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By R. H. Widmyer, G. M. Wood

This investigation was prompted by the absence of a simple, accurate method to predict optimum second stage separation pressure in three stage separation operations. Three stage separation as used here includes two separators plus the stock tank. The first stage pressure is usually fixed by gas sales conditions and the third stage is at atmospheric pressure. Thus, the second stage pressure is the only one that may be varied in-discriminantly during production operations. No variations in temperature were considered in this study, even though it will vary among systems, for a change in temperature has little effect on the optimum pressure. Optimum pressures may be determined from flash calculations, but these are tedious unless a computer is available. An early attempt to develop a simpler method&apos; yielded an equation which gave the optimum pressure only as a function of initial and final pressure. Experience, however, confirms theoretical relationships which show that composition as well as pressure and temperature must be a factor. This indicates that the basic relationship should be an equation of the form, where P, is second stage pressure, P, is first stage pressure, A is a function of P. (stock-tank pressure) and the system composition, and n is a function of the number of stages and the system composition. Fig. 1 shows the basic variation of P2 with P for a fixed system composition. A series of such figures clearly showed the effect of composition. The peak of each curve reflects that second stage pressure at which the stock-tank recovery (gal/MMcf) residue gas is a maximum value. DEVELOPMENT OF NEW CORRELATION Wellstreams having 17 different analyses, ranging from low gravity crude to condensate, were used to determine the effect of composition. Each wellstream was flashed through three stages to determine the optimum second stage pressure for each first stage pressure. Equilibrium vaporization ratios proposed by Latham and Campbell were used throughout. The heptane plus fraction, for simplicity, was assumed to have the properties of octane. The results were subjected to an empirical analysis in an attempt to develop a correlation- that would be (1) simple, (2) accurate, and (3) eliminate the need for any flash vaporization calculations. This analysis yielded two equations, one for wellstreams having a specific gravity greater than one (air = 1.0) and one for those less than one. For crude streams (specific gravFor condensate (specific gravity < 1.0),

By Henry Ferguson

THIS paper is a preliminary statement, intended to present the more important results of the recent studies of the ore deposits of the Alleghany district in advance of the publication of the complete report, now in preparation. The Alleghany district (Fig. 1) has been a producer of gold since the early days of California gold mining. As in other California gold camps, placers yielded the bulk of the earlier production, but during the last 30 years lode deposits have been the only important source of output. The district differs from other California gold-quartz districts in that nearly all the production is from small shoots of high-grade ore. The mining camps of Alleghany and Forest are on the western flank of the Sierra Nevada range about 20 miles west of the crest. The gently sloping lava-covered plateau which controls the upland topography has been trenched by deep canyons of the westward flowing streams, which are cut to depths of as much as 2000 ft. below the crests of the ridges. The district is about 18 miles from Nevada City but the automobile road which connects the two places is 31 miles long. The senior writer first visited the district in 1913 and published a short description of the lode deposits.1 The increasing importance of the district made further study desirable. A detailed topographic map was therefore made by W. B. Upton, Jr., of the U. S. Geological Survey, in the spring of 1924, and the senior writer spent parts of the field seasons of 1924 and 1925 in the district. For the second field season the Geological Survey was fortunate in securing the services of R. W. Gannett, who had already done geologic work in the district for several of the mining companies. Owing to the death of Mr. Gannett in October, 1925, just before the close of his field work, the work of preparation of the entire report fell to Mr. Ferguson. He takes this opportunity of acknowledging how deeply he is indebted to Mr. Gannett for his excellent work in the field, and his realization of how greatly the completion of the report on the district has suffered from lack of Mr. Gannett&apos;s assistance in the office. In October, 1.928, after the completion of the first draft of the manuscript, Mr. Ferguson made a short visit to the district.

