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By Alfonso Rizo-Patrón, A. M. Gaudin

PREVIOUS studies of activation in flotation have directed attention to the action of the activator on the mineral to be floated rather than to the relationship of the activator to the collector. The latter phase of the problem, however, seems to have definite scientific, if not also practical, interest. In the investigation reported in this paper, experiments were carried out, largely with quartz as subject, barium as activator, and oleate as collector. The results obtained indicate that a I : I ratio of collector ion to activator ion gives optimum results, and that a 2:I ratio almost fails to achieve activation and flotation. Yet, a 2:I ratio would have been expected on stoichiometric grounds, had the coating been a normal salt of the activator ion with the collector ion, since barium is a divalent cation and oleate a monovalent anion. To interpret and rationalize the observations, considerations of the crystal chemistry of quartz are helpful. The point of view to which these considerations lead may be of general applicability to systems involving suspensions of solids in liquids; they confirm that an adsorbed coating is inescapable. APPARATUS AND SUPPLIES The experimental work consisted in barium-ion abstraction tests, hydrogen-ion and hydroxyl-ion abstraction tests, flotation tests, and determinations of the surface of the crushed quartz. The flotation machine was built according to the design of D. W. McGlashan.* It consists of a drill press in which the bit has been replaced by a stainless-steel impellor surrounding a stainless-steel stator, as in the Fagergren laboratory machine. The air intake is controlled by a valve, and the cell consists of a beaker. The quartz was obtained from vein quartz stored in large chunks. It was first crushed to 20 mesh, then sized on a 28-mesh screen. The 20 to 28-mesh size alone was retained for use. This size was freed of coarse iron by passage through a Ball Norton magnetic separator, bleached with boiling hydrochloric acid to remove residual abraded iron, washed with distilled water until the washings were thoroughly free of ferrous, ferric, and excess hydrogen ion, and stored in covered Pyrex beakers under water until used. The barium was used as barium chloride, Baker's analyzed C. P. The oleate was used as sodium oleate. It was prepared from sodium hydroxide, Baker's analyzed C. P., and oleic acid purified by R. R. de Arellano3 in the laboratories at the Massachusetts Institute of Technology. The purification procedure was elaborated from the recent researches of Brown and Shinowara.2 It consisted in: (I) saponification of olive oil with potassium

Jan 1, 1942

By G. M. Ritcey

The concentration of metals in the solution, the .value of the metal being recovered, together with the flow through- put, may singly or in combination conbribute to the decision on the possible use of solvent extraction. Also, as noted earlier, the upstream and downstream aspects of the overall process have to be considered. The economic considerations may be divided into: 1. Capital investments 2. Operating costs Capital Cost The capital costs can be influenced by the following: 1. number of stages; 2. kinetics; 3. coalescence; 4. entrainment; 5. flow rates and ratios; 6. building requirements; 7. ancillary equipment; 8. environment constraints or requirements; 9. engineering design.

