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By W. S. CAYPLESS, H. O. Hofman, E. E. HARRINGTON

1. INTRODUCTION. AT the Lake Superior meeting, September, 1904, Messrs. A. Gibb and R. C. Philp presented a paper entitled " The Constitution of Mattes Produced in Copper Smelting,)' in which they concluded that ferrous and cuprous sulphides formed the chemical compound, 5 Cu2S, fee. They arrived at this inference from the observed fact that a matte containing Cu2S, 90.4, and Fee, 9.6 per cent (or, in round figures, Cu2S, 90, and Fee, 10 per cent.), did not contain any metallic copper, while one with more than 10 per cent of FeS readily dissolved copper, and with less than this amount retained copper in mechanical suspension. Although they determined the melting-points of five mattes containing from 32.6 to 80.1 per cent of copper, they did not draw a freezing-point curve, as the necessary apparatus was not available. A microscopical examination of 11 polished samples, gave them a grayish-black field of very uniform appearance, except that 5 of the specimens showed the presence of metallic copper. The object of the present investigation was to supplement the above paper by drawing the freezing-point curve of the series ferrous sulphide cuprous sulphide, and to see how the constitution could be further, revealed by microscopical work. The results obtained lead to conclusions very different from those of Gibb and Philp. While their paper bears the date 1904, it was published only in 1906.2 In the meantime, Bolles3 had presented his paper, "The Concentration of Gold and Silver in Iron Bottoms." The raw material which formed the basis of the research was a matte containing Fe, 61.68, and Cu, 11.20

Jan 1, 1907

By O. U. Bradley

THE extent of losses, due to evaporation, sediment, and water, in crude oil stored in steel tanks, is a very interesting question, and particularly so at this time, when every reasonable measure should be employed to eliminate all possible losses of this important natural product. Available information on this subject is incomplete; e.g., during the development of the Cushing Field, considerable surplus oil was stored in steel tanks, but from time to time, owing to changes in weather, somelosses by evaporation and short storage room on the leases, these tanks were topped out, thus rendering inaccurate any system designed to determine the average rate of evaporation or other losses of the oil over a given period. , Furthermore, the losses, as shown by the records at the time, as a result of hasty gages, failed to take into account the temperature and gravity of the oil. Losses may be classified roughly as occurring from evaporation, presence of sediment and water, and leakage. The coefficient of expansion and contraction of crude oil, in relation to temperature conditions, is of material importance; also, the rate of evaporation is dependent upon the gravity of the oil, as the escape of the lighter hydrocarbons in fresh Cushing oil, of from 40 to 42 gravity, on a warm day is considerable, and from available records of temporary storage, it is safe to assume that a loss of 1 to 13 per cent. in volume will easily occur in light crude oil of Cushing grade over a period of. 6 months, including the summer season. The presence of sediment, water, and other impurities, in the oil will also cause, more or less deterioration in quality, particularly when the fresh production is run direct from the. gage tanks, or from the wells on the lease to steel storage, as is often the case when an oil field is being rapidly developed. The bad oil will settle to the bottom of the tanks and may be determined by thiefing and running a centrifuge test on the sample. The amount of water in the oil depends entirely on the conditions under which it is produced. Sometimes in large producing wells, with heavy gas pressure, some water may come in with the oil, particularly if the well has been drilled to the top of a water sand. Under these conditions, cut oil is often produced, which, if not settled out, is carried over into the steel tanks.

Jan 7, 1918

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 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

