Search Documents

By Botelho Junior, Amilton Barbosa, Denise C. R. Espinosa, David B. Dreisinger

Copper and cobalt can be found on nickel laterite ores, and cobalt can be found also on copper ores, and many contaminants such as iron, aluminum, and magnesium are associated with these ores. In hydrometallurgical process, a purification step is necessary after leaching due to the presence of these impurities. Chelating resins are more selective for some metals than others, making them more efficient than cationic resins. This overview discusses chelating resin applications to recover copper, nickel, and cobalt from mining process and mining tailings and the effect of contaminants in leach solution. Chelating resins with iminodiacetate functional group can be used for selective copper recovery, and both iminodiacetate and bis-picolylamine resins are highly selective for nickel and cobalt. Chelating resins with the same functional group can have different performances on the kinetics of loading, because of variations of structure, the density of functional group, and degree of cross-linking. This article reviews commercial chelating resins that can be applied in leach solutions with different compositions, and also possible innovations for uses of chelating resins to recover metals from mining process and mining tailings.

By Ashis Bhattacherjee, Rahul Upadhyay, Nearkasen Chau, Aditya Kumar Patra, Dhanjee Kumar Chaudhary

Heavy earth-moving machineries used in open-pit mines intensively expose the drill operators to whole-body vibration and shocks and thus to musculoskeletal disorders. The roles of an individual, machine, and rock-related factors in their exposure remain poorly understood. This cross-sectional study investigated their role among 39 drill operators from Indian iron ore mines. It shows that 70% of the operators were exposed to high levels of vibration, above the limit values recommended by ISO 2631-1. Multiple linear regression models showed that the whole-body vibration and shock exposures were strongly associated with operator’s age, drill machine model, rock’s hardness, uniaxial compressive strength, and density. The role of body mass index was close to significance (p = 0.08). Univariate analyses found that drill’s age, seat pad thickness, and seat backrest height were also strong predictors. These results help in identifying risky operators, materials and occupational situations, and in implementing appropriate prevention and intervention to reduce and monitor the exposures and health risk.

By Justyna Swolkień, Nikodem Szlązak, Dariusz Obracaj

Polish coal mines are characterized by severe geological conditions and the co-occurrence of natural hazards. These hazards are associated with methane and dust emissions during mining processes which can provide methane, dust or methane-dust explosions. Besides, there are such natural hazards as gas and rock outbursts, rock bursts, spontaneous combustion of coal and environmental heat load. The mutual influences of various geological conditions, as well as the natural hazards, intensify the increase of the methane explosion hazard. The occurrence of methane explosions in the Polish mining industry between 2013 and 2108 are analyzed. Fatal accidents are compared with similar events in the global mining industry. The methods of preventing the explosion hazard as well as methane emission control in the Polish coal mining sector are presented. Methane hazard prevention should be adapted to levels and other natural hazards, especially those related to ventilation of underground mine. The methods of preventing methane emissions into mine excavations are often contrary to the means of preventing other ventilation-related hazards in the underground mine, e.g. the prevention of spontaneous combustion of coal in the goaf of longwall panel. Therefore, the design of longwall panels should be preceded by a detailed analysis of the results of both methane emission prediction and forecast of other ventilation-related hazards.

By A. M. Starfield

Discussion J. de V. Lambrechts (Fellow): The author's paper is a brilliant follow-up of an earlier paper by Starfield and Dickson.1 I have no quarrel with Dr Starfield's computerization of a complex problem, but I do not believe that he is getting quite the right answers from his programme. My impression is that his predictions about wet bulb temperature increases in very deep mines are over optimistic; in other words, that it will be hotter than Dr Starfield predicts. This is putting my views in a nutshell. This is not the occasion on which to indulge in lengthy argument about the original paper by Starfield and Dickson, but the present paper is, after all, based directly on that earlier paper and if the one fails, the other cannot succeed. I did level certain criticisms at the first paper and cannot say that the authors' replies were very convincing. I do not think it is a sin to admit that I belong to the old school which believes in thorough field experimentation and practical trials and no amount of mathematical manipulation or physical theorizing, no matter how excellent, can make up for inadequate practical confirmation. This, as I see it, is still the crux of the matter. The original paper by Starfield and Dickson still rests on somewhat scanty practical evidence and I would be much happier if Dr Starfield's computer programme, based on the Starfield-Dickson model, had been checked against a large mass of observations in the practical mining situation. This is what both Wiles2 and myself3 had tried to do previously. What we lacked in mathematics and/or computer aids, I think the present paper by Dr Starfield lacks in practical substantiation. This is no condemnation of the author's paper which, taken by itself, is excellent but I think the final stage is still lacking, namely the bringing together of theory and empiricism in a manner acceptable to all. This may be wishful thinking on my part but I hope, within the next year or so, to come up with a modified Starfield-Dickson model in such a way that the computer answers will agree in the majority of cases with the few hundred field observations which are already on record. It might be a case of applying the proverbial 'Cook's Law' to the Starfield-Dickson model! REFERENCES 1. STARFIELD, A. M., and DICKSON,A. J. 'A study of heat transfer and moisture pick-up in mine airways.' J. S. Air. Inst. Min. Metall., 68, (5), 1967. 2. WILES, G. G. 'Wet bulb temperature gradients in horizontal airways.' J. S. Air. Inst. Min. Metall., 59, (7), 1959, p. 339. 3. LAMBRECHTS, J. DE V. 'Prediction of wet bulb temperature gradients in mine airways.' J. S. Air. Inst. Min. Metall., 67, (11), 1967, p. 595. R. Hemp (Visitor): Dr Starfield's paper has very effectively rounded off one particular aspect of the general problem of heat flow in mines. The ease with which this computer programme can be used to calculate temperature increases in horizontal airways must lead to its wider use in ventilation planning and, in developing this rapid method, Dr Starfield has indeed rendered a valuable service to the mining industry. One could consider further instances of heat flow in airways in which the availability of a rapid computer method would be desirable, e.g. the flow of air down a shaft, where there is an increase in temperature due to adiabatic compression, as well as an increase in virgin rock temperature as the depth increases. However, this particular case would not present any new problems and would merely require an extension of the exisitng work. I should like in this contribution to talk about an aspect of environmental control in mines which, I think, will become more important in the future. It is well known that wet bulb temperatures are subject to fluctuations underground. In some instances, particularly in stopes, the fluctuations, both with time and position, can be considerable. The theