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By T. S. Lundy, R. A. Padgett

The fact that cobalt diffuses in silver at a much slower rate in a region near a free surface than in bulk material has been demonstrated in a variety of experiments. Various possible mechanisms of this near-surface effect (NSE) are examined in light of experimental evidences. The tendency for surface segregation of some solute atoms appears to be a likely mechanism to explain the effect. UNIDIRECTIONAL and isothermal diffusion from a plane source of radioactive tracer into an isotropic, homogeneous medium follows the Gaussian solution to Fick's second law, or: where A(x,t) is the position and time-dependent concentration of the diffusing species, M is the quantity of diffusant per unit area initially at x = 0, and D is the diffusion coefficient. For a given time, say t = tl, one can easily see that: d In Aixji)_____1_ r2] d(x2) 4Dti Thus, if diffusion data obtained by serial sectioning are plotted as In A(x,tl) vs x2, the diffusion coefficient is obtained from Eq. [2]. The ideal behavior seldom is observed in real systems. Deviations from ideality generally occur either at small or large values of penetration distance. The overall picture is shown schematically in Fig. 1 where Regions I, 11, and 111 are due, respectively, to some near-surface effect or effects (NSE), volume diffusion, and short-circuiting effects. For different systems and conditions of specimen preparation and analysis, the relative importance of Regions I, 11, and I11 may be drastically different. Region I is completely absent in many systems and there is no NSE. In others, however, there may be considerable difficulty in determination of volume diffusion coefficients due to the overshadowing influences of Region I. Such is particularly true when indirect techniques such as the surface concentration decrease or the Gruzin method' are used to find D. In this paper several experiments which had as their goal a better understanding of near-surface effects are reported. Specifically, it is well-known that unusual penetration behavior results for the diffusion of several impurities in ilver- and that considerable controversy exists with regard to interpretation of the published diffusion data. We chose to examine those unusual results which occur for cobalt diffusion in monocrystalline silver395 primarily because knowledge of experimental procedures and materials were readily available. Both radioactive co60 and co5' could be utilized to offer a wide range of available concentration of the diffusing species. Experiments were also performed on the diffusion of AgnO in silver. They gave base-line data for the system—both for technique evaluation and for examination of the vacancy distribution near the surface. I) PROCEDURES Cylindrical-shaped specimens 1.25 cm diam and 1 to 1.25 cm long were cut from 99.999 pct Ag single crystals obtained from Monocrystals Co., Cleveland. One end surface of each specimen was polished flat and etched with a mixture of 20 ml saturated Cr03 solu-tion-20 ml H20-3 ml concentrated HC1. Radioactive tracer (co60 or co5' or Ag'lO, each having a radio-chemical purity of greater than 99 pct) was deposited onto the prepared surface either dropwise with evaporation to dryness of the solution containing the tracer (0.5 N HC1 solution for the co60 and co5' and 0.6 N HNO3 solution for the A"'), by electroplating, or by evaporation from a tantalum or tungsten filament in an evacuated bell jar. The amount of deposited cobalt was varied from many atomic layers of cobalt containing the co60 to approximately one co5' atom per lo6 surface atoms of silver. This large variation in amount of deposited cobalt yielded information about both the influence of a thick-source layer of tracer and solubility effects on the NSE. Such variations were possible because of the large differences in half-lives,

Jan 1, 1969

By J. L. Carne

ORE control is a matter of planning and supervision based on a foreknowledge of the content and distribution of ore. The Inspiration orebody is predominately a copper-sulphide blanket, overlain by an oxidized zone of copper silicates, copper carbonates, and barren capping. Most of the ore is treated by leaching, and the optimum requirement of this method is the goal toward which the mining schedule is aimed. Both open-pit operations and underground mining are used. The problems of ore control at Inspiration are: 1-maintenance of metallurgical balance, 2-conservation of oxide ore, and 3-mining out of the orebody at an average grade which parallels that of the reserve figure. Prior to the fall of 1926 all of the Inspiration division ores were treated by flotation, but the mixed ores of the Live Oak-Keystone section carried too large a proportion of copper in the form of chrysocolla for satisfactory flotation. For this type of mixed ore the leaching process now in use had been worked out, and the plant was put into operation in the fall of 1926. The process is known as the ferric sulphate leach, and the leaching solvents contain both ferric sulphate and free sulphuric acid. Sulphide copper in the form of chalcocite is leached by the ferric sulphate, and the oxidized copper minerals are dissolved by the sulphuric acid. From the beginning of operations to the present time the plant has treated some 67 thousand tons of ore having an average copper content of 1.142 pet, of which 0.605 pct has been in the form of oxidized copper minerals. The plant is currently being operated at the rate of 11,500 tons per day, 7 days per week. However, this tonnage is produced in 6 days of mine operation. The average current grade is approximately 1 pct copper, of which about 50 pct is present as oxidized or acid-soluble copper. Close control of metallurgical procedures is a vital factor in operation of the plant and is in turn dependent upon careful regulation of feed. An excess of sulphide copper requires the presence of more ferric sulphate in the leaching solvents. On the other hand, an excess of ferric sulphate in the presence of a low sulphide feed seriously reduces the efficiency of electrolytic precipitation in tank house operations. This condition must be avoided at all costs. An additional factor must be considered. It is known that the sulphide content is predominant in the ore which remains in the reserve. To maintain the necessary sulphide-oxide proportion, so that the entire reserve will mine out at both a grade and a sulphide-oxide ratio that will be permissible throughout the remaining life of the property, it is obvious that the oxide reserve must be currently preserved to as great an extent as possible. Fortunately much of the oxide reserve is found in the open-pit operation. This happy circumstance adds flexibility to the procedure and makes it possible to maintain the close regulation necessary to insure best overall results, both mining and metallurgical. The two ore streams from the pit and underground operations join at the coarse-crushing plant, and proper control must be exercised before the ore reaches this point. The open pit is currently providing about 55 pet of the ore and underground operations the balance of production. Both operations are under a single superintendent so that the closely interrelated problems may be more readily controlled. The least flexible of the two producing units is the underground mine, where the mining method is block caving. Although a block of ground may be undercut and developed, characteristics of the material determine its caving action. The ore in the chutes must be drawn. The area currently mined from underground is in a zone predominately sulphide and is generally