Jan 1, 1978

By Tibor Stefansky, John E. Dorn

MOTT and Nabarro1-5 were first to illustrate the importance of the flexibility of dislocations in accounting for the strengthening that metals undergo due to the presence of internal-strain centers. Such strain-centers might arise from a number of causes such as radiation damage, the presence of semicoherent and coherent precipitates and clusters, as well as individually dispersed interstitial and misfit substitutional solute atoms. Each strain-center induces positive and negative shear stress fields on the slip planes of the surrounding alloy matrix. In order to effect plastic deformation, therefore, the alloy must be subjected to sufficiently high applied shear stresses to push dislocations past all such internal stress fields. If dislocations were inflexible and moved as rigid lines, they would be equally pushed and pulled by internal stress fields. At this extreme the strengthening would be vanishingly small. Dislocations, however, are not rigid; they are flexible and extensible. They wiggle between positive and negative strain-centers, thus increasing their line energy at the expense of their interaction energy with strain-centers. cottrel16 and Friedel7,8 have independently presented lucid reviews of the significance of the Mott-Nabarro dislocation-flexibility concept to the strain-center strengthening of alloys. Their analyses however were only semi-quantitative. There is evidence in the recent literature of renewed interest in a more rigorous analysis of flexibility. Thus, Gleiter9 and Gerald" have shown that the calculated strain-energy interaction between a dislocation and the stress fields of coherent precipitates can be seriously in error if the flexibility of the dislocation is not taken into account. This report will be concerned with a more detailed analysis of the problem based on the following approximations: 1) Although many types of strain-centers exist, the following analysis will be limited to the case of solute-atom strain-centers in fcc substitutional alloys. 2) To facilitate the analysis by avoiding statistical considerations, the strain-Centers are assumed to be in regular arrays on the slip plane. Although the quantitative results are somewhat dependent on the type of array that is assumed, the qualitative trends are similar for various arrays that were studied. 3) An adjustment of the results from those for square arrays to those for the more realistic case of a random distribution of strain-centers is accomplished by adopting the interesting statistical theory first introduced by Kochs,11,12 elaborated on by Dorn, Guyot, and stefansky,13 and analyzed by Foreman and Makin14 in their computerized experiments. 4) For simplicity the dislocation lines are taken to wiggle about their edge orientation and no correction is applied to their line energy for deviations from edge configurations or for the elastic interaction between segments of the now curved dislocation. It will be shown that for extremely low concentrations of atomic strain-centers the strengthening increases with the square root of their concentration. For slightly higher concentrations the strengthening rate becomes less rapid. At a critical concentration a maximum strength is obtained and a decrease in the strengthening takes place as the concentration of solute atoms is further increased. These trends are a direct consequence of dislocation flexibility. They arise from changes in the amplitude of the waviness of the dislocation line at the yield stress with solute atom concentration. Despite the simplifying assumptions that were made, the results agree qualitatively with appropriate experimental data. I) STRESS FIELDS ON SLIP PLANES Internal stresses are introduced in a lattice whenever a host atom of radius ro is replaced by another that has a different atomic radius. According to the classical theory of linear elasticity,15 the stress field about a solute atom at the origin of a spherical coordinate system is given by arr=-4G€(?_0)3 ffflfl ="W =2G€{t) f°rr^ro(l+e) UJ where G is the shear modulus of elasticity and Y, = ro(l + E) is the radius in situ, of the substituted atom. As shown by ~shelb~,'~ this approximation assumes that the bulk modulus of elasticity of the substituted atom is identical with that of the host species. ~abarro'~ suggested that the strain E can be deduced

Jan 1, 1970

[President MRS. REED W. HYDE 84 Mountain Ave. Summit, N. J. First Vice-President MRS. WILLIAM A. SCHEUCH 37 Trent St. Great Kills, S. I., N. Y. Second Vice-President MRS. RUSSELL B. PAUL 6 Brooklands Bronxville, N. Y. Third Vice-President MRS. JOHN C. BURTON 271 Fox Meadow Rd. Scarsdale, N. Y. Fourth Vice-President MRS. DANIEL C. JACKLING Redwood City R. F. D., Woodside, Calif.]

Jan 1, 1940

President MRS. REED W. HYDE 84 Mountain Ave. Summit, N. J. First Vice-President MRS, WILLIAM A. SCHEUCH Trent St. Great Kills, S. I., N. Y. Second Vice-President MRS. THORNS E. LLOYD Box B Netcong, N. J. Third Vice-President MRS. H.. T. HAMILTON 24 Ridge Rd. Summit, N. J.' Fourth. Vice-President MRS. R. A. PALLANCH 1342 Laird Ave. Salt Lake City, Utah

Jan 1, 1939

By G. B. Gould

FROM the very inception of the price-control experiment in the bituminous-coal industry, the problem of price differentials was of major importance. In fact, assuming that there will be no legal or Govern- mental obstacles to price control, the successful maintenance of the present or any other method designed to control bituminous-coal prices will depend upon the discovery of some satisfactory way to determine these differentials in price, among: individual mines and groups of mines. Being of organic origin, bituminous coal is a commodity that presents an almost infinite variety of qualities. It is inevitable, therefore, that a work- able price-control system must attempt

Jan 1, 1935

By Arthur Knapp

OIL-WELL depletion curves, to be of value, should show when a well or lease may no longer be operated at a profit. The difference, at any time, between the total expenditures and the total income of a lease or well may be called the lease status. Plotting this lease status against time will give a curve subject to more accurate and different interpretations than the barrels-time curves. According to the hypothetical barrels-time curves shown in Fig. 1, well A, at the end of 16 mo., is producing twice as much oil as well B and will continue to produce for another year whereas well B will cease producing in about 6 months. DATA FOR LEASE STATUS-TIME OR DOLLARS-TIME CURVE TIME LEASE MONTHS STATUS Lease purchased for $3000 0 -$ 3,000 No expenses chargeable to lease for 3 mo 2 - 3,000 Well A is started; cost of drilling for month is $16,000 3 - 19,000 Well is completed at additional cost of $10,000 4 - 29,000 Well A is brought in and flows 10,000 bbl. first month (see Fig. 1). Necessary to invest in tanks, boilers, pipe lines, etc.: difference between expenditures and receipts gives profit for month of $5,000 5 - 24,000 Investment is small, cost of operating well A is small, so profits are $15,000 6 - 9,000 Well ceases to flow so there is additional investment for pumping equipment and additional operating expense; net earnings from 6,000 bbl. of oil produced is $4,000.... 7 - 5,000 Lease operation now becomes normal and curve becomes smooth 8 - 500 9 2,000 10 4,500 11 6,000 12 7,700 13 8,700 14 9,000 15 9,500 16 10,000

Jan 1, 1921

By Francis P. Sinn

LOW prices have made 1938 a difficult year for the zinc industry of the world. Particularly in the United States, output had to be radically curtailed to bring production into line with consumption. Despite these unfavorable conditions, some additional plant construction is contemplated. In Jugoslavia, through co-operation with the Government, Trepca Mines is lo build a zinc plant to produce 10,000 metric tons annually, the plant to be ready for operation in July, 1941). Cerro de Pasco is proceeding with its plans for an electrolytic plant in Peru. A pilot plant, to be ready next summer, is under construction. In eastern Canada an electrolytic plant is planned in Quebec to treat concentrates from Yoranda and other mines but no defi-

Jan 1, 1939

By Rossiter W. Raymond

The manufacture of ferromanganese in the blast furnace having been the subject of considerable attention in the Institute, I beg to put on record a contribution to the discussion from a quarter hitherto not directly represented, namely, the St. Louis furnaces, near Marseilles in France, belonging to a company of which M. Jordan, a member of the Institute, is Managing Director. These furnaces commenced in 1862 to manufacture specular pig (fontes facettes) containing from three to six per cent. of manganese. In 1864 the regular production of spiegeleisen (fontes miroitantes), containing seven to ten per cent. of manganese, was inaugurated. At that time the Rhine was the only locality of this manufacture, and the Bessemer works of England and France obtained from Gernlany all their spiegel. From 1864 to the present time, the St. Louis furnaces have been advancing steadily the percentage of manganese in their product. From ferromanganese of thirty per cent. they had arrived, about two years ago, at a product containing seventy to seventy-five per cent., and for some time past they have been turning out what, as M. Jordan remarks, may fairly be Termed fonte de manganese, or manganese pig, instead of iron, since the percentage of iron it contains is not more than 8.5, while the percentage of manganese is 85, or ten times as great. This very high grade material has a peculiar appearance, entirely different from that of ordinary cast iron or spiegel. It is granular, and steely gray in color. The following analyses, communicated to the Sociètè des Ingenieurs Civils, by M. Jordan, show the composition of various products of the St. Louis furnaces:

Jan 1, 1879

By Magnus Troilius

The heat-calculations of gas-analyses involve cumbrous multiplications, which are apt to lead into errors. The foliowing tables and formulae have been found useful as facilitating such calculations, and therefore I hope that they will be of interest to some of the members. By "heat-unit" will, in the following, be understood the amount of heat required to raise the temperature of 1 kilogram of water l° Cent. All the tables refer to cubic meters at O0 and 760 mm. pressure. The following gas is chosen as an example: C02, - 4.0 vol. per cent. co, = 20.0 " CHI, - 3.5 " H, - 7.0 " N, - 65.5 " " 100.0

Jan 1, 1884

By FRANK R. VAN

I. INTRODUCTION. IN the summer of 1908, R. B. Cochran, Superintendent of the Compania Metalurgica Mexicana at Sierra Mojada, Mexico, presented to the Department of Geology and Mineralogy at Case School of Applied Science an interesting series of silver-, copper-, and lead-ores from the Veta Rica mine. These ores contained several interesting minerals which were associated in a somewhat peculiar manner, so that I was impelled to make a closer study of their occurrence. The investigation has brought out several new facts concerning the geology of the district and the geological occurrence of the ores, and therefore has seemed worthy of record. Two papers have been published previously about the region, one by Chism1 in 1887, and the other by Malcolmson2 in 1902. These articles, however, treat of the district more from the stand-point of the metallurgist and mining engineer, and not much attention is devoted to its mineralogy and economic geology. II. GEOGRAPHICAL LOCATION OF THE DISTRICT. The Sierra Mojada is situated in the extreme western part of the State of Coahuila, near the Chihuahua boundary. It is reached best via the Mexican Central railroad from El Paso, Tex., to Escalon, Chihuahua, a distance of 494 miles. From this point, a branch line, the Mexican Northern railroad, runs 78 miles in a NE. direction to the mines, which are its northern terminus. The railroad was built about 1890, practically on account of the Sierra Mojada mining-district. 1 Sierra Mojada, Mexico, by Richard E. Chism, Trans., xv., 542 (1886-87). 2 The Sierra Mojada, Coahuila, Mexico, and Its Ore-Deposits, by James W. Malcomson, Tram., xxxii., 100 (1901).

Aug 1, 1912

By Paul A. Farrar, Sanford Adler

The Tz-Zr system was reinvestigated using both metallographic and X-ray diffraction techniques. It mas found that titanium and zirconium are soluble in all proportions in both the a and 0 phases. The minimum in the transformation was found at 50 at. pct and 535°C. THE Ti-Zr system has previously been the subject of several investigations.1-6 A study by Hayes et al.5 using magnesium-reduced titanium and zirconium melted in graphite crucibles indicated that the system was a continuous series of solid solutions in both a and 0 phases with a minimum at approximately 545°C and 65 pct* Zr. These conclusions were substantiated by the work of Duwez4 as well as by the limited data of Craighead et al.,3 Fast,2 and deBoer.1 However, a more recent investigation of the titanium-rich region by Ence and Margolin6 indicated that the solubility of zirconium in a, titanium at 500°C is approximately 22 pct with the a + 0 field extending to approximately 47 pct Zr. Therefore in order to resolve this discrepancy the following investigation was initiated. EXPERIMENTAL PROCEDURES The alloys used in this investigation were prepared as 20- to 30-g buttons by nonconsumable electrode melting in a helium atmosphere. The starting materials were Bureau of Mines titanium BHN 71 and Foot Mineral iodide crystal bar zirconium. The titanium was premelted before the alloys were prepared to avoid excessive weight losses in the final melting. The compositions of the alloys prepared were as follows: Ti-12.0, 22.2, 29.0, 39.6, 50.0, 58.0, 72.4, 83.5. and 90.8 pct Zr. Prior to heat treatment the alloys were cold-worked 10 to 20 pct, stopping at the first signs of cracking. Specimens for heat treatment were wrapped in molybdenum sheet and annealed in argon-filled quartz capsules for the following times and temperatures: 750°C-40 days, 675°C-61 days, 600°C—109 days, 575°C-112 days, 550°C-112 days, 525°C—127 days, and 450°C —153 days. Quenching was accomplished by breaking the capsules in an iced-brine solution. The standard techniques used for polishing the specimens involved belt grinding, grinding on emery paper, polishing electrolytically, and etching with Remington "A" etch7 or "R" etch 8 Debye-Scherrer X-ray powder photograms were obtained for a number of samples using a 114.6-mm camera and CuK, radiation. Exposure times were from 19 to 23 hr. The powder samples were obtained by filing to 270 mesh size. After filing the samples were wrapped in molybdenum foil capsuled in quartz and reannealed at the temperature of original heat treatments; following the heat treatment the samples were quenched into iced brine without breaking the capsules. RESULTS AND CONCLUSIONS On the basis of the microstructural examinations of the heat-treated samples and of the X-ray diffraction data, the Ti-Zr system shown in Fig. 1 was constructed. The data indicate that a, and 0 titanium form a complete series of solid solutions with a, and ß zirconium. The minimum was found to occur at 65 pct (50 at. pct) Zr and 535°C, in excellent agreement with the earlier investigations,1-5 see Fig. 2. Typical microstructures are shown in Figs. 3 to 7. Figs. 3, 4, and 5 show the 22.2, 39.6, and 50.0 pct Zr alloys after heat treatment at 675°C for 61 days with the 22.2 pct Zr showing equiaxed a, and the 39.6 pct Zr alloy a + transformed ß, while the 50 pct Zr alloy shows only transformed B. Figs. 6 and 7 show the 29.0 and 39.6 pct Zr alloys after heat treatment for 109 days at 600°C. The 29 pct Zr alloy has an equiaxed a structure while the 39.6 pct alloy has a partially recrystallized a+ß structure. X-ray diffraction data obtained from the 50 pct Zr alloys after heat treatment at 525° and 450°C as well as from the as-cold-rolled material showed only those lineos which couid be indexed a: a titanium, good agreement with the previously published values. 2,4,5,9 Chemical analysis* of the 50 pct Zr alloy

