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By G. Gutierrez, D. A. Elgillani, M. C. Fuerstenau

The zero-points-of-charge of apatite, calcite, and fluorite are pH 6.4, 10.8, and 10.0, respectively. Scheelite is negatively charged above at least pH 3. In this article, the flotation responses of these minerals in the presence of potassium oleate and sodium silicate are described and compared with electrokinetic data. Colloidal silica appears to be the species principally responsible for calcite depression, while silicate anion is the species responsible for fluorite depression. Additions as high as 1 x 10-3 mole/liter silicate have no effect on the flotation responses of apatite and scheelite. Selective flotation of nonmetallic minerals is difficult to achieve with fatty acids or soaps by themselves. As a result, specific reagents are added to aid these separations, and one of the reagents commonly employed for this purpose is sodium silicate. Flotation separations of various calcium-bearing minerals such as fluorite from calcite1-3 and scheelite from calcite2,4 and apatite,2,5 for example, almost always involve the use of sodium silicate. The mechanisms by which sodium silicate functions as a depressant are still not understood, probably for a number of reasons. For one thing, the dissolution process of sodium silicate is complex, giving rise to a number of ionic and colloidal species.' Moreover, the type and concentration of these species depend on the ratio of Na2O to SiO2, the concentration of sodium silicate, and the pH of the system.' At the present time, it is not known which species, colloidal silica or silicate anion, is responsible for depression. If colloidal silica is the species that is adsorbing, then adsorption must occur by electrostatic attraction between the colloid and the mineral surface. Silicate anion, on the other hand, may adsorb either physically or chemically. The objective of this paper is to determine first the active species of sodium silicate and then the conditions under which this species will adsorb and function as a depressant. EXPERIMENTAL MATERIALS AND METHODS Pure samples of apatite (Durango), calcite (Iceland-spar), fluorite, and scheelite were used in this investigation. Pure potassium oleate was used as collector, while reagent-grade HC1 and KOH were employed for pH adjustment. The sodium silicates used were samples obtained from the Philadelphia Quartz Co. In one series of experiments, various sodium silicates containing different ratios of SiO2 to Na2O were added to calcite systems. These sodium silicates contained SiO2-to-Na2O ratios of 3.75 to 1, 3.22 to 1, 2.40 to 1, and 1.60 to 1. All other experiments were conducted with the sodium silicate containing the ratio of 3.22 to 1, which is the one that is normally used in industry. Flotation experiments were conducted with 21/2-g charges of 48 x 150-mesh material in conductivity water with an apparatus and technique described previously. Electrokinetic experiments were conducted with both a Zeta Meter and streaming potential apparatus. Particle size was 48 x 65 mesh for the streaming potential experiments. EXPERIMENTAL RESULTS The first series of experiments involved flotation of scheelite in the absence and presence of sodium silicate. As shown in Fig. 1, flotation response was not affected with even the relatively high addition of 1 x 10-3 mole per liter sodium silicate. Interestingly though, no flotation was effected below pH 6 with this collector addition. The responses of apatite to flotation under these same conditions are given in Fig. 2. Similarly, no depression was obtained in basic media under these conditions. Similar experiments were conducted with fluorite, and in this case, depression was noted above about pH 11 with 1 x 10-3 mole per liter sodium silicate (Fig. 3). When calcite was floated with these same levels of addition of sodium silicate, essentially no flotation was possible above pH 7 (Fig. 4). The effect of collector addition with a constant addition of sodium

Jan 1, 1969

By D. Turnbull, J. H. Hollomon, J. C. Fisher

UNDERSTANDING of the diffusion problem has recently been furthered by the analysis of Birchenall and Mehl.1 They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,2 Jost,3 Dehlinger,4 and Darken,' who assumed the net flux of dif¬fusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's' activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Hargreaves.7 The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinski10 in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitutional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitutional alloys were analyzed on the basis of the concepts of the chemical rate theory. CHEMICAL RATE THEORY According to the theory of absolute reaction rates8 the reaction [A,+A2+ ... +.A;->X,+X2 +...+X; EqI] is viewed as taking place in two steps. First the reactants A1, A2, . . . A[i] combine to form an activated complex M with which they are in equilibrium; [A, + A2 + .. . + Ai = M. Eq 2] Second the activated complex decomposes to give the products X1, X2. . .. X[j]; [M->X1+X2+ ... +.X;. Eq3] It has been shown8 that the number of activated complexes decomposing per unit volume per unit time is given by the expression† [kT]

Jan 1, 1948

By Orlando E. Romig

As metals and alloys are composed of an aggregate of allotriomorphic crystals or grains, each possessing an individual orientation, the physical characteristics of a metal or an alloy are closely related to the properties of the individual crystals. The preparation and study of single metallic crystals are, therefore, matters of considerable importance. The advent of the X-ray spectrograph as a valuable metallurgical tool has magnified the importance of this subject, because the interpretation of some X-ray spectrographs is difficult unless single crystals are used in these studies. Previous Work The first paper, as far as the writer knows, on the behavior or preparation of single crystals of metals is by Baker.' He describes the behavior of extruded wires of sodium and potassium. These wires, when pulled in tension, instead of showing the usual conical fracture common to most metals, had a chisel-shaped fracture when they were broken. I and 11, Fig. 1, have a similar fracture. Baker checked his results by preparing single crystal wires from molten sodium and potassium and observing their properties. He pre- pared the wires by filling glass tubes, under oil, with the molten metal. The surfaces of the strained wires showed slip bands of remarkable clearness of which photographs are shown in his paper. He concluded that these wires were single crystals and "that the portions of the metal brought into play are cubes. Such cubes, when placed so that a plane through two opposite edges was parallel to the axis of the wire, would allow of lateral contraction by faces gliding over one another in one direction only and not in the direction at right angles."

Jan 1, 1927

Apr. 26-May 11, Liege International Fair, Liege, Belgium. May 4-8, Electrochemical Society, Inc., Spring meeting, Benjamin Franklin Hotel, Philadelphia. May 5-6, National Air Pollution Symposium, Huntington Hotel, Pasadena. May 5-7, American. Mining Congress, coal convention, Netherland Plaza Hotel, Cincinnati. May 6-9, Scientific Apparatus Makers Assn., annual meeting, Edgewater Beach Hotel, Chicago. May 9-10, AIME, joint meeting, Industrial Minerals Div. and Metals Branch, Davenport Hotel, Spokane, Wash. May 11-14, American Institute of Chemical Engineers, Atlanta Biltmore Hotel, Atlanta. May 17, AIME, Chicago Section, President's night dinner dance, Shoreland Hotel, Chicago. May 27, AIME, Morenci Subsection, Longfellow Inn, Morenci, Ariz. June 2-4, Chemical Institute of Canada, annual conference, Montreal. June 4-14, Mechanical Handling Exhibition and Convention, Olympia, London.

Jan 1, 1952

Meeting, June 26, 1913).-On the petition of 29 members residing in and near San Francisco, Cal., the San Francisco Local Section was established. The territory of the St. Louis Local Section was established to include the following States and parts thereof: All the State of Missouri ; That part of the State of Illinois south of and including the city of Urbana ; That part of the State of Indiana south of and including the city of Indianapolis ; That. part of the State of Kentucky west of and including the city of Frankfort ; That part Of the State of Tennessee west of and including the city of Nashville That part of the State of Arkansas north of and including the city of Little Rock.

Jan 7, 1913

By E. H. Wells, A. Andreas

Greater progress than in any previous year was accomplished by the oil industry in New Mexico in 1936. The total number of completions in the state was 631, of which 549 were oil wells, 21 were hydrocarbon gas wells, three were carbon dioxide gas wells, and 58 were dry holes. The total oil production for the year was 26,804,446 bbl. Compared with the production for 1935 of 20,228,947 bbl., this represented a gain of 32.5 per cent. Of the total production, 25,337,382 bbl. came from Lea County. The average daily nonmarginal well allowable for that county was 115 bbl. the first of the year and 86 bbl. at the close. Production was regulated by the New Mexico Oil Conservation Commission,

Jan 1, 1937

By B. Yarar, J. Kaoma

[Introduction The critical surface tension of wetting of hydrophobic materials has been investigated extensively by Zisman et al. (1973) and relates the spreading of a liquid on a solid to the surface tension of this liquid. Thus, the Zisman ap¬proach shows that a plot of Cos 0 versus ?LV where, 0 is the contact angle and ?LV is the surface tension of that liquid in contact with its own vapor at equilibrium, produces a straight line which can be extrapolated to Cos 0 = 1. The intercept corresponds to a given ?LV, termed the critical surface tension of wetting. In instances, however, Cos 0 - ?LV plots show deviations from linearity. Alternative approaches have also included the plotting of adhesion tension (YLV COs 0) versus ?LV that can be interpreted in terms of critical surface tension data (Lucassen-Reynders, 1963). It has, on the other hand, been customary to correlate contact angle (0) with flotation data, although it is recognized that surface inhomogeneities and related contact angle hysteresis limit the interpretations pertaining to solid surface structures purely based on contact angle measurements. It is nonetheless true that 0 = 0, when the liquid is water, corresponds to a hydrophilic solid. Determination of ?c by contact angle measurements in conformity with the Zisman approach can encounter experimental difficulties, especially when solids are in a powder form. Following the reasoning that 0 = 0 corresponds to the hydrophilic state of a solid, froth flotation experiments can be expected to produce critical surface tension of wetting values for powders. The technique that consists of plotting recovery (% R) versus YLV data and extrapolating the linear part of the curve to % R = 0, has been described elsewhere (Yarar and Kaoma, 1984). This paper describes some of the results obtained by the extrapolation technique mentioned above, using various sulfide minerals. Experimental Materials Molybdenite (MoS2), sphalerite (ZnS), chalcopyrite (CuFeS2), chalcocite (Cu2S), and galena (PbS) were handsorted from massive samples and ground by mortar and pestle, and the -147 Fan fraction used in experiments; sulfur (S) was a C.P. Fisher Scientific Co. product. Method One gram powder samples were conditioned for three minutes in methanol-water solutions of predetermined surface tension values and the percents recovered by flotation using a Partridge-Smith Cell (Partridge and Smith, 1972), were plotted against each ?LV value. Results and Discussion The percent recovery versus ?LV for two naturally hydrophobic solids, i.e., natural molybdenite, MoS2 and sulfur are given in Fig. 1 where it is seen that ?c for sulfur is obtained as 31.5 mNm-1 whereas for MoS2, it is 26 mNm-1. Figure 1 also shows that the new flotation technique described, for estimating ?c is in good agreement with the Zisman method. Curves obtained by the same method for the minerals Cu2S, PbS, and ZnS are given in Fig. 2, where it is seen that for Cu2S, ZnS, and PbS, the extrapolation to % R = 0 produces ?c values of 36, 39, and 49 mNm-1, respectively. CuFeS2, on the other hand, gives a curve that does not permit such an extrapolation to obtain a ?c value with certainty. Nonetheless, treatment of the powder with 8.95 X 10-5 molar Na2S solution followed by washing with distilled water prior to flotation effects the curves as shown in the insert of Fig. 2. The type of curves given in Fig. 1 appear to be typical of hydrophobic solids as can also be observed in Fig. 3. The composition of solid and minute quantities of inclusions seem to play an important role as regards the surface properties of solids as reflected by the slope of the linear part of the % R - ?LV plot and thus the value of ?c obtained by this technique. For example, MoS2 of three different stoichiometric compositions produced the data given below. [MoS2MoS2.14Mo1.002S2 ?c mNm-126.029.031.0 dR/d?8.95.23.0]]

Jan 1, 1985

By Thomas T. Read

IN reviewing the field of mineral industry education last year reference was made to recent assertions, mostly emanating from sources not in a position to know the facts, that mining engineers as a class are disappearing. Attention might also then have been called to a statement that appeared in Engineering News, August 11, 1892 (p. 130), ". . . the great absolute decline in number of mining graduates, which last amounts almost to a complete abandonment of mining engineering as a distinct branch of study." Evidently we outrank opera stars in the number of farewell appearances we are able to make; 43

Jan 1, 1936

By W. E. Field

In the Coast Mountains approximately 110 miles north of Vancouver, the gold mine of Bralorne- Pioneer Mines Ltd. lies at an elevation of 3500 ft. The deepest or 41 level in the mine is at an elevation of 1400 ft below sea level, and the rock temperature on this level is 122.5°F. The thermal gradient is 1 "F increase in temperature for each 67.5 ft increase in depth. The mine produces between 500 and 600 tons per clay, utilizing an adit two internal shafts, and one service shaft from surface. The Queen shaft, extending from the 26 to the 41 level, IS the deepest, and most production now comes from this area. Stoping in by cut and fill using mill tailing hydraulic backfill.

Jan 12, 1963

By T. S. Washburn

THE grades of commercial steel produced in large quantities can be divided into two general types from the standpoint of ingot structure-killed and rimmed. Killed steel covers a wide variety with carbon contents throughout the range of the steel portion of the iron-carbon diagram, and is the kind usually used in the production of alloy steels. Rimmed steel is normally associated with carbon ranges under 0.30 per cent, and is not yet used to a large extent in alloy practice, except for copper-bearing steels. The fundamental differences in the ingots made from these two types of steel can be seen most easily in Figs. 1 to 7. In the rimmed ingot shown in Figs. 5 to 7 there are two lines of blowholes approximately parallel to the sides and coming together at the top and at the bottom of the ingot. In the killed ingots shown in Figs. 1 to 4 these blowholes are not present. Also, the rimmed ingot has no well defined pipe, as com-pared to the deep pipe on the killed ingots, and there are numerous pri-mary blowholes in the lower portion of the rimmed ingot perpendicular to the surface and close to it, while on the killed ingot there are no blowholes of this type in the ingot shown in Fig. 1 and very small ones close to the surface in the lower part of the ingot shown in Figs. 2 to 4. With respect to the presence of pipe and the primary blowholes, the structure may vary considerably in both rimmed and killed ingots, therefore these cannot be considered as fundamental structural characteristics differ-entiating the two types of steel. The primary blowholes in rimmed ingots may be much less pronounced than those in the ingot shown in Figs. 5 to 7-as, for example, in "ingot iron," which is entirely free from them. An example of a cross section of an ingot-iron ingot is shown on page 16 of "Research and Methods of Analysis of Iron and Steel," published by the American Rolling Mill Co. (1920). A certain amount of pipe may also occur in rimmed ingots, though it is normally porous and not as well defined or deep as in the killed ingot of Fig. 1. In killed ingots, pri-mary blowholes may occur near the surface, as in Figs. 2 to 4, and

Jan 1, 1937

By NEWTON C. MARSHALL

AS every school boy knows, the Andes mountain range forms the backbone of South America, extending the full length of the continent along its western edge and fairly close to the Pacific coast. But in Colombia these mountains are divided into three distinct ranges known as the Western, Central and Eastern ranges of the Andes. United at the southern end, they spread out like three fingers in a northerly direction across the Republic of Colombia. These great natural barriers have only in recent years been tarried by railroads or wagon roads, and they have had their effect upon the history of the country, both political and ethnological. Each of the three ranges dies out and dwindles away before reaching the boundary of Colombia on the Caribbean Sea. When I studied my geography as a youngster 1 used to think that the

Jan 1, 1935

By Elwin L. Fisk

The Cordero mine is located in the Nevada portion of the Opalite Mining district that straddles the Oregon-Nevada state boundary. The mercury deposits of the district occur along the margins of the broad east-west graben valley of McDermitt Creek. The only other major producers, the Opalite and Bretz mines, on the northern margin of the graben have thus far exploited only shallow deposits within 100 feet of the surface. Through December 1965, Cordero has produced 94,680 flasks of mercury, the most of which came from the large underground cinnabar deposit. Nearly all of the mercury ore deposits in this district have been found in Miocene rhyolitic intrusives, flows, tuffs, and lake beds. These rhyolites have been argillically altered at depth and extensively silicified at or near the surface. These silicified areas or "opalite" masses were the original cinnabar-bearing outcrops.

Jan 1, 1968

By H. L. Miaw, A. M. Gaudin, D. W. Fuerstenau

A quantitative method for evaluating density of slime coatings has been developed and applied to formation of iron oxide slime coatings on quartz and on corundum. Slime coating density is related to flotation recovery and to properties of the electrical double layer at mineral surfaces. IN spite of considerable study, the nature of slime coatings in flotation is still not completely understood. However, phenomena that control floc-culation and dispersion of colloidal systems are now interpreted in terms of electrical double layers.",' Colloids will flocculate even though the particles carry the same charge, but when two dispersed colloids of opposite charge are mixed. flocculation ensues even more rapidly. Analogous phenomena seem responsible for slime coating on minerals in flotation systems. To shed new light on the issue it was considered desirable to devise a tool that would measure slime coatings. The usual method has been to examine photographs of presumably representative surfaces, after. an intervening washing in running water. But such an examination is non-quantitative, and the changes in chemical environment represented by the washing may have removed the slime coatings that existed during flotation. To provide the possibility for a correlation with electrical double layer phenomena, the experiments were made with quartz, corundum, and iron oxide, for which elec-trokinetic data are available.'-" Since the properties of the electrical double layers of these oxides depend on the pH of the solution, pH will be the most important variable. Furthermore, because the zero point of charge for silica, iron oxide, and alumina occurs at pH 3.7, 8, and 9.5, respectively, the relative charge on the slime and mineral can be changed over wide ranges. Because of its practical importance in quartz flotation, iron oxide powder was chosen as the slime. Also, its uniform composition, contrasting color, and ease of analysis make experimentation simple. In this investigation, correlation was sought between the effect on flotation recovery of slime addition and slime coating density. Materials and Methods Details are available in a thesis by Miaw." The quartz was selected from pure Brazilian crystalline quartz, crushed, sized (65/150 mesh) acid-cleaned, washed, and stored in conductivity water. The corundum (synthetic alumina of high purity prepared by Linde Co., Chicago) was crushed, sized (65/100 mesh) deslimed, boiled in nitric acid, washed, and stored in conductivity water. The iron oxide slime, reagent-grade ferric oxide (—400 mesh) from Allied Chemical & Dye Corp., was heated to 160°C, cooled, and stored in a vacuum desiccator. In the electron microscope the slime particles appeared to be about 0.3µ in size, but their large specific surface (87,900 cm per g, by gas-adsorption method, using krypton) suggests that the actual particles are smaller than 0.3r. Had they been perfect nonporous spheres, they would have had a diameter of 0.13µ.

Jan 1, 1959

By E. H. Kelton, R. D. Grissinger

In designing structural members of steel and some other materials the design engineer has available recognized values of elastic modulus and safe working stress that may be substituted in well-known engineering formulas to give him desired cross-sectional areas and deflections for a particular part. Zinc, on the other hand, has no generally recognized modulus. It flows under continuously applied loads. Therefore, the designer of structural members must use a range of working stresses depending on the continuous load and the amount of permissible distortion. The only method of obtaining these values is by creep testing. Creep testing of zinc has been carried on for some 20 years by this laboratory, covering a wide range of zinc and zinc alloys. Types of test included tension, compression, and simple and cantilever beams at temperatures ranging from o to I50°C. Specimen conditions ranged from as-cast or as-rolled to accelerated aged in steam or dry air. Effects of plating were investigated also. It is not the intention of this paper to expound all these factors but rather to present the final data on well-known zinc die-casting alloys and to suggest means of applying these data to engineering design. Early Work In the early work on creep testing of zinc, the direct-loading tension method was used. However, direct loading of die castings was unsatisfactory because of the high loads required. For instance, a standard die-cast tension bar having a cross-sectional area of about 0.049 sq. in. would require a direct load of about 1000 lb. for a unit stress of 20,000 lb. per sq. in. Also, tests were made at nominal room temperature, but normal variations caused fluctuations greater than those due to experimental error or other causes, so that control of this variable within ±1/2°C. seemed essential. These two factors led to the development of an apparatus described by J. Ruzicka,' in which the specimens were loaded by means of a lever and were held at constant temperature by means of an oil bath. While Ruzicka's apparatus yielded excellent check results, it seemed desirable to have some setup by which literally hundreds of die-cast specimens could be tested at the same time. This would permit the conducting of a number of low-load tests designed to run 10 years or longer and still leave capacity for current high-load work. Beam testing in a constant-temperature room was the answer. Test Method Preliminary work indicated that die-cast beams of various lengths and cross scctions yielded the same result within reasonable limits regardless of whether they were tested as simple beams, uniformly loaded beams, or cantilevers. Accordingly, the simplest type was adopted. This was a,

Jan 1, 1945

By R. K. Agarwal

In this paper, a new technique developed to analyze two-dimensional nonhomogeneous models is described. A simple three-layered medium with a circular hole centrally located in the intermediate layer is considered. The layered sheet is loaded uniaxially perpendicular to the stratification. The Young's modulus of the intermediate layer is lower than that of the outer layers. The stress distribution around the circular hole in a stratified medium is significantly different when compared to the case of a continuous homogeneous medium. The distribution depends upon the ratio of the height of the intermediate layer and the hole diameter. A comparison of stress distribution and procedures for preparation and testing of the model are given. The potential of the technique is outlined. In the process of applying the techniques of stress analysis to problems of rock mechanics, the recent discernible trend has been to postulate highly idealized models of physical situations. As new techniques have been developed, more complicated models have been conceived to simulate mote accurately the physical environment to which the analysis results are eventually applied. In this investigation, a new technique is developed to analyze two-dimensional nonhomogeneous models. The technique is used to determine the stress concentration around a circular hole in a soft material overlain and underlain by a hard material. In mining practice, such situations arise commonly in coal deposits and frequently in bedded or vein-type metallic mineral deposits. DEFINITION OF THE PROBLEM A plate, consisting of three layers with a circular hole in the intermediate layer, is loaded uniaxially, Fig. 1. The variable in the experimental investigation is the height of the intermediate layer, H. The diameter of the hole, D, is kept constant. The stress concentration factors around the periphery of the hole, for various values of H/D, are evaluated using the technique of photoelasticity, Table I. TECHNIQUE OF EXPLORATION Photoelastic analyses of composite models have hitherto been limited to the study of lap and butt joints between glued metals and dissimilar materials.1-3 In mining, Haber and Oudenhoven used composite models to study the stress distribution around a circular hole in two-layered media and the behavior of elastic liners in shallow underground openings.4-5 They used the stress freezing technique devised by Dally et a1.6 The procedure used in this investigation is outlined below: Casting of Layer A: Flat sheets of plastic were cast in a silicon-coated mold using Araldite 502 with hardener 951 in the ratio of 100:8 by weight. After

Jan 1, 1969

By P. E. Fitzgerald, J. C. Gindlesperger

1. The Acidizer (Trade Publication of Dowell Inc.): No. 1. Aspects of Acidizing. No. 2. Inhibited Acid. No. 3. The Value of Acidizing. No. 4. The Chemistry of Acidizing. No. 5. Jelly Seal in Acidizing. No. 6. Loosening Stuck Drill Pipe. No. 7. The Geology of Acidizing. 2. J. C. Albright: Acid Is Being Used for Cleaning Intake Wells in Water-flooded Areas. Oil Weekly (Sept. 23, 1935) 24. 3. D. H. Bancroft: Acid Tests Increase Production of Zwolle Wells, Miller County, Arkansas. Oil and Gas Jnl. (Dec. 22, 1932) 42. 4. A. H. Bell: Possible Areas for Acid Treatment in Illinois. Pub. of Illinois- Indiana Petr. Assn. and lllinois Geol. Survey (1934) 49. 5. N. A. Best: Treating Limestone Formations Consists of More than Pouring Hydrochloric Acid in the Well. Oil and Gas Jnl. (April 5, 1934) 54. 6. L. G. E. Bignell: Sealing Off Salt Water from Oil-bearing Formations. Oil and Gas Jnl. (Jan. 30, 1936) 59. 7. L. G. E, Bignell: Acidizing Upper Limestone Formation Facilitated by the Use of Jelly Seal. Oil and Gas Jnl. (March 5, 1936) 30. 8. L. G. E. Bignell: Bailing, Shooting, Tubing and Acidizing Have All Been Tried in Deep Test at Binger, Oklahoma. Oil and Gas Jnl. (May 10, 1934) 38. 9. L. G. E. Bignell: Dowel1 Incorporated Increasing Its Field Service for Acid Treatment of Wells. Oil and Gas Jnl. (June 7, 1934) 62. 10. L. C. Chamberlain, Jr. and P. E. Fitzgerald: Oil Well Acidizing in Michigan. Mich. Acad. Sci. Papers (March 1937). 11. M. E. Chapman: Some of the Theoretical and Practical Aspects of the Acid Treatment of Limestone Wells. Oil and Gas Jnl. (Oct. 12, 1933) 10. 12. C. E. Clason and J. G. Staudt: Limestone Reservoir Rocks of Kansas React Favorably to Acid Treatment. Oil and Gas Jnl. (April 25, 1935) 53. 13. W. F. Cloud: Cleaning and Reconditioning Oil Wells—Reconditioning by Use of Acid (Petroleum Production 1937), 389. University of Oklahoma Press, 1937,' 14. K. A. Covell: Developments in Eastern Production Practice. Acid Treatment of Michigan Wells. Amer. Petr. Inst. Prod. Bull. 213 (1934) 77; Oil and Gas Jnl. (May 31, 1934) 89; Oil Weekly (May 28, 1934) 17. 15. B. A. Cunningham: Acid Treatment of Lime Formations. Amer. Petr. Inst. Paper 901 (1933) 9D, 1-7. 16. 0. I. DeSchon: Pondera Production up 22,000 Barrels. Montana Oil & Min. Jnl. (Jan. 26, 1935) 1.