Jan 1, 1952

By M. Hansen, C. C. Wang

THE 6 phase of the Cu-Sn system (Cu,Sn, = 32.53 pct Sn) was considered to be stable down to room temperature until Owen and Iball showed by X-ray analysis that it undergoes a eutectoid decomposition into the a and e phases at a temperature near 300°C. Their findings have been confirmed by other investigators,2-5 a11 of whom used X-ray diffraction studies of powdered specimens. The transformation temperature has been reported by various authors as lying between 300" and 380°C. To our knowledge, no microscopic evidence of the eutectoid reaction has been published, as yet. It was in connection with other work that longtime annealings at 300°C were conducted with alloys containing 22, 32.6, and 35 pct Sn (nominal compositions) prepared from electrolytic copper and electrolytic tin and cast in a small iron mold. The specimens were first annealed at 700°C for 5½ hr and quenched from 400 °C after cooling to, and annealing at, that temperature for 9½ hr. After this treatment the sample with 22 pct Sn was cold worked for 15 pct reduction in thickness; the 32.6 and 35 pct alloys were too brittle to be cold worked. The final anneal at 300°C was done in a sealed pyrex glass bulb for 63 days. Fig. 1 represents the microstructure of the annealed alloy with 22 pct Sn. It shows primary a solid-solution crystals in a matrix of the (a + 8)-eutectoid formed at 520 °C. The a crystals contain 8 inclusions which precipitated from a due to the decrease in the solubility of tin in copper with fall in temperature. The decomposition of the 8 phase into a (light) and E (dark) can clearly be seen in some areas of the (a + 8)-eutectoid matrix. However, the decomposition is far from being completed, even after the long-time anneal used. Figs. 2 and 3 depict the microstructures of the annealed 32.6 pct alloy, which was intended to consist entirely of 6 phase. Due to some loss in copper on melting, the composition is slightly higher in tin. Accordingly, the sample after quenching from 400 "C consisted of grains of the 8 phase with the e phase arranged along the grain boundaries and as a Wid-manstatten precipitate within the 6 grains. After an annealing time of 63 days, the eutectoid decomposition, 6 + a + e, is still in its early, initial state. The pearlitic type of eutectoid is nucleated at the c crystals, preferably those surrounding the grain boundaries of the 8 phase. The appearance of the (a + €)-eutectoid in the 35 pct Sn alloy was very similar to that shown in Figs. 2 and 3. Again, the eutectoid decomposition nucleated at the 6 phase and proceeded from there into the 8 areas. As is evident from Fig. 2, the rate of decomposition of the 6 phase at 300°C is extremely sluggish: In the representative area shown only about 5 pct of the 8 phase has undergone the eutectoid trans- formation after annealing for 63 days. On the other hand, Owen and Williams2 have reported that X-ray photographs of powdered samples with between 17.5 and 34 pct Sn did not show 8 lines after annealing for only five to seven days at 300°C. This is in accordance with the fact that the rate of reaction in powdered samples is higher than in massive specimens, as a result of the excess free energy of the powder (due to its greater surface area). The authors wish to express their thanks to C. A. Johnson for preparation of the micrographs.

Jan 1, 1952

By W. Crafts, J. L. Lamont

Electrolytic extraction of carbides from quenched and tempered steel and their examination under the electron microscope were found to be helpful in understanding the mechanism of secondary hardening in alloy steels1 and the same technique has been applied to isothermally transformed steels. A preliminary survey of the utility of the method has indicated that it has promising possibilities for investigating the characteristics of pearlite and bainite. The examination of a few carbon and chromium steels has suggested that pearlite is formed with carbides of two varieties representing the lamellar and nonlamellar forms and that bainite appears to form with a structure analogous to, but significantly different from, martensite. Procedure The method used for examining the carbides was similar to that described previously.1 The chromium steels used in the investigation were made from an Armco iron base in an induction furnace and were not treated with grain-refining deoxidizers. The composition of the steels is given in Table 1. Three-inch square ingots were forged and rolled to 1/8-in. thick sheet for use in the isothermal studies. After rolling, the sheets were sandblasted to remove the rolling scale. Specimens approximately 3/4-in. wide and l1/2-in. long were prepared from the 1/8-in. sheet. They were heated in a salt "bath at 2100°F (1150°C) for 1/2 hour, transferred to other salt baths at 1300°F (704°C), 1000°F (538°C), 800°F (426°C), or 600°F (315°C), held for various periods up to 100 hr and finally quenched in water. After quenching, the specimens were cut in half, one half being submitted to microscopic examination and the other half being used for the electrolytic extraction. The isothermally transformed specimens were submitted to examination under the light microscope to determine the degree of transformation and type of structure and were photographed at 2000 X. Carbide residues were obtained by electrolyzing in 10 pet hydrochloric acid and collecting the residue in glycerine to minimize attack by the acid. As pointed out in the earlier paper, the carbides are attacked to some degree during electrolysis. This attack is relatively minor on the coarser carbides but may be quite severe on the fine bainitic carbides. The residues were washed free of the glycerine with water and alcohol. The alcohol was removed by repeated washings of amyl acetate, and the amyl acetate suspensions were transferred to stoppered vials. Debye-Sherrer X ray diffraction patterns of the residues were prepared using a chromium target. A selection based on the microstructure and X ray data was then made of samples considered most illustrative of the progress of transformation. Electrolytically extracted residues from these samples were submitted to examination by W. D. Forgeng and A. C. Jenkins on the electron microscope at the Research Laboratories of The Linde Air Products Co. and electron micrographs were made at X 5000 and enlarged to 25,000 X. The micrographs obtained with both the light and the electron microscopes are mounted side by side in the accompanying figures. Although no effort was made to establish the T-T-T diagram for the chromium steels, the times for holding in the salt bath were adjusted with the intention of making the samples represent different stages in the transformation at temperatures of 600, 800, 1000, and 1300°F. The degrees of transformation and results of X ray examination are shown in Tables 2—4. The carbide designations refer to orthorhombic or trigonal carbide types and are not meant to imply that the compositions are exactly as indicated. X ray Diffraction Data The occurrence of Fe3C and Cr7C3 in these steels was found to be consistent with published data on comparable chromium steels. Steels A and B with relatively low ratios of carbon to chromium contained Cr7C3 in the pearlitic structures and FeuC in the

Jan 1, 1950

By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami's reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."' A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. ' J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