Jan 1, 1967

By Myron Rodgers

IN rock- or ore-crushing tests all data, in order to be valuable for study and comparison, should be obtained and tabulated under conditions as uniform as possible. The results of many such tests have no value for comparison, because of incomplete data and the lack of uniform conditions, screens and scale of sizing, etc. The purpose of this paper is to suggest a form of standard specifications which may be developed by the Milling Committee and approved by the A. I. M. E. for rock-crushing tests. It is not intended to discuss any theories of rock crushing. Reports of rock-crushing tests should include the following details: 1. Description of the machine employed (jaw or gyratory crushers, rolls, stamps, tube mills, Chilean mills, etc.). 2. Method and material (timber, concrete, etc.) of foundation. Much power is dissipated in the vibration of poor foundations. 3. Locality from which the rock or ore was obtained, and geological, mineralogical, and physical characters of the material. 4. The power consumption of the machine running with no load and with full load, the unit of power being 1 hp, per 24 hr. 5. The capacity of the machine in tons (of 2000 lb.) per 24 hr. 6. The duty in tons per horsepower-day. 7. The screen analysis of feed and product by the proposed A. I. M. E. standard screen scale. On the foregoing statement, the following remarks are offered.

Jan 9, 1915

George E. Collins, Nacoochee, Ga. (communication to the Secretary): The results tabulated below were obtained at the Reynolds mill, White county, Ga. They were noted, not with a view to investigating the point discussed by Mr. Clark, but in course of a test on a working scale to determine the com parative saving from a given free-milling ore on copper and silvered plates respectively. In every case the bullion assayed was the result of a separate clean-up on a considerable quantity of ore. The ore varied widely in grade and in other respects, but the runs bracketed in the table were made at the same time, in adjoining batteries, and on similar types of ore. In a * Result modified by the addition to the bullion-shipment of a little impure bullion left over from previous clean-ups.. On these occasions, the strips of copper were removed from the tables, and: their lower surfaces were cleaned. Hence the higher yield reported.

Jan 1, 1900

By F. H. Spedding

CONSIDERABLE confusion exists in the literature concerning the phase transformations exhibited by the lighter rare earth metals; namely, lanthanum,1-8 cerium,1,3,5,8,9-15 praseodymium,8 and neodymium.1,8,16,10 To obtain further information