Jan 1, 1929

By Austin E. Dwight

IT has been shown by Oelsen and Wever&apos; that the effect of a solute element on the allotropic transformation in iron is dependent upon the quantity

Jan 1, 1957

By F. Keller, E. H. Dix, L. A. Willey

The consideration of alloying elements for aluminum has led to a series of investigations of the equilibrium relations between aluminum and those alloying elements. Therefore, the aluminum end of the aluminum-antimony diagram has been studied. The general form of the aluminum-antimony equilibrium diagram has been worked out by Campbell and Mathewsi and by Tammann.2 Canlpbell and mathews described principally the beginning of solidification. They found the curve of beginning of solidification rising gradually from the melting point of pure alunlinum to a maximum at about 67 per cent. aluminum. After a slight lowering of the curve at a little greater antimony concentration the curve again rises to a maximum at 18.4 per cent. aluminum, which corresponds to the compound AISb. The curve then drops to the melting point of pure antimony. Tamrriarln explained the maximum occurring at about 67 per cent. aluminum as the result of the slow formation of the single compound AISb. The space lattice of the compound AISb, according to Owen and Preaton,³ is face-centered cubic, the antimony atoms being intermeshed with an identical aluminum lattice. Very little, if any, work has been done on aluminum alloys containing small amounts of antimony. The Present Investigation It has been the purpose of this investigation to determine the solid solubility of antimony in aluminum and also to investigate the eutectic temperature and concentration. The experimental work has been carried out in a manner similar to that described in a previous paper4 from this laboratory.

Jan 1, 1931

By M. J. Mullikin, J. B. Conway

Equations capable of representing combined first -and second-stage creep behavior include the Andrade, Cottrell-Aytekin, Garofalo, and de Lacombe equations along with a third-degree polynomial in t1/3. Employing some recent high- temperature creep data for arc-cast tungsten the effectiveness of these expressions was evaluated. It was found that, in this instance, the most accurate representations were afforded by the third-degree polynomial in t1/3 and the de Lacombe equation. Also noted was the fact that the Andrade equation gave results just slightly inferior to those obtained with the third-degree polynomial, definitely better than those due to the Cottrell-Aytekin equation, and slightly superior to those furnished by the Garofalo equation. EXPRESSIONS designed to describe combined first -and second-stage creep behavior must possess certain specific characteristics. At time zero the equation must reduce to a strain value corresponding to the instantaneous deformation on loading. Then in the early moments following load application transient-creep behavior must be described to reflect a creep rate which constantly decreases with time. And finally at larger time values linear (or at least nearly linear) strain-time behavior must be accounted for to yield the steady state or minimum creep rate. Some equations, such as the one based on the parabolic creep law, yield fairly satisfactory results in transient analyses but are not effective at all when combined first- and second-stage data are to be analyzed. Other equations give equally accurate results in both instances although in general the complexity of the equation is slightly increased. For example the Andrade1 equation: has found fairly general application in expressing first-stage creep behavior. Furthermore the contribution of the exponential term becomes more and more prominent as the time increases and causes this equation to exhibit a point of inflection at large values of time. With a proper selection of equation constants the curve can be made fairly flat in the region of the inflection point indicating a desirable equation form for combined first- and second-stage creep analysis. Another equation form with the proper characteristic is that of Cottrell and Aytekin:2 e =a +bt1/3 +ct [2] Obviously as time increases the first derivative of this expression approaches a constant value to suggest application to combined first- and second-stage creep analysis. Similarly a third-degree polynomial in t1/3: e -a + bt1/3 + ct2/3 +dt [3] has the same characteristics. Expressions of this type have been shown3 to be very effective in the analysis of transient-creep behavior and the fact that the first derivative has the same characteristic as Eq. [2] suggests use in the combined analysis.