By J. L. Carne

ORE control is a matter of planning and supervision based on a foreknowledge of the content and distribution of ore. The Inspiration orebody is predominately a copper-sulphide blanket, overlain by an oxidized zone of copper silicates, copper carbonates, and barren capping. Most of the ore is treated by leaching, and the optimum requirement of this method is the goal toward which the mining schedule is aimed. Both open-pit operations and underground mining are used. The problems of ore control at Inspiration are: I—maintenance of metallurgical balance, 2—conservation of oxide ore, and 3—mining out of the orebody at an average grade which parallels that of the reserve figure. Prior to the fall of 1926 all of the Inspiration division ores were treated by flotation, but the mixed ores of the Live Oak—Keystone section carried too large a proportion of copper in the form of chrysocolla for satisfactory flotation. For this type of mixed ore the leaching process now in use had been worked out, and the plant was put into operation in the fall of 1926. The process is known as the ferric sulphate leach, and the leaching solvents contain both ferric sulphate and free sulphuric acid. Sulphide copper in the form of chalcocite is leached by the ferric sulphate, and the oxidized copper minerals are dissolved by the sulphuric acid. From the beginning of operations to the present time the plant has treated some 67 thousand tons of ore having an average copper content of 1.142 pct, of which 0.605 pct has been in the form of oxidized copper minerals. The plant is currently being operated at the rate of 11,500 tons per day, 7 days per week. However, this tonnage is produced in 6 days of mine operation. The average current grade is approximately 1 pct copper, of which about 50 pct is present as oxidized or acid-soluble copper. Close control of metallurgical procedures is a vital factor in operation of the plant and is in turn dependent upon careful regulation of feed. An excess of sulphide copper requires the presence of more ferric sulphate in the leaching solvents. On the other hand, an excess of ferric sulphate in the presence of a low sulphide feed seriously reduces the efficiency of electrolytic precipitation in tank house operations. This condition must be avoided at all costs. An additional factor must be considered. It is known that the sulphide content is predominant in the ore which remains in the reserve. To maintain the necessary sulphide-oxide proportion, so that the entire reserve will mine out at both a grade and a sulphide-oxide ratio that will be permissible throughout the remaining life of the property, it is obvious that the oxide reserve must be currently preserved to as great an extent as possible. Fortunately much of the oxide reserve is found in the open-pit operation. This happy circumstance adds flexibility to the procedure and makes it possible to maintain the close regulation necessary to insure best overall results, both mining and metallurgical. The two ore streams from the pit and underground operations join at the coarse-crushing plant, and proper control must be exercised before the ore reaches this point. The open pit is currently providing about 55 pct of the ore and underground operations the balance of production. Both operations are under a single superintendent so that the closely interrelated problems may be more readily controlled. The least flexible of the two producing units is the underground mine, where the mining method is block caving. Although a block of ground may be undercut and developed, characteristics of the material determine its caving action. The ore in the chutes must be drawn. The area currently mined from underground is in a zone predominately sulphide and is generally

Jan 1, 1953

By Philip D. Anderson, Ralph Hultgren

Heat contents of extremely pure iron were measured over the range 300"to 1433"K, using a diphenyl ether calorimeter. Results from three samples containing widely differing impurities agreed with one another and with Previously reported results at higher temperatures (1184 ° to 1809°K) by Olette and Ferrier. From these data a table of heat contents of iron has been Prepared which is believed to be more accurate than those previously available. CP values have been derived which are consistent with these heat contents, with the best experimental Cp data, and with the thermodynamic conditions of equilibrium between bcc and fcc iron. The opinion is expressed that low-temperature extrapolations of presently known Cp values for y-Fe are not reliable. It would seem that the thermodynamic properties of iron, which is by far our most important metal, should have been well established long ago. This is not the case, however. As discussed by Olette and Ferrier,' there is objection to every earlier heat content measurement. While the best true Cp determinations agree well at temperatures below the Curie point, there is wide divergence at higher temperatures. Several investigators have examined available data and attempted to calculate thermodynamic functions for iron that are consistent with the two equilibrium temperatures of bcc and fcc iron. The two primary efforts were those of Austin' in 1930 and Darken and smith3 in 1948. The recommended values differ considerably; integration of Austin's Cp values leads to a heat content at 1100°K which is 300 cal per g-atom higher than the value recommended by Darken and Smith. The compilation of Fisher4 in 1949 was based on the selection of Austin. In 1956, Weiss and Tauer obtained yet another set of values by resolving Cp values into components due to dilation, lattice vibration, electronic excitation, and magnetism. The magnitude of contribution by each component and its dependence on temperature was estimated by semiempirical means. Their values are not self-consistent in that they do not form smooth curves when plotted vs temperature; moreover, their calculations cannot easily be repeated since they do not give the values of some of the parameters used. Clearly, experimental values for iron were in a most unsatisfactory state. The presently described measurements of the heat content of iron were therefore undertaken, covering temperatures as high as 1433°K. While the work was in progress, the high-temperature (1193" to 1789"K) heat content measurements of Olette and Ferrier' were published; in the region of temperature overlap the present results agree with Olette and Ferrier well within experimental accuracy. It is believed that the present results, combined with those of Olette and Ferrier, provide for the first time a reliable set of heat contents of iron from room temperature to the melting point. From these data, guided by available Cp measurements, it proved possible to derive Cp, entropy, and free energy function values for @-iron from room temperature to the melting point, and for y- iron in the temperature region of its stability. Exhaustive study led to the conclusion that extrapolations of y-iron functions to room temperature were not reliable enough to be useful; hence these have been omitted from the tables. EXPERIMENTAL Materials. Three samples of extremely high purity iron from different sources, containing widely different impurities, were measured. The first of these, designated "Chipman", was kindly supplied by Dr. K. K. Kelley of the U. S. Bureau of Mines from a lot which was made many years ago by Dr. John Chipman of the Massachusetts Institute of Technology. The second, designated6'Teddington", was supplied by the National Physical Laboratory, Teddington, England, from a lot zone-refined by them. The third sample, designated "Irsid", was supplied by the Institute de Recherches de la

