very brief period of time by the collapse of a cavity. This pressure wave is radiated in all directions from the collapsed cavity. If the temperature of the melt is slightly below its equilibrium melting temperature at atmospheric pressure, stable growth can follow; that is, once nucleation occurs, growth becomes the main driving force of the solidification process. This proposal has been extended to water which expands on freezing by assuming that nucleation occurs during rarefaction following the pressure pulse. This negative pressure pulse should follow immediately after the positive pressure pulse with its magnitude approaching the critical tensile strength of the liquid. The negative pressure developed during this period would raise the melting point of water and thus promote nucleation. Hunt and jackson12 have suggested this for water. Similarly, it could be postulated that bismuth which also expands on freezing could be nucleated during the negative pressure pulse. 2) Nucleation by a High-pressure Phase. An extension of the Clapeyron equation to systems where density decreased on freezing at atmosphere pressure has been proposed by Hickling.13 The phase diagram for water initially shows the well-known decrease in

Jan 1, 1969

By Thorp D. Sawyer

In June 1914, one week before I was to be awarded my sheepskin in upper New York State, I received a telegram from New York City which read "Can offer you position as engineer in Chile at $115 a month contract for one year. (signed) Chile Copper Co." That night, Friday, I took a sleeper to New York and arrived at the Guggenheim Brothers' company office at 165 Broadway, just as it was opening up on Saturday morning. Saturday was no holiday in that era. Presenting the telegram at the office, I was ushered into a sub-executive's office and shown a mimeographed contract which 1) agreed to pay me $115 per month from the date of leaving New York until I returned, and with travelling expenses both ways, 2) fixed a charge of $46 per month for board and lodging in company quarters, and 3) stipulated a contract term of one year with the right to retain my services for another year if the company so elected. While a bit huffed at the year's "kicker" I nevertheless accepted. I was then told to prepare to leave the following Wednesday (June 17) on a United Fruit Co. steamer for Panama. Objecting that I still had to receive my degree on the 17th and had planned a vacation in Ohio for a week or so…

Jan 12, 1960

By Craig R. Barreft, Oleg D. Sherby

The steady-state creep characteristics of pure polycrystalline copper were studied in the temperature range 400" to 950°C and in the stress range 400 to 7000 psi. Tests were conducted in dry deoxidized hydrogen and all specimens exhibited high ductility before fracture. Two activation energies for creep were established as a function of temperature. Above about T/T, = 0.65, the activation energy for creep was 48,000 cal per mole whereas between 0.5 and 0.65 T, it was 28,000 cal per mole. The observed temperature dependence of the activation energy for creep follows the same trend as exhibited by the self-diffusion coefficient of copper in copper single crystals and silver in silver single crystals. It is therefore believed that the rate-cmtrolling mechanism in creep of copper in the stress and temperature range studied is diffusion-dependent and is probably associated with a dislocation-climb process. The low activation-energy region is attributed to enhanced volume difFusion from the presence of dislocations which act as short-circuit paths for diffusion. THERE is extensive experimental evidence1,2 that the activation energy for creep, Q,, for pure poly-crystalline metals tested at temperatures above one half the absolute melting temperature (0.5 Tm) is a constant and equal to the activation energy for volume self-diffusion, Qsd This equality is generally interpreted as meaning that creep in this temperature range is controlled by a dislocation-climb process. The existence of high-temperature creep activation energies not equal to the respective self-diffusion values has been suggested both theoretically3"5 and experimentally.6-8 Two examples of apparent nonequality between Q, and Qsd have been reported for the cases of silver7 and copper,' where activation energies for creep much lower than those for self-diffusion persist to rela- tively high temperatures (up to 0.6 T,). These observations suggest that dislocation climb may not be the only important process in the high-temperature deformation of these metals. That dislocation climb does indeed occur relatively slowly in these two metals due to their low stacking-fault energy has been suggested by many investigators.9-10 Although the creep behavior of copper has been studied extensively at low temperatures, the high-temperature activation energy for creep is not well-defined. The data of Feltham and Meakin8 indicated that Q, is temperature-dependent above one half the melting temperature, equaling a value of -30,000 cal per mole at temperatures up to 550°C and increasing to a value of -49,000 cal per mole at 700°C. No data has been reported above 700°C. The value of 49,000 cal per mole is very near the value of Qsd for copper reported by Kuper et al." as 47,100 cal per mole. In view of the lack of high-temperature creep data and the apparent temperature dependence of Q, for copper the present investigation was undertaken to determine the value of Q, over the temperature range of 400" to 950°C. It was hoped that such a study would clearly document the temperature dependence of Q, and yield significant information as to the nature of the rate-controlling creep mechanisms. MATERIALS AND PROCEDURES The material used in this investigation was high-purity OFHC copper. After rolling and recrystal-lization treatments spectrographic and chemical analyses showed only 0.0008 pct Ag, 0.0002 pctCa, 0.0002 pct H2, and 0.002 pct O2 as trace impurities indicating a purity of greater then 99.995 pct. Specimens were machined from cold-rolled sheet and the gage sections polished with 2/0 emery paper prior to annealing treatments. Annealing was done in both vacuum and dry deoxidized hydrogen atmospheres. No variation in creep strength was found as a result of the different annealing atmospheres. The final annealing temperature was either 700°, 800°, or 1000°C depending on the temperature range to be studied. These treatments resulted in average grain diameters of 0.03, 0.4, and 1.0 mm, respectively. The precise mechanical-thermal history of these