Jan 1, 1967

By T. C. M. Pillay, John Chipman

The Si-0 equilibrium in liquid iron was investigated in some detail by Gokcen and Chipman1 who reported equilibrium constants of the following reactions: In each case the thermodynamic equilibrium constant K was obtained by extrapolating K&apos; to infinite dilution. Their results on reaction [I] were consistent with those of earlier observers, and there seems to be little doubt as to the approximate validity of the equilibrium product determined. On the other hand, the results on reactions [2] and [3] indicated unusual curvilinear relationships between the activity coefficients of silicon and of oxygen and the silicon concentration. Since a linear relation is observed in all other similar instances, it was concluded that some source of error had affected the gas-metal equilibrium relationships. Recently the authors undertook a restudy of these equilibria with the view especially to establishing the equilibrium constant of reaction [2]. Their experiments, however, were discontinued before a tbroughly satisfactory answer had been obtained and consequently have remained unpublished until the present time. Quite recently Matoba, Gunji, and Kuwana2 published the results of a very thorough study of these equilibria. It is the purpose of the present note to Compare these three sets of experimental data, a comparison which leads to Confirmation of the results of Matoba and coworkers. The experimental arrangements described by Dutilloy and Chipman were employed. A controlled mixture of Hz, H,0, and argon was led into the induction furnace over the surface of the Fe-Si melt contained in a silica crucible. On account of the slow approach to equilibrium, runs were continued for at least 8 hr and, in some cases, as much as 12 hr. Samples were taken by means of silica tubes at the start and during the final 4-hr period of each run. Out of twelve runs only seven appeared to have approached equilibrium with sufficient certainty to be reported here. The results of these experiments, all at 1600°c, are shown by the triangles in Fig. 1. Equilibrium was approached from both oxidizing and reducing conditions and the direction of approach is indicated by the shape of the triangle. Attempts to extend the study to higher silicon concentrations were unsuccessful on account of the transfer of silica from the metal bath to the upper portions of the crucible by means of a silicon-monoxide mechanism. Matoba, Gunji, and Kuwana used similar methods and approached equilibrium from both sides. Their results at three temperatures are shown by the solid lines of Fig. 1. A line corresponding to 1600 deg is interpolated from their equations and is shown by the dotted line. The results of Gokcen and Chipman at 1600 deg in the range 0.02 to 2.0 pct Si are also shown. At concentrations up to about 0.6 pct Si, these investigators approached equilibrium from both directions, and their results in this range appear to be trustworthy. Above 1 pct Si, however, all of their experiments involved oxidation only, as shown by a decrease in the silicon content of the bath. It now seems certain that they failed to reach equilibrium at these higher silicon concentrations and that the curvilinear relation shown by their results is incorrect. It is evident that their results in the lower silicon range are in good agreement with those of Matoba and coworkers. In fact, a straight line drawn through their results would parallel the dotted line and would differ from it by only 0.05 in log K. The new data also lie close to that line. It may thus be concluded that the three sets of data are in good agreement and that the equations proposed by Matoba and coworkers for reaction [2] are satisfactory . They take the limiting value of log K&apos;, at 0 pct Si as log K ,. The slope of each line gives the value

Jan 1, 1962

Jan 1, 1890

By Arthur Nomann

Recording instruments may be conveniently described under the headings of: (1) geophones, (2) amplifiers, (3) recording cameras, (4) miscellaneous parts. Geophones Geophones or seismometers are actuated by slight earth movements, and generate electrical currents, which are amplified and recorded. In all geophone desigm there is provision for differential movement between parts of the mechanism and the signal voltage is generated as a function of this differential movement. The part that conforms to the movement of the ground is called the support, and the part that remains more nearly stationary with respect to more distant unactuated parts of the earth is called the steady mass. The mechanical period of the geophone is the time required for an oscillation of the steady mass after an initial impulse is given it, and is determined by the effective stiffness of the spring joining the two parts together in relation to the weight of the suspended part. Geophones have been used with frequencies varying all the way from less than 10 cycles per sec. to several hundred cycles per second. Those with a natural frequency of less than, say, 100 cycles