Jan 1, 1958

By C. E. Sims, C. A. Zapffe

AN investigation of the behavior of inclusions in steel several years ago1 led to the conclusion that some of the commonly occurring inclusions in steel have appreciable solubilities, particularly in liquid steel. In the belief that further study and clarification of this matter was warranted, a laboratory study of oxides in liquid steel was started. These oxides are generally the result of deoxidation treatment, and the basis of an understanding of their behavior must be, therefore, the behavior of the deoxidizer in liquid iron. The Fe-Si-O system was selected for the first study, and the apparatus used and experiments conducted are described herein. APPARATUS The apparatus is shown in Fig. I and the system is shown by diagram in Fig. 2. Furnace Atmosphere Commercial hydrogen (1) passes through an orifice (2) into a manometric system that measures the tankside pressure (3) and the back pressure (4) in the system. A water trap (5) guards against excess tankside pressure. A by-pass with stopcocks (6 and 7) is provided, so that the hydrogen can be routed directly from the tank to the furnace if desired. When stopcock 7 is closed and stopcock 6 is open, the gas proceeds through the conditioning train, of which the first unit is a furnace (8) that contains platinized asbestos at 350°C. The temperature is measured by a thermocouple and potentiometer (9) and is controlled by a slidewire resistance (10). In [ ] this furnace free oxygen is converted to water vapor. The exiting gas passes over a water bath (11) kept slightly below boiling temperature by an auxiliary heating unit (12). This unit also heats a surrounding copper coil (13) containing water, and the heated water rises through a collar (14)

Jan 1, 1942

By J. B. Clark, A. S. Yue

IN recent years, zone melting1 has been applied extensively to the purification of metals having a very low vapor pressure.2-4 This note describes the zone melting of a high vapor-pressure metal, magnesium, where the melting takes place inside a refractory surface skin. The effects of zone speed and the number of passes of the molten zone on the purification have been determined and the effective distribution coefficients for the principal impurity elements were calculated. A schematic diagram of the zone-melting apparatus is given in Fig. 1. The Vycor tube containing the graphite boat with its magnesium charge (an extruded rod—3/8 in. in diam, 10 in. long) is pulled through the stationary furnaces. A molten zone approximately one-fourth the length of the charge is produced under each of the two central furnaces. Two grades of magnesium were studied—electrolytic magnesium and magnesium with a very low alloy content. The spectrographic analyses of these materials, within * 5 pct of the values stated, are given in Table I. Molten magnesium will vaporize severely if protected only by an inert atmosphere such as argon. Consequently an enveloping container is required. In zone melting, a rigid opaque container surrounding the charge is inconvenient because visual control of the zone length is prevented. A more satisfactory container is a strong flexible skin on the surface of the metal charge which is capable of supporting the molten zone. SO2 reacts with magnesium to form a thin coherent surface film of MgSO, and MgO. An atmosphere of SO, of commercial purity was maintained during the zone melting. Enough oxygen was present within the system and the commercial SO, for the satisfactory formation of the protective skin, so that any rupture of the skin during the zone refining was healed immediately.

Jan 1, 1959

By T. E. Scott, D. H. Sherman, C. V. Owen

Mechanical properties and optical metallographic characteristics of vanadium containing 53 ppm (wt) H were investigated from, 77° to 298°K. A sharp ductile to brittle transition induced by the presence of hydrogen was observed between 238° and 223°K and a mar-tensitically formed hydride appeared at 200°K. While there appears to be a subtle relationship between the hydride formation and the ductile-brittle transition, it was concluded that the hydride per se was not sufficietzt to cause the severe em brittletnent. On the basis of the metallographic experiments and the results of a Petch analysis it is suggested that the mechanism of the embrittlement involves a reduction of the true surface energy, or cohesion, of the uanadiunz. THAT hydrogen can severely embrittle vanadium is well-documented;'-5 however, the mechanism by which hydrogen induces the observed embrittlement has not been established. It is not known whether the embrittlement of vanadium is caused by the formation of vanadium hydride or by a more subtle role of hydrogen. Until very recently6>' the solid solubility of hydrogen in vanadium at temperatures in the,range of the embrittlement was not known to a useful accuracy. In general, a severe embrittlement of the type produced by the presence of hydrogen in vanadium can be caused by changes in either of two properties of a metal. Either the yield stress of the metal is raised to the extent that plastic deformation at the tip of a crack cannot occur or the cohesive properties of the metal are reduced, at least locally, to the point at which cleavage is the natural response to applied loads. Of course a combination of these is possible. It is not known which of these properties of vanadium is influenced most by the addition of hydrogen. The purpose of this investigation was to determine the role of hydrogen in the embrittlement of vanadium. Accordingly, the solubility of hydrogen in vanadium in the temperature range where embrittlement is most severe was determined, the appearance of vanadium hydride was examined in relation to the initial ductile to brittle transition temperature, and an attempt was made to evaluate the effect of hydrogen on the yield stress and cohesive properties of vanadium. MATERIAL AND PROCEDURES Sample Preparation. The vanadium used in this investigation was prepared by the iodide refining process described by Carlson and owen.' Three ingots, 3 in. diam by 6 in. long, were cold-swaged to 0.096 in. diam, cut into short lengths, and then arc-melted under purified argon into one ingot. This process was repeated to insure a uniform composition in the final ingot. Chemical analysis of the metal is given in Table I. On the basis of work of Loria et a/ .' the following sequence of treatments was performed in order to obtain a uniform equiaxed ultimate grain structure: a) cold swage q-in.-diam ingot to 0.230 in. diam; b) anneal 6 hr at 1000°C in vacuum; c) by cold swaging reduce 81 pct in area in three steps: 0.230 to 0.187 in. diam, 0.187 to 0.150 in. diam, 0.150 to 0.096 in. diam. This sequence provided the desired grain structure after subsequent annealing treatments. Because annealing in evacuated quartz capsules resulted in contamination by oxygen, all anneals in this investigation were performed in a 304 stainless-steel chamber under a dynamic vacuum of 10- I Torr with the vanadium wrapped in tantalum foil. Prior to all annealing treatments the wires were electropolished for 1 min at 16°C in an 80 pct methanol-20 pct sul-furic acid electrolyte at 12.5 v. Following the final reduction the 0.096-in.-diam wire was cut into 2-in. lengths. A 1-in. gage section was reduced to 0.090 in. diam by electropolishing as above. Five different grain sizes were obtained by annealing the 2-in. samples at different temperatures for 8 hr to insure uniform grain size and residual hydrogen removal. The annealing temperatures used and the resulting grain sizes are given in Table 11. The final step in sample preparation was to charge half of the specimens of each grain size with hydro-

Jan 1, 1969

By Kenneth L. Cook

THE five serpentine masses exposed within the northern half of Riley County, Fig. 1, constitute a major part of the few exposures of igneous rock in Kansas.' Although not many subsurface data are available for this part of Riley County,2 six deep wellsV indicate that the basement complex lies between 2500 and 3000 ft below the earth's surface. A northwestward-trending ridge in the present basement surface, which extends across the northern half of Riley County, is indicated on Mettner's contour map.' The serpentine masses lie in a region that was active during Pennsylvanian and Permian time along two main tectonic trends, which may, in part at least, have developed contemporaneously." One trend is northeasterly, as evidenced by the Nemaha anticline, the Abilene anticline, the Voshell anticline, and many other smaller northeastward-trending folds. The other trend is northwesterly, as evidenced by the central Kansas uplift, the Salina basin syncline, and smaller northwestward-trending folds. The area of the Abilene anticline was actively deformed during much of this time, and the present surface rocks, for the most part Permian in age, show many normal faults." The Bala and Leonardville intrusions lie within a mile of the axis of the Abilene anticline, Fig. 1, as mapped by Wallace Lee;' the Randolph No. 1 and Randolph No. 2 intrusions lie within about 5 miles of the axis; and the Stockdale intrusion lies within about 8 miles of the axis. The igneous rocks have intruded horizontal or gently dipping limestones and shales that are late Permian in age.V he period of intrusion, according to Moore and Landes, was probably Cretaceous.' At present a detailed description of the petrography is available for only the Bala intrusion. Moore and Haynes' describe the rock at Bala as a green, serpentinized, porphyritic, peridotite breccia containing inclusions of shale. The ground mass consists chiefly of serpentine and calcite with considerable chromite (5 to 10 pct) and some magnetite. The phenocrysts consist principally of altered olivine with some altered augite and biotite. Although probably different in petrographic details, all the serpentine masses are somewhat similar in that 1) they consist of a dark green, fine-grained ground mass of igneous rock containing many xeno-liths composed of fragments of the neighboring sedimentary rock; 2) they tend to form small mounds on the landscape, thus indicating their greater resistance to weathering and erosion; and 3) they are magnetic. Previous Magnetic Survey of the Bala Intrusion: To the writer's knowledge, only the Bala intrusion had been surveyed with a magnetometer prior to the magnetic surveys discussed in this paper. Dreyer8 interprets the intrusion as a vertical, eastward-plunging dike, on the basis of the results of his magnetic survey, Fig. 1, with a vertical magnetom-