[Separates of all the Technical Publications published in 1929 are available at lnstitute headquarters. All the papers are on file in public, university and technical libraries, and when so indicated in the list, may be found in the Transactions.] Metal Mining Technical Pdbli- Title Author Meeting Trans. cation . Volume No. and Page* 182-A-23 The Royal Commission on Mining Henry Louis New York Subsidence Feb., 1929 183-A-24 Cycles in Metal Production D. F. Hewett Nen. York T29, 65, 95 Feb., 1929 199-A-25 Ventilation at the United Verde Oscar A. Glaeser New York T29,- 114. Mine Feb., 1929 206-A-26 Air Conditioning In Deep Mines R. W. Waterfill New York T29. 99, 112 Feb., 1929 245-A-27 Bumps in No. 2 Mine, Springhill, Walter Herd New York Nova Scotia (with discussion) Feb., 1929 257-A-28 Misfires: Their Causes, Prevention New York and Treatment on Occurrence Feb., 1929 Misfires in Anthracite Coa1 T. D. Thomas Mines (With Discussion) Misfires in Bituminous Coal W. H. Forbes Mines (With Discussion) Misfires in Non-metallic Mining A. W. Worthington (Limestone) (With Discussion) Milling and Concentration 195-B-15 A Study of Differential Flotation C. R. Ince New York Feb., 1929 196-B-16 Elements of Operation of the Arthur F. Taggart New York Pneumatic Table H. L. Lechmereoertel Feb., 1929 202-B-18 Silver-bearing Minerals of Some A; W. Habn New York T29, 325 Ores from Tintic Mining District Feb., 1929 204-B-17 Experiments with Flotation Re- A. F. Taggart New York agents T. C. Taylor Feb., 1929 C. R. Ince 208-B-20 Cyanide Regeneration or Recov- C. W. Lawr Sun Francisco ety as Practiced by the Com- Oct., 1929 pania Beneficiadora de Pachuca, Mexico 214-B-19 Calculations in Ore Dressing W. Luyken New York E. Bierbraer Feb., 1929 217-B-21 Differential Grinding Applied to Leon M. Banks San Francisco Tailing Retreatment George A. Johnson Oct., 1929 224-B-22 Reducing and Oxidizing Agents Research Staff San Francisco and Lime Consumption in Flo- of United Verde Oct., 1929 tation Pulp Copper Co. 247-B-23 Copper Sulfate as Flotation Acti- 0. C. Ralaton San Francisco vator for Sphalerite 0. R. King Oct., 1929 F. X. Tartaron

Jan 1, 1929

By J. Geertsma, F. de Klerk

During the hydraulic fracturing treatment of an oil or gas well the liquid pressure in the borehole is increased until tensile stress in the surrounding rock exceeds tensile strength. Once a tensile fracture is initiated, it is penetrated by liquid from the borehole and fracture propagation under continuous hydraulic action takes place. The fracturing liquid carries a propping agent to ensure a highly permeable flow channel after pressure release. Field results range from failure to obtain increased production to outstanding success. In all cases, however, it unfortunately remains uncertain whether the values chosen for the operational parameters, such as injection rate, pumping time and fluid viscosity, were in fact the ideal ones. Though experience provides a lead, a more satisfactory way to predict results would seem to be to subject the fracture propagation process to a theoretical analysis that (1) makes the maximum use of the relevant physical information and (2) so simplifies the resulting calculations that the field engineer gets practical data that he can handle comfortably. We are attempting here to do this in connection with the prediction of fracture width and areal extent before pressure release. What remains of the fracture afterwards depends on the distribution of the propping agent between the fracture walls, and that is a separate story. Idealization of the Problem To keep the problem tractable, a number of simplify- ing assumptions have had to be made: 1. The formation is homogeneous and isotropic as regards those of its properties that influence the fracture-propagation process. 2. The deformations of the formation during fracture propagation can be derived from linear elastic stress-strain relations. 3. The fracturing fluid behaves like a purely viscous liquid; i.e., any peculiar flow behavior due to the addition of gelling agents or other additives is neglected. Moreover, the effect of the propping agent distribution on the distribution of fluid viscosity in the fracture is not taken into account. 4. Fluid flow in the fracture is everywhere laminar. 5. Simple geometric fracture-extension patterns are assumed — either radially symmetrical propagation from a point source (Fig. 1A) or rectilinear propagation originating from a line source (Fig. 1B). In the first case the periphery of the fracture is circular, in the second case it is rectangular. 6. A rectilinear propagation mode can be accomplished only by injection over a large perforated interval, thus forming a line source. Such a rectilinear fracture must therefore be located in the vertical plane. A circular propagation mode might be expected from injection through a narrow band of perforations. This forms a point source. Because gravity effects are excluded from our considerations, the fracture propagation plane may in this case assume any angle with respect to the wellbore as far as the