Jan 1, 1937

By A. E. Dwight, A. F. Berndt

Binary and ternary alloys of uranium with transition metals were prepared with U2X stoichiometry. The compounds U2Tc, U2Rh, U2Os, and U2lr were formed by peritectic or peritectoid transformations, and were shown to be isostructural with U2Ru. The lattice constants are presented. Miscibility relationships obtained from the study of ternary alloys are graphically summarized in terms of an area-of-stability plot. The compound U2Re is not isostructural with either U2Ru or U2Mo. A series of compounds with stoichiometry U2X has been prepared in which X is technetium, rhodium, rhenium, osmium, or iridium. The only other U2X compounds, for which X is related to the above transition metals by proximity in the periodic table, are U2Mo and U2Ru. The structure of U2Mo is the tetragonal C11b type (MoSi2 type)1 and U2Ru is monoclinic, with a new structure type.' This investigation was undertaken to determine if any of the above compounds are isostructural with either U2Ru or U2Mo and to find the range of occurrence of these phases. EXPERIMENTAL Alloys were prepared from stoichiometric amounts of electrolytic uranium (99.99 pet pure) and transition metals of 99.5 pet purity (98+ pet pure Tc), by arc melting on a water-cooled copper hearth under an Ar-He atmosphere. Weight losses were negligible. The buttons were homogenized at temperatures between 700o and 800°C (900°C for U2Tc) in evacuated capsules and air-cooled. The X-ray powder specimens were annealed briefly at the temperature of homogenization. Except in the case of the technetium alloy, metallographic examination was used to determine the number of phases present. The radiation hazard involved in handling technetium precluded the use of metallography to examine U2Tc. The temperature and mode of formation of the U2X phases were determined by heating the metallographic specimens to successively higher temperatures, until examination indicated the presence of chilled liquid or a peritectoid transformation. RESULTS The U2X compounds investigated were found to be formed under the following conditions: UzTc unknown U2Ru peritectic 897o ± 3°C U2Rh peritectoid 755o ± 5°C U2Re peritectoid3 below 750°C Uas peritectic4 920°C U2Ir peritectoid 775o ± 5oC Debye-Scherrer patterns for the above U2X phases were made with CuKa radiation (nickel filter). The similarities in the positions and intensities of the strongest lines in the front-reflection region strongly suggested that U2Tc, U2Ru, U2Rh, U2Os, and U21r are isostructural with only minor differences in the unit-cell dimensions. The known lattice constants and intensities of the Debye-Scherrer rings for U2RU2 were used as a guide in order to index the low-angle X-ray reflections of the U2TC, U2Rh, U2Os, and U2Ir powder patterns. Approximate lattice constants for these compounds were thus obtained and were used along with the intensities observed for U2Ru to index the strongest lines in the back-reflection regions. A sin2 2? correction term was included and the lattice constants were refined and standard deviations estimated by least squares. Comparison of observed and calculated values of Q(= 4 sin2?/?2) used in these calculations are given in Table I. In each case when the positions of lines could not be resolved on the films they were not measured. The final lattice constants, with their standard deviations, are given in Table 11, along with the unit-cell volume and X-ray density. The values of the atomic volume5 of the transition ele-

Jan 1, 1965

By R. F. Rolsten

VAN Arkel 1 prepared ductile tantalum by the thermal decompoiition of tantalum pentachloride on a resistively heated wire (2000° C) in an evacuated bulb maintained at 100°C. Burgers and Basart2'3 observed the formation of a mixture of tantalum carbide and free metal when a carbon deposition base was used. campbel14 suggested the thermal decomposition of the iodide if a lower decomposition tem- perature was desired. To date, the details for preparing high-purity iodide tantalum have not been disclosed. EXPERIMENTAL The tantalum to be purified was symmetrically placed around the clear quartz deposition surface centrally located within a 64 mm cylindrical Vycor bulb. The deposition vessel usually employed5 was modified6 by incorporating a reentrant fin,mer in place of the customary metal filament in the head