Jan 1, 1964

By Z. Moser, W. Ptak

The experiments were carried out by the method of measuring the electromotive force of concentration cells having zinc as a reference electrode, the second electrode being the liquid alloy Zn-Sn-Cd-Pb. The electrolyte consisted of liquid chlorides and had zinc ions. The measurements were made for seventy -five alloys of different mole fractions within the temperature range of 714° to 877°K. The experimental results enabled the calculation of the activity of zinc in tested solutions. The activities of zinc were calculated by means of Krupkowski's formulas.3 In addition, the formulas for coefficients of activity of zinc, tin, cadmium. and lead as the function of composition and temperature were given. Activity of zinc was compared with the values obtained from experimental results, and good agreement has been observed. On this basis it can be stated that the theoretical formulas are suitable for determining the thermodynamic properties of liquid quaternary metal solutions. IN the metallurgical processes being carried out at present multicomponent liquid metal solutions take part. For the thermodynamic analysis of these processes it is necessary to know the thermodynamic properties of these solutions. Therefore, many experimental and theoretical papers deal with this problem. The theoretical papers are generally based on the assumption that the structure of liquid metals is similar to their structure in the solid state. In this manner the model of liquid solution, consequently described by means of statistical thermodynamics, has been accepted. This method is being lately developed, especially for solid solutions. Statistical thermodynamics was applied among others by Guggenheim 1 for describing the thermodynamic properties. Unfortunately, the formulas of statistical thermodynamics are often not suitable for the interpretation of experimental results. Attention should be drawn to the relations obtained by means of formulas of phenomenological thermodynamics which always have constants derived with the aid of experimental methods. In the case of the multi-component solutions which contain some additions of impurities besides the basic metal, wagner2 introduced interaction parameters. Equations for the relationship between the activity coefficients and composition were also given by Krupkowski." he application of these formulas requires a good knowledge of the thermodynamic properties of the corresponding binary systems. In these formulas, as in Wagner's, there appear constants which should be determined from ex- perimental data. Nowadays, different experimental methods are applied for evaluating the thermodynamic functions of solutions, for instance: vapor pressure measurements, calorimetric methods, and the measurements of electromotive force of concentration cells. In the present paper this last method for evaluating the thermodynamic properties of four-component systems, Zn-Sn-Cd-Pb, was applied. For instance in the case of Zn-Sn solutions Alabyshev and Landratov, 4 Fiorani and Valenti, 5 and ptak6 performed the investigations. The Zn-Pb system was worked out by Kleppa 7 and Cd-Pb and Cd-Sn by Elliot and chipman.' This method was also applied for determining the activity of zinc in ternary solutions. 1) EXPERIMENTAL METHOD The experimental arrangement with detailed description is given in Fig. 1. It consists of resistance furnaces, one serving for melting samples and the other containing the flat-bottomed, measuring quartz tube with the liquid electrolyte. Liquid metals and alloys are in glass supremax tubes, which have an opening in their lower part above the metal level. This opening allows the filling of the tubes by the electrolyte. In these tubes tungsten wires are placed which by means of suitable conductors are connected with a potentiometer. It is assumed that tungsten dissolves Fig. 1—Schematic diagram of the experimental arrangement for the investigation of the thermodynamic properties of liquid metal solutions: 1, resistance furnaces; 2, autotransfor-mers; 3, galvanometers; 4, regulator of temperature; 5, gas purifier with concentrated H2SOP; 6, U-tube with P2O5; 7, thermostats; 8, steel block for thermostating; 9, supremax tubes for alloys; 10, tungsten electrodes; 11, inlet and outlet of argon; 12, measuring quartz tube; 13, tube for melting samples; 14, tube for thermocouple; 15, cover of quartz tube; 16, rubber seal; 17, bottom cover; 18, outlet of electrodes to potentiometer; 19, outlet of thermocouples to potentiometer; 20, upper view of the quartz tube cover; 21, orifices for cover screws; 22, orifice for argon inlet; 23, orifice for thermocouple; 24, orifices for tubes containing liquid metals; 25, inlet for water-cooling system.