Jan 1, 1970

By B. E. Warren

Jan 1, 1965

By G. F. Butterworth

The metallographic structures most frequently encountered in rifle barrels, and which are illustrated by the accompanying photomicrographs, fall naturally into two groups, distinguished by the method used to, produce in the stock a physical condition having the requisite properties. The fist group consists of "rolled" barrels; that is, barrels subjected to hot working by rolling in or near the critical range. In the second group, the stock, which is smaller in diameter than the first, is upset to form the butt end and is then heat treated by giving it a quench and a draw. These barrels will be referred to as " heat-treated " barrels. The structure of the rolled barrels resembles closely that of the same steel after annealing. There is the same network of excess ferrite outlining the grain boundaries, but the grains themselves are composed of sorbite rather than pearlite. The grain size is closely related to the rolling temperature. The critical-point curves of this grade of steel, which is approximately 0.50 to 0.60 per cent. of carbon and 1.00 to 1.30 per cent, of manganese, show a single very pronounced point between 1300" and 1350" F. (704" and 732" C.). Barrels rolled within this temperature range give an exceedingly fine grain, shown in Fig. 1. In fact, the grains may be so fine that, at a low magnification, they may be confused with the heat-treated structure shown in Fig. 6. A magnification of 500 diameters, however, will always resolve a rolled barrel into the characteristic structure shown in Fig. 2. As the temperature is increased, the grains are found to be larger. If, on the other hand, the rolling temperature is below the critical range, the structure previous to rolling will not be obliterated, the only effect of rolling being to elongate the coarse sorbite grains in the direction of rolling, Fig. 3. This distortion is greatest at the muzzle. Heat-treated barrels are quenched in oil from above the critical range, which should give a martensitic structure, Fig. 4, but the presence of some troostite in the martensite is frequently noted when the quench has not been sufficiently drastic, Fig. 5. The structure brought about by the subsequent draw is not so striking, though quite as typical. It is sorbitic or sorbito-pearlitic, and under a low magnification appears almost homogeneous, as in the case of fine grains of pepper and salt well mixed together, Fig. 6. This structure is substantially the same for all

Jan 1, 1920

By AIME AIME

MOST recently elected to the limited group of Honorary Members in the A.I.M.E. is the distinguished Australian metallurgist, Guillaume Daniel Delprat. His citation reads: "in recognition of his distinguished achievement as metallurgist, engineer, and administrator in the production of ferrous and nonferrous metals," Mr. Delprat's ability and experience in both the ferrous and nonferrous fields at once distinguishes him from most of his professional brothers. Mr. Delprat's nativity was neither Australian nor English, for he was born in Delft, Holland, in 1856, and educated in Amsterdam. At the age of 22 he went to Spain, as metallurgist for the Tharsis Sulphur and Copper Co., Ltd. Afterwards he spent some time with the Bede Metal and Chemical Co., which had mines in both Spain and Norway, and of which company he became general manager. Other positions of responsibility held by Mr. Delprat before he went to Australia included the managing directorship of the Cordova Exploration Co., with properties in Spain and Canada; of the Rincon Silver-Lead Mining Co., in Spain; and of the Deloro Gold Mines, in Canada.

Jan 1, 1936

By Steven Mitchell

BACKGROUND Homestake Mining Company began milling operations at the Bulldog Mountain Mine near Creede, Colorado in 1969. The Bulldog Mill, rated at 350 tpd, produces a bulk flotation condentrate assaying about 180 oz/T Ag and 20% Pb, from heads of about 16 oz/T Ag and 2% Pb. The circuit is straightforward with two-stage grinding to 1-5% plus 65 mesh, followed by rougher and cleaner flotation. Reagents used are Z-6, Z-11, Aerofloat 242 and Aero Promoter 404, with an Aerofroth 65-MIBC mixture for a frother. Additional information on the geology, mine and mill are available in references (1) and (2). A flow sheet for the mill and CIP plant together is attached as Figure 1. Final flotation tailings normally vary from 1.5 - 2.0 oz/T Ag. These tailings are cycloned to produce sand for underground backfill. After cycloning, the sands are repulped and given a final scavenger float. This sand scavenger recovers a small additional amount of silver which recycles back to the main flotation circuit. The tailings are recycloned and pumped to the mine or, if the mine cannot accept sand, to tailings. The majority of the silver in the flotation tailings exists in the fine fractions; cycloning upgrades the slimes and lowers the assay of the sand. The sand, after scavenging, typically assays 0.5 oz/T Ag, and the slimes assay about 3.0-3.5 oz/T Ag. From 1969 to 1976 all of the slime tailings and the sand tailings not used underground were impounded in a tailings pond located about

Jan 1, 1983

By H. F. Dunlap, R. R. Hawthorne

A method of calculating formation water resistivities from chemical analyses is presented which is somewhat faster and more accurate than previously described methods. For 26 formation water samples taken from wells in the Texas Gulf Coast, the average deviation of calculated from measured water resistivities was 3.3 per cent, with an average bias of + l.l per cent in the calculated values. This compares with average deviations of 4.6 per cent and 7.8 per cent, with corresponding average biases of +3.2 per cent and -6.3 per cent, for the two methods previously described in the litera-

Jan 1, 1951

By R. R. Hawthorne, H. F. Dunlap

A method of calculating formation water resistivities from chemical analyses is presented which is somewhat faster and more accurate than previously described methods. For 26 formation water samples taken from wells in the Texas Gulf Coast, the average deviation of calculated from measured water resistivities was 3.3 per cent, with an average bias of + l.l per cent in the calculated values. This compares with average deviations of 4.6 per cent and 7.8 per cent, with corresponding average biases of +3.2 per cent and -6.3 per cent, for the two methods previously described in the litera-

Jan 1, 1951

By Jack F. Harang, P. B. Leavenworth

Development during the year 1941 on the Texas Gulf Coast resulted in the dis covery of 27 new fields as compared to 26 fields for the year 1940. Drilling.—During the year, 1405 wells were drilled. Of this number, 1031 were completed as oil wells with 375,000 bbl. daily of new production; 50 were com pleted as gas wells and 324 were failures. The most active area was Jackson County, where 375 wells were drilled and 336 of them accounting for 190,000 bbl. daily of new production. Types of Fields.—Of the 2 7 new fields, 14 are considered to be oil fields, 8 are listed as gas-distillate fields and 5 as gas fields. This may be compared to 26 fields found in 1940, of which 14 were oil fields and 12 gas-distillate fields. Producing Sections.—Frio discoveries retained their predominant position by having 10 Frio fields discovered in comparison to 6 fields in the Wilcox, 4 in the Yegua, 5 in the Miocene and 2 in the Jackson. In the previous year 15 Frio fields were found, 4 in the Wilcox, 2 each in the Yegua, Cook Mountain and Miocene, and I in the Jackson. Production.—Production increased over 1940 approximately 10 per cent, being 113,726,893 bbl. for the year 1941 and 104,127,247 bbl. for 1940. The statistics in Tables I and 2 include distillate and condensate as oil production because no separate reports have been compiled. It is hoped that this separation may be possible some day, but as a great many fields produce both oil and distillate and these arc commingled in pipe lines, separation of statistics will be more difficult than for other areas. New Fields Big Hill, Jefferson County.—Stanolind Oil and Gas Company's No. I George D. Anderson was completed as a gas well from a Frio sand at 8705 to 8720 ft., on Dec. 24, 1941, after having been drilled to a depth of 9500 ft. Additional development is being carried on but it is not possible to evaluate this discovery at this time. Brushy Creek Field, Lavaca County.— Shell Oil Corporation's No. I D. G. McManus was completed as the discovery well in the Brushy Creek field on Oct. 29, 1941, from a Wilcox sand through perforations at 7225 to 7230 ft., making gas and 180 bbl. of 59° gravity distillate. This well was bottomed at 10,998 ft. in the Wilcox. No statement can be made at this time as to the importance of this discovery. Chenango Field, Brazoria County.—J. N. Rayzor et al. completed their No. I Sarah J. Christian through perforations at 8564 to 8572 ft. in a Frio sand, for 453 bbl. of 37.7° gravity oil, on Feb. 6, 1941, after having drilled to 9564 ft. Several wells were drilled in this area during the year but failed to establish important production. This is considered a minor discovery. Clodine Field, Fort Bend County.—Providence Oil Company's No. I Hatfield was the discovery well of the Clodine field, being completed through perforations at 7499 to 7502 ft. for 108 bbl. of 51.2° gravity distillate, on June 19, 1941. The well was bottomed at 8090 ft. Several wells

