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Impact Transition Temperatures of Some Pearlite-Free Mild Steels As Affected by Heat Treatments in the Alpha Range H. P. Tardif (Canadian Armament Research and Development Establishment, Quebec)—Mr. Josefsson is to be congratulated for his study of a most difficult subject and for the theories proposed to explain the re- sults. One point which, however, might not have received proper attention is that of the shape of the stress-strain curve at the yield point of quenched and furnace-cooled specimens and of specimens strain aged

Jan 1, 1956

By John Hays Hammond

This is an era of " expansion; and, conformably with the change in commercial conditions, the function of the mining engineer, as well as that of his confreres in many other professions, has also expanded. From the position of an engineer, limited to the determination of technical questions, the engineer of to-day has come to assume an economic importance in those branches of industry dependent upon engineering skill for their development. He is indeed an engineer of limited usefulness who does not go further professionally than to submit a purely technical report on subjects presented for his consideration. While he has the same responsibility as formerly in the solution of the technical problems involved, he is further expected to supplement his report with advice on the financial and commercial aspects of these problems. For the great majority of problems presented to the engineer ultimately involve the determination of the pecuniary, relations of the propositions under consideration. The great corporation lawyer no longer earns his fee by merely submitting his opinion as to the legal issues involved in law-suits affecting the corporation; he now assumes charge of the entire legal work, including both the organization of the corporation and the maintenance of its legal status thereafter. In like manner, the engineer, whose report was, as I have said, formerly confined to the determination of the geological and other cognate features of a mining enterprise, is now expected, not. only to embody information on these subjects in his report, but also to give his opinion whether the property offered for sale in pursuance of such an enterprise is worth the price asked for it. Moreover, if he recommends the purchase of a property, he incurs a certain moral responsibility for its efficient manage-

Nov 1, 1908

By AIME AIME

AT the end of September, ' the metal-producing industries were almost prostrate, the production of fuels was largely curtailed, there was a fair degree of activity in general manufacturing, while retail trade was moderately good. Looking at industry on the whole, there was a large percentage of unemployment, the degree of which has increased, progressively, month by month since the beginning of 1921. There is the prospect of much destitution and misery this winter; yet while' in some, quarters, idle workers are already being fed from, commissaries; in other quarters profligacy; in "spending continues, unabated. Amid this confusion in conditions there is;' much that appears paradoxical, but in fact it is not so and indeed everything is running pretty true to form: Such activity in production as there is to be seen is mainly in textiles; - leather goods, foodstuffs, etc., i.e., consumption goods for immediate use. Even in hard times 105,000,000 people must buy a good deal of clothing and food. Besides this there is indispensable repair work and- maintenances. Thus, the good business of the year in white lead for painting. The chief uses for the metals, however, are in the production of capital goods, and except for occasional and special reasons nobody in his senses is capitalizing anything at present prices for labor. Hence several millions of men are idle. The impoverishment of Europe and the exhaustion of her credits adds to this by curtailing our export trade.

Jan 1, 1921

By Wing L. Lew

LEAD, silver, and zinc, in quantities of economic importance are found in the Aguilar ore. The lead occurs as galena and the zinc as sphalerite and marmatite. The silver occurrence is more complex. Pyrargyrite and proustite have been identified only occasionally. Galena is silver-bearing and so are the various other sulphides, though to a lesser degree. The principal nonsulphide gangue minerals include calcite, quartz, wollastonite, rhodonite, and various calcium, aluminum, and iron silicates. A typical analysis of, the ore is: Pb, 11.2; Zn, 12.3; Fe, 4.4; Mn, 2.2; Cu, 0.15; S, 11.2; CaO. 7.6; "Insoluble," 50.1 percent; and Ag 263 g per ton. Crushing is done in three stages. The primary crusher at the mine is set to deliver about a 5-in. product. The crushed ore is then transported to the secondary crushing plant by a 3-km cableway where the general practice is to hold the product of the first Symons to about 1 in., and of the second Symons to about 1/2 in. When the ore is soft and rich the product of the first Symons is by-passed directly to the ball-mill bins. Dust control in the secondary crushing plant is effected by enclosing the dust-emanating sources and exhausting the enclosures with a Clarage No. 18 fan driven at 1300 rpm by a 20-hp motor. Use is also made of spray water at one or two critical places. Every effort is made to keep the air free from visible dust. Dust counts taken at the working places show dust concentrations of less than six million particles ner cu ft. The composition