Jan 1, 1969

By THOMAS G. FEAR

THE COAL DIVISION started its share of the annual meeting Monday morning with a study of coal classi fication. A. C. Fieldner was in the chair. The report of the tellers of the ballot for division chairman, stating that Thomas G. Fear had been elected to that office, was read by M. D. Cooper. Mr. Fear acknowledged the honor in a few words. In reviewing the history of the Coal Classification Committee the chairman pointed out that this was its third symposium, the last previous one having been held at the 1930 Annual Meeting. Throughout its work the com¬mittee has had the active cooperation of the Canadian workers who are interested in the subject which should result in a uniform scheme of classification in Canada and the United States. F. E. Lathe, of the National Research Council, Ottawa, abstracted the first two papers of the session entitled "Determination of the Alkali-Soluble Ulmins in Coal," by Edgar Stansfield and K. C. Gilbart, and "Moisture Determination for Coal Classification," by the same authors. The third paper "Condition of Water in Coals of Various Ranks"' was presented by its author, A. W. Gauger. Written discussions of these papers were presented by H. C. Porter and Gilbert H. Cady. In the oral discussion which followed, W. T. Thom, Jr., brought out the advisability of considering age as a factor in classification. Mr. Fieldner favored retaining bed moisture as a partial classification basis, stating that a review of many coal analyses revealed a remarkable consistency in this item in samples from a given mine particularly where the moisture content was not high. Mr. Porter pointed out that the structure and porosity of coal often have much to do with its moisture content and that these vary in different parts of a seam, particularly in anthracite. Mr. Gauger expressed doubt as to whether the Stansfield method gives the true moisture content of coal, which is needed for classification purposes.

Jan 1, 1932

By E. A. Gulbransen, W. S. Wysong

The behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a a Or as an important component in alloys in high temperature Oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a micro-balance study of the following problems: (1) the oxidation behavior in the ternperature range of 25 to 550°C (') the reduction with pure hydrogen Of thin Oxide films formed On tungsten, and (3) the volatility Of thin Oxide films On tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the Oxide to to ratio is greater than one, the oxide is not considered protective, ('1 the meta1 readily Oxidizes at temperatures from 30" to 55o°C (3) the oxides WO² and WO³ are reduced at temperatures as low as 500°C. by hydrogen, and (4) the Oxide WO3 is volatile at temperatures from 800 to 1100°C. Literature The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°c. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides, Schei14 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bed-worth's5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.? They have reported that WO3 is the stable oxide in contact with the metallic substrate up to approximately 600°C while wo³ forms first at 7oo°c. Hagg and Magneli8 have recently reported a study of the lattice structures . observed in the tungsten oxidcs using the X-ray diffraction method. In addition to an a-phase WO3 and a '-phase WO2, they reported the existence of two new phases. A 8' phase, homogeneous between

Jan 1, 1949

By John M. Lovejoy

CURRENT production of petroleum on such a vast scale presents many interesting problems- the solutions of which are important not only to those directly interested in the business, but to the nation as a whole. The industry is relatively young. Until the discovers of the Lucas gusher at Spindletop in 1901 petroleum production had not exceeded 60,000,000 bbl. per year compared with 1,100,000,000 bbl. in 1936. In 36 years then, the modern oil business, production, transportation, refining, and marketing has developed. I will first present a brief history. of oil production as a background for consideration of the present situation.