Jan 1, 1942

By P. B. Leavenworth, Jack F. Harang

Development during the year 1941 on the Texas Gulf Coast resulted in the dis covery of 27 new fields as compared to 26 fields for the year 1940. Drilling.—During the year, 1405 wells were drilled. Of this number, 1031 were completed as oil wells with 375,000 bbl. daily of new production; 50 were com pleted as gas wells and 324 were failures. The most active area was Jackson County, where 375 wells were drilled and 336 of them accounting for 190,000 bbl. daily of new production. Types of Fields.—Of the 2 7 new fields, 14 are considered to be oil fields, 8 are listed as gas-distillate fields and 5 as gas fields. This may be compared to 26 fields found in 1940, of which 14 were oil fields and 12 gas-distillate fields. Producing Sections.—Frio discoveries retained their predominant position by having 10 Frio fields discovered in comparison to 6 fields in the Wilcox, 4 in the Yegua, 5 in the Miocene and 2 in the Jackson. In the previous year 15 Frio fields were found, 4 in the Wilcox, 2 each in the Yegua, Cook Mountain and Miocene, and I in the Jackson. Production.—Production increased over 1940 approximately 10 per cent, being 113,726,893 bbl. for the year 1941 and 104,127,247 bbl. for 1940. The statistics in Tables I and 2 include distillate and condensate as oil production because no separate reports have been compiled. It is hoped that this separation may be possible some day, but as a great many fields produce both oil and distillate and these arc commingled in pipe lines, separation of statistics will be more difficult than for other areas. New Fields Big Hill, Jefferson County.—Stanolind Oil and Gas Company's No. I George D. Anderson was completed as a gas well from a Frio sand at 8705 to 8720 ft., on Dec. 24, 1941, after having been drilled to a depth of 9500 ft. Additional development is being carried on but it is not possible to evaluate this discovery at this time. Brushy Creek Field, Lavaca County.— Shell Oil Corporation's No. I D. G. McManus was completed as the discovery well in the Brushy Creek field on Oct. 29, 1941, from a Wilcox sand through perforations at 7225 to 7230 ft., making gas and 180 bbl. of 59° gravity distillate. This well was bottomed at 10,998 ft. in the Wilcox. No statement can be made at this time as to the importance of this discovery. Chenango Field, Brazoria County.—J. N. Rayzor et al. completed their No. I Sarah J. Christian through perforations at 8564 to 8572 ft. in a Frio sand, for 453 bbl. of 37.7° gravity oil, on Feb. 6, 1941, after having drilled to 9564 ft. Several wells were drilled in this area during the year but failed to establish important production. This is considered a minor discovery. Clodine Field, Fort Bend County.—Providence Oil Company's No. I Hatfield was the discovery well of the Clodine field, being completed through perforations at 7499 to 7502 ft. for 108 bbl. of 51.2° gravity distillate, on June 19, 1941. The well was bottomed at 8090 ft. Several wells

Jan 1, 1942

By Paul F. Kerr

The uranium-producing areas near Marysvale, Utah provide an unusual group of veins and replacement deposits associated with a Pliocene-Oligocene intrusive and extrusive igneous complex. Aside from several scattered occurrences in older volcanics, uranium-bearing veins occur in intrusive quartz monzonite or granite and in nearby rhyolite. The veins in general trend within a few degrees of N55-65°E, are more or less vertical, and are found along the western margins of a quartz monzonite intrusive. The replacement deposits are found in rhyolite intrusives and also in the lower portions of rhyolite flows close to places where veins forming solutions rising through quartz monzonite came into contact with the rhyolite. At least 14 veins have been mined since uranium mining operations began at Marysvale some 16 years ago, while ore has been extracted through about 10 miles of underground workings. The active mmmg area is approximately 3000 feet long and in the central portion 1500 feet wide. Ores have been found over a vertical spread of almost 2000 feet, between the highest occurrence on Jungfrau Hill ( ca. 7200 feet) and the deepest discovery of ore in a drill hole near the Prospector Mine (ca. 5200 feet). Under existing mining and marketing conditions, mining along the veins in the main area appears to have reached an economic limit at about 500-600 feet below the surface. However, orebodies in the rhyolite and in the upper portions of veins close to the rhyolite are subject to active mining. Isotopic dates indicate that the uraninitebearing veins and replacements are late Miocene or Pliocene (ca. 10-13 m.y.), the rhyolite is Miocene (avg. 17.5 m.y.), and the quartz monzonite and granite intrusives are late Oligocene (23.6 to 26.0 m.y.). The older Bullion Canyon Volcanic Series which encircles the area is Oligocene (28 to 31.1 m.y.). Two generations of alteration occur: ( 1) Earlier alunitic veins and replacement bodies are found in the Bullion Canyon Volcanic Series, none of which have produced uranium; (2) Later argillic alteration associated with the introduction of uranium is found along veins, replacing glassy rhyolite dikes and replacing phases of the rhyolite.