Jan 1, 1962

By J. P. G. Farr, R. Brownsword

THE role of solute segregation in the formation of cellular solidification substructures in tin and its dilute alloys is well-established, see, e.g., Ref. 1. Segregation has been shown to persist during cooling, enabling solidification structures to be studied from sections taken at some distance behind the interface. In the present work, a single crystal of commercial nickel, 99.965 pct, was examined in this way. The crystal was cut from the center of a rod given a single pass in an electron beam floating zone melter. Polished sections of a nickel specimen taken normal to the growth direction showed a very fine precipitate phase, the distribution of which varied over the section. The identification of the phase proved difficult because of the small amount present and the small particle size, about 1 p: but it was shown by probe microanalysis to contain only nickel and oxygen in detectable concentrations and was probably nickel oxide, NiO. Bulk analysis of the material before melting showed there to be only 3 to 4 ppm of oxygen present, thus demonstrating a very considerable segregation concentration effect. In some areas of the section the precipitate formed a discontinuous hexagonal network suggesting decoration of the cellular boundaries known to be present in the sample2 whereas in a restricted region the precipitate formed small clusters. Occasionally it could be seen that the clusters were at the intersections of an hexagonal network of cellular dimension. It was suggested3 that this was the result of enhanced segregation to the cell boundary intersections whereas general cell boundary segregation was insufficient to give a precipitate. Enhanced nodal segregation has since been demonstrated in a number of systems.1, 4-8 The development of a suitable electrolytic etching technique (perchloric acid 20 pct v/v; ethyl alcohol 70 pct; glycerol 10 pct; current below electropolishing plateau; 1 to 2 sec etching) suggested the association of the phase with regions of solute segregation (where ko < 1); in these regions anodic attack produced grooves or depressions. In a study of the variation of solidification substructures with degree of constitutional supercooling, Biloni et a1.&apos; appear to have used standard growth conditions and varied the solute concentration. They were able to produce in a series of individual tin crystals examples of substructure ranging from planar interface through various cellular structures to den- Fig. 1—Electroetched section taken normal to the rod axis; the center of the rod lies to the left and the periphery to the right of the micrograph. The variation of structure across the section is evident. Magnification 60 times. drites. It was possible in the present nickel crystal to observe a continuous range of substructures varying with degree of supercooling across a single section as shown in Fig. 1. Growth rate, 13 mm per min, and temperature gradient were essentially constant; the variation in structure is thought to be due to a radial gradient in solute concentration ahead of the solid interface. The liquid at the interface is likely to have been richer in solute toward the periphery of the zone, the result of curvature of this interface. The type of substructure was seen to vary with increasing constitutional supercooling as follows: a) region free of precipitate. top left, Fig. 1: 6) region of nodal precipitates which became arranged in hexagons on passing from the center of the rod: c) irregular hexagonal cells with incomplete boundary precipitation; d) regular hexagonal cells of decreasing size with complete boundary precipitation. Fig. 2 shows the transition from stage 6 and Fig. 3 shows the structure in stage d. Within stage 0, the range of conditions over which irregularly positioned nodes occur appears to be small and the nodes are soon recognizable as taking up positions at the intersections of an hexagonal network as the supercooling increases.

Jan 1, 1970

By R. F. Mitchell, G. F. Dillon, A. F. Armington

In this paper the present methods of boron preparation are discussed with emphasis on the iodide intermediate. Several methods of boron triiodide preparation were investigated, the most satisfactory method being the preparation from the elements. A yield of 60 pct based on iodine is found for this method. Zone-refining, sublinzation, distillation, and fractional-recrystallization results are given for the boron triiodide, with distillation producing the best results. Several methods of decomposition are also discussed. The purity of the resulting iodide boron approximates the puritjl of the best available bromide boron, ELEMENTAL boron has been suggested as a possible high-temperature semiconductor by several workers,&apos; but has never been exploited as a device material. The principal difficulty with boron is the unavailability of pure crystalline material from which accurate information on electrical properties could be obtained. Most boron crystals presently produced are very imperfect in structure and of questionable purity, particularly in relation to carbon content. Several methods of boron purification have been reported in the past few years, all of which produce material with a purity better than 99.0 pct. Most of these methods have been the subject of a recent review by Starks&apos; and will not be elaborated upon in this report. However, of all the purification methods reported, only those using halide intermediates produce a purity approaching that usually required for electronic applications. The bromide intermediate has been most used for the preparation of high-purity boron.&apos;y3 This material is easily prepared from the elements and can be effectively purified by distillation and decomposed by hydrogen reduction. The resulting product contains a trace of silicon, and an uncertain amount of carbon, believed to be approximately 100 ppm. It has been recently reported by Russian workers that high-purity boron can be produced using an iodide intermediate.&apos; In the work cited, boron is reported free of spectro-scopically determined impurities, but the reported detection limits are quite high (- 100 ppm). In addition, no data is given on the carbon content of the product. In the present paper, boron triiodide was chosen as the intermediate for several reasons. First, carbon tetraiodide, which could be a major impurity, is reported to be unstable above 200" and hence could be easily separated from the boron triiodide by its decomposition, since temperatures greater than this are attained during the purification process. The low melting point (45°C) and boiling point (20B°C) and the relatively high vapor pressure of boron triiodide should allow the application of any physical purification technique to the material. The possibility of a lower decomposition temperature than that used for the bromide process is another advantage which might cut down extraneous contamination. The iodide, however, does have certain disadvantages when compared with the bromide, the production cost being the most significant. This is the result of a higher halide-to-boron weight ratio, which means more intermediate must be employed. The cost of the starting material is also greater for the iodide. This cost could be considerably reduced however, by recycling the iodine byproduct. Epitaxial growth of boron, which is probably the best method of producing junctions, should be possible with either the bromide or the iodide as the intermediate. However, this has been attempted only on a limited scale up to the present time because of the unavailability of good crystals. The authors have been relatively successful in laying down a heterotaxy of boron on silicon, however. This will be reported at a later date. Several crystalline modifications have been reported for boron, four of which are now believed to be real.&apos; These are the a! and 0 rhombohedral and the a, and 0 tetragonal. In general, the a! rhombohedral is the low-temperature form and the B rhombohedral is the high-temperature form. The tetragonal structures are detected between 1000"