Jan 1, 1940

By Arthur Nomann

Recording instruments may be conveniently described under the headings of: (1) geophones, (2) amplifiers, (3) recording cameras, (4) miscellaneous parts. Geophones Geophones or seismometers are actuated by slight earth movements, and generate electrical currents, which are amplified and recorded. In all geophone desigm there is provision for differential movement between parts of the mechanism and the signal voltage is generated as a function of this differential movement. The part that conforms to the movement of the ground is called the support, and the part that remains more nearly stationary with respect to more distant unactuated parts of the earth is called the steady mass. The mechanical period of the geophone is the time required for an oscillation of the steady mass after an initial impulse is given it, and is determined by the effective stiffness of the spring joining the two parts together in relation to the weight of the suspended part. Geophones have been used with frequencies varying all the way from less than 10 cycles per sec. to several hundred cycles per second. Those with a natural frequency of less than, say, 100 cycles

Jan 1, 1940

By F. T. Havard

(Canal Zone meeting, November, 1910.) I. INTRODUCTION. THE present truce in litigation between Western smelting and ranching interests gives opportunity for a summary of the results achieved by metallurgists in condensing fume and de-acidifying furnace-gases. In the absence of complete records of past experiments, there has been a good deal of unnecessary duplication of attempts and&apos; failures. Yet, especially under the recent policy of our large corporations, looking to the economic recovery of the values of by- and waste products, original and, in some cases, effective measures have been developed by American metallurgists. In the case of Bliss vs. the Anaconda Copper Mining Co., the Montana Supreme Court, recognizing the progressive efforts made to render the flue-gases innocuous, and the value to the community of the smelting company&apos;s operations, refused to hamper its work, and returned a verdict in favor of the defendant. In the trial, the experimental firms of the company in the so-called "affected region" were proved to be thriving perfectly, showing that immunity was guaranteed to vegetation and stock by the wide distribution of the sulphurous acid gas in the dry air of Montana. Indeed, L. S. Austin has proved that by the time the fume is 4,000 ft.. distant from the stack, the percentage of sulphurous acid has been diminished from 2.28 to 0.00045; and Angus Smith has shown that rain must contain 40 parts per million of free acid before vegetation is affected. The arsenic in the stack-gases is but a very small part of the original content of the ore, of which 80 per cent. and over is rejected in the concentrator and furnace waste-products or recovered in the flues. Nevertheless, neither the peace in Montana nor the armistice

Aug 1, 1910

By L. W. Berger, and R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were stzdied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.&apos; This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

By E. A. Gulbransen, J. W. Hickman

DURING the past two decades considerable progress has been made in the art of manufacturing heater alloys. The conventional iron-chromium-nickel alloys have been improved by the addition of small quantities of other elements. Up to the present time, to our knowledge, there has not appeared a systematic study of these alloys where the newer tools of investigation have been brought to bear on the problem. It is not yet clear what roles the additional elements play in increasing life time in usage. As a first approximation one might guess that elements such as manganese, silicon, zirconium, calcium and aluminum would aid in the formation of a protective film on the alloy surface, thus retarding the oxidation rate and increasing lifetime. If these additional elements do form protective oxides in the outer surface of the oxide film, it may be possible to identify them by means of reflection electron diffraction. It is also possible that the additional elements may not diffuse to the surface but may remain at the interface between the oxide and the metal. Then, too, the major elements in the alloys undoubtedly form oxides which are stratified on the surface. If the minor elements concentrate in a layer in contact with the substrate where they undergo oxidation and if this oxide film offers resistance to the diffusion of iron, chromium and nickel ions, then the lifetime of the heater element might be expected to increase. It is also possible that preferential reduction in the diffusion rates of the several ions may Occur to such a degree that oxides may form in the body Of the film and On the outer surface which are different from those that would normally form if the additional elements were not present. The use Of transmisson electron diffraction may aid us in jnterpreting these phenomena. UP to the Present time all Of the factors which influence the lifetime of a given heater element are not definitely known. Among these are: (I) The rate of oxidation of the alloy. This may be dependent upon the composition and the physica1 state of the "alloy. (2) The stability of the structure of the coating which forms. Transitions from one structure to another or solid phase reactions resulting in a change of composition may occur. The tendency of the film to adhere to the substrate when heated and cooled successively will be important. (3) The evaporation of various constituents from the alloy such as the remova1 of carbon by Oxygen in a decar-burization reaction. With these possibilities in view, an electron diffraction study of the oxides occurring on six different nickel-chromium alloys was undertaken with the hope that the results of this study could be correlated with oxidation rate studies as determined by means of the vacuum microbalance method1 and with lifetime tests carried