Jan 1, 1960

By D. F. Gibbons

THIS investigation was undertaken in order to gain further information on the mechanism of plastic deformation of iron at temperatures between room temperature and 77.2°K, and also to contribute to our understanding of the low temperature brittleness phenomenon that occurs in both the tensile and impact tests. It was decided to study as pure an iron as possible and to use the tensile test in order to simplify the problem as much as possible. Two series of iron were used throughout the investigation: iron A, obtained from the National Research Corp. and supplied as gas-free, high purity iron; and iron B, obtained from Fast' and produced by melting iron under purified hydrogen. Typical analyses of samples of both irons, after fabrication, are given in Table I. The main difference in composition of these irons is in their nickel and oxygen contents. Nickel has a very large solid solubility in iron. However, oxygen has an extremely small solid solubility. An attempt was made to reduce the oxygen content still further by remelting under purified hydrogen. This was successful in reducing the oxygen content to -0.0006 pct. However, no results on tests of this iron are included, since difficulty was encountered in fabricating the ingot. Wire specimens 1 mm in diameter were used for the investigation. The wires were produced from the ingots, as supplied, by cold rolling and swaging, with intermediate vacuum anneals at 700°C. Care was taken to reduce preferred orientation in the wires to a minimum by keeping the percentage of reduction in area between anneals of 30 to 40 pct. X-ray transmission photographs showed no indication of preferred orientation. The final grain size of iron A was 20 to 24 grains per linear mm and of iron B, 16 to 18 grains per linear mm. All specimens were tested in the decarburized and denitrided condition unless otherwise stated. The procedure was to pass hydrogen, saturated with water vapor at 26oC, over the specimens at 730°C for 2 hr. The specimens were quenched in iced water and then annealed in a vacuum of - 5x10-6 mm Hg for one day at 560°C to remove hydrogen. Higher temperatures were used for the vacuum anneal but this temperature was found to be quite satisfactory in removing hydrogen. The specimens were slow-cooled after the vacuum anneal. Where it is stated that the specimens were carburized, the specimens were given an identical decarburizing treatment and then carburized by passing hydrogen, saturated with pure n-heptane vapor at 0°C, over the specimens at 730°C. The specimens were then homogenized at 730°C for 2 hr in dry hydrogen. After the carburizing treatment the specimens were given the same vacuum anneal as for the decarburized specimens. The carbon content was determined from the maximum value of the internal friction carbon peak.2 Apparatus Fig. 1 shows a diagram of the tensile apparatus, with half the cooling coil removed. The cooling coil enabled temperatures from 200" to 77.2oK to be obtained. The apparatus was designed to fit a standard Tinius Olsen Universal tensile machine. The apparatus consisted of the rigid plate A which carried two carefully machined hooks H. These hooks attached the plate firmly to the moving crosshead of the tensile machine. The lower grip B was rigidly suspended from the plate A by three stainless steel rods. The upper grip C was joined to the upper grip of the tensile machine by the stainless steel rod E. The lower part of the apparatus was surrounded by a Dewar vessel, which was made a sliding fit inside the brass collar D. The specimen was held in a clamp which fitted into the grip, forming a ball and socket joint (see inset a). This was to attain as nearly pure

Jan 1, 1954

By Avnulf Muan, Egil Aukrust

The activity-composition curve for cobalt oxide in (Co,Fe)304 solid solutions with spinel-type stmcture has been determined experimentally by studying the equilibrium between the spinel phase and a coexisting cobaltowüstite phase, "(Co,Fe)O", at 1200°C. A large negative deviation from ideal behavior prevails in the spinel at low cobalt oxide concentrations and a positive deviation at high cobalt oxide concentrations. The activity-composition curve for iron oxide in the solid solution is determined from the above curve by integvation of the Gibbs-Duhem equation along the join Co3O4,-Fe3O4. The standard free energy of formation of cobalt ferrite, CoFe2O4, from the oxide components CoO and Fe2O3 is calculated to be -8.2 kcal. ThERMODYNAMIC properties of (CO,Mn)3O4 solid solutions with spinel-type structure have been presented recently.' The present paper deals with similar relations in another spinel solid-solution phase, that represented by the system Co3O4-Fe3O4. The principles involved in measurements and calculations of thermodynamic properties for the system Co3O4-Fe3O4 are analogous to those used and discussed in detail in the work on (CO,Mn)3O4. A (CO,Fe)3O4 solid solution coexists in equilibrium with a (Co.Fe)Ot solid solution over a considerable Here acOo1.33 and aao are the activities of cobalt oxide in the spinel and the oxide solid solutions, respectively, pO2, is the oxygen pressure of equilibration, and pb, is the oxygen pressure at which CoO and CosO4 coexist in equilibrium in the binary system Co-O at the same temperature. The activity-com position curve for cobalt oxide in the (Co,Fe)O solid solution in contact with metal has been determined in a previous investigation by the present authors.' The system shows a small positive deviation from linear behavior. Because of the large defect concentration in wiistite and in (Co,Fe)O solid solutions, one cannot assume that the activity-composition relations in the oxide phase coexisting with a spinel phase at relatively high oxygen pressures are the same as those prevailing in the oxide solid solution coexisting with metal. However, a Gibbs-Duhem integration over the ternary Co-Fe-0 solution can be used to determine activities of cobalt and iron, and hence of CoO and FeO, from a knowledge of the oxygen potentials. Several papers have dealt with the subject of application of the Gibbs-Duhem equation to multi-component systems. 3-6 In the present case, it was

Jan 1, 1964