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By Yingchang Tsenshan Wang

UUIN L&SS 1» Paqb I. Introduction........................................................658 1. Subject and Scope...............................................658 2. Acknowledgments...............................................659 3. Review of Previous Work........................................659 Field Data...................................................659 Experiment.a1 Data............................................662 4. Plan of Present Investigation.....................................662 Method of General Procedure...................................663 I1. Experimental Work..................................................663 A. The Solution of Sphalerite..............................:........663 1. The Solvent Effect of Iron Sulphates upon Sphalerite...........663 2. The Solubility of Sphalerite in Salt Solutions of Silver, Copper and Lead...............................................668 B. Formation of Zinc Carbonates....................................674 3. The Reactions of Carbonates and Bicarbonates With Solutions of Zinc Salts............................................674 4. The Reaction of Zinc.Sulphate Solution With Limestones.......684 C. Peculiar Conditions Affectitig the Formation of Zinc Silicate (calamine) and Zinc Carbonate (smithsonite)..........................686 5a. The Effect of Carbon Dioxide Upon the Basic Silicate and the Carbonates of Zinc in Water, and Its Bearing Upon the Conditions of Theii Precipitation..............................686 5b. The Reactions of Solutions of Soluble Silicate With calamine and Smithsonite in Solution in Presence of Carbon Dioxide..689 6. The Reactions of a Mixture of Hydroxide and Silicate of Sodium with a Dilute Solution of Zinc Sulphate...................691 D. High-Temperature Methods.....................................692 7a. The Influence of Temperature on the Formation of Calamine..692 7b. Possible Effect of Heat on Calamine and Srnithsonite.........697 E. Summary of the Experimental Work..............................698 III. Petrographic Work....................................................700 1. The Occurrence of Sphalerite in Limestones or in Cherts............701 Summary of the Blende in Limestones and in Cherts.............7432 2. The Partially Altered Sphalerite and the Oxidation Products........702 a. Smithsonite with Blende....................................702 b. Calamine with Blende......................................703 c. Smithsonite and Calamine..................................703 d. Summary on the Partially Altered Sphalerite and Its Oxidation Products..............................................704 IV. Concl~~siom ........................................................-705 V. Microphotographs and Photographs with Their Explanations.............705

Jan 1, 1916

By Harvey Cline, Donald P. Ferriss

THE violent outgassing of commercial tungsten and other refractory metals when melted in an electron beam zone refining apparatus1"3 is dealt with experimentally by one or both of two approaches. One is to provide a suitable emission current control1,2 the other is to purify the metal in the solid state before melting.4 The first of these is usually sufficient, but the authors chose also to investigate the source of the troublesome gases and to devise means of solid-state purification. Some further insights into the use of tungsten as a structural material at temperatures near its melting point were also revealed in the course of the work. One may speculate on the causes of gas formation in tungsten at high temperature by inferences from the literature and an examination of the impurities in commercial wire. Davenport5 observed microporosity in both tungsten and molybdenum filaments heated to several hundred degrees below their melting points. Studying the function of oxygen in molybdenum welds, Perry, Spacil, and wulff8 attributed similar porosity to the disproportionation of Moo2 to molybdenum metal and Moo3. Tungsten dioxide also disproportionates7 above 2000oC to yield WO3 vapor at considerable pressure. Commercial tungsten contains some 5 to 20 wt ppm O and a similar concentration of carbon depending on the details and precautions of processing. Therefore, evolution of CO is also a strong possibility as a source of gas at high temperatures. Furthermore, even for activities in the order of 0.01, it may be calculated that the pressure of CO at 3000°C would be over 4000 psi, which is in excess of the tensile strength of tungsten at this temperature.9,10 Powder metallurgy tungsten contains some 0.02 pet Fe and 0.002 to 0.005 pet of the elements Ni, Si, Al, Ca, Mn, Mg, and Mo; at temperatures over 2800°c, therefore, these elements will exhibit appreciable vapor pressure, though small compared to that of WO3 and CO. Some of these impurities may react to form high-pressure monoxides such as SiO and A10. Finally, dissolved and occluded nitrogen is an ever-present source of high-pressure gas. Commercial Type 218, General Electric filament wires, 0.025 in. diam, were heated by resistance in 10 -4 mm of Hg and in argon or hydrogen at pressures from 50 µ to atmospheric. For temperature determinations in vacuo, the Jones - Langmuir8 current-temperature relationship was employed. For gaseous atmospheres, the burn-out temperature was assumed to be the same as in vacuo so that a small, constant correction could be made for temperatures below burn-out conditions (i.e., local heating to failure). Several dozen experiments may be summarized by pointing out some structural observations. At 3050oC in 1 atm of A, porosity is very evident after 30 min, as shown in Fig. 1. For the section in Fig. 2, failure occurred 200°C below the melting point and many voids have grown in the grain bound-