Jan 1, 1964

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

At very low concentrations, carbon dissolves interstitially in molybdenum resulting in a linear expansion of lattice parameter with increase of carbon in solid solution. Geometrical consideration of the relative size of carbon atom to size of interstice approximately predicts the observed volume expansion. THE element carbon, occurring in molybdenum, either as an unavoidable impurity, or purposely added, markedly affects the mechanical properties of molybdenum. Several investigators1-" have noted the occurrence of molybdenum carbide at the grain boundaries of cast molybdenum, and Fischer and Rengstorff&apos; have shown that this intergranular constituent can induce intergranular brittleness. The appreciable change, with temperature, of the solid solubility of carbon in molybdenum, found by Few and Manning," suggests other important effects upon mechanical properties. Finally the relative atom diameters of carbon and molybdenum (the ratio of atom diameters is 0.59) are indicative, by analogy with iron (ratio of carbon atom diameter to iron atom diameter is 0.65), of a possible interstitial solid solution. If carbon dissolves intersti-tially in molybdenum, anelastic effects and age-hardening effects, similar to those observed in other body-centered cubic metals, could be expected. However, from the work of Sykes, Van Horn, and Tucker," it might be inferred that carbon forms only a substitutional solid solution with molybdenum. These considerations made it desirable to study the effect of carbon on the lattice parameter of molybdenum in greater detail than heretofore. All heat treating was done in a high temperature furnace7 built specifically for heat treatment of molybdenum. The temperatures and times of heat treatment were determined from the a solubility limit for the Mo-C system." These heat treatments were carried out in argon which was purified with respect to N, and H.!0." Purification of the argon was accomplished by passing the argon over hot (750°C) titanium and then through a magnesium perchlorate drying tower. As many as six samples were run concurrently and quenched at different times without interrupting the furnace cycle. Both the purity of the furnace atmosphere and ability to quench samples from any temperature up to 4000 °F were of prime importance in the successful heat treatment of samples for the lattice parameter investigation. Carbon Analysis The Leco Combustion apparatus was used for carbon analysis. This apparatus is capable of an accuracy of & 0.003 pct for a 1 g sample in the range below 0.10 pct. However, it is felt the degree of accuracy is somewhat better than this limit in view of the consistency evident by cross checking a number of determinations. The Battelle Analytical Laboratory consistently reported check results to within k 0.001 pct C. X-ray Measurements The molybdenum wire specimens (20 mils) were carefully filed down to about 12 mils and then etched with nitric acid to 8 mils. Carbon analyses were made on specimens before reduction in size; however, since there was no evidence of surface carburization, it is probable that the carbon was uniformly distributed throughout the sample. The resultant specimens were strain free and small enough to minimize the error in the lattice parameter determinations due to X-ray absorption. Diffraction patterns were obtained with a Debye-Scherrer powder camera 114.59 mm in diam utilizing the Straumanis type asymmetrical film mounting. Nickel-filtered copper. Ka radiation and zirconium-filtered molybdenum Ka radiation were used. Line positions on the film were measured with a traveling microscope equipped with a vernier scale permitting measurement to 0.001 cm. The average of five readings was used to determine the position of each line. The lattice parameter for each specimen was determined from the data by the extrapolation method of Bradley and Jay, Y.e., the intercept at 90" of the straight line obtained by plotting the apparent lat-

Jan 1, 1953

By Denton R. Wieland, Harvey T. Kennedy

The frequency of bubble formation is measured for oils from the East Texas field and the Slaughter field in cores from these fields. East Texas oil was also tested in a Slaughter core. The data checked previous results in that a definite supersatrtration may exist without the formation of bubb1es in periods of observation totaling 158 hours. Measured frequencies varied from zero at supersaturations below 14 psi to 3.1 bubbles/sec/ cu ft of rock at 40 psi supersaturation INTRODUCTION The formation of bubbles is essential in a solution gas-drive reservoir in the displacement of oil. In formations where the basic pore structure consists of fine pores or fractures connected to larger pores or crevices, bubble formation in the fine pores may be the most effective means by which the oil may be displaced, even if secondary methods are applied. The most efficient oil displacement would occur where at least one bubble would form in every pore. As the pressure decreased, the bubbles would expand, due to the gas diffusing into the bubbles, and displace the oil toward the lower pressure area around the wellbore. Kennedy and Olson&apos; have shown that the total number of bubbles formed in a reservoir is primarily dependent upon the rate of pressure drop, the rate of diffusion of gas through oil, and surface area of the rock. The surface tension of the liquid and other characteristics of the rock may also exert an important effect, which would give a different frequency to different rocks and oils and various combinations of different rocks and oils. The purpose of this paper is to present frequency measurements on two rocks and two oils. A hydrocarbon liquid is at equilibrium with gas when it contains the maximum volume of gas in solution that it can have at the prevailing temperature and pressure. If the temperature is maintained constant and the pressure is reduced below the equilibrium pressure, the liquid is supersaturated to the extent of the difference in the two pressures until the gas comes out of solution as a free phase. As shown by previous work, and confirmed in the present investigation, the number of bubbles formed per second increases with an increase in supersaturation. Kennedy and Olson showed that a tenfold increase in the rate of pressure decline resulted in a tenfold increase in the number of bubbles formed per cubic foot of reservoir rock, e.g., for decline rates of 0.1, 1, and 10 psi/day, the number of bubbles formed per cubic foot would be 40, 400, and 4,000, respectively. For another hypothetical system, Stewart, Hunt, and Berry&apos; estimated that for pressure declines of 0.1, 1, and 10 psi/day, the number of bubbles formed would be approximately 10, 100, and 1,000 cu ft of reservoir rock. Their value of bubbles formed is lower than given by Kennedy and Olson; however, the order of magnitude agreed satisfactorily. The rate of diffusion will also affect the number of bubbles formed. If the diffusion coefficient is high, the gas in solution in the oil surrounding a single bubble will tend to diffuse into the bubble rather than forming other bubbles. On the other hand, the formation of more bubbles will tend to occur if the diffusion coefficient is very low. In his thesis dated Aug., 1953, Wood" reports on the frequency of bubble formation in a system consisting of oil and rock from the Rangely field. In the present work, the apparatus of Wood was redesigned to allow greater precision, especially at low supersaturations, where bubble growth is slower, and detection is more difficult.

Jan 1, 1958

By D. B. Smith, John Chipman

THIS investigation was undertaken as a prerequisite to the study of sulphur activities in the liquid system Fe-Cu-Ni, a continuation of the work of Sherman, Elvander, and Chipman,¹ using the same equipment and the same experimental technique. Temperature measurements are made with a disappearing filament optical pyrometer, sighting through a prism onto the surface of the melt which is heated by induction. To obtain true temperatures by this means, a calibration is necessary, since, in the absence of true black-body conditions, the observed temperature is always lower than the true temperature. This calibration is actually an emissivity correction, since the emissivity is a function of both temperature and melt composition. The original furnace was used with a deeper metal bath to provide sufficient depth of immersion for the thermocouple which was inserted through the sampling hole. The atmosphere was a 50-50 mixture or argon and hydrogen passing through the furnace at a rate of 1000 ml per min, and preheated by means of a molybdenum resistance coil. It was assumed that the rapid gas flow effectively eliminated any error which might have resulted from the presence of metallic vapor. The charge in each case consisted of about 300 g of metal, contained in a high purity, dense alumina crucible. At each melt composition, readings of the optical pyrometer and of a thermocouple immersed in the molten metal were taken simultaneously. Calibration curves of optical vs. true temperature were then made for each melt composition investigated. Thermocouples were made of 0.010 in. platinum and platinum-10 pct rhodium. They were checked against the melting point of chemically pure copper. Silica protection tubes with an outer diameter of approximately 1/8 in. were used. The depth of immersion of the tip in the molten metal was approximately 1 14 in. The life of these small thermocouples was relatively short, varying from approximately 1 min at 1550°C to 10 min or longer at 1300°C. Melts containing iron corroded the protection tubes more than those without iron present. Measurements taken while heating checked those taken while cooling, indicating the absence of a temperature gradient between the molten metal and the thermocouple. Results The temperature range of the. measurements on copper-free metals extended from the melting point to 1600°C. For copper the upper limit was 1380°C, and the data were extrapolated linearly for comparison with observations on the other metals and alloys at 1535°C. Examples of typical calibration curves for various melt compositions are shown in Fig. 1. These curves, besides providing a calibration system for the given experimental conditions, also give a basis for the calculation of true emissivities at the effective wavelength of the pyrometer, 0.65 micron. The starting point of the calculations is the value of the emissivity of iron at its melting point. Taking the melting point of electrolytic iron under hydrogen as 1535°C, and using the corresponding emissivity value of 0.43, as determined by Dastur and Gokcen,² the emissivities can be determined as functions of composition (and temperature, if desired). The relationship used is the Wien equation: ln(Ea)=C2/?(1/T1-1/Ta where E is the emissivity; a, the transmissivity of the optical system; C,, the fundamental constant, 14,380 micron-degrees; A, the wave length of light used (0.65 micron); Tt, the true temperature, OK; and T., the apparent temperature, OK. At the melting point of iron the observed temperature was 1358"; this gives 0.62 for the transmissivity, which compares with 0.65 in the similar system used by Dastur and Gokcen. The emissivities of all the compositions investigated were determined at 1535°C, after obtaining from each calibration curve the corresponding temperature. These results