Jan 1, 1937

By Robert L. Clayton, Arthur Baker

Two massive sulfide zinc-copper ore bodies are in quartz-sericite schist (probably formed by regional metamorphism of sediments) and andesite of the Precambrian Yavapai Series, on opposite sides of a large rhyolite mass. The Copper Queen ore body is conformable with bedding of its schist host rock, but the Old Dick ore body probably crosscuts the strata. A lens of low-grade mineralization in chlorite schist, associated with the Old Dick ore body, crosscuts through 150 feet of strata. The ore bodies are almost entirely enclosed by premineral faults with less than 150 feet of displacement. The minerals of the ores are pyrite, sphalerite, and chalcopyrite, with minor arsenopyrite and galena and small amounts of intimately associated chlorite, sericite, and calcite. Old Dick sphalerite-chalcopyrite intergrowths have mutual boundaries, and sphalerite grains contain abundant exsolved chalcopyrite. Copper Queen sphalerite-chalcopyrite intergrowths have extremely ragged boundaries, the sphalerite contains no exsolved chalcopyrite, and the ore overall has a schistose texture. The pre-mineral fault on the hanging wall of the Copper Queen ore body has had 100 feet of post-mineral displacement. Wall rocks of the Old Dick ore body locally have been sericitized. Andesite and quartz-sericite schists for at least several hundred feet around both ore bodies have been chloritized erratically and contain traces of copper.

Jan 1, 1968

By Jesse Betterton

IN the Parkes process of lead refining, after desilverization has been completed by means of zinc additions, there will remain in the lead from 0.5 to 0.6 per cent zinc. At this stage in the refining practically all impurities are reduced to refined lead specifications except zinc and antimony. All excess of copper and nearly all the arsenic goes out with the silver. Silver remaining should not exceed 0.1 oz. per ton. It thus remains only to remove zinc and antimony to produce refined lead. The older practice was to complete refining by means of oxidation processes in reverberatory furnaces. Essentially this consisted of heating the lead to 1200° to 1300° F. and allowing it to come in contact with a considerable excess of air passing through the furnace, or accom-plish the same result by blowing the lead with steam by means of pipes introduced for that purpose, at the same time allowing air to enter the furnace. Usually some procedure involving alternate oxidation and reduction with fine coal or coke was employed in order to reduce the weight of dross or skim finally removed from the furnace. This practice had many elements of weakness in that the main flow of lead, after the preceding expensive operations had been performed, and the whole refining process nearly completed, was subjected to an operation at a comparatively high temperature, which involved much lead loss if the furnaces were not on bags, and the production of 3 to 5 per cent of the weight of the lead as dross or skim, which had to be resmelted and the lead either refined or produced as antimonial lead. In addition, the operating expense of the process was a considerable item. The, process of dezincing with chlorine was developed as a substitute for the foregoing described oxidation process, and finally resulted in such advantages as nearly equal operating costs, a practical elimination of the lead loss, and the direct production of a very valuable byproduct, zinc chloride, that may be sold as such or retreated for its zinc and chlorine contents, both of which can be reused in the refining processes.

Jan 1, 1933

(Under this heading will be published notes sent to the Secretary of the Institute by members or other persons introduced by members.) Member, mining engineer, technical education, married, 15 years' experience as foreman, superintendent, manager of examination and exploration work. Prefers Pacific Coast or Alaska, but will go anywhere. Available Nov. 25. No. 422. Mine manager or mill superintendent. U. S. A., Canada or Mexico preferred. Age, 33. Member. Five years mill superintendent, mills up to 2500 tons a day-gold, silver and lead; 6 years mining from bottom up to manager. No. 423. Member, mining engineer, technical graduate, age 40, 17 years' experience, having filled every position at a mine; superintendent of large mine at present. Familiar with all kinds of mining machinery. 'Best of reference. Available after Jan. 1, 1918. No. 424. Member, age 41, with 20 years' experience in design construction and operation of mining and smelting works and steam, electric and water-power plants, etc., who has held positions of responsibility in important concerns, desires a position requiring executive or engineering ability, or both. No. 425. Member, age 37, graduate mining engineer, with 29 years' experience in all phases of anthracite and bituminous mining, at present engaged as manager of one bituminous mine and consulting engineer for others, desires position as manager of a coal mine or consulting engineer for banking interests. No. 426.