Jan 1, 1968

By Waldemar Lindgren

THE following pages present data accepted by many geochemists and geologists regarding the succession of minerals and the temperatures of formation in ore deposits affiliated with igneous rocks. They also present the individual views of the author on the composition of the solutions that were active and on the mode of deposition. He does not regard these views as speculations or hypotheses but as forming a well motivated and consistent theory. It is not certain, however, that all investigators will subscribe to them.

Jan 1, 1936

By John T. Norton

N order to attempt to arrive at a better under-Jl standing of the whole basic problem of sintering, these remarks will serve as an introduction for discussion that is included and will, perhaps, help to isolate specific questions which need to be answered or to suggest some definite avenues of investigation which should be followed. To bring some sort of logical order into the presentation, I will consider the various types of interaction between the metal to be sintered and the atmosphere which surrounds it, depending upon whether the phenomena are essentially chemical or physical in nature. For example, when the only necessary criterion for the satisfactory sintering of a certain powder is the removal of an oxide skin, then the problem of choosing a suitable atmosphere is primarily chemical; however, if a special surface condition as a consequence of the oxide skin removal is necessary for particularly effective sintering, then the problem becomes a physical one. Of course, the two aspects overlap considerably, but it may be possible to make a distinction in principle if not in practice. The chemical characteristics of the phenomena will be emphasized, since these are the better known. Metal-gas reactions involved in sintering are controlled primarily by the thermodynamics of the processes involved. In which direction will a reaction go and how far before it stops? The answer is to be found in the magnitude of the free energy change associated with the reaction. If a constituent is to be removed from the specimen as completely as possible or if a constituent is to be formed in the specimen as completely as possible, then one chooses conditions which are far from equilibrium so that the reaction is driven toward completion. On the other hand, if the composition is to be maintained at a desired value, then conditions are adjusted as closely as possible to the equilibrium point. This aspect of the problem is susceptible to quite precise analysis, provided, of course, that the significant reactions can be recognized and the required thermodynamic data are available. Conversely, if one asks how fast the reaction goes or how far it proceeds in a given time, the answer is frequently much more difficult to answer in quantitative terms. Yet the rate-con trolling factors of the reactions may be of primary importance in the success of a particular operation, especially where competing processes are at work. Both equilibrium and rate factors must be understood if a clear picture is to be obtained. For instance, in a process for carburizing titanium dioxide, is the difficulty of obtaining a stoichiometric Tic due to a true limitation of the equilibrium or simply to a very slow rate of reaction? An example of this appears in the work of Kalish and Mazza.' They showed that the oxygen content of sintered iron compacts was lower when sintered in pure hydrogen than in the case where the hydrogen was diluted with either argon or nitrogen. The equilibrium oxygen content of the iron would be the same in the two cases, since it is determined by the ratio of the partial pressures of water vapor and hydrogen and this pressure ratio is unchanged by dilution. The rate of oxygen removal, however, under the conditions of a constantly replaced furnace atmosphere, depends upon diffusion and thus upon the concentration of hydrogen in the furnace atmosphere. Possibly the clearest way to illustrate the interplay of these two factors is to consider in more detail some of the typical metal-gas reactions. Adsorbed Gases It is common experience that fine metal powders with their very large surface areas often contain large quantities of gas. This gas, which results from exposure to air or perhaps from some step in the