Jan 1, 1962

By John V. Beall

There is an underlying surge to mining in the Philippines." So said A. R. "Ham" Reed, general manager Itogon-Suyoc Mines, Inc., to this reporter last November. Itogon-Suyoc is a small company with a struggling gold mine, a mixed sulfide mine and some prospects. In the Republic of Philippines (ROP), politics, which have an effect on mining, create some uncertainties. By July 1974, no mining company may have more than 40% foreign ownership. The ownership provision is a matter of concern to such important companies as Atlas and Benguet Consolidated and is generally considered a deterrent to new foreign investment. Under these circumstances, Reed's comments are of interest. On foreign prospectors: Don't come in cold; find a Philippine partner or buy into a company already here. Physical conditions of exploration are tough-terrain, communications -but the mineral potential is excellent.

Jan 4, 1969

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

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

Jan 1, 1959

By E. M. Wise

MANY of the platinum metal alloys are hot-forged in the early stages of reduction from ingot and substantial quantities of platinum alloys are commercially employed at very high temperatures in ammonia oxidation units, orifices for forming glass rods and fibers and as cathodes in long-life thermionic amplifiers. They are used also for electrical heating resistors, safety blowout disks, thermocouples and crucibles. The tensile prop-erties at elevated temperatures are important in many of these situations but data on the subject are limited. Creep data also are important, but will not be covered at this time. SCOPE AND CONCLUSIONS Tensile tests were carried out at room temperature and elevated temperatures up to 1100° C. on previously well annealed samples of platinum, palladium and several of their important alloys with composi-tions shown in Table 1. The results are presented graphically in Figs. 1 to 4. The tensile strengths of platinum and the platinum-base alloys (with the exception of the 10 per cent rhodium-platinum alloy) at 1100° C. are from 16.6 to 18.8 per cent of the strengths of the same alloys (well annealed) at room temperature. The strength ratio of the 10 per cent rhodium-platinum alloy is 22.3 per cent, which is appreciably higher than that of the other materials tested.