Jan 1, 1953

By L. Hartsell Cash

INTRODUCTION Created in 1944 to help rebuild those economies, principally in Europe, which were seriously damaged or destroyed during the Second World War, the World Bank--or to use its correct name, the International Bank for Reconstruction and Development-began its operational phase by making a loan to the Government of France to accomplish two tasks: (i) to import coal for space heating purposes; and (ii) to buy new machinery and equipment to help rehabilitate its coal mines. Once the thrust of reconstruction in postwar Europe was largely accomplished, the World Bank Group (for today the World Bank has three separate lending windows) turned to mobilizing funds to improve living standards in developing countries, which remains its primary goal today. Over this period of time, the World Bank Group has continued to assist the world mining industry in various ways and, since 1955 the World Bank Group has financed mining or mineral processing projects with loans/credits totalling $1.5 billion. The World Bank Group consists of two institutions--the World Bank itself and the International Finance Corporation (IFC), which was founded as a separate institution in 1956 and three separate lending windows--the World Bank, the International Development Association (IDA), and IFC. The World Bank loans are provided at commercially-related interest rates but have grace periods usually of up to 3 to 5 years and repayment periods ranging from around 15 to 20 years. Since the World Bank raises its operating funds on the international capital markets in varying currencies and in varying interest rates, it relends a basket of currencies at floating interest rates which are fixed every six months to reflect the Bank&apos;s own borrowing cost. At the present time, the interest rate is just below 10% per year and in addition, a one-time front-end fee of 1/4 of 1% is charged. Also, a commitment fee of 3/4% per year is charged on the undisbursed amount of the loan itself. For loans to industrial and mining projects, it is normal to charge an additional guarantee fee of 1 to 1.5% in addition to the annual interest rate. This guarantee fee is payable to the government of the country in which the project is carried out since, by its charter, the World Bank is required to have the guarantee of the host government for each loan made in a specific country. By far the greatest source of lending funds within the World Bank Group is that of the World Bank itself and for the fiscal year ending June 30, 1984, the World Bank approved loans totalling $12 billion. The second lending window within the World Bank Group is IDA which performs the same functions as the Bank itself and has the same staff. Nevertheless, its loans (called credits) are made on much softer terms and are made to the poorest nations only. IDA funds are subscribed by the wealthier countries, usually as grants, and these are relent as credits to those countries with the lowest per capita income. IDA credits are made for 50 year periods, including 10 years of grace, to the government itself. The credits are interest free, but there is a service charge of 3/4% per year on the amount withdrawn and outstanding to defray the administrative costs of IDA. Credits approved during fiscal 1984 totalled $3.5 billion. The third lending window is IFC. While IFC is a separate corporation and operates quite separately from the World Bank and has its own staff and regulations, it works very closely with the World Bank on its overall approach to the mining sector and to a particular country. IFC&apos;s mission is essentially to supply venture capital and to stimulate development of the local private sector in capital markets as well as to promote the international flow of private capital to developing countries. Unlike the World Bank and IDA, the IFC does not lend directly to governments

Jan 1, 1985

By W. D. Robertson

SINCE the comprehensive paper of Moore, Beckin-sale, and Mallinson,&apos; little consideration has been given to the mechanism of mercury stress cracking of copper-base alloys, apart from extensive work on metallurgical and fabrication variables employing mercurous nitrate as an evaluation test. However, with the phase diagrams now available and the recent considerations of interfacial tension at grain boundaries, developed by Smith,2 it appears that the elements of a detailed solution to the problem are available. The facts that require explanation are: 1—Pure copper is not embrittled by mercury, with or without an applied or residual stress. 2—Cu-Zn and other copper-base alloys, in excess of some undefined solute concentration, are embrittled provided an external or residual stress is acting; cracking is not observed in the absence of stress. 3—The path of fracture is invariably intergranu-lar. 4—Copper and copper-base alloys do not dissolve readily in mercury at room temperature.&apos; Consideration of the Cu-Hg phase diagram% hows that, at room temperature, solution of copper in mercury is probably limited by the formation on the surface of a microscopically thin layer of inter-metallic compound, CuHg, having a very limited range of solubility which effectively restricts diffusion of copper and mercury. But, above 150°C (the highest peritectic temperature) copper solid solution is in equilibrium with a liquid Hg-Cu solution and, consequently, copper should dissolve freely in a large volume of mercury with the formation of an equilibrium dihedral angle at grain boundaries in contact with the liquid phase. Depending on the magnitude of this angle, mercury will or will not penetrate the solid phase along grain boundaries and spread over grain faces. Thus the measurement of the dihedral angle of grain boundaries in equilibrium with the liquid phase above 150°C should indicate whether copper is intrinsically resistant to embrittlement by mercury. In view of the fact that mercury is appreciably soluble in copper, it may also be anticipated that diffusion of mercury will take place at higher temperatures in the absence of the intermetallic compound and possibly at a more rapid rate along grain boundaries than through the grains, resulting in a Cu-Hg alloy of unknown properties. In the case of brass, the ternary system Cu-Zn-Hg is involved and, from the resistance of brass to general solution in mercury at room temperature, it is probable that a compound of limited solubility range also exists, similar to the binary Cu-Hg sys- tem. Also, compared with copper, a change in the dihedral angle at grain boundaries in contact with mercury may be expected to result from the addition of zinc to copper. The preceding generalizations appear to be confirmed by the following experiments. Experimental Results Oxygen-free copper wire, annealed at 700°C for 3 hr in copper foil, was immersed in mercury at 170°C, with and without an applied stress. After 24 hr immersion, specimens which were spring loaded to a nominal stress of 10,000 psi had not failed, and there was no apparent embrittlement as indicated by a 180" bend around a diameter approximately equal to the diameter of the wire (0.125 in.) : General solution of the surface had taken place, indicated by a change in diameter of the wire, and the resulting structure of the surface is shown in Fig. 1. It is apparent that angles have developed at grain boundaries and examination at a high magnification indicates that the angle is in excess of 120°, completely excluding penetration of mercury. In view of the measurements made by Smith n the