Jan 1, 1957

By James C. M. Li, J. Weertman

James C. M. Li (United States Steel Covp.)—The author has discovered a single analytical relation between the minimum, or the steady-state, creep rate and the applied stress confirming a statement made earlier by orn" that such relation should exist and should reduce to the power law at low-stress levels and to the exponential law at high-stress levels. However, as pointed out by the author, all the available theories of creep are not adequate to explain such a single relation. Inspired by such a statement, I have made a suggestion concerning a possible explanation13 of the new relation. This is based on the concept that the rate-controlling step is the cooperative motion of a short dislocation segment. The nature of and the reason for the cooperation have been discussed13 as well as the reason why the motion of the dislocation could be controlled by the mobility of the short segments. A natural short segment has been proposed13 to be the node formed at the intersection of two dislocations. The reason why the node may contain only a few atoms has not been discussed and the application of the proposed model to all the metals and alloys reported in this paper has not been attempted. It seems appropriate to include these in this discussion. The model was partly inspired by the substructure recently observed in the electron microscope on creep specimens. One such example is shown in Fig. 48 in Darken's Campbell Memorial Lecture. The substructure is a collection of dislocation intersections and irregular networks. No pileups have ever been observed in such specimens. A closer look at the network indicates that one set of dislocations is more straight than the other set sug- gesting that the other set may be mobile in the plane of the net. Since, for the network to survive the creep deformation, some dislocation reaction has to take place at the intersection of the two sets of dislocations, the mobile dislocation, even if it can slip in the plane of the net, will have difficulty in moving at these intersections. To illustrate, an idealized network is shown in Fig. 9. The thin lines represent the set of dislocations which are mobile and can slip in the plane of the net except at the nodes which are formed at the intersection of the two sets of dislocations. The other set of dislocations, represented by the thick lines, may have a Burgers vector which is not parallel to the plane of the net, and therefore may be immobile. Because of this nonparallel Burgers vector, the Burgers vector of the node, which is avectorial sum of the Burgers vectors of the two sets of dislocations, will also be nonparallel to the plane of the net. Therefore, the node cannot slip in the plane of the net and the set of mobile dislocations will have to drag the node along as indicated in Fig. 9. Now the problem is how many atoms could be involved in the nodes. Exact calculation of the length of the node is a difficult task especially since the length should be a steady-state length and not an equilibrium length. An estimate of the equilibrium length can be made by balancing the line tension of all the dislocations. The results would be a small fraction of the length 1 between nodes as shown in Fig. 10. In some instances such a calculation shows that the node will not be formed. But, since the calculation is only approximate, it does not rule out the possibility of the formation of a short node. In other instances the equilibrium length of the node is an appreciable fraction of I. Such a node would