Jan 1, 1938

By W. O. Philbrook, K. M. Goldman, G. Derge

T. Rosenqvist—The most interesting point in this paper is the observed transfer of iron into the slag in the initial stage of the desulphurization process, after which the iron again is reduced to the metallic state. The authors interpret this observation as showing that the sulphur enters the slag as an iron-sulphur compound which subsequently is decomposed by the slag. The present writer has previously suggested the following equation for the desulphurization process: S + O2- ? S2- + O For equilibrium in the blast furnace the oxygen potential is defined by equilibrium with graphite and CO of 1 atm pressure: C + O ? CO [2] During the desulphurization process the reactions proceed in the direction of the arrows. If one assumes eq 2 to be significantly slower than eq 1, the transfer of sulphur into the slag, in accordance with eq 1, will build up a local oxygen potential at the metal-slag interface very much higher than that corresponding to the value defined by eq 2. This is possible because the equilibrium oxygen potential in eq 1 is high as long as the sulphur content in the slag is low. This oxygen potential will again be able to oxidize some iron: Fe + O ? Fe2+ + O2- and an increase in the iron content of the slag will be observed. Adding up eqs 1 and 3 one obtains: S + Fe ? S2- + Fe2+ The net effect is thus in harmony with the experimental observation but is obtained without assuming any close ties between the sulphur and iron atoms during the process. Furthermore, it follows from eqs 1 and 2 that when the sulphur content in the slag increases, and equilibrium with C and CO is finally approached, the local oxygen potential at the metal-slag interface will decrease, and the iron in the slag will be reduced back into its metallic state. C. E. Sims-—The data and conclusions presented in this paper are thoroughly convincing in establishing the mechanism of sulphur transfer from iron to slag as in a blast furnace. The evolution of gaseous CO in step 3 of the reactions given on p. 1112 makes the process virtually irreversible. Assuming that the process is similar in slag-metal systems other than in the blast furnace, it is readily seen why free CaO and re-ducing conditions so greatly favor desulphurization. On the other hand, the very effective desulphurization obtained in oxidizing slags when strongly basic, must be attributed to the relatively high stability of CaS as compared to FeS. The ease and simplicity with which the reactions of classic chemistry agree with the experimental data and explain the mechanism is noteworthy. The concept of molecules of FeS, soluble in both phases (metallic iron is not soluble in the slag), migrating from the iron to the slag and there reacting with CaO, which is soluble only in the slag phase, is clear and uncomplicated. This is likewise true for step 3. Those who would deny the existence of molecules or molecular-type combinations in liquid iron, must strain to provide a mechanism so lucid. In the absence of molecules, the Fe and S exhibit a remarkable collusion. L. S. Darken—The investigation and interpretation of rate phenomena in the range of steelmaking temperatures is a difficult task. Most of the laboratory investigations of steelmaking reactions have been concerned with equilibrium. Having determined the equilibrium, our attention naturally focuses next on the mechanism and rate of approach to equilibrium. The authors seem to have contributed substantially to our understanding of these factors for the case of sulphur transfer. I should like to ask the authors whether they consider that the sulphur transfer reaction is diffusion controlled as many high-temperature reactions seem to be. If so, it would seem reasonable to suppose that the slow diffusion step of the process is the transfer across a pseudo-static layer or film similar to that considered in heat flow problems. As the diffusivity and fluidity are smaller for the slag than for the metal, it may tentatively be assumed that the sulphur gradient exists in a thin layer in the slag adjacent to the slag-metal interface and that the metal and the main mass of slag are each maintained uniform by convection. On this basis the amount of sulphur transferred across unit area per unit time is D p (?S%)/100 ?1, where D is the diffusivity, p the density, (?S%) the difference in percent sulphur on the two sides of the layer, and ?l is the layer thickness. At the beginning of the experiment the main body of the slag and hence one side of the layer contains no sulphur; therefore (?S%) may be replaced by (S%), the sulphur content of the slag at the slag-metal interface, which in turn is equal to L[S%] where [S%] is the sulphur content of the metal and L is the distribution coefficient. The rate of transfer thus becomes DpL[S%]/100 ?l, which the authors designate K[S%]. Equating these two quantities and setting D = 10-6 cm2 per sec, p = 3 g per cm3, L = 40, and K = lo-+ g cm-2 sec-1, it is found that ?l, the film thickness, is about 0.01 cm—a value of the order of magnitude of that found in heat transfer problems in liquids. The uncertainty of the numerical values used leaves much to be desired, but at least it can be said that this calculation tends to support the proposed model involving diffusion through a film. Although this does not seem to affect the general argument, I should like to call attention to the fact that the diffusivity3 of sulphur in hot metal is found (on conversion of units) to be about 10-4 cm2 per sec rather than 104 cm2 per sec as stated by the authors. The three equations written by the authors to express the steps in the overall process of sulphur transfer may alternatively be written ionically as only two Fe + S = Fe++ + S-- Fe++ + O-- + C (graphite or metal) = CO (gas) + Fe where the underscore is used to designate the metallic phase; ionic species are slag constituents. After the authors have so neatly demonstrated that iron and sulphur transfer together (at least initially), this fact seems almost self evident; from eq 4 it is seen that if sulphur acquires a negative charge during transfer

Jan 1, 1951

By H. A. Wriedt

A method of calculating activities in binary systems having miscibility gaps is described. The method, which applies only to the phase in which the gap occurs, is exact when the function defined by the equation varies linearly with composition. Analytical and numerical solutions (as a function of the conjugate phase compositions) are presented for two coefficients A and B from which the thermodynamic activities can be calculated. Deviations from Henry's law, calculable by the method presented, are shown graphically for the particula~ case of the component i at the edge of the miscibility gap more remote .from pure component i. For symmetrical gaps, the deviation from Henry's law at this gap edge becomes smaller as the gap becomes wider, The interrelation of gap location, the direction of departures from Henry's law and the occurrence of maxima and minzma in these departures is discussed in some detail. Values for a and for activity calculated from phase diagrams show fair to excellent agreement with corresponding experimental values in the Al-Zn and CaO-SiO2 systems. WHEN structurally similar phases, B and 6, lie at the sides of a two-phase region in a constitution diagram, it can be assumed that, stably or metast-ably, they will become completely miscible at a higher temperature. The B and 6 phases are particular composition ranges of a single B6 phase region with a miscibility gap. Below, as above, the critical solution temperature, the free energy of formation of the 06 phase is a continuous function of composition through the range of the miscibility gap. It is the purpose of this paper to use this continuous free-energy function in order to develop a simple method for computing the thermodynamic activities in the B6 solution of a binary system. To make these calculations it is assumed that the function ai, familiar from Gibbs-Duhem integrations and defined by the equation