Jan 1, 1947

By AIME AIME

ABOUT one hundred were in attendance when Donald M. Liddell opened the session* on non-ferrous metallurgy at 2 p. m. on Tuesday. F. F. Col- cord was vice-chairman. For the first part of the session the chair was turned over to Frank G. Breyer, who introduced G. L. Spencer, Jr., to read his contribution (T.P. 378), "High Silica Retorts at the Rose Lake Smelter," which was an account of the method of manufacture of high-silica zinc retorts at the Rose Lake smelter, and of the service given by these retorts. The materials used are, by volume, 50 per cent clay, 25 per cent silica flour and 25 per cent grog. Written discussion of the paper by E. M. Johnson, W. R. In- galls and M. M. Neale was read by Mr. Breyer. Mr. Johnson explained that their practice in manufacture differed very little from Rose Lake practice, but that their retorts did not last as long, possibly because Eagle-Picher does not use a hydraulic retort press or sintered ore. He ascribes the longer life of silica re- torts to the fact that they do not bend under heat. Mr. Ingalls pointed out that silica retorts are no better as heat conductors than clay retorts, but that they do have a superior rigidity in the furnace. The character of the retorts does not affect the density of the charge. Mr. Neale gave the procedure in the manufacture and use of high-silica retorts at the Donora zinc works, not

Jan 1, 1931

By R. W. Raymond

(Cleveland Meeting, October, 1912.) UNDER the names of Conservation, Social Justice, the New Nationalism, and Progressive Democracy, many earnest reformers are calling for a new system of Federal government to replace the one which they ascribe to our fathers, and declare to have been outgrown. They are proposing the lease by the United States of certain natural resources on the public domain, for the profit of the U. S. Treasury, instead of the sale of such resources to private citizens or associations of citizens. In the present paper, I shall try to show that this notion is neither new nor good. It is clear that the United States is owner, as well as sovereign, of public lands acquired through conquest or purchase from other nations, as it was owner of the public lands expressly ceded to it by the original thirteen States. Its policy with regard to such lands involves, therefore, two entirely distinct questions: What shall it do as owner ? and, What shall it do as sovereign ? The latter question, it must be confessed, has played but a small part in our history. All the prerogatives of sovereignty which were not explicitly conferred upon the Federal government by the original States were retained by them. The ownership or control of precious or other metals or minerals in the earth, for instance, was thus reserved to the several sovereign States. New York, South Carolina, and other States have passed laws on this subject, without regard to Federal authority. As new States have been successively admitted to the Union, the tacitly accepted theory has been,. that they thereby acquired all the reserved rights of the original States. These newer States largely outnumber the first. thirteen; and it is inconceivable that they would submit to any deprivation of sovereignty based on historical grounds. One of them-Texas-came into the Union by its own voluntary

Oct 1, 1912

By P. K. Currie, J. V. Walters

Solution mining of magnesium salts (Carnallite and Bischofite) is taking place near Veendam, in the northeast Netherlands. The magnesium salts are used for the production of magnesia sinter, used as a base material for the manufacture of refractory bricks for furnaces. This paper gives, first, an introduction to the operational procedure followed in Veendam, with the emphasis on some of the unique aspects, and then discusses rock-mechanical aspects of the cavity behaviour. The creep behaviour of magnesium salts is described, and Finite Element calculations on cavity stability and potential surface subsidence are discussed.

Jan 1, 1985

By Charles H. Fulton

CHARLES H. FULTON, chairman, presided at the first session of the Mineral Industry Education Division on Wednesday morning. Reporting for the program committee, Edward Steidle, its chairman, pointed out that its function was not to arrange programs for meetings but to plan a program for the Division to follow in the development of its activities. This was appropriately followed by presentation and discussion of his paper, "Basic Trends in Mineral Industries Education," which, being available in printed form, was only presented in oral abstract. Jay A. Carpenter submitted interesting written discussion that was read, in his absence, by A. M. Smith. Most of the morning was devoted to the discussion of the paper, which was too extensive and ranged too widely to attempt to report in much detail. H. T. Mann, H. P. Hammond, Cadwallader Evans, C. H. Fulton, T. T. Read, D. F. McFarland and P. B. Bucky joined in the discussion, Mr. Hammond making a plea for more unification in mineral industry education, saying that in the study he made for the Society for Promotion of Engineering Education about 35 different curricula preparatory to work in the mineral industry were discovered to exist. He felt that most of the needs of the mining industry could he met by men who had had four years of engineering training of good enough basic quality to permit them to advance along special lines. However, there was apparently a growing demand, as reflected by the increasing number of candidates for the Master's degree in engineering, for men with more thorough training in the fundamentals.