Jan 1, 1918

By M. N., Short

TIE Pioneer mining district, better known as the Superior district, from its principal town, is located in Pinal County in south-central Arizona about 80 miles east of Phoenix and 22 miles west of Miami. The region embraces a confused series of mountain ranges of moderate FIG. I.----SUPERIOR, LOOKING NORTH FROM SOUTH BANK OF QUEEN CREEK. MAGMA MINE IS INDICATED BY WASTE DUMP IN GULCH TO RIGHT OF CENTER. height but precipitous slopes, between which lie irregular valleys filled with alluvial detritus. The average elevation is about 2800 ft. in the valleys and the summits of the ranges reach 2000 ft. above this. Superior is situated on the north bank of Queen Creek where it emerges from one of those ranges into a more or less basin-shaped valley. The drainage of Queen Creek is to the southwest and the flood waters spread out and lose themselves in the desert northeast of Florence, the county seat of Pinal County.

Jan 2, 1926

By P. C. Claspy, P. H. Smakula

The electro-optic coefficients of LiNbO, and KTao.,5Nboe3,O3 (KTN) have been experimentally determined at the HeNe laser wavelengths of 0.6328, 1.15, and 3.39 µ. The coefficients were calculated fronz the retardation induced by an applied electric field. The retardations were measured by observing one or move transmission maxima and minima as a function of the applied field, and by measuring the retardation directly with a Babinet-Soleil compensator. The values obtained agree quite well with those previo~lsly reported by others. Extinction ratios as high as 3000:l have been observed. Resistivities and Curie temperatures have also been measured. Light-induced optical inhornogeneities in LiNbO, repovted by others have been observed. CONSIDERABLE interest has recently been shown in the electro-optic properties of LiNb03 (Refs. 1 and 2) and KTN.3, 4 These crystals have a number of advantages over such well-known materials as KDP. These advantages include: 1) the infrared transmission of KTN and LiNb03 extends to 5 p whereas that of KDP cuts off at 1.5 p ; 2) driving voltages required for modulators using these materials are considerably lower than those required for KDP. After first discussing some theoretical considerations of the electro-optic effect, we will report the results of measurements of the dc electro-optic coefficients of these materials at wavelengths of 0.6328, 1.15, and 3.39 p. THEORY The generalized equation for the electro-optic effect can be written: Although lattice polarization is the fundamental variable, rather than the applied electric field, we follow the convention of expressing the linear electro-optic effect in terms of the applied field. For LiNbO the quadratic terms are negligible. Since KTN has a center of symmetry the rijk tensor is 0. After applying the usual symmetry considerations and index contractions,* the rijk and gijkl tensors can be expressed as follows: LiNbOaT If field directions are now chosen, the change in refractive index and the angle between the induced optic axes and the crystallographic axes can be found. The induced rotations of the principal axes of the index ellipsoid for fields in principal crystallographic directions are given in Table I. Since KTN is initially isotropic, the principal axes in the zero-field condition are parallel to the crystallographic axes. The induced retardations are given in Table 11. EXPERIMENTAL We obtained the various electro-optic coefficients by measuring the induced retardation as a function of