Jan 1, 1962

By H. I. Aaronson

ONLY limited studies have been made of pro-eutectoid a morphology in hypoeutectoid Ti-Cr alloys during previous investigations, 1-3 The nature of the eutectoid reaction, ß?a + TiCr2, has been considered in somewhat more detail.1,2,4,4 Inasmuch as the proeutectoid ferrite reaction in plain carbon steels has recently been extensively investigated in this laboratory, advantage has been taken of the opportunity to compare the morphologies developed in two rather different eutectoid systems in order to permit a preliminary estimate to be made of the degree of generality which may be ascribed to the various results obtained. Experimental Procedure The chemical analyses of the alloys used are given in Table I. The 7.22 pct Cr alloy was prepared by the Battelle Memorial Institute from iodide titanium and high purity chromium. The initial ingot was made by arc melting a master alloy and iodide titanium. The resultant ingot was twice remelted. by the consumable electrode technique. Upset forging at 950°C reduced the final ingot to 3/4 in. sq bars. The 10.94 pct Cr alloy was prepared by the Titanium Metals Corp. of America from sponge titanium and chromium of ordinary purity. This alloy was melted twice by the consumable electrode technique, forged at 1200° to a 3/4 in. sq bar, and rolled at 815°C to a 1/2 in. round. Specimens 1/4 in. x 1/4 in. x 1/16 in. were cut from the 7.22 pct Cr alloy; halves of disks 1/2 in. in dlam and 1/16 in. thick served as specimens of the 10.94 pct Cr alloy. These specimens were individually encapsulated in Vycor, Each capsule was evacuated three times to a pressure of 2 to 6 x lo-' mm Hg and flushed twice with a reduced pressure of argon prior to sealing. The inclusion of two small packets of zirconium chips permitted the capsules to be outgassed and internally gettered, without heating the specimen, prior to heat treatment. The specimens were solution annealed for 40 min at 1000°C, isothermally reacted in deoxidized lead pots, and quenched in iced water. Most of the isothermal reaction treatments were carried out at 25" intervals between 725° and 550°C on specimens of the 7.22 pct Cr alloy and at 650°C on specimens of the 10.94 pct Cr alloy. Results and Discussion Morphologies of Proeutectoid a*—Kinetics of the ß?a Reaction: Fig. 1 shows the TTT-curves for the beginning of the proeutectoid a and the eutectoid reactions in the temperature range investigated in the 7.22 pct Cr alloy. The M, temperature in this alloy is below 0°C. The curve for the beginning of the proeutectoid a reaction is in good agreement with that of Frost, Parris, Hirsch, Doig, and Schwartz' for a 7.54 pct Cr alloy, appears at considerably earlier reaction times than the corresponding curve presented by Rostoker4 for a 7 pct Cr alloy, and lies athwart the curve of Spachner and co-workers11 for an 8 pct Cr alloy. Differences in criteria for the beginning of the a reaction and the relatively high rate of this reaction at lower temperatures presumably account for some of these divergences and may also explain, in part, the apparent failure of an iodide-base 7.22 pct Cr alloy to react more slowly than sponge-base 7 to 8 pct Cr alloys. Grain Boundary Allotriomorphs: Crystals of this morphology nucleate at and grow preferentially and more or less smoothly along the matrix grain boundaries.5-7 Allotriomorphs are the first morphology to precipitate at most grain boundaries at reaction temperatures from 725°C, the highest temperature studied, at least through 575°C. Fig. 2 Shows typical allotriomorphs, formed during an early stage of transformation at 725°C. Grain boundary allotriomorphs are not the predc=iaant morphology at late reaction times at any temperature studied. However; from 725" through

Jan 1, 1958

Jan 1, 1906

By L. G. Jones, A. S. Odeh

A theoretical developtment is presented which provides a straightforward method of handling the drawdown analysis for both oil and gas wells flowing at variable rates. In the past our inability to analyze variable-rate drawdowns has been a major obstacle in using them for formation evaluation. This method should permit wider use of these tests in the future. INTRODUCTION Pressure build-up analyses are widely used to obtain reservoir data such as the effective flow capacity of the formation. On the other hand. although pressure drawdowns have been run for a long time, they have not been used extensively to evaluate reservoirs because they are difficult to analyze. One of the difficulties in analyzing pressure drawdowns has been that the theory developed until now has required the test to be run at a constant rate. For both oil and gas wells this is a difficult requirement to satisfy. especially during the early period of a well's life when drawdown tests are usually run. In spite of this limitation, drawdown tests are often run with build-ups as a check. In this paper a theory, which handles the drawdown analysis for variable rates, is presented for both oil and gas wells. Thus, one of the biggest deterrents to running drawdowns is removed, and they should become a much more useful engineering tool in the future. THEORETICAL CONSIDERATIONS 011, RESERVOIRS The general equation used for describing the unsteady-state radial flow of slightly compressible fluids in homogeneous porous media can be written in cylindrical coordinates as where r is the radial distance in cm, t is the time in seconds, p is the pressure at r and t in atmospheres, + is the fractional porosity, p is the viscosity in cp, c is the compressibility in vol/vol/atm, and k is the permeability in darcies. There are a number of solutions of Eq. 1 for various boundary conditions. One of these is the so-called "point-source" solution, which approximates the case of an infinite oil reservoir with a well located at r = 0 and produced at a constant rate. The point-source solution of Eq. 1 is