Jan 1, 1933

THE great development of the mines and metallurgical works of this country during the last few years, accompanied as it has been by the investment of enormous sums of money in purchasing lands, and in the erection of improvements, requires that advantage should be taken of the accumulated knowledge of engineers, superintendents, and' others, in mastering &he problems which are constantly presenting themselves for our action. Among those may be mentioned the consideration of more economical systems of mining in our coal and metal-liferous mines, improved methods of transportation above and below ground, unwatering and ventilating mines, the mechanical preparation of coal and other minerals, the various metallurgical processes, and, in fact, every question tending to the attainment of two great objects : 1st. The more economical production of the useful minerals and metals. 2d. The greater safety and welfare of those employed in these industries. In European countries, where the arts of mining and metallurgy have long been the subject of the most careful study, no means have been found so effectual in attaining the end above proposed as the free interchange of experience among those actually engaged in these industries, and this object has been accomplished, mainly, through the medium of institutes, associations or societies, composed of those engaged in these occupations, and by the periodical publication of essays or papers, communicated to such societies by their members. I t must be evident to all practical men that the interchange of the varied experience of those engaged in such occupation in this country could not fail to advance very materially the desired objects; it is, therefore, proposed to establish an American Institute of Mining Engineers, which will hold its meetings periodically in the great mining and metallurgical centers, where works of interest, such as mines, machine shops, furnaces, and other metallurgical works, can be inspected, and the members exchange their views, and consult for mutual advantage upon the difficulties encountered by each; these transactions or proceedings, when published, would form a most valuable and greatly-needed addition to our professional literature. I t is proposed that a meeting of those sympathizing with the object above mentioned shall be called for the purpose of organizing such an association, the place and time of meeting being Wilkes-Barre, Pa., and the month of April or May. Communications indicating the opinion and wishes of all, both as to these points, and also as to the organization and objects of the Institute, will be gladly received by any of the undersigned, and a notice of the date of meeting, which will be arranged to suit the greater number, will be duly communicated. Any

By R. C. Buehl, J. P. Morris

F. D. Richardson—The authors are to be congratulated on this further contribution to our knowledge of the thermodynamics of the interaction between sulphur and carbon and silicon in liquid iron. As the authors state, the influence of carbon and silicon on the activity coefficient of sulphur in liquid iron is clearly of great importance in the blast furnace, since it must cause a three to fourfold improvement in the partition of sulphur between slag and metal. The influence of increasing temperature in further increasing the activity coefficient of the sulphur in the metal in the blast furnace by increasing the carbon content is also of interest. This effect, however, is probably only part of the reason for the general observation in blast furnace practice, that the sulphur content of the metal is lowered by increasing temperature. Other contributing factors are the lowering of the oxygen potential in the presence of carbon by increasing temperature and the probable increase in the activity coefficient of the lime in the slag for the same reason. The former of these effects, which works via the (CaO) + [S] = (CaS) + [O] equilibrium, might possibly account for a 70 pct improvement in the sulphur partition and the latter might give a further 50 pct improvement. C. Sherman—I would like to compliment the authors on their very careful research. If I may, I would like to show results of calculations on the carbon-sulphur-iron system similar to the ones that were shown in our paper for the silicon-sulphur-iron system. For Fe-S-C ternary system k=PHgs/PH2 x 1/(f1°) (f2°) (%S) where fs = sulphur activity coefficient fs' = fs for Fe-S system of equal pct S f3° = f2/f2 for Fe-S-C ternary system This same analysis has been used on other systems, but the results shown in fie.- 7 are for carbon and silicon. L. S. Darken—I would like to make two brief comments in addition to complimenting the authors on an apparently very precise and accurate investigation. The first is that the present work is in agreement with a calculation by Larsen and myself." Our calculation (much less precise than the present work) was based on: (1) Unpublished work on the sulphur content of molten iron (1.5 pct at 1500°C) in equilibrium with graphite and an iron sulphide slag; (2) the distribution coefficient of sulphur between slag and carbon-free liquid iron. We expressed the result in a form equivalent to log 7. = 0.18 [%C] which gives an activity coefficient (?s.) of sulphur only slightly higher than the authors find and certainly within the precision of the earlier work. My second comment concerns the correlation of the thermodynamic findings with atomistics. A rough pic- ture of the atomic arrangement in the liquid solution is rather easily conceived for this particular liquid solution containing iron, carbon, and sulphur. Carbon has a very much stronger affinity for iron than for sulphur. Hence we may conclude that a sulphur atom will but seldom be adjacent to a carbon atom—since this would be a position of high energy. From the metallic radii of iron and carbon we know that six iron atoms pack neatly around one carbon atom. Thus each carbon atom in retaining this shell of iron atoms (which latter may not be replaced by sulphur on account of the high energy requirement) decreases the available positions for each sulphur atom by six. Hence each atomic percent of carbon decreases the equilibrium sulphur content by 6 pct (of itself). Or, at low concentration each atomic percent of carbon increases the activity coefficient of sulphur by 6 pct. This is in good agreement with the observed increase (6 or 7 pct at low carbon content). It is indeed gratifying to find a case where, by such simple reasoning, quantitative agreement is found between precise data and the modern picture of the atomistics of the metallic state. J. P. Morris (authors' reply)—We would like to point out that there is an error in the equation on p. 322 of the paper. The third equation should read: ½S2 (gas) + H2 (gas) = H2S (gas) The authors wish to thank everyone for the interest they have shown in the paper. In regard to the general observation in blast furnace practice, that the sulphur content of the metal is lowered by increasing the temperature, Dr. Richardson is correct in stating that the cause can be attributed only in part to the increase in activity coefficient of sulphur resulting from the rise in carbon plus silicon content of the metal with rise in temperature. However, this factor is probably an important one. The results of one experiment, performed since this report was written, indicate that at a constant temperature the addition of silicon to a melt saturated with carbon causes an increase in the activity coefficient of sulphur even though the carbon solubility is lowered. In this test, 2.5 pct silicon was added to a melt saturated with carbon and maintained at 1400°C. Although the carbon content dropped from 4.85 to 4.1 pct, the activity coefficient of sulphur was increased by about 20 pct.