Jan 1, 1956

By David T. Peterson

Calcium metal was found to deoxidize thorizcm at 1000° to 1200° C. The reaction kinetics were determilled and related to the diffusion coefficients of oxygen in thorium. The solubility of oxygen in thorium, the minimum oxygen concentration, and the diffusion coefficient were determined from 1000° to 1200°C. This firocess results in the lowest oxygen concentrations zohich have been reported for thorium metal. FOR many years it has been known that calcium metal will reduce thorium oxide to thorium metal. This reaction has been the basis for several methods of preparing thorium metal. From the equations giv-by Kubaschewski and vans, ' AF" for the reaction Cao, + Tho,(,) - CaO(,, + Th(,) was calculated and found to be -3.4 kcal at 1000°C, -2.5 kcal at llOO°C, and -2.0 kcal at 1200°c. Thorium is very slightly soluble in liquid calcium, and the solubility of calcium in solid thorium is very low. Consequently these metals would be in essentially their reference states. If thorium containing oxygen were equilibrated with liquid calcium between 1000° and 1200°C, the oxygen content of the thorium would have to be below the solubility limit in thorium. Oxygen is one of the impurities most difficult to remove from thorium and is the most abundant impurity in metal prepared by almost all known methods. Fortunately, oxygen does not have a large influence on the properties of thorium because the solubility in solid thorium is very low. EvenT in thorium containing 100 ppm of 0, particles of thorium oxide can be observed in the microstructure. In view of the incompatibility of thorium oxide and liquid calcium and the low solubility of thorium oxide in thorium, the deoxidation of thorium by this method was investigated. For thorium containing an amount of oxygen well in excess of the solubility limit, the reaction should proceed in the following sequence. The oxygen content of the thorium matrix near the surface would be depleted by the diffusion of oxygen to the surface. At the surface, the oxygen would react with calcium to form calcium oxide. To maintain equilibrium within the thorium, thorium oxide would dissolve to keep the matrix saturated. Consequently, the thorium-oxide particles would disappear first at the surface and then the particle-free rim would grow in thickness. If the rate-controlling step were the diffusion of oxygen through this layer of thorium which was growing in thickness in direct proportion to the amount of oxygen removed, the well known parabolic time law should be observed. If the oxygen concentration at the surface of the thorium and at the inner surface of the deoxidized rim were known, the diffusion coefficient of oxygen in thorium could be calculated from the parabolic rate constant. EXPERIMENTAL PROCEDURE The thorium metal used in this study was prepared by calcium reduction of ThF, by the method described by Wilhelm.' The analysis of this metal is given in Table I. The carbon was determined by combustion, the oxygen by the HC1-insoluble residue method, nitrogen by the Kjeldahl method, and the other elements by emission spectroscopy. A section of this ingot was hot rolled at 600°C to 1/4 and 1/8-in. thick plates. Specimens approximately 7/8 in. square were cut from these plates, and all surfaces of the specimens were cleaned and smoothed by filing with a clean file. Individual specimens were placed in 1-in. diam by 2-in.-long tantalum capsules. Approximately 1 g of clean, high-purity calcium was placed in the capsules and an end closure arc-welded in place. The tantalum capsules were sealed in Inconel crucibles to protect the reactive metals from oxidation. The entire loading procedure was done in a glove box filled with pure argon. The loaded crucibles were placed in a muffle furnace, controlled within 2OC of the desired temperature, for a measured length of time. After the specimen had cooled to room temperature, it was sectioned perpendicular to the large faces and through the mid-point of two of the sides. The sectioned specimen was mounted and polished through Linde A abrasive. The rim which was free of thorium-oxide particles could be clearly observed microscopically as mechanically polished. Twenty measurements of the thickness of the rim were made at equally spaced points far enough from the end of the

Jan 1, 1962