Jan 1, 1968

By N. E. Rogen, N. J. Grant

WHILE direct measurements of the growth of precipitate particles during aging is of fundamental value, few such measurements have been made. Direct measurements by means of optical or electron-microscopy and X-ray techniques are preferred, however, many of the aging studies have been based on indirect methods such as electrical resistivity and hardness. Because of the minute size of most precipitate particles (less than 1000A) the light microscope is of limited use while electron microscopy is subject to slowness, etching problems and consequent resolution problems. It is fortunate that alloys of the Nimonic type, based on Ni-Cr-Ti-Al, lend themselves to accurate and relatively easy particle size measurements. With proper balance of titanium and aluminum, the only aging precipitate is the gamma prime (r') Ni3,(Al, Ti)2 phase and this phase is the basis of the high-temperature strength of these allos.3-6 The Ni3(Al, Ti) phase is a face-centered-cubic, ordered structure with nickel atoms occupying the cube faces. Titanium atoms can replace three out of every five aluminum atoms and when substituting do so preferentially.2 Electron microscopy has shown that during aging of most of the commercial alloys of this type, precipitate particles are unusually uniform in size and distribution, and that the volume of (r') phase is large (20 pct).4,7 The aim of this investigation was to measure the growth of (y') phase during aging. In so doing, it was hoped that a clearer understanding of the aging process would be attained. X-ray line broadening was used as the measure of precipitate particle size. This technique was selected because it can measure and average the diameter of thousands of particles in one operation. The variations in hardness and matrix lattice parameter with aging were also studied and related to the particle size. EXPERIMENTAL PROCEDURE An alloy of the following composition was studied: Cr Ti A1 C Ni Wt pct 20.71 2.98 1.43 0.04 bal. At. pct 22.06 3.47 2.95 0.18 bal. The alloy, a 15- lb vacuum melt, was forged to 1/2-in. diam at a temperature of 1900" to 2200°F; was solution heat treated for 4 hr at 2000°F and water quenched; and was then aged in various ways. The ASTM grain size was 4 to 5. No (7') phase could be detected by X-ray analysis after solution treatment and electrolytic extraction. Aging was performed on 2-in. long specimens at 1400°, 1500°, and 1600°F for increasing times. One-half inch sections were removed after each time increment and were then electropolished in a solution of H3P04 saturated with chromium trioxide at a potential of 30 v and rectified with a tantalum electrode. Rockwell hardness measurements were taken using one side of the polished specimen. Matrix lattice parameter determinations were made on the other side using filtered chromium radiation references with the position of the (220) line of a silicon standard. To enable the precipitate particles of the (y') phase to be measured using X-ray line broadening techniques, it is first necessary to separate and concentrate this phase by electrolytic extraction. Extraction is necessary because the difference between matrix and precipitate lattice parameters is only approximately 0.5 pct and intensities of.the (y') phase lines are very weak relative to those of the matrix. The extraction techniques employed have been described before and found to produce a reasonably quantitative separation.398 A water solution of 15 pct H3Po4 is used at a current density of 0.5 amp per sq in. at 6 v. The precipitate particles are separated from the liquor by centrifuging and decanting and are then washed, dried and repowdered. A plot of the X-ray intensity vs diffraction angle for the (111) line of the precipitate particles was used as a measure of particle size. The intensity curve approximated the shape of Gaussian distribution function and its breadth was measured at the half height. The (220) line of a silicon standard was used to correct the measured line breadth for instrumental and other broadening errors. The Scherrer formula was used to calculate particle

Jan 1, 1961

By Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

By Werner Goldsmith, Akihiko Kumano

An experimental investigation was conducted to study the response of soft, porous rock, green shale, under dry and liquid-filled conditions to normal impact of hemispherically-tipped cylindrical steel projectiles with diameter and mass of 6.35 mm and 31 g, respectively. Disk-shaped green shale specimens with nominal thickness and diameter of 32 mm and 127 mm, respectively, were tested in the initial projectile velocity range of 18 to 42 m/s. For the liquid-filled tests, the green shale specimens were saturated with kerosene. A total of eight impact tests were conducted. Information on the extent and pattern of the damage in the rock and velocity histories of the projectiles were collected. It was found that while the penetration depth was quadratically related to the initial projectile kinetic energy for the dry case, the penetration depth for the liquid-filled case was directly proportional to the initial projectile kinetic energy. The results of the impact tests under dry and liquid-filled conditions conformed well to a linearly viscous model and a Coulomb frictional model, respectively. The major deformation processes in the dry specimens were found to be compaction and equivolumnial distortion of the material. In the liquid-filled case, however, formation of cracks and equivolumnial distortion with less material compaction were observed. Furthermore, craters were formed as a result of the crack formation in the liquid-filled specimens.