Jan 1, 1949

By G. Thodos, R. B. Grieves

A method has been developed for the accurate calculation of the cricondentberm and cricondenbar temperatures of multicomponent hydrocarbon mixtures of known composition. The mixtures may contain any number of components including paraffins and isoparaffins, olefins, acetylenes, naphthenes and aromatics. This approach is based upon the mole fraction of the low-boiling component in the mixture and graphically presents the ratios of the cricondentherm and cricondenbar temperatures to the pseudocritical temperature as {unctions of a boiling-point parameter. The only requirements are the critical temperature, normal boiling point and the approximate vapor pressure behavior of each component. For mixtures of more than two constituents a stepwise calculation procedure is necessary where the pseudocritical temperature is based upon the critical temperature of the pure low-boiling component and upon the actual cricondentherm or cricondenbar temperature of the mixture of all the remaining higher-boiling components. From an analysis of 22 binary systems (123 compositionsl, the average deviation of calculated cricondentherm temperatures from reported values is 0.87 per cent, based on degrees Rankine; and for 10 multicomponent mixtures containing from three to six components, the average deviation is 0.98 per cent. From an analysis of 18 binary systems (104 compositions) the average deviation of calculated cricondenbar temperatures from reported values is 0. 79 per cent; and for 15 multicomponent mixtures, 1.47 per cent. Equations, derived from the graphical relationships, are presented which enable rapid calculations for both binary and multicomponent systems. INTRODUCTION With the increasing tendency towards the use of high pressure processes, the need for an accurate method of calculation of the properties of a multicomponent hydrocarbon mixture in the critical region is becoming more essential. Critical region phase relations are also significant in gas condensate reservoirs, for which a knowledge of the fluid phase boundaries and regions of retrograde condensation make it possible to evaluate optimum operating conditions. The possibility of liquefaction in the underground structure may be established, and information on the feasibility of the use of repressurizing may be determined. A typical phase diagram for a multicomponent hydrocarbon mixture is presented as Fig. 1. This figure also shows the regions of retrograde behavior encountered by following lines AB and AC. If accurate methods of calculating the temperatures and pressures at the critical, cricondentherm (maximum temperature) and cricondenbar (maximum pressure) points of multicomponent hydrocarbon mixtures of known composition were available, it would be possible to estimate closely the entire phase diagram of any mixture. Several methods have been presented in the literature for the estimation of the critical temperatures and pressures of multicomponent mixtures containing all types of hydrocarbons and including the fixed gases.4-8,21 Considering the cricondentherm and cricondenbar points, the work is more limited. Etter and Kay5 have developed rather complex equations for

By Irving Palmer

DURING the past 15 years in this country there have been few additions to the literature of lead smelting. After the consolidation of the principal smelting companies at the beginning of this period it became the policy of the larger company not to permit the publication of details in regard to many of its metallurgical processes. This led to similar action on the part of some of its competitors. The result, of course, was a decided decrease in the number of papers written upon the practical side of the subject. Even upon the theoretical side the contributions have been few. It would seem that the industry as a whole has suffered from this general unwillingness to exchange information. While it is true that a given company is entitled to the reward that may come from its own development of a new process, it is also true that a still greater reward might be the result of a free exchange of ideas with other plants. This principle has been recognized for a long time in other metallurgical industries, notably those engaged in the smelting of iron and the manufacture of steel. It is pleasing to note that the leading lead-smelting company has very recently decided to modify its policy of secrecy, and to permit the publication of papers covering some details of its metallurgical methods. The statement has been made that there has been but little progress in lead smelting during the period just referred to. This impression is due in part to the scarcity of papers written on the subject. There has been, it is true, some discussion of the new sintering processes, but with little reference to detail, and to the effect that blast roasting has had upon the industry as a whole. In spite of the prevailing belief, it may be said that lead smelting, in common with other metallurgical industries, has made steady and substantial progress. It is the purpose of the present paper to discuss briefly some features of the industry as it is now conducted, with special reference to the blast-furnace practice in the larger silver-lead smelting plants of the United States and Mexico.