Jan 1, 1966

By G. Sachs, S. I. Liu

Introduction In a previous investigation on the effects of repeated strains of large magnitude on the aluminum alloy 24 ST, it was found that the reduction in ductility by straining in tension was partially restored by a subsequent compression.&apos; As illustrated by the dashed line in Fig I,$ the ductility (e~) retained after prestraining in tension by a certain amount (el) and measured in a subsequent tension test is represented by a straight line sloping down under 4s°. If a compression of the same magnitude as the first tension is inserted (€2 = — €1) between prestraining and final testing in tension, such a "balanced" tension-compression cycle yields a ductility considerably higher than that present after prestraining in tension only. The results of these tests can be correlated with those of an investigation on the effects of prestraining in compression.~ As also shown in Fig I, the ductility in subsequent tensile tests decreased with com- pression, at a rate considerably slower than that after prestraining in tension. The above discussed testing conditions can be considered as special cases of a general straining cycle, consisting of first, straining in tension by an amount el, subsequently straining in compression by an amount e2, and finally determining the retained &apos;ductility, e,, in a tensile test. Prestraining in tension is then represented by el > o and e2 = o. Prestraining in compression is given by e~ = o and e~ < o. Balanced cyclic straining is defined by the condition el > o and cz = — 61. In order to obtain further information on the effects of straining cycles consisting of tension and subsequent compression, further tests were made, varying both the tension strain, el, and the compression strain, e2, within extreme limits; el varied between 0.06 and 0.28 and e2 between — 0.008 and —0.h approximately. Apparently, such tests have not been previously performed. They revealed phenomena which have not been recognized to date, The results of the investigation are herewith reported, without attempting to correlate them with internal processes within the metal structure. However, in order to assist in an analysis of this type, the results have been represented in various manners. In addition, further test data on the effects of prestraining by compression were provided by using specimens of various contours (notched specimens) in the sub-

Jan 1, 1949

"The power development at these falls, three miles below the city of Great Falls, was made in 1891 by the original Great Falls Water Power & Townsite Company, and the Boston & Montana Consolidated Copper & Silver Mining company, the predecessor of the Boston & Montana Reduction Department mentioned above.The dam is 746 feet long, placed a short distance above the crest of the falls, and giving an effective head, as now constructed, of from 42 to 44 feet. There are power houses on both banks, those on the south bank belong to the Great Falls Power company, the successor of the Great Falls \!\Tater Power & Townsite Company, and the Great Falls Electric properties. The water is led from the dam to these power houses through sheet iron pen-stocks the water wheels are of the horizontal turbine type, and of various sizes.The water is here carried from the dam to the power houses by an open canal or headrace, the walls of which are concrete. This headrace is 100 feet wide at the widest point. The available head was originally less than 40 feet, but this was increased to about 44 feet by means of flashboards and tailrace wall, seperating the tailrace from the main river and delivering the water to the river at a considerable distance below the power house, thus taking advantage of a considerable fall in the river below the sheer fall at Black Eagle.A total of about 12,000 horse power 1s developed at these falls, the Great Falls Power Company, and Great Falls Electric properties developing about 2,000 horse power, and the Anaconda Copper Mining Company developing the balance."

Jan 1, 1913

By Erwin Pink

It has been pointed out in a previous publication&apos; that, for a given strain rate, serrated yielding can be observed only at certain test temperatures. Fig. 1 shows the results obtained for polycrystalline and re-crystallized tantalum, Va group in the periodic table of elements, where serrations in the course of deformation match the decrease of total elongation. However, there was no evidence of repeated yielding when testing molybdenum or tungsten, VIa group, at similar conditions, i.e., annealed and air-cooled samples (serrations have been found in quenched tungsten2). The reason for the observed serrations in the stress-strain curve are dissolved impurities on interstitial sites of the lattice. Of importance is the concentration of oxygen, carbon, and nitrogen, which are in random solution. Two methods to calculate the limiting concentrations for serrated yielding have been evaluated and applied with more or less success in estimating the role of carbon and nitrogen in mild steel.3 J. Friedel4 has given two equations, which determine the upper and lower strain rates i for the appearance of serrations at a certain test temperature: W denotes the binding energy of the interstitial atom, -1 ev for refractory metals;5 e&apos; the portion of continuous strain in the discontinuous stress-strain curve, measured as -3x10-3; b the Burgers vector, c the concentration, see Table 11, in atom fractions; p the dislocation density, -2 X l09 per cm2 at an average stress ?, -15 kp per mm2 at medium strain. k stands for the Boltzmann constant, T for the absolute temperature, and D for the diffusion coefficient. Table I. Eq. [1], for a given strain rate, determines the minimum temperature, and [2] the maximum temperature, below or above which no "dynamic strain-aging" can occur. According to the calculation, which uses the given quantities, serrations should only be observed within the cross-hatched temperature regions in Fig. 1, and this is in good agreement with the experiment. The effect of varying impurity concentrations is indicated schematically in Fig. 2: only Eq. [I] is affected. Setting Eq. [I] equal to [2], one can calculate the limiting concentration cmin which first causes serrations. The second method uses the aging condition by Cottrell and Bilby6,7 \£i/ \ n. a / where n(t) is the number of impurity atoms, which segregate at a dislocation line of 1 cm length after the time t (t in our case is the time between "repeated yield drops" in the serrated curve, or, the time until the above mentioned strain E&apos; is obtained, i.e., -1 sec for medium intensity or serrations). no is the number of impurity atoms in 1 cm3 and A = Qb4ep[(1 + v)/(l - v)], derived from equations given in Ref. 7. p is the shear modulus, 18,800 kp per mm2 for tantalum, 12,200 for molybdenum, AE the tetragonal distortion caused by interstitial impurities in a bcc lattice (approximately 0.4 for both tantalum and molybdenum) and v Poisson&apos;s ratio (0.35 for tantalum, 0.30 for molybdenum). From Eq. [3], combined with the condition for a pronounced yield drop as formulated by cottrel16 (at least one impurity atom segregated at the unit length of a dislocation), again a no min, and hence the concentration Cmin can be calculated.

Jan 1, 1970

By GUY C. RIDDELL, Donald M. Liddell

THE electronic arts today constitute the outstanding development in the field of rare metals, if not indeed in the arena of scientific progress at large. The year 1930 may become known as the year in which the electronic tube took hold of the wheels of industry; it is the year in which the tube&apos;s emancipation from the art of communication was proclaimed. The little tube which made a $500,000,000 industry out of a vacuum has now been applied to mining, manufacturing, transportation, chemistry, and other industries. Not many appreciate the extensive utility that e1ectroni.t tubes have already found in transportation, where they control the speed and security of express trains, as well as operate traffic lights on important highways-in the case of the Detroit-Windsor bridge counting the traffic and instantly turning the reports into the superintendent&apos;s office some distance away. In an Ohio steel mill, ten-ton ingnts &apos;rash back and forth through the rolls, reversed by their own shadows. The vacuum tube also starts, stops, and levels, fast passenger elevators.

Jan 1, 1931

By G. Barbery

Since the original paper, two methods have been introduced to compute the parameters of the three parameter size distribution equation: [ ] Both of them are based on graphical means, which are time-consuming and of little statistical significance. A program has been developed, using the Gauss-Newton method to compute by nonlinear regression analysis the parameters of the equation. Although the method is quite general in curve-fitting applications, it does not appear to be used in the field of size analysis, and a brief description is given. As applied here, the Gauss-Newton method involves the minimization of the least squares: [ ] where n is the number of sieves used. The second member of Eq. 2 can be approximated by a multiple Taylor&apos;s series expansion of first order about a starting value [ ] The minimization of Q (r,s,Xo) means: [ ] Putting Eq. 3 into Eq. 2 and differentiating, we obtain a system of equations which can be represented in matrix symbolism (box) The system can be solved for: [ ] and the operations repeated with new values: [ ] The starting values for r and s are taken as 1, for Xo, a value higher than the maximum sieve opening value. Applied to the data given by Herbst 5,6 for batch grinding of 7 X 9 mesh dolomite, the parameters given in Table 1 were obtained. The discussion of the significance of the residual sum of squares is a difficult subject in multiple nonlinear

Jan 1, 1972

By J. S. Browning

The U.S. Bureau of Mines has been experimenting with flotation processes to separate the spodumene-beryl ores mined at Kings Mountain, N.C. The success to date as well as the present status of the process is discussed. Further experimentation is underway and studies will be made on the milling costs involved in the flotation process. The pegmatites of the Kings Mountain-Lincoln ton, N.C., area constitute the largest known domestic reserve of beryl and spodumene. The reserve is estimated to contain 90 million tons of pegmatic material with 1,280,000 tons of recoverable Li,O(lithia) as spodurnene.&apos; The pegmatites also contain 0.4 to 0.5 pct beryl disseminated throughout the orebodies. The pegmatites may contain a potential reserve of 240,-000 tons beryl, equivalent to approximately 34,000 tons of BeO. Different flotation methods for separating beryl from feldspar or quartz, or both, have been developed by various investigators.2-7 On the other hand, published information is limited on concentration of spodumene-beryl ores. As the response of beryl and spodumene to flotation is essentially the same, a successful separation of the two minerals depends upon use of a selective depressant or a selective collector for one of the minerals. Several years ago, the U.S. Bureau of Mines, recognizing the need for developing a large domestic supply of strategic beryl, undertook studies to develop improved methods of recovering this mineral. Because of the low beryl content of the pegmatites, economic production of the beryl entails its recovery as a byproduct of spodumene flotation. Thus, the development of procedures that would provide for maximum recoveries of the spodumene, as well as the beryl, was a primary objective of the studies. Tests were made on run-of-mine ore and spodumene flotation tailing from the Foote Mineral Co.&apos;s spodumene concentrator at Kings Mountain (Fig. 1). Pet-rographic analyses of the ore and flotation tailing are given in Table I. Detailed analyses and examinations of the ore and tailings revealed that the beryllium was present in the form of a low-alkali beryl. The crystals were small, rarely larger than 14-mesh diam, and were clear and colorless. About 10 pct of the Li20 content of the ore was present in the mica and feldspar components of the pegmatite. In some weathered ores the associated clays also contained small amounts of lithia. This is typical of pegmatites in the Kings Mountain area. LABORATORY TESTS In the past, a vigorous chemical treatment of the spodumene surfaces with acid or caustic soda has been considered essential for satisfactory selective flotation of the spodumene from the other minerals in pegmatites. Many tests were made during this investigation to determine if chemical treatment of the spodumene could be eliminated in favor of a reagent combination that would depress the other minerals while selectively floating the spodumene. A simple reagent combination and process was developed that gave better spodumene recovery and grade of concentrate than the more elaborate acid or caustic treatment methods previously used. The finely ground ore pulps were conditioned with either an ammonium, alkali, or alkaline earth lignin sulfonate and sodium fluoride, and the spodumene was floated and cleaned using oleic acid as the collector. The spodumene tailing was deslimed, conditioned with sulfuric acid and coco amine acetate, and floated to reject mica. The mica tailing was thickened and conditioned with hydrofluoric acid, then washed to remove the acid. The washed pulp was conditioned with sodium hydroxide for pH control, and the beryl was floated and cleaned with oleic acid as the collector. Table II summarizes the results of the laboratory test work. About 77 pct of the spodumene and 75 pct of the beryl were recovered from the pegmatitic material. The spodumene concentrate assayed 6.1 pct Li20 and 0.01 pct BeO, and the beryl product assayed 3.0 pct Li20 and 1.57 pct BeO. Similar results were ob-

Jan 1, 1961

By V. Jares

DESPITE the fact that a combination of metals-aluminum-zinc-tin, and sometimes aluminium-zinc-cadmium-is extensively used for aluminum solders, as well as for die-castings, the constitution of these alloys has not yet been made clear. I. BINARY SYSTEMS The system aluminium-zinc is the basis of the ternary alloys under consideration. Their composition was made sufficiently clear by the investigations of Roscnhein and Archbutt,1 Bauer and Vogel,2 Sander .and Meissner,3 Hanson and Gayler4 and Isihara.5 Only the temperature of decomposition of the crystals s seems still to be doubtful, whether it is considered as a compound of Al2Zn3 (according to Bauer and Vogel) or as an intermediate phase of variant composition (according to Hanson and Gayler). This temperature is given by most of the authors, as in the neighborhood of 256° C., only Isihara giving 280° C. As its accurate determination is of special importance in the study of the ternary alloys under consideration it was experimentally controlled in the following manner: An alloy corresponding in composition to the formula Al2Zn3 was made, in which the temperature effect was found to be the greatest. This was drilled and a silver-constantan thermoelement inserted into the cavity so as to be in direct contact with the alloy. The whole was then very slowly heated and the heating and cooling curves determined. The transition temperature from the heating curve was found to be 281° C., whereas-from the cooling curve it was 252° C.