Jan 1, 1951

By H. Foster Bain

THE "miracle of production." which was such an essential element in winning the European war, was nowhere more in evidence than in our Western States. In shipbuilding alone the Pacific Coast States -et a mark never before equaled, and in production of war goods of many kinds, both Rocky Mountain and Coast States accomplished more than their proportionate share if measured by population standards. This was only possible because of the building of immense new plants of many types, largely financed with Government money. Their operation has built up payrolls in the West and brought a measure of prosperity which Westerners are naturally anxious to have made permanent. A widespread doubt obtains, however, throughout the nation and even in the Western States themselves, as to whether, and if so to what extent, this may prove possible. The question has been raised as to whether the national treasury has not been raided to stock the Western ranges with a voracious breed of white elephant .

Jan 1, 1945

By G. V. Jere, V. Krishnan, C. C. Patel

Standard free energy and standard enthalpy changes as a function of temperature have been calculated for the chlorination reactions of different oxides constituting columbite and tantalite. The tallies of standard lee-energy change (F) indicate the possibility of pvefeential chlorination of different oxides but the ease 0.f chlorination of columbium pentoxide at about 250°C and the chlorinating tendency of columbium pentachloride in promoting the chlorination of tantalum and other metal oxides, p7-evetzt the separation of columbiu?n and tantalum from other oxides and pom each othel.. It is likely that low temperatuves of chlorination and continuous 1err2oval of columbium pentachloride from the ..eaction zone may help partial separation of columbium from tantalum as well as from titanium. The standavd enthaply change (AH?) values shotr that 1ou.-temperature chlorination around 300" to 500°C is likely to sustain the chlorination , without external heating. COLUMBIUM (niobium) and tantalum metals, their alloys and interstitial compounds are finding extensive uses in nuclear reactors and high-temperature equipment.la-3 These metals also find uses in chemical process plants, electrical rectifiers and capacitors and as "getters" in electronic tubes.la With the development of Kroll process of reduction of volatilized titanium tetrachloride by magnesium for the production of titanium metal, chlorine metallurgy is receiving greater attention. Chlorine metallurgy has several advantages, the foremost amongst them are: the ease of chloride formation, separation of the different constituents of minerals by selective chlorination, and the reduction of the chlorides in vapor phase to the respective metals. Recently, Si-bert, Kolk, and Steinberg4 have considered a number of methods for the preparation of columbium metal and the most promising is found to be the halide reduction. Since the minerals columbite and tantalite are comparatively abundant in nature, the future of the metallurgical processes depends on the utilization of these minerals for the production of columbium and tantalum chlorides by chlorination. In this paper, an attempt has been made to interpret thermodynamically the chlorination of individual oxides constituting columbite and tantalite, with the help of the recent thermodynamic data.5-8 For this purpose, standard free energy and standard enthalpy changes of the chlorination reactions of the oxides with chlorine, both in absence and presence of carbon as the reductant, have been calculated as a function of temperature and represented graphically. Similar calculations for the reactions employing carbon tetrachloride and carbonyl chloride as chlorinating agents have also been incorporated in this paper. REPORTED WORK ON CHLORINATION Cuvelliezg has patented a process for the separation of columbium and tantalum from their concentrate, wherein 75 pct Cb05 is claimed to be chlorinated at 1050°C in the course of 7 hr using chlorine or chlorine containing nonreducing gases, the products of reaction being CbC1, or CbOC1,. At this temperature, Ta,05 is claimed to remain unaffected. It is further claimed1° that at higher temperatures, the proportion of Ta205 chlorinated increases while that of Cb205 diminishes. During the studies on the action of chlorine on individual metal oxides, Kangro and Jahn" have observed that Ta,05 is not chlorinated even at 1200" in the stream of chlorine, while 75 pct of Cb,05 is converted into CbOC1, around 900 to 1100°C. The chlorination of Cb205 by chlorine in the presence of carbon, investigated by Lind and Ingle,' and