Jan 1, 1952

Council and Standing Committees, 1975-1976 President: Dr R. E. Robinson. Vice-Presidents: Dr M. D. G. Salamon and P. A. von Wielligh. Honorary Treasurer: J. K. E. Douglas. Immediate Past President: Prof. R. P. Plewman. Members of Council: Dr M. G. Atmore, J. D. Austin, C. T. Fenton, J. A. Holmes, P. Holz, Dr P. R. Jochens, Prof. R. P. King, Dr D. G. Krige, Dr D. I. Legge, D. G. Malan, C. T. Shaw, D. A. Viljoen, R. A. von Maltitz, H. M. Wells. Chairman, Witbank-Middelburg Branch: E. J. Jackson. Chairman, Orange Free State Branch : G. J. C. Young. Past Presidents Serving on Council: R. J. Adamson, H. Britten, H. E. Cross, J. K. E. Douglas, R. C. J. Goode, Prof. D. D. Howat, Dr J. P. Hugo, D. M. Jamieson, D. G. Maxwell, Dr J. T. McIntyre, V. C. Robinson, P. W. J. van Rensburg. Seven Council meetings and five Executive Committee meetings were held during the year, and the standing and sub-committees held fifty-five meetings. Standing Committee Chairmen Membership, P. A. von Wielligh ; Technical Programme-Metallurgy, D. A. Viljoen; Technical Programme-Mining, D. G. Malan; Vacation School-Metallurgy, Dr P. R. Jochens ; Vacation School-Mining, H. M. Wells; Awards, Dr R. E. Robinson; Excursions, Dr D. I. Legge; Adjudicating, Dr R. E. Robinson; Constitution, Rules and Policy, Prof. R. P. Plowman; Mines and Works, C. T. Shaw; Education, Prof. R. P. Plewman; Foundry Colloquia, Prof. D. D. Howat. Representatives on Other Bodies Associated Scientific and Technical Societies: Members : Dr R. E. Robinson and Prof. R. P. Plewman. Alternates : P. A. von Wielligh and Dr M. D. G. Salamon. Federation of Societies of Professional Engineers: Members : J. K. E. Douglas and Prof. R. P. Plewman. Alternates: Dr R. E. Robinson and Dr M. D. G. Salamon. FSPE Technicians Committee: Member: D. M. Jamieson. FSPE Rationalziation Committee: Member: Dr M. D. G. Salamon. South African Council for Professional Engineers (Institute Nominees) Member : R. C. J. Goode. Alternate: G. H. Grange. South African National Committee on Tunnelling: Member : D. G. Malan. Alternate: Prof. R. P. Plewman. Engineers&apos; Liaison Committee (Pretoria) Member : Dr J. P. Hugo. Alternate : P. W. J. van Rensburg. Government Certificate of Competency Liaison Committee: Member: Prof. R. P. Plowman. Alternate: D. M. Jamieson. James Moir Memorial Lectures: Member : Prof. D. D. Howat. World Mining Congress-National Committee: Members : Dr M. D. G. Salamon, Prof. R. P. Plewman, and H. M. Wells. I.F.A.C. Symposium: Member: P. W. J. van Rensburg (Chairman-Organising Committee). Alternate : Dr J. P. Hugo. I. U.P.A.C. Symposium: Member: Dr P. R. Jochens. Membership Nine Fellows, twenty Members, six Associate Members, thirteen Graduates, nine Associates, twenty-nine Students, and ten Company Affiliates were elected during the year. One Fellow was elected to Honorary Life Fellowship, eight Members and one Graduate were transferred to Fellows, twelve Graduates and two Students were transferred to Members, three Students were transferred to Graduates, and one Student was transferred to the grade of Associate. Six Fellows, two Members, and two Associates were admitted to retired membership. Nine Fellows, fifteen Members, three Graduates, one Associate, two Students, and one Company Affiliate resigned. A statement of membership as at June 30th, 1976, and the end of the previous year is shown in the following tabulation. 30th June, - 30th June, 1975 1976 Honorary Life Fellows 16 - 17 Honorary Fellows 8 - 8 Life Fellows 171 - 171 Fellows 549 - 547 Members 523 - 517 Associate Members 15 - 21 Graduates 132 - 123 Associates 209 - 205 Students 173 - 179 Company Affiliates 71 - 80 1866 -1878 Obituaries Your Council records with deep regret the death during the year of the following members: P. A. Creewell, Life Fellow; A. S. Davis, J. S. Hay, P. 0. Lange, N.

Jan 10, 1976

By James O. Lewis

Gravity drainage is the self-propulsion of oil downward in the reservoir rock. Under favorable natural and operational conditions, it has been found to effect recoveries comparable to water displacement. With modern technical knowledge, the operator can often make a choice between dissolved gas drive, water drive and gravity drainage as the principal recovery agent in a reservoir. It is desirable that the opeator be able to determine which of the three agents will be most effective under each set of conditions. So far, gravity drainage has received less consideration than the other two. In this paper. an endeavor is made to set forth some of the principles of gravity drainage, to point out the types of reservoirs favorable for it, and to show how it may be applied in them. Field examples are described and discussed. Introduction Since early in the history of the oil industry, it has been recognized that gravity is one of the three important natural forces for expelling oil from the reservoir rock. As knowledge of the technology of oil recovery progressed, ideas changed with respect to the relative importance of the three forces and with respect to the manners in which they functioned. For a time, disproportionate emphasis was placed on the importance and function of gas and the need for conserving gas pressures. More recently, disproportionate emphasis has been placed on encroaching edge water. Only lately has there been evidence that the function and importance of gravity was to receive due consideration. Study of this neglected phase of oil recovery is needed to round out our knowledge of reservoir behaviors and to gain a balanced viewpoint of the interplay of forces that may operate in varying importance in reservoirs. The purpose of this paper is to discuss mainly in a qualitative way, the functions of gravity, to present some concrete instances where it has been important and to raise some questions that should be investigated further. Oil-recovery Agents The important natural agents for effecting oil recovery that may be originally available in a reservoir are gas, both dissolved in the oil and free in gas caps, encroaching edge water and gravity. Each of these agents can act in a dual capacity—physically to overcome the surface energies that hold the oil within the pores and mechanically to overcome viscous . resistance and to propel the oil through the porous reservoir rock to the wells. Advancing edge water displaces the oil from the pores and lifts it updip to structurally lower wells. Gravity drains the oil from the pores and flows it downdip to the wells. Gas displaces oil from the pores, entrains it in the gas stream and flows it to the wells, but gas in solution also affects the physical properties of the oil and thus can influence oil recovery by the other agents, whether or not the mechanical energy in the gas is utilized. Of the two functions of these agents, the more important is the ability to dis-