Jan 10, 1926

By Richard W. Smith

THERE are three distinct varieties of phosphate rock, in Tennessee, known commercially as: (a) the "brown" rock, which is the residual pro- duct of the weathering and natural concentration of certain phosphatic Ordovician limestones; (b) the "blue " rock, which is an unaltered phosphatic stratum of Mississippian or Devonian age; and (c) the "white" rock, which is the result of chemical replacement and deposition. Before 1894, South Carolina and Florida had supplied most of the phosphate of the United States, South Carolina leading until that date and Florida from then until the present time. In December, 1893, the blue phosphate of Tennessee was discovered almost simultaneously on Swan Creek, in Lewis County, by two independent parties-by one as the result of a careful and systematic search for a workable deposit of the long known kidney phosphate, and by the other through mistaking it for a "bloom" of coal. Leases were taken and, with further prospecting disclosing other deposits in the region, the development progressed as rapidly as &apos;could be expected without railroad transportation

Jan 1, 1924

By C. S. Samis, J. C. Mitchell

Sodion activity data have been obtained for the Na-A1 system for sodium concentrations in aluminum between NN, = 25 . 10-and 300 x 10&apos;. This concentration intert-a2 encompasses those sodium concentrations nor1)zally encountered in aluminum reduction cell operation. The sodium activity data were measured by a two-phase equilibration of sodium between a lead and an aluminam rich phase. The Na-Pb system was emplojed as a reference for the determination of the actiz7itj 0.f sodium. The activity of sodiin in aluminuwz exhibits large positi2.e deviations frorn ideality and a strong dependence, on concentration below NN, = 100 x 1K6. The inteated data indicate that the activity of aluminium is equal to its mole fraction over the range of miscibility of the Na-A1 sgstem. The data on the Na-A1 binary have been combined with experimental data on the cryolite-A1 system at 1025°C to obtain the activities of Na F and AlF, in liquid cryolite oz2er the cornposition 1-ange encountered in aluminum cell operation. The results are in agreement with activities calculated from the NaF-AlF, phase diagram. ALUMINUM is produced commercially by the electrolytic reduction of aluminum oxide dissolved in molten cryolite. There is considerable controversy over the actual mechanism of the discharge processes, but sodium potentials in the systems appear to play an important role in the reduction mechanism. The metal-salt reaction involving NaF and aluminum to produce A1F3 and sodium is responsible for the presence of sodium in the aluminum metal phase. Additional sodium may be produced from the simultaneous deposition of sodium and aluminum at the cathode as a result of a cathodic overvoltage. runert&apos; has suggested that sodium gas at atmospheric pressure would be the result of reaction between cryolite and aluminum at 1000°C. Subsequent investigations have shown that production of sodium at atmospheric pressure does not occur. These later investigations can be conveniently separated into two categories. The first involves sodium, aluminum, and cryolite, in which the sodium activity was measured. The second includes a lead phase for sodium activity measurement. Jander and errmann,&apos; studied the reaction: at 1090°C in alumina crucibles under an atmosphere of dry, oxygen-free nitrogen. The equilibrium constant for the reaction was expressed in terms of concentration. Their results in Fig. 1 show an increase in sodium content of the aluminum with increasing NaF/A1F3 weight ratio. Pearson and waddington3 performed similar experiments at 1000°C. Their results are included in Fig. 1. Dewing and ollinshead have measured the sodium content of aluminum as a function of the NF/AF, ratio at 1025"C, Fig. 1, and ewin&apos; measured the sodium content of the aluminum in a system involving the solid reactants NaF, cryolite, and liquid aluminum. This reaction is different from those discussed above. Two solid phases, NaF and Na3A1F6, and a liquid aluminum phase were present. The sodium concentration in the aluminum was determined by the temperature. Dewing&apos;s measurements covered the temperature range 679" to 896°C. Omo, Matsushima, and 1t02" investigated the equilibrium 6NaF ential thermal analysis. Stokes and Frank6 determined sodium activities by

Jan 1, 1970

By Thomas M. Drown

The process for determining phosphorus in iron now in most general use in the laboratories of iron and steel works, is, I think, the one proposed bv Mr. Emmerton." In this process the solution of the iron for precipitation by ammonium molybdate is effected by treating the iron with nitric acid, evaporating to hard dryness in a dish, taking up with hydrochloric acid and driving off the greater portion of the hydrochloric by nitric acid. This procedure accomplishes, first, the destruction of all the carbonaceous matters; and, second; it renders all the silica insoluble. Experience has proved the former—the complete oxidation of the carbon—to be absolutely essential; but the explanation usually given, namely, that unless the carbon compounds are destroyed they will have a solvent action on the yellow precipitate, I am inclined to

Jan 1, 1890