Jan 1, 1982

By W. D. Robertson, A. S. Tetelman

The technique of decorating dislocations was employed to investigate deformation and fracture resulting from Precipitation of hydrogen in Fe-3 pet Si single crystals. It is shown that cracks are produced on (100) planes inside crystals, as a consequence of the precipitation of hydrogen gas, either when crystals are quenched from a hydrogen atmosphere at elevated temperatures or cathodically charged with hydrogen at room temperature. Plastic deformation in the vicinity of cracks, observed as arrays of decorated dislocations, is in conformity with the calculated stress distribution about a crack containing an internal pressure, and the observations provide information permitting a detailed analysis of the mechanics of crack growth. The fracture characteristics of crystals containing internal cracks were evaluated at 25o and -196°C and the results are related to the mechanism of hydrogen embrittlement in terms of the growth of preexisting cracks. HYDROGEN in bee iron or steel produces two characteristic changes in mechanical properties: I), a decrease in ductility (macroscopic strain at fracture) that depends on temperature and strain rate, and 2), spontaneous fracture under static load that depends on time and apparent stress. Resolution of these phenomena into the microscopic processes that combine to produce the macroscopic effects is especially difficult in the Fe-H system in which the active component cannot be directly observed and only maintained in equilibrium with great difficulty in the temperature and pressure range in which embrittlement phenomena appear. As a result of these complications, verification of the numerous hypotheses'-5 that have been proposed to explain the microscopic mechanism of embrittlement depends on self-consistency with measured changes in macroscopic properties that are averaged over the volume of a specimen. It is obviously important to obtain a more direct evaluation of the microscopic processes that combine to produce embrittlement. Accordingly, the present investigation was designed to identify and observe, as directly as possible, the microscopic effects of introducting hydrogen into a bee crystal. It was concluded from a previous investigation6 of X-ray line broadening, produced by introducing hydrogen into pure iron at room temperature, that the only effect that could be associated with the introduction of hydrogen was plastic deformation; in particular, dilation of the lattice was not observed, within ± 0.01 pet, and no evidence was found that could be interpreted to support the idea7'* that hydrogen occupies tetrahedral interstitial sites in the iron lattice. The absence of lattice dilation is consistent with the extremely small solubility of hydrogen in bee iron9,10 (0.015 at. pet at 900oC and 1 atm pressure), and the evidence of plastic deformation is consistent with the fact that hydrogen, introduced by cathodic charging, eliminates the carbon yield point.11-13 Following this investigation, the immediate problem was to devise a method by which plastic deformation could be observed directly. The technique employed by Hibbard and Dunn14 to observe the movement of dislocations during bending and subsequent polygonization of Fe-3 pet Si single crystals was adopted and modified for the present purpose to include the observation of dislocation arrays in the volume of the crystal, and their association with the fracture process. EXPERIMENTAL PROCEDURE Single crystals of a high purity Fe-3 pet Si alloy, containing 0.007 pet C, were grown in vacuum by

Jan 1, 1962

[The following discussion, comprising both remarks made at the Chicago meeting and contributions since forwarded to the Secretary, is based upon the following papers, presented at that meeting : "Segregation and its Consequences in Ingots of Steel and Iron," by Alexandre Pourcel, Paris, France. (See p. 105, mans. xxii.) " Microscopic Metallography," by F. Osmond, Paris, France. (See p. 243, Trans. xxii.) " Microstructure of Ingot-Iron in Cast Ingots," by Prof. A. Martens, Berlin, Germany. (See p. 37.) " Microstructure of Steel," by Albert Sauveur, South Chicago, Ill. (See p. -546, Trans. xxii.) "Farther Observations on the Relations Between the Chemical Constitution and Physical Character of Steel," by William R. Webster, Philadelphia, Pa. (See p. 113.) "The Heat-treatment of Steel," by H. M. Howe, Boston. Mass. (See p. 466.) Since all these papers were considered together, no attempt has been made to separate the discussion strictly under the several heads.] William R. Webster, Philadelphia, Pa.: I desire to say that in my first paper (Trans., xxi., 766) the actual ultimates were subtracted from the estimated ultimates, whereas in the paper submitted at this meeting the estimated ultimates are subtracted from the actual, thus giving contrary signs. The latter method corresponds with the direct effect. of low and high finishing-temperatures ; that is, a plus difference indicates low, and a minus difference high, finishing-temperature. I make this explanation to prevent confusion in comparing the two papers. Mr. Sauveur has shown that there is a close relation between the size of the grain and the ultimate strength, and also that the size of the grain depends on the temperature at which the material is finished in rolling, and on the chemical composition of the steel. I have shown that there is a close relation between the chemical

Jan 1, 1894