Jan 1, 1944

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

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria &apos;Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By James O. Lewis

Gravity drainage is the self-propulsion of oil downward in the reservoir rock. Under favorable natural and operational conditions, it has been found to effect recoveries comparable to water displacement. With modern technical knowledge, the operator can often make a choice between dissolved gas drive, water drive and gravity drainage as the principal recovery agent in a reservoir. It is desirable that the opeator be able to determine which of the three agents will be most effective under each set of conditions. So far, gravity drainage has received less consideration than the other two. In this paper. an endeavor is made to set forth some of the principles of gravity drainage, to point out the types of reservoirs favorable for it, and to show how it may be applied in them. Field examples are described and discussed. Introduction Since early in the history of the oil industry, it has been recognized that gravity is one of the three important natural forces for expelling oil from the reservoir rock. As knowledge of the technology of oil recovery progressed, ideas changed with respect to the relative importance of the three forces and with respect to the manners in which they functioned. For a time, disproportionate emphasis was placed on the importance and function of gas and the need for conserving gas pressures. More recently, disproportionate emphasis has been placed on encroaching edge water. Only lately has there been evidence that the function and importance of gravity was to receive due consideration. Study of this neglected phase of oil recovery is needed to round out our knowledge of reservoir behaviors and to gain a balanced viewpoint of the interplay of forces that may operate in varying importance in reservoirs. The purpose of this paper is to discuss mainly in a qualitative way, the functions of gravity, to present some concrete instances where it has been important and to raise some questions that should be investigated further. Oil-recovery Agents The important natural agents for effecting oil recovery that may be originally available in a reservoir are gas, both dissolved in the oil and free in gas caps, encroaching edge water and gravity. Each of these agents can act in a dual capacity—physically to overcome the surface energies that hold the oil within the pores and mechanically to overcome viscous . resistance and to propel the oil through the porous reservoir rock to the wells. Advancing edge water displaces the oil from the pores and lifts it updip to structurally lower wells. Gravity drains the oil from the pores and flows it downdip to the wells. Gas displaces oil from the pores, entrains it in the gas stream and flows it to the wells, but gas in solution also affects the physical properties of the oil and thus can influence oil recovery by the other agents, whether or not the mechanical energy in the gas is utilized. Of the two functions of these agents, the more important is the ability to dis-

Jan 1, 1944

By G Chitombo, M Ruest

In surface mining, studies of the kinematics of blasted rocks using high speed film/video image analysis have allowed the estimation of the starting time, direction and magnitude of visible movement of fixed sections of the free face. Horizontal displacement versus time plots from discrete targets at the face generally report changes in slope over very small time intervals. These changes indicate step increases in velocity due to the action of explosive gases. In practice, the onset of rock mass movement, different to localised spalling, has been associated with a response time which exceeds the combined times of detonation, propagation and reflection of stress waves. This time is referred to as minimum response or burden movement time. As an engineering index, burden movement time has been used to provide guidelines for the selection of inter-hole and inter-row delay sequences in production blasting. With respect to improving breakage and fragmentation, it has been demonstrated that the delay interval between adjacent explosive charges should be less than the expected burden movement time. Similarly to reduce confinement between rows, delay intervals should exceed the expected burden movement time. The Hybrid Stress Blasting Model (HSBM) is a modelling framework that dynamically links an ideal and non-ideal explosives detonation code to a geomechanical rock model. This blast simulation tool is aimed at analysing the role played by different explosive formulations in fragmenting and/or damaging various rock types under different degrees of confinement. In the current framework, the rock behaviour under extremely high pressures and loading rates is calibrated from shock tests and the role of the explosive in fracture growth is accounted for and assumes a compressible fluid flowing through the explicit fracture network. The model is being developed as part of an international collaborative research project funded by a consortium of companies comprised of explosive and equipment suppliers and major mining houses. As part of the development and validation of the HSBM project, data from literature addressing the kinematics of the rock mass (ie burden displacement, face velocities and response times) has been collated and used to evaluate the current version of the code. A series of numerical experiments have been conducted with the view to: evaluate the response of the rock mass to changes in burden distance given by the impact of both stress waves and radial gas flow pressure;compare the modelling outcomes in terms of displacement, response time and face velocities to documented field observations; andcompare stress induced and stress/gas induced modes in terms of burden displacement outcomes. Results from these experiments have shown that in its current form the model is able to capture the trends observed and measured in practice. This is with respect to the simulation of burden displacement, response time and average face velocities for different geometries and charging conditions. The experiments have served as consistency checks which form part of an ongoing and comprehensive evaluation and validation of the HSBM code also aimed at addressing some of its current limitations.

Jan 1, 2007

An investigation into the causes of variable sulphur content in blast furnace metal produced at No. 4 blast furnace at the Port Kembla works of Australian Iron and Steel Pty. Ltd. was carried out. Theprogramme included an extended and detailed experimental study of a great number of the operating variables of the furnace, on a cast-bycast or four-hourly basis, over fourteen days.Possible causes of the variation were found in irregular operation due to sinter variability, and it was also clearly shown that slag conditions were most important in controlling sulphur contents of pigiron. Some decrease in sulphur variability was achieved, arising partly from this investigation, and it is hoped to try magnesia additions to modify slag conditions for better desulphurizing.INTRODUCTIONSulphur in pig iron is a problem common to many blast furnace operators throughout the world, but the direct causes and means of overcoming them are functions of the available raw materials, and are hence more particular to each plant and its operating practice. Sulphur in hot metal influences the steel-making operations, the rolling operations and the quality of the finished steel. The main problem associated with high sulphur in steel is &quot;hot shortness&quot;, which leads to cracking of ingots and billets in rolling, to poor surface finish and to poor welding properties in the finished steel. On the other hand, sulphur is sometimes a desired additive to steel in order to promote free machining properties.Normal means of controlling sulphur A small degree of control of sulphur in steel is available to open hearth operators by alteration of slag volumes and basicity, but any large degree&apos; of sulphur elimination is...

Jan 1, 1961