Jan 7, 1914

By Homer S. Frankhouser

Materials may be dredged, processed, stored and loaded for shipment at a single site in water depths ranging from 250 to 1200 ft. Solution mining may also be accomplished in deep sea situations. And, open air subsea mines with direct surface access may be developed and worked under the ocean floor. These concepts for deep sea mining are the results of extensive testing of individual components of the proposed systems by Dravo Ocean Structures, Inc., a subsidiary of Dravo Corp. A basic structure in these systems is the articulated platform. The platform consists of a gravity- type base and a buoyant cylindrical column which is constructed at an onshore location, towed to the offshore site and installed in a matter of days without use of heavy equipment. The base is also buoyant for towing purposes. This allows for gradual flooding to the point of negative buoyancy for positioning and anchoring to the ocean floor.

Jan 1, 1971

By L. W. Berger, R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were studied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.&apos; This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

By A. P. Watts

FOREWORD THE problem of concentrating the disseminated lead ore of southeast Missouri is extremely simple. The economic mineral is galena and the gangue is dolomite. The ore assays from 4 to .6 per cent. lead, 80 per cent. of which is recovered in a 70 per cent. concentrate.. The ore is crushed through 10 mm. and sized on 2 mm.; the oversize is jigged, while the undersize is tabled, and the slime treated by flotation. The district is the largest lead producer in the world, the output of metallic lead for the year 1915 being 183,906 tons. Over 20,000 tons of ore a day is being treated. The management of the different properties is progressive and always open to suggestion. The fact; however, must not be lost sight of, that the problem in the district is peculiar, as the average ore contains but 80 to 120 lb. of a metal normally selling at about 4c. per lb. The low price of the metal limits the treatment system to one of low cost. An elaborate treatment is neither logical nor advisable. An engineer first visiting the district may consider that the method of treatment could be improved

Jan 10, 1917

For the use of those who prefer manila rope to wire rope for light hoisting and hauling, the Ingersoll-Rand Co. has brought out a new model Little Tugger Hoist which is designated No. 11. The square piston, reversible driving engine, automatic lubrication, inclosed gearing, rum release clutch and worm-operated band brake are essentially the same as in the No. 1 model which was introduced about two Years ago. The main differences are in the diameter and length of the drum, the width of the flanges and, necessarily, the main frame and overall dimensions. The new No. 11 Little Tugger has a hoisting drum 7 in. in diameter by 17 in. long with 5-in. flanges. This accommodates 300 ft. of 7/8 -in. manila, rope. The maximum capacity of this hoist is conservatively rated at 600 1b. The weight of the hoist itself is 358 lb. It is 21 ½ in. long, 31 ¼ in. wide and 23 in. high.