Jan 1, 1963

By T. R. A. Davey

The fundamental principles by which bismuth may be removed from lead by pyrometallurgical processes are enumerated. Qualitative discussion of the phase diagrams concerned is followed by presentation of quantitative diagrams. Brief mention is made of the practical aspects. Data presented show how chemical lead (<0.005 pct Bi) may be produced by the Jollivet, Dittmer, and Kroll-Betterton processes. BISMUTH is an element whose properties are very similar to those of lead, and its minerals are associated to a greater or lesser extent with nearly all the major lead ore deposits of the world. In consequence, the lead produced contains bismuth unless a special debismuthizing process is practiced. There does not appear to be any published comprehensive review of the effect of bismuth as an impurity on the properties of lead, and there is some uncertainty as to the beneficial or detrimental effects of small amounts of bismuth in lead used for particular applications. Standard specifications of most countries stipulate a maximum bismuth content of 0.005 pct for chemical lead. With one exception, this specification is met only by lead producers whose ores are relatively bismuth-free, or whose refineries are electrolytic. In lead for certain applications a higher bismuth content is preferred by some fabricators.&apos; In contrast to the refining for silver, copper, and antimony, the refining for bismuth does not usually result in a large overalil economic gain from the sale of byproduct. Thus, debismuthizing is customarily practiced only if market conditions demand a lead with a bismuth content lower than that produced by classical refining; i.e., softening, desilverizing, and zinc refining. Until this century, debismuthizing was carried out only a:; an incidental result of desilverizing, as later described. This century has seen the development of the Betts electrolytic process—the only successful one of many electrolytic processes proposed and patented —and a number of precipitation processes based on the pioneering work of Kroll,&apos; although only one of these, the Kroll-Better ton process,&apos; is in wide commercial use today. It is proposed in this paper to deal only with the pyrometallurgical processes, excluding those based on aqueous electrolysis. Historical Background Prior to 1833 silver (and incidentally bismuth) could not be removed from lead. To recover silver from rich bullion, the only course available to lead refineries was to cupel the bullion, forming a slag of litharge. The first slag tappings or skimmings, on reduction, yielded soft lead of very low silver and bismuth contents. Intermediate skimmings yielded a lead of somewhat higher silver and bismuth contents, which could if desired be recupelled. The last skimmings yielded a litharge very high in bismuth, which could by successive oxidation and reduction cycles be separated into high purity bismuth, and lead returns. This oxidation reduction process, with modern operating techniques, can still be used today to produce a portion of a lead refinery&apos;s output of very low bismuth content, as discussed later. In 1833 Pattinsone discovered that lead bullion could be purified of silver and bismuth by fractional crystallization, the primary lead crystals formed by partial freezing being purer than the melt. Repeated processing in pans produced a lead containing as little as 0.02 pct Bi. The simple explanation of this

Jan 1, 1957

By R. W. Heins, N. Street

An investigation was made of the Rehbinder-Kuznetsov pendulum as an instrument to aid in the study of rock drillability and of the effect of surface active agents on rock drillability. The "critical weight", i.e., the pendulum weight at greatest sensitivity, was determined for several solids and it was shown that a change in surface environment changed the maximum value of the apparent hardness but not the critical weight, and the critical weight increased with increase of hardness of the solid used. Using silver halides as the solid material, and solutions of either silver nitrate or the appropriate alkali halide, it was shown that there is a hardness maximum at the zero point of charge of the particular silver halide. INTRODUCTION The development of relative hardness measurement by the method of damped oscillations, or what has been called the pendulum sclerometer, is due largely to the Russian workers P. A. Rehbinder and V. D. Kuznetsov and their co-workers.1,2 The apparent simplicity of the method has led to its use in a number of fields, particularly those where relative hardness has to be determined on a brittle solid. As will be shown, the simplicity of the method belies its complexities. THEORY OF THE PENDULUM SCLEROMETER The operation of the pendulum is quite simple. Make a sharp point such as a diamond, hardened steel or tungsten carbide, as the fulcrum of a pendulum, with the center of gravity of the system below the point of support. The attenuation of this pendulum is a function only of air friction, provided no fragmentation, breakage or other work is performed by the point. However, when the solid surface breaks or disintegrates under the point, and the latter penetrates the solid, part of the energy of oscillation is absorbed in the work of creating new surface, and the rate of attenuation increases. In the case of brittle solids, the point of the pendulum produces fragmentary particles, whereas the point produces plastic deformation in a plastic solid; but in both cases damping occurs. This pendulum damping is a function of the hardness or strength of the solid. Whereas a pendulum oscillating on a hard material attenuates primarily by air friction, in the case of a soft material, the points penetrate the surface of the solid, producing new surface, and the pendulum damps much faster. Thus the attenuation rate is a function of the hardness or strength of a material in both plastic and brittle substances. Russian workers initially used a single support for the pendulum, but this created many problems because of oscillation of the pendulum in more than one plane. A revised version used two points, or sometimes a prism as support, successfully confining oscillation to one plane. The version using two points was constructed and used throughout this investigation, making the recording of the attenuation as a function of time relatively easy. That both points should be in contact with the solid during the damping is implied. Rehbinder (c.f. Kuznetsov2) proposed that the hardness H as measured by this method could be expressed by a quantity which is inversely proportional to the relative initial rate of attenuation of amplitude. where H = hardness parameter (arbitrary units) a, = initial amplitude da/dt = rate of attenuation of amplitude with time. In the simplest case of damping with a constant logarithmic decrement, H can be regarded as a constant for the duration of the whole damped oscillation process. That is

Jan 1, 1966