Jan 1, 1962

By W. I. Duvall

A brief review of the resonant frequency and ultrasonic pulse methods for obtaining elastic constants of rock samples shows that the equations for an iso-tropic elastic solid commonly used to calculate Young's modulus, modulus of rigidity and Poisson's ratio can result in appreciable error if the rock is even slightly anisotropic. Consideration of the equations that relate bar velocities and free medium velocities to elastic constants for orthotropic, transversely isotropic and isotropic solids shows that a combination of the two methods can be used to determine average elastic constants for a single sample of rock. The determination of elastic constants in different directions requires a large number of tests on oriented samples. The use of both the resonant frequency and ultrasonic pulse methods is recommended so that the determination of both Young's modulus and modulus of rigidity is independent of the determination of Poisson's ratio. The dynamic elastic constants of rock can be determined in the laboratory from measurements on small samples which may be in the form of right circular cylinders (diamond drill core). Either the resonant frequency6 or ultrasonic pulse method1 can be used to determine the longitudinal and shear velocities in the same specimen. The resonant frequency method provides a measure of the longitudinal bar velocity, V,, and the torsional bar velocity Vt; whereas the ultrasonic pulse method provides a measure of the free medium longitudinal velocity, Vp, and the free medium shear velocity, V, . The elastic constants (Young's modulus E, modulus of rigidity G, and Poisson's ratio v) are calculated from the density of the specimen, p, and one of the pairs of velocities by means of equations from isotropic elastic theory. For the resonant frequency method the equations are: It should be noted that Eq. 5 is derived from Eq. 4 and 6 and the relation between the elastic constants for an isotropic solid as given by the first part of Eq. 3. The in situ determination of dynamic elastic constants is accomplished by generating a complex seismic pulse in the rock and measuring the arrival times for the longitudinal and shear phases of the pulse at two distant points.5 From these travel times and the distance of the travel path both Vp and Vs are determined. The density of the rock is determined from samples in the laboratory, and Eq. 4 to 6 are used to calculate the elastic constants. These three methods involve the assumption of isotropy and perfect elasticity, and require the use of the relation v = (E/2G) - 1, which holds only if the elastic constants are the same in at least two directions. The calculation of v by means of Eq. 3 introduces considerable error, as a 1% error in V, and V, results in a 20% error in v. If frequencies for samples with a length-to-diameter ratio greater than four and a length greater than 8 in. are measured carefully, the experimental error can be kept to 1%. However, it is not unreasonable to expect that the variation in Vb and Vt with direction may exceed 1%. Thus, for even a small percentage of anisotropy the use of Eq. 3 can result in considerable error in v. The calculation of v by Eq. 5 also involves some uncertainty as a 1% error in Vs and Vp can result in a 6% error in v. By means of the pulse method both

Jan 1, 1965

By J. P. Heller

The purpose of this discussion is to comment briefly on one of the points raised in the paper. The topic is that referred to in the Conclusion 2, in which the authors note a "disproportionate increase in mixing rate" as they proceed from a displacement performed at viscosity ratio 0.998 to one at 1.002. The recovery curve of this displacement, Fig.2A, shows a quite noticeable difference between the two runs in which displaced and displacing liquids were interchanged. This difference is ascribed by the authors to the change in viscosity ratio between the two experiments. This interpretation of the experimental results must certainly be based on rather precise measurements of the fluid viscosities or, at least, of the ratio of their viscosities. The ordinary Ostwald viscometer, employed in the usual way, is only just able to distinguish between liquids whose viscosities differ by two or three parts per thousand. The experimental refinements which then must have been necessary to measure with any precision a viscosity ratio of 1.002 would be worthy of mention. Indeed, one would have expected the authors to devote at least a paragraph to the display of this technique. For the same reason - to emphasize that the details of such unusually critical experimental work should be reported and discussed in the literature — I would have liked to see some comment by the authors on the requirements for temperature control during both the viscosity measurements and the displacement experiments. The temperature coefficient of viscosity of Soltrol C at room temperature has been measured in this laboratory at about - 1.9%/1°C. How much did the coefficients for the fluid mixtures used in the experiment differ from this and from each other Even if the two fluids were identical in this respect, it would appear that a temperature difference of .l°C between them in the flow system would produce a viscosity con- trast equal to that imposed by their composition. Reference to the experimental solutions of these problems would render Conclusion 2 more credible. Published theoretical work on the stability problem contains no indication of such extreme sensitivity to the viscosity ratio in the immediate neighborhood of unity. On the contrary, perturbation calculations such as those made by Chuoke1 and Perrine2 lead to initial finger growth rates proportional to the first power of the viscosity difference. The later instability growth calculated by Scheidegger,3 using the assumption of zero pressure gradient perpendicular to the average flow, is also simply proportional to the viscosity difference. The conflict regarding the sensitivity of the dependence of instability growth or mixing rate on the viscosity contrast needs explicit recognition in the literature. In particular, it would seem that the experimental work reported here should be supported by a more detailed description of the viscosity controls. Further discussion of possible alternative interpretations of the data would also be in order. For instance, is it possible that the unconsolidstted bead pack used changed its characteristics between the runs (due, perhaps, to the handling and inverting involved in the injection of the front) Or, are the data points of Fig. 2A averages from several runs performed in a series in which the two liquids alternated as displaced and displacing fluids? To summarize, it seems to me that the relationship asserted by Conclusion 2 in the paper needs the support of more detailed experimental evidence. REFERENCES 1. Chouke, R. L., van Mews, P. and van der Poel, C.: "The Instability of Slow Immiscible Viscous Liquid-Liquid Displacements in Porous Media", Trans., AIME (1959) Vol. 216, 188.