Jan 12, 1916

By T. Kunitake, H. W. Paxton

The self-diffusion coefficient of chromium in various alloys in the iron-chromium system has been measured. A variation in Dofrom 10-4 for pure chromium to a maximum of 102 near 60 pct Cr appears with a range of activation energy from about 50 to 80 kcal per mol. The general pattern of behavior observed is not consistent with present theories of diffusion by a vacancy mechanism. Suggestions are made for further clarifying experiments. RECENT work on the self-diffusion of chromium,&apos; ?-uranium2-4 and ß-zirconium,23, 26 has indicated that these elements have very low Do (10-3 to 10-4) compared to that conventionally expected for vacancy diffusion. Pound et al.5 have suggested that this may be due to ring diffusion being operative, and have proposed a model which gives Do of the correct order of magnitude. The essential difference between this model and Zener&apos;s earlier model6 is that whereas Zener assumes tight coupling between atoms in a ring to establish a vibrational frequency, Pound&apos;s model allows the atoms to vibrate essen- tially each in their own normal modes. The probability of each atom moving in the correct direction to cause a ring of n atoms to rotate by 2p/n must then be calculated as a "synchronal entropy" which may be -20 e.u. for a 4 atom ring. In iron, the latest determinations of self-diffusion yield Do in the range 18 to 522.7-9 The most accurate is probably that of Borg and Birchenall8 which is 118 ± 3. This value is not inconsistent with that expected for a vacancy mechanism. Since iron and chromium are very closely similar in size, are both transition metals, and their solution is thermodynamically ideal at temperatures of interest in diffusion, it appeared that a determination of self-diffusion coefficients, Do and Q as a function of composition would be of substantial interest to diffusion theory. The following measurements were made with this purpose in mind.

Jan 1, 1961

By K. Takahashi, I. Iwasaki

it is well known1 that racemic mixtures of optical isomers can be separated by passing their solutions through a column packed with r- or 1-quartz powder so that one of the isomers becomes adsorbed selectively on the asymmetric quartz surfaces. Although the natural occurrence of r- and 1-quartz is more or less equally distributed, some localities show enough deviations toward a higher proportion of l-quartz2 to suggest that optical isomerism might influence quartz flotation. Beta-amines have an asymmetric carbon atom, and therefore optical activity may be expected. Beta-amines are reported to behave quite differently from alpha-amines in the flotation upgrading of certain oxidized iron ores.3 It is of interest, for both practical and theoretical reasons, to determine whether or not optical isomerism plays a role in the amine flotation of quartz. In this article the results of Hallimond tube flotation tests and of adsorption measurements using d-beta-phenylisopropylamine on both r- and 1-quartz are compared. D-beta-phenylisopropylamine was chosen for the tests because it is commercially available in optical isomers. MATERIALS AND METHODS Brazilian quartz crystals were hand-sorted according to the difference in trigonal trapezohedral faces, and each crystal was further checked by the Airy&apos;s spiral.4 The respective crystals were then crushed, and the -150 + 200-mesh fractions were screened out for the Hallimond tube tests. The samples were cleaned by brief leaching with warm, dilute hydrochloric acid, and then by repeated rinsing with distilled water. In preparation for the adsorption measurements, they were then dry-ground in a pebble mill for several hours, washed a few times with distilled water, and finally dried in a vacuum desiccator. By means of the Krypton gas adsorption method, the specific surfaces of r- and 1-quartz samples were determined to be 27,700 and 19,800 sq cm per gm respectively, the difference being due mainly to the decantation procedure rather than to the inherent difference in their grindability. D-beta-phenylisopropylamine was the only collector used in the study. It was solubilized by neutralizing with 110% of the stoichiometric requirement of 0.1 N hydrochloric acid. The specific rotation of the d-beta-phenylisopropylamine was determined with a polari-meter using sodium D line to be, Although the d-beta-phenylis~prop~lamine showed absorption maxima in the wave length region of 250 to 270 millimicrons, due presumably to the phenyl group, these peaks were too sensitive to be used for colorimetric determination of the residual concentration in the adsorption measurements. The amine-picrate method, used in the colorimetric analysis of dodecylammonium chloride,&apos; was found to work satisfactorily for the d-beta-phenylisopropylamine. The adsorption densities were thus determined after equilibrating 40 gm of the ground quartz sample with 300 ml of solution by tumbling in separate glass-stoppered Erlenmeyer flasks for one hour. EXPERIMENTAL RESULTS Fig. 1 presents the adsorption densities of d-beta-phenylisopropylamine on the r- and 1-quarts in the pH range of 6 to 7.5. In agreement with data reported in the literature, the adsorption density of d-beta-phenylisopropylamine was slightly higher on the r-quartz than on the 1-quartz, although the difference was not as pronounced as one might expect from the capacity of r-quartz and 1-quartz to separate racemic

Jan 1, 1969