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By K. J. Brondyke, P. D. Hess

Two processes have been developed for improving the quality of molten-aluminum alloys before casting. The Filtration Process. which involves passing molten metal through a packed bed of granular filter material, is a rapid means of removing finely divided particles. It has the most potential in those instances where removal of inclusions is of primary importance. The Combination Fillration-Inert Gas Fluxing Process inuolzles introduction of an inert gas so that it will diffuse countercurrent to metal flow through the filter bed of granular material. Dissolved hydrogen is removed from the metal in addition to removal of finely divided particles. The Combination Process is most useful where both inclusion removal and attainment of conistently low-hydrogen-content metal are important. Metal treated by the Combination Process is of higher and more uniform quality than heretofore attainable with prolonged chlorine fluxing. Costs of the Combination Process can, for the most part, be offset by savings derived from high recoveries and increased production of superior-quality products. IMPROVEMENT in the quality of molten-aluminum alloys is secured generally through the use of some fluxing practice in a crucible, holding furnace, or ladle involving either gaseous or solid fluxing media. Typical fluxing agents may include the gases nitrogen, argon, or chlorine used either singly or as mixtures and the solids aluminum chloride or hexachloroethane. Regardless of the fluxing means used, the primary objectives are the adequate removal of both metallic and nonmetallic inclusions and reduction of hydrogen content to an acceptably low level. The ultimate goal is to produce ingots and cast products of high quality free from inclusions and porosity. The development of ultrasonics for measurement of internal quality, tightening of quality controls, and the application of the aluminum alloys to new or different commercial fields have been responsible for an ever increasing demand for improvement of quality of both cast and fabricated products. This demand for high quality has not been restricted to any single type of product. On the contrary, the demand encompasses about the entire variety of products including those for fabrication, those to be machined, buffed, or finished for decorative purposes, and those for critical applications where both surface and internal quality is of utmost importance. In many instances products acceptable in the 40's would now be scrapped as unacceptable by these higher present-day standards. With this ever increasing demand for higher quality, it became apparent at Alcoa that conventional means of melt treatment were inadequate in many instances and new approaches were necessary. Consequently the research program was intensified with attention focused on metal treatment during transfer in order to reduce the furnace processing time to a minimum in an effort to attain the desired results at a minimum of additional expense. As a result of this intensive research program which covered numerous variations and adaptations of conventional methods in addition to new methods of melt treatment, several new processes were developed, two of which will be described here. The first of these, a method of melt filtration, was patented in February, 1959.l The second process involving combination filtration—inert gas fluxing was patented in June, 1962. 2 Other melt-treatment processes developed during this period of investigation were patented as listed.3 FILTRATION PROCESS General Description. The Filtration Process, which involves passing molten metal through a packed bed of granular filter material, is a rapid method of effectively removing finely divided particles. It is an impingement-type filter; hence the size of the particles removed from the metal are considerably smaller than the interstices of the

Jan 1, 1964

By T. Egleston

The importance of condensing the gases which escape from furnaces so as to save both the fine particles of ore carried off mechanically and those which are volatilized, has for a long time occupied the serious attention of metallurgists in all parts of the world. It was my good fortune during the last summer to visit the lead and silver works at Ems, near Coblentz on the Rhine, and through the politeness of Mr. Freudenberg, general director of the works, to study in detail their methods of condensation, and to receive from him the important results which have been obtained through a series of experiments lasting over a number of years. I have thought, that these results would be of great interest to the members of the Institute and to other metallurgists in the United States, and I have, therefore, with the assistance of Mr. Freudenberg, prepared a careful, detailed description of the construction of the flues, as well as an account of the various experiments which have been made with them, and the conclusions arrived at as the result of these experiments. It may be said, in general, that the reason why so little attention has been paid in the metallurgical works of the United States to the collection of flue-dust, is that we are not generally aware of the large amount of material carried off by the gases. This is owing partly to the fact that little or no attention is paid to the subject, and also to the fact that the assays, which are almost invariably made in the dry way, show a result so much below the real contents