By M. E. Wadsworth, J. S. Cho

Colloidal silica dissolved in aqueous suspensions of high surface area thoria was permitted to adsorb on the thoria surface. Silica in three forms was identified by means of infrared spectroscopy and characterized by Si-O vibrational modes in the 9.0 to 10.5 region. A band at 9. 1 was attributed to free unad-sorbed silica, while adsorbed silica resulted in bands of greatest absorbency at 9.4 or 10.3p, depending upon the character of the surface bonding. Size considerations, the amount of silica adsorbed, and the character of the infrared spectrum for strongly adsorbed silica has been interpreted as evidence of formation of chain or layer silica linkages on the thoria surface. Infrared spectroscopy has been used successfully in recent years for the identification of minerals and synthetic inorganic substances. Unfortunately, infrared studies of silicate minerals have not proceeded to the point that unambiguous assignments may be made for Si-O vibrational modes as affected by lattice substitutions and structures. Several investigators have presented infrared spectra of silicate minerals, 1,7 and their work has pointed to the potential value of infrared to identify minerals as well as to note the sensitivity of various Si-O modes to structural and substitutional environments. The strong infrared absorption of various Si-O vibrational modes makes the infrared method a very useful tool for the study of silica adsorbed on the surface of solids of high surface area. Spaepen et a18 studied the adsorption of silica on thoria surfaces from aqueous solutions of silicic acid up to 300°C. A general review of the application of the infrared method to the study of surface adsorption has been presented by Pliskin and Eischens.9 EXPERIMENTAL Du Pont colloidal silica, Ludox SM (16.36% SiO2) and Ludox HS (30.25% SiO2) in aqueous suspensions were used as the sources of silica for the adsorption studies. The thoria used for this study was supplied by Union Carbide Nuclear Co.* under the preparation *Chemical Technology Div., Union Carbide Nuclear Co., Oak Ridge, Tenn. . number D-16-650. It was fired from the oxalate at 650°C and had a surface area of 32.4 ± 0.6 m2 per g measured by nitrogen adsorption. The chemical analysis of the D-16 thoria in ppm was: CO3= (5500), NO3- (< 4), so4±PO4 (100), and Si (20). The Ludox silica was placed in contact with the thoria in a two-liter autoclave10 between room temperature and 250°C. Slurries were made by placing 1 g of thoria in one liter of distilled water containing various additions of the silica sol. Samples were removed from the autoclave by opening a small stainless steel valve. Extracted samples were centrifuged for 10 min and excess solution was decanted. The sample was then dried for several hours at 80°C. Infrared samples were prepared by thoroughly mixing 10 mg of the thoria with 400 mg KBr in polystyrene vials on a "Wig-L-Bug" amalgamator. Pellets were pressed under vacuum and had final dimensions of 1.2 cm diam and 1.2 mm thick. Infrared spectra were

Jan 1, 1963

By J. Gurland

The wmk is concerned with the estimate of the degee of continuity of a particulate phase dispersed in a matrix. The first section is a verieu: of the parameters nzeasurable by quantitative rnetallogvaphy, namely the contact area and, under certain conditions, the number of contacts between particles of one phase. In the second section, the frequency of particle contacts is related to the degee of continuity of a randomly embedded phase orz the basis of the lattice-percolation model of Hamrnersley and others. THE extent of continuity of the constituent phases may greatly influence the structure-sensitive properties of phase mixtures, particularly if the phase properties differ significantly. An example from the literature1 is shown in Fig. 1. The marked decrease of the electrical resistivity of sintered silver-alumina bodies near 25 pct by volume of silver presumably occurs because the more conductive phase changes from a discontinuous to a continuous structure. Other example of electrical- and thermal-conductivity transitions are cited by kingery In view of these observations, a knowledge and understanding of the connectivity of the microstructure may be of considerable practical importance. This study is concerned with one aspect of the genera1 problem, namely the estimate of the degree of continuity of a particulate phase dispersed in an opaque matrix. The first section reviews the parameters measurable on a polished cross section by auantitative metallography, such as the contact area and under certain conditions, the number of contacts between particles of one phase. In the second section, an attempt is made to relate the frequency of particle contacts to the degree of continuity of a randomly embedded phase. For the purpose of this discussion, the aggregate has two constituents: the particulate phase and the matrix. The latter is considered to be homogeneous. The term "particle" is used with the meaning of "grain", i.e., a minute unit of matter which is usually a single crystal of a readily distinguishable substance within the confines of a simply connected boundary. While many of the concepts which are used here to describe the structural variables characterizing the microstructure of phase mixtures are qualitative and ill-defined, they are presented with the intent of stimulating further work of a more general and rigorous nature. I) PARTICLE CONTACT, CONTIGUITY, AND MEAN FREE PATH 1) Measurement of Contiguity. The fraction of the total internal surface of a phase a shared with particles of that same phase in a two-phase mixture of and $ is indicated by the contiguity ratio:3 whereis the area of the interface between o particles, and Sap is the area of the interface between a particles and matrix P, per unit volume of mixture. The contiguity ratio ranges from 0 to 1 as the distribution of the a phase changes from a completely dispersed to a completely agglomerated structure. The interfacial areas may be obtained from simple intercept measurements on a random plane, after Smith and Guttman where and N are the numbers of intercepts between a random line of unit length on a plane of polish and the interparticle and interphase interfaces, respectively. The equations are valid for any distribution of particle sizes and shapes.

Jan 1, 1967

By M. S. Seltzer

In a previous paper1 it was shown that activation energies for steady-state creep in lead sulfide single crystals varied with the concentration of electronic defects. For n-type lead-excess crystals, values for the creep activation energy, Qc, decreased from 2.9 to 2.2 ev as the carrier concentration increased from 1017 to 1017 electrons per cu cm, while Q, increased from 1.6 to 2.3 ev for p-type sulfur-excess crystals as the concentration of holes increased from 6 X 1017 to 1018 per cu cm. It was also shown in Ref. 1 that the Q, values could best be correlated with the sum of the self-diffusion activation energies in PbS, i.e., for a given concentration of electrons or holes Q, = QPb + Qs, where Qpb and QS are the activation energies for diffusion of pb210 and s35 in PbS. This result suggests that creep rates are controlled by at least two atomic defects, one for lead migration and one controlling sulfur transport. It would be most desirable to interpret these creep energies in terms of an atomic defect disorder model for lead sulfide. Studies of creep rates as a function of sulfur pressure2 indicate that the defects controlling creep rates are singly ionized lead and sulfur vacancies, VPb and Vs. This hypothesis can be more firmly established by determination of Q, under conditions of constant atomic defect concentration rather than constant electronic defect concentration as has been previously done. Therefore, several measurements have been made of Q, on crystals whose con- centration of lead vacancies or sulfur vacancies has been fixed by equilibration under appropriate sulfur pressure and temperature. It was indicated in Ref. 2 that high-temperature isotherms are available which show how the concentrations of various atomic point defects in PbS vary with composition over the entire homogeneity range for the compound. Two such isotherms are shown in Fig. 1 for 900" and 1000°K. Utilizing these isotherms the concentration of a given defect, say Vbb, may be held constant over a particular temperature range by adjusting the sulfur pressure as the temperature is changed. Thus the concentration of one defect suspected of controlling creep rates may be held constant while other defect concentrations vary. The apparent activation energy for formation of these defects can be obtained from the isotherms giving their concentration as a function of sulfur pressure. Activation energies for creep obtained under conditions of constant defect concentration can then be compared with defect formation energies and certain possible atomic defects can be eliminated as creep-controlling species. We have performed creep experiments as a function of temperature at a stress of 244 g per sq mm under conditions which fixed the lead vacancy concentration, V&apos;, at 1016, 3.2 x 1016, and 3.2 x 1017 cm-3, and one were the sulfur vacancy concentration, Vs, was held at lo17 cm-3. The results are presented in Fig. 2 as creep rate, k, vs reciprocal of absolute temperature, 1/T. Specimens 34, 35, and 36 were deformed under constant lead vacancy concentration while specimen

Jan 1, 1969

By H. Stuart, L. Zwell, N. Ridley

specimen that was subjected to 700°C for 250 hr is shown in Fig. 2(c). The precipitates in this foil appear round and exhibit only very faint strain contrast. From this evidence, along with that described above for the symmetry of the strain field, it may be concluded that this coherent precipitate is spherical, which is generally the favored shape for coherent precipitates when the lattice parameter mismatch is small.12 These observations are consistent with the assumption that this precipitate is the y&apos; (Ni3Al, Ti) phase. y&apos; is known to be spherical in the early stages of precipitation. It is fcc and is similar in composition to the matrix and thus would have contrast similar to that of the matrix as do these precipitates. Direct identification of the spherical precipitate did not prove possible because of its low volume fraction and small size. The results of this investigation suggest that the increases in yield strength and the decreases in elongation observed in 45-Fe 30-Ni 20-Cr alloys containing about 0.4 pct A1 and 0.4 pct Ti on prolonged aging at 550" to 700°C are very likely due to the presence of a coherent, spherical precipitate, thought to be y&apos;. Mi-crohardness measurements indicated that the precipitation of semicoherent M23C6 resulted in some matrix hardening. However, this precipitation process occurs much more rapidly than the changes in mechanical properties at these temperatures. 1C. L. Clark, J. J. B. Rutherford, A. B. Wilder, and M. A. Cordovi: J. Eng. Power, 1962, vol. 84, p. 258. 2 F. A. Comprelli and U. E. Wolff: USAEC Report GEAP-4745, General Electric Company November, 1964. 3C. N. Spalaris: A Monograph, USAEC Report GEAP-4633, General Electric Company, July, 1964. THERE have been many X-ray investigations of the room temperature lattice parameters of austenite which has been retained in quenched steels of various carbon contents. The results of these investigations have been collected by Wrazej,1 Wever et al.,2 and by Roberts3 and are included in Fig. 1 due to Pearson.4 The dashed line in Fig. 1 was considered by Roberts3 to most reliably describe the variation with carbon content of the lattice parameter of retained austenite. This line is given by the equation: a (Å) = 3.555 + 0.044 wt % C and recent unpublished measurements by one of the authors (LZ) support this relationship. The object of this communication is to draw attention to a relationship which describes the variation of the room temperature lattice parameter of &apos;equilibrium&apos; austenite with carbon content, and which is different from that for retained austenite. The relationship a(Å) = 3.573 + 0.033 wt % C has been obtained from lattice parameter measurements made on equilibrium Fe-C austenites at elevated temperatures, which have been extrapolated to room temperature. The room temperature lattice parameter of 3.555Å which the Roberts&apos; relationship gives for pure y-Fe is no: in agreement with the value of 3.573Å obtained when the high temperature lattice parameter data of Basinski et aL.5 and of Goldschmidt6 is extrapolated to room temperature. A linear extrapolation was

Jan 1, 1970

By D. W. Fuerstenau

MEASUREMENT of zeta potentials is a useful tool to study the surface chemistry of minerals under flotation conditions.1,2 Because there is continued interest in this approach, the apparatus for obtaining zeta potentials of nonconducting solids by the streaming potential method is outlined here. Fig. 1 illustrates the streaming potential apparatus." The streaming potential cell or plug consists of two 24/40 standard ground joints (4) joined with a piece of pyrex tubing 60 mm long and 12 mm in diam (5). The electrodes are made of bright platinum disks 19 mm in diam and 1 mm thick through which 0.5-mm holes have been drilled (6). To the surface of each is welded a piece of 80-mesh platinum gauze. Each electrode is permanently mounted on the ends of the inner parts of the two standard joints by means of a platinum wire (7) which connects it to the tungsten seal at the end of the cell (8). For ease in cleaning and handling the apparatus, the streaming cell is fastened to the 500-ml reservoir flasks (1) by means of two 18/9 ball and socket joints (2). This particular arrangement permits passage of the solution in either direction through the plug of particles. Flow of solution can be stopped by a stopcock (3). One of the reservoir flasks has a large opening to permit insertion of either a thermometer or a pair of electrodes for measuring pH of solutions within the system. In making the experiments, the plug is filled with 48 to 65-mesh particles, but a layer of 28 to 35-mesh particles is placed at each electrode to prevent any of the finer particles from passing through holes in the electrodes. The assembled apparatus is shown schematically in Fig. 2. To eliminate CO2 from the solutions, all experiments are conducted in a nitrogen atmosphere. Nitrogen, used to drive solutions through the plug, is passed through a bottle of concentrated KOH solution to remove CO2 (9). A 9-liter ballast reservoir (10) is used to maintain a more nearly uniform pressure. A series of stopcocks controls the direction of flow nitrogen to the flasks (11). Tubes of as-carite prevent backflow of CO2 into the system (12). Driving pressure, which can be set at any desired value, is measured with either a water manometer (13) or a mercury manometer (14). Reservoir flasks have side arms for making pressure corrections for the difference in water levels in the flasks. Streaming potentials are measured by the circuit illustrated in Fig. 2. The electrodes from the plug are connected through mercury wells (15) to a reversing switch (16), which reverses the polarity of the electrodes depending on the direction of flow of solution through the plug. The streaming potential is measured with a Leeds and Northrup type K2 potentiometer (17). Proper choice of null instrument is important because Eq. 1 assumes that the current which escapes through the measuring instruments is negligible. An ordinary galvanometer cannot be used to determine the null point because

Jan 1, 1957

By Francis P. Sinn

IN the zinc smelting industry the year 1947 seems to have been one of putting one&apos;s house in order rather than one of any material technical development or radical change in operating conditions. Labor generally has been in better supply but several plants report a scarcity of skilled workmen. Some plants continue to operate on the basis of a six-day week and will probably continue to do so until labor is more plentiful. Only one plant is known to have operated on a curtailed basis because of labor shortage, but here the difficulty was lack of proper housing facilities. Necessary materials and equipment for much-needed maintenance and modernization have been in short supply so these programs have often been delayed. Laborsaving devices of the "Payloader" type have been more generally used for handling materials. Slab zinc production was discontinued during the last months of the year at Danville, 111. and at Langeloth, Pa. Both of these plants used the Hegeler type of furnaces fired with producer gas. It is understood that the rolling mill and possibly the acid plant at Danville will continue to operate. At Langeloth acid will be produced from

Jan 1, 1948