Jan 1, 1883

The Climax Molybdenum Company' s newest operation is the Henderson project, which is located on the east side of the Continental Divide. Ore reserves are estimated at more than 300 million tons at a grade of 0.49% MoS2. For mining the ore a modified panel caving system is used. The ore is transported to the Henderson mill on the west side of the Continental Divide on a 42 in. (1.07 m) gauge railroad through 9.6 miles (15.4 km) of tunnel and 4. 8 miles (7.7 km) of surface track, a total distance of 14.4 miles (23. 2 km). Each train consists of 30 ore cars with capacity of 22 st (20 mt) of ore or 660 st (599 mt) per train. The unmanned trains operate completely automatically. At the 54 in. by 84 in. primary gyratory crusher, the bottom dump ore cars pass over a dump scroll to discharge at a maximum rate of 100 st (91 mt) per minute. Dumped ore falls onto a rock box before passing over a 17 ft long by 46 ft wide (5. 2 m by 14 m) grizzly set at a 40° angle with bar spacings of 7 ½ and 8 ½ in. (191 mm and 216 mm) openings. An estimated 30 to 50% of the ore (which at times is wet and sticky) passes through the grizzly. The operators report that a shallower angle on the grizzly, perhaps 35º to 37º, would have been sufficient and would have prevented impact on the back of the crusher pocket by large boulders. This pocket as well as the crushed ore pocket under the crusher is lined with AR plate. The accompanying drawings show a "future splitter" and the operators are planning the installation of this unit to prevent impact and subsequent damage to the crusher spider. Crushed ore at an 8 to 9 in. (203 mm to 229 mm) size joins the grizzly undersize in the pocket beneath the crusher. This pocket is sized at 660 live st (599 mt) so that it will accept an entire trainload of ore. Crushed ore is removed from the pocket by a four-speed, 84 in. (2. 1 m) apron feeder operating at 9.6 to 29. 3 fpm (2.9 to 8.9 mpm). A 60 in. (1.5 m) takeaway conveyor operating at 480 fpm (146 mpm) delivers the crushed ore to a 58,000 st live and 193,000 st total (52,600 and 175, 100 mt) open stockpile under an A -frame supported tripper gallery. Impact idlers on the takeaway conveyor under the apron feeder discharge are mounted on wood blocks for a cushioning effect and ripped belt detecting bars are located behind each impact idler. The conveyor tunnel is of corrugated and galvanized steel construction rather than concrete. The concrete crusher enclosure is circular in design from its lowest level at elevation minus 110 ft 4 in. (minus 33. 6 m) to elevation

Jan 1, 1978

By F. C. Schora, H. P. Meissner

Both a graphical and an analytical technique are presented for calculating stream compositions and temperatures in adiabatic staged systems in which solids travel countercurrently to a gas stream. Such a system might be a tower containing several plates, on each of which the descending solid is fluidized by the rising gas stream. Examples are presented in which chemical reactions occur, including the oxidation of SO, by a solid catalyst and the gaseous reduction of iron oxides. COUNTERCURRENT staged processes involving reactions between solid and gas streams are becoming more common. These operations are generally carried out in a series of beds of fluidized solids, with each bed or "plate" acting as a stage. Fig. 1 is a schematic diagram of such a series of stages located in a column, down through which a solids stream moves from stage to stage counter to a rising gas stream. Typical reactions carried out in such systems are the dehydration of aluminum trihydrate, the calcining of limestone, and the gaseous reduction of iron oxides. Calculation of the performance of these counter-current systems rapidly becomes more complex with increases in the number of stages and in the number of chemical reactions occurring. Calcula-tional procedures for isothermal operations of such systems have been described.4 Actual tower operations, however, are generally adiabatic, and in consequence far from isothermal. The object here is to present both graphical and analytical techniques applicable to such adiabatic towers operating continuously and in steady state. In this introductory discussion, the graphical techniques presented are of the McCabe-Thiele type, rather than of the Pon-chon type. In all the examples presented, it will be assumed that both thermal and chemical equilibrium are attained in each bed. The assumption that the gas and solid streams leaving each bed are at the same temperature as the bed is in accordance with the familiar behavior of actual fluidized solid systems. Chemical equilibrium, on the other hand, is not necessarily attained in any given stage between these two streams, even with deep beds, since reaction rates may be slow. In the last section of this paper, discussion is presented of methods suitable for use when chemical equilibrium is not attained. The adiabatic tower in Fig. 1 has "n" stages numbered from 1 to n, starting with the bottom stage as number 1. In analyzing this tower's performance, it is important to express gas flow rates in terms of a key component or element which remains completely within the gas stream throughout the tower. Similarly, solid flow is best expressed in terms of a key compound or element which remains within the solid phase throughout the tower. Thus, in burning limestone with a hot flue gas, the gas flow might be expressed as G, the pound mols of nitrogen flowing through the tower per unit time, while solid flow might be expressed as S, the pound atoms of calcium in all forms in the solid stream per unit of time. Defined in this way, both G and S are constant throughout the tower. The enthalpy of the gas and solid streams are now best expressed in terms of these key components. That is, the gas stream enthalpy H is expressed as Btu in the total gas per mol of the key component in the gas. Similarly, the solids stream enthalpy h is expressed as Btu in the total solid stream per pound mol (or pound atom) of the key component in this stream.

Jan 1, 1962

By I. R. Kramer

In his technical note entitled "Specimen Temperature During Electropolishing of Aluminum Crystals" Dr. Nakada 1 reported that the temperature of his aluminum specimen increased 65°C when it was polished electrolytically; he therefore concluded that the temperature of the specimens used in our work (Nakada's Refs. 4 and 5) similarly increased by this amount. From this he further concluded that the change in plastic-flow characteristics associated with the removal of the surface by electropolishing during deformation were due solely to a temperature effect. We believe that these conclusions are not justified. It is, of course, realized that the amount of the temperature increase is associated with the total heat transfer of the entire system, including the efficiency of the stirring action, heat flow through the grip on the specimen, and so forth. Of great importance is the type of electrolyte used for polishing. For example, in Dr. Nakada's experiment a methanol-perchloric acid solution was used. This solution has a relatively low conductivity and for the current densities of 0.3 amp per sq cm the electrical input appears to be 30 to 40 w. In our research a methanol-nitric acid solution was employed and for the size of specimen employed by Dr. Nakada the power never exceeded 7 w. There are major differences in his test apparatus which also appear to affect the temperature rise. In our case a steel specimen holder was used in order to provide a good heat sink and conduction path. The cathode was a coiled aluminum tube through which a coolant was passed to provide additional cooling capacity near the specimen. The stirrer was placed in a position to obtain maximum cooling efficiency. On the other hand Dr. Nakada used a teflon grip to support the specimen at one end only and a flat copper cathode, thus providing a much less efficient heat sink as compared with the metal grips used in our studies. The relationship between current density and the temperature increase for two sizes of aluminum crystals tested in our tensile apparatus is shown in Fig. 1. The temperature measurements were determined from a thermocouple spot-welded to the surface of the specimen. The thermocouple was protected from the acid by means of a thin film of stop-off lacquer which covered just the outer surface of the thermocouple junction. Whereas Dr. Nakada reported a time delay of 8 min to obtain thermal equilibrium, our temperature change occurred in less than 15 sec. This emphasizes the importance of the heat transfer in the entire system. However, readings were taken over a period in excess of 5 min to assure thermal equilibrium. The data given in Fig. 1 were also confirmed by determining the thermal expansion of the specimen in a sensitive creep apparatus. As may be seen, for the smaller specimen the increase in temperature is 8°C for a current density of 1.5 amp per sq in. The majority of our data on the effects of surface removal on the plastic behavior of aluminum were obtained at current-density values at or below this value. Above 1.5 amp per sq in. the temperature rise is uncertain; for under certain conditions, especially in the vicinity of 2 amp per sq in., the anode can become polarized and the current flow is erratic. This condition is easily recognized because wide fluctuations in the creep and stress-strain data make it virtually impossible to obtain reliable results, a condition which was always avoided in our work. The temperature increase for the larger specimen is less than that of the smaller specimens below a current density of 1.5 amp per sq in. At a current density of 2 amp per sq in. the temperature increased 13°C. The above temperature data are in accord with observations made during creep experiments. Using a transducer capable of detecting strain in the order of 10 -6, temperature changes in excess of 8°C were not detected when the current density was increased to as high a value as 1.5 amp per sq in. Finally we wish to point out that our experimental data cannot be explained solely in terms of a heat effect. For example in Fig. 1 of Ref. 2, the change in slope of Stage II as a function of the rate of re-

Jan 1, 1965

Discussion of the paper of Earl S. Bardwell, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 79, July, 1913, pp. .1429 to 1441. H. O. HOFMAN, Boston, Mass. (communication to the Secretary*) :-It is pleasing to the originators of the planimetric determination of oxygen in refined copper to see that the method has been taken up by a large smelting plant to be used in every-day work after it has been simplified to suit the new conditions. Several years ago Huntington and Desch 1 had improved our mode of working. They projected the developed negative on to a screen, traced the outlines of the picture with a pencil, drew a border, and measured one constituent with. the planimeter. In order to give the work greater precision, they divided the area into squares of 1 cm. side, shaded the

Jan 11, 1913

[Trans. No. Place Date Vol. Page 1. Wilkes-Barre, Pa May, '71.. 1 3 2. Bethlehem, I's Aug., '71.. 110 3. Troy, N. Y Nov., '71.. 113 4. Philadelphia, PaFeb., '72.. 117 5. New York, N. YMay, '72120 6. Pittsburgh, Pa Oct., '72.. 125 7. Boston, MassFeb., '73.. 128 8. Philadelphia, Pa.*May, '73.. 23 9. Easton, PaOct., '73.. 27 10. New York, N. Y Feb., '74211] [ ]

Jan 1, 1925

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors' determined the constitution of copper-silicon-manganese alloys containing over 90 per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper .2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 20 c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. Table I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. A few other changes will be noted (No. 138 at 450°C., No. 149 at 550°C., Nos. 153 and 149 at 750°C.). The change from liquid to beta in equilibrium with kappa in No. 139 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. 1 to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the [K = a + ?] change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300° and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 ± 0.03 per cent or 2.42 ± 0.05 per cent were cast in ingots of 3-in, diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 900°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Robert Isaac Williams

The Questa mine is located in northern New Mexico on the western flank of the Sangre de Cristo Mountains about 75 miles north of Santa Fe and ranges in elevation from 6,800 to 10,000 ft. GEOLOGY The rocks of the area are Precambrian metamorphic rocks covered by Tertiary extrusive andesites and rhyolites and intruded by Tertiary granitic rocks. These Tertiary intrusives are localized in an east-west belt about 20 miles long and 2 miles wide, extending from Questa to Red River. The Questa orebody is associated with a north-trending aplite intrusive about 3/4 mile wide and 1 3/4 miles long. In the area of mineralization, the metasomatism of aplite has produced a mottled porphyritic rock. This hybrid rock has caused much of the controversy about the Questa mine intrusive. The orebody is essentially monomineralic and consists of numerous closely spaced molybdenite veins varying in thickness from ' 'paint" to 3 in. and occurring in both the andesites and the intrusive. In the intrusive the veins are often siliceous. Common alteration minerals associated with the molybdenite ore vary with the original composition of the rock. The alteration of the aplite has produced phenocrysts of orthoclase, albite, oligoclase and biotite; veins of quartz, orthoclase, and biotite; and graphic myrmekitic intergrowths of feldspars and quartz. In many places near the contact, the andesite is indistinguishable from the metasomatized aplite. The dominant alteration in andesite, however, is the development of fine-grained biotite with apatite, rutile, and sphene.

Jan 1, 1969

By H. F. Beeghly

UNTIL recently the only criteria by which steels were judged were their cost and their mechanical, chemical, and physical properties. The user was concerned with such properties as corrosion resistance, tensile strength, response to thermal treatment, hardness, ductility, and, to a growing extent in recent years, with behavior at high temperature. As plans were made to build power reactors, a new set of properties became important—the nuclear characteristics, which had to be considered by the designer and engineer in building his plant. The nuclear engineer developed methods for the rare and new metals and produced them in high purity, often at great expense. The pure metals then provided the raw materials for tailor-made alloys. For more common structural metals, such as steel, the nuclear industry depended on commercially available materials. Generally, the quantities required were small and specifications were rigid. It is not surprising, therefore, that difficulty was frequently encountered in procuring structural mate-

Jan 1, 1957

By Fred C. Bond

Many grindability tests have been made in the Allis-Chalmers laboratory since the tabulated results were last published.' The lists of standard ball-mill and standard rod-mill grindability tests are brought up to date in this paper, and considerable new material is added. This includes a tabulation of open-circuit grinding tests, with impact and compression-crushing tests. The standard ball-mill grindability tests (Table I) were made in a standard laboratory ball mill, 12 by 12 in. inside, running at 70 rpm, with a charge of 285 iron balls ranging from 1½ to 3/4 in. in diameter and weighing 20,125 grams. Seven hundred cubic centimeters of minus 6-mesh stage-crushed dry feed was used, and the circulating load was maintained constant at 250 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 28 to 200, and the grindability is the number of net grams of screen undersize produced per revolution. The table includes 479 tests. It has been calculated that the ball mill does 52.3 joules of useful work on the ore per revolution2 with 93 joules input to the mill. The standard rod-mill grindability tests (Table 2) were made in a laboratory tilting rod mill, 12 in. in diameter by 24 in. long inside, with a wave-type lining, running at 46 rpm. The grinding charge consisted of six I1/4-in. diameter and two 13/4-in. diameter steel rods, all 21 in. long and weighing 33,380 grams. The mill was rotated level for eight revolutions, then tilted up 5' for one revolution, down 5° for one revolution, and returned to level for eight revolutions. It was discharged by tilting downward at 45° for 30 revolutions. Feed consisted of 1250 cc of minus in. stone and the circulating load was maintained constant at 100 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 3 to 65, and the rod-mill grindability is the number of net grams of screen undersize produced per revolution. The table includes 105 tests. The impact and compression-crushing tests (Table 3) are given in a table that is an extension of a previous publication8 in which the method of testing was described in detail. Two equal hammers weighing about 30 lb each were arranged to strike simultaneous blows on opposite sides of the test specimen. Broken pieces of rock passing a 3-in. square and retained on a 2-in. square were set up with the smallest dimension between the hammers, and this distance was measured. The height of the hammers was increased slightly before each blow until the specimen broke, and the foot-pounds per inch of thickness was calculated. Ten pieces

Jan 1, 1949

By A. E. Gorum, J. Washburn, E. R. Parker

Experimental evidence was obtained in support of the idea that cleavage fracture can be initiated by dislocation pile-up. The high ductility of MgO crystals when tested in bending comPared to their relative brittleness in tension was explained on the basis that large pile-ups are more likely in a tension specimen. CLEAVAGE fractures have been a problem of major concern for many years. A number of large steel structures have failed in a brittle manner, usually suddenly and without warning; often the failures occurred for no obvious reason and at nominal stress levels well within the generally accepted range. A great deal of data have been collected about factors that contribute to failures,1 but the physics of the fracture process has never been revealed. cottrel12 has recently developed a theory of brittle fracture in ductile materials which was based upon the concept that dislocations moving on two intersecting planes can unite to form a crack nucleus. This theory accounts for the known effect of grain size and for the effect of testing temperature. There has, as yet, been no experimental evidence published that would substantiate this or the earlier theories based on stress concentrations due to piled-up dislocations. The study reported herein was conducted to obtain information that would either substantiate or disprove the

Jan 1, 1960

By J. D. Livingston

THE hardening of alloys by the precipitation of a second phase has long been an important technological process. One approach towards improving our understanding of this phenomenon has been a correlation of mechanical properties with such parameters as particle size and inter par ticle spacing.' Several reviews of such data have appeared.2-4 A major limitation to this approach has been that for most alloys the particles are submicroscopic in size in the range of optimum hardness. Precipitation-hardening copper-cobalt alloys, therefore, are of interest, because the ferromagnetic properties of the precipitate make it possible to measure particle size, number of particles, and so forth, from magnetic measurements alone.5, 6 Livingston and Becker7 have applied these techniques to a study of precipitation hardening in an alloy of 2 pct Co in copper. It was found from magnetic measurements that nearly all the cobalt to be precipitated was out of solution within a few minutes at 600°C, whereas the peak in tensile yield stress was not attained until a much longer aging time. Thus during the first 1000 min of aging time at 600°C the Yield stress was increasing while a constant volume of precipitate was coarsening, i.e., while particle size and interparticle spacing were increasing. Peak yield stress was reached at an average particle radius of about 70A. The earlier study was confined to one alloy at one aging temperature, so that the volume fraction of precipitate was fixed and, therefore, particle size and interparticle spacing could not be independently varied. The work has now been extended to several alloys of varying percentage cobalt in copper, and to aging at various temperatures. It was hoped that such a study might clarify the relative importance to precipitation hardening of particle size, interparticle spacing, and volume fraction of precipitate. EXPERIMENT The alloys studied contained 0.7, 1.3, 2.0, and 3.2 wt pct Co in copper. They were prepared from electrolytic copper and electrolytic cobalt in a vacuum -induction furnace, worked to 3/8-in.-diam rod, and machined into tensile specimens with a gage section 1 1/2 in. long and 3/16 in. in diam. All specimens were given a solution treatment consisting of a 30-min anneal in nitrogen at 1000° C followed by a quench into iced brine. Subsequent aging was done in nitrogen and followed by a water quench. Average grain diameter was approximately 0.01 in.

Jan 1, 1960

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By Ulick Evans

I SHOULD like to commence by saying how much I appreciate the honor which the American Institute of Mining and Metallurgical Engineers has done me in inviting me to visit your country, and to deliver this lecture before you. In choosing a subject, and in deciding what to include and what to omit, I have endeavored to discuss as far as possible work carried out recently in Europe with which you may not be unduly familiar. It would be poor return for your hospitality, and a mistaken sort of compliment indeed, if I were to load the lecture with accounts of researches 'carried out in your own country-researches with which you are probably better acquainted than I. Not that I have in any way excluded work done on, this side of the Atlantic from my survey; one would indeed find it difficult to write on this, or on any other branch of science, without mentioning American work. But I have endeavored as far as possible to concentrate on aspects of the case which will, I hope, be comparatively fresh to you, and I feel fairly certain that this will be in accordance with your own wishes. If a strip of iron is heated strongly at one end, the other end remaining cold, there is produced over the heated portion a layer of oxide scale, the thickness of which diminishes steadily with the distance from the hot end. Somewhere in the middle of the strip, the thickness of the oxidized layer will become comparable .to the wave length of light, and over this region the thin films give rise to a series of beautiful interference tints, commonly known as "temper colors." The colors are caused by the fact that two trains of light waves are reflected respectively from the outer and inner surfaces of the oxide film, .and the possibility arises that the "crests" of one series of waves may coincide with the "troughs" of the other, thus diminishing the intensity of the light of some particular wave length. The state of affairs in this part of the strip is shown diagrammatically in Fig. 1, in which the film thickness is enormously exaggerated, of course, in comparison with the length of the strip; the

Jan 1, 1929

By W. D. Lowry

As most of the industrial activity of Oregon is centered in the Portland area, the foundries there consume the bulk of the foundry sand produced in Oregon. Although a number of the larger towns scattered throughout the state have gray-iron foundries, the sand used by most of them is of local origin. The yearly consumption of foundry sand of all types for the past few war years in Oregon is estimated to have been approximately 40,000 tons valued at about $285,000, of which an estimated 18,000 tons was shipped in from the Ottawa, Ill., district for use largely by the steel foundries. Until 1945 much of the silica sand consumed by the steel foundries in the Pacific Northwest, approximately 50,000 tons in 1944, came from Ottawa, Ill. and surrounding regions. Although some silica sand was shipped in from Belgium in the past, none is known to have been imported in recent years. Early in 1945, a very promising high-grade silica sand being produced near Eugene, Oregon, was introduced, and all but two of the Portland steel foundries are using this new sand. Until a few years ago, the search for good local (Oregon) foundry sands was carried on largely by the foundry supply houses. Recently the Oregon Department of Geology and Mineral Industries has investigated a number of deposits and has carried on and fostered research on the most bromising deposit near Eugene, about 120 miles south of Portland. High-grade silica foundry sand from this deposit is now being marketed in Oregon, Washington, and British Columbia. The Eugene sand is one of the very few outstanding western steel-foundry sands. Field investigations by the Oregon Department show that there are relatively few deposits of sand in Oregon suitable for foundry use. A knowledge of the geology of the state makes this readily understandable. The only major primary sources of the quartz present in sandstones in Oregon are the intrusive masses of granite, granodiorite, and quartz diorite of late Jurassic or early Cretaceous age found in the Siskiyou Mountains of southwestern Oregon, a part of the old Klamath Mountain highland, and in the Blue Mountains of northeastern Oregon. Transportation militates against the development of any possible deposits of foundry sand found east of the Cascade Mountains in central and eastern Oregon because few railroads traverse that area. East of the Cascades, which separate western from eastern Oregon, many of the older sediments of Paleozoic and Mesozoic age have either been metamorphosed or contain much volcanic eruptive material, and even if some of the Mesozoic sediments are highly quartzose in places, they are in relatively inaccessible areas. All the Tertiary sediments there are of continental origin and contain much ash and other volcanic debris, for there was great volcanic activity during much of that period. In western Oregon much the same is true of the Paleozoic and Mesozoic rocks

Jan 1, 1948

By W. D. Lowry

As most of the industrial activity of Oregon is centered in the Portland area, the foundries there consume the bulk of the foundry sand produced in Oregon. Although a number of the larger towns scattered throughout the state have gray-iron foundries, the sand used by most of them is of local origin. The yearly consumption of foundry sand of all types for the past few war years in Oregon is estimated to have been approximately 40,000 tons valued at about $285,000, of which an estimated 18,000 tons was shipped in from the Ottawa, Ill., district for use largely by the steel foundries. Until 1945 much of the silica sand consumed by the steel foundries in the Pacific Northwest, approximately 50,000 tons in 1944, came from Ottawa, Ill. and surrounding regions. Although some silica sand was shipped in from Belgium in the past, none is known to have been imported in recent years. Early in 1945, a very promising high-grade silica sand being produced near Eugene, Oregon, was introduced, and all but two of the Portland steel foundries are using this new sand. Until a few years ago, the search for good local (Oregon) foundry sands was carried on largely by the foundry supply houses. Recently the Oregon Department of Geology and Mineral Industries has investigated a number of deposits and has carried on and fostered research on the most bromising deposit near Eugene, about 120 miles south of Portland. High-grade silica foundry sand from this deposit is now being marketed in Oregon, Washington, and British Columbia. The Eugene sand is one of the very few outstanding western steel-foundry sands. Field investigations by the Oregon Department show that there are relatively few deposits of sand in Oregon suitable for foundry use. A knowledge of the geology of the state makes this readily understandable. The only major primary sources of the quartz present in sandstones in Oregon are the intrusive masses of granite, granodiorite, and quartz diorite of late Jurassic or early Cretaceous age found in the Siskiyou Mountains of southwestern Oregon, a part of the old Klamath Mountain highland, and in the Blue Mountains of northeastern Oregon. Transportation militates against the development of any possible deposits of foundry sand found east of the Cascade Mountains in central and eastern Oregon because few railroads traverse that area. East of the Cascades, which separate western from eastern Oregon, many of the older sediments of Paleozoic and Mesozoic age have either been metamorphosed or contain much volcanic eruptive material, and even if some of the Mesozoic sediments are highly quartzose in places, they are in relatively inaccessible areas. All the Tertiary sediments there are of continental origin and contain much ash and other volcanic debris, for there was great volcanic activity during much of that period. In western Oregon much the same is true of the Paleozoic and Mesozoic rocks

Jan 1, 1948

By Allen Garrison

THE chemistry of clays and shales has been assuming increasing importance in the petroleum industry, and two factors have greatly influenced this trend. The first has been the growing evidence that the marine shales are source beds, and that the petroleum compounds have migrated to the sand reservoirs overlying or underlying these shales: the second has been the demand for drilling, fluids better adapted to penetrate these marine shales without difficulty and expense. ORIGIN AND GENERAL COMPOSITION OF CLAYS AND SHALES Clays, shales and surface soils are all closely related materials. They are mixtures of finely divided compounds formed during the weathering of the solid crust of the earth. Their nature is essentially colloidal; that is, their behavior is determined by the state of division of the materials and the surface reactions of the smallest grains. Many of their chemical changes affect only the exposed areas and do not involve the interior of the grains of matter. The extent of these reactions is more nearly proportional to the area of the substances than to their mass, therefore it is possible for a small. amount of a material in an extremely fine state of division to completely dominate the character of the mixture. More than 83 per cent of the crust of the earth is composed of three elements-oxygen, silicon and aluminum. Consequently, the corrosion products of the crust are predominantly aluminosilicates, or compounds of aluminum, silicon and oxygen. If we add the compounds of six elements-iron, calcium, sodium, potassium, magnesium and hydrogen-more than 98 per cent of the crust has been accounted for. These six elements, together with the first three, also appear in soils, clays and shales. But direct chemical analysis is of little value in describing the nature of such materials. Many chemical individuals may be present in variable amounts,. and the extreme subdivision of any one of the individuals may contribute qualities that dominate the mixture.

Jan 1, 1939

By d&apos, John C. Entremont

Pure iron was inductively melted in small refractory crucibles and optical pyrometer and immersion thermocouple readings were simultmzeously taken. The resulting emissivities of the liquid iron surface obtained were found to be greatly affected by both the gaseous atmosphere and geometrical changes in the physical setup. Quantitative values for these effects are indicated. FOR many applications in both the laboratory and plant, optical pyrometry is still the best means of measuring temperatures in the incandescent range. A prerequisite in evaluating the correct temperature is a good value of the emissivity of the surface. To obtain the emissivity from the tabulated values of the literature can be very confusing and often far from correct. There are many reasons for these difficulties, and it is not within the scope of this paper either to enumerate or to discuss them all. Its purpose is to show quantitatively how several factors affect the apparent emissivities obtained from experimental measurements on liquid iron surfaces. The black body is the reference state for the quantitative values of emissivities and is defined1 as a body which absorbs all radiation incident on it, reflecting none; such a surface emits more radiation per unit area per unit time than any surface which reflects any radiation, and is given a value of unit emissivity. All bodies having reflective power thus have emissivities less than unity and are considered nonblack or grey bodies. The ratio of the radiant energy emitted by the flat, nonblack surface to that of a perfectly black surface of equal area and temperature is the emissivity of the surface. The above definitions are applied to flat, polished, opaque surfaces, very seldom encountered in actual measurements, and for this reason many authors have suggested that the word "emittance" be used for real bodies rather than emissivity. The emittance has reference to the material and its configuration rather than to its properties in the idealized state. Recent observations of molten iron in a small refractory crucible indicate that not only the configuration of its surface but the geometrical arrangement of its surrounding and the nature of the surrounding atmosphere have a pronounced effect on the emittance. Neglect of changes in such conditions may lead to errors as large as 40°C at 1600°C. Thus it is suggested that the term "apparent emissivity" be used and that it be recognized that its value pertains to a particular experimental arrangement only. As a result of not recognizing these differences in emissivities, which are obtainable from changes in the physical setup of an observation, many investigators have incorrectly quoted their values as those of the emissivities of particular materials rather than as an apparent emissivity for their particular arrangements. As a consequence, values of the emissivity of liquid iron ranging from 0.3 up to 0.55 are found in the literature. In an effort to establish an accurate optical temperature scale for liquid iron solutions in which de-oxidation studies were to be carried out, it was observed that the temperature relationship, obtained by simultaneously taking immersion thermocouple

Jan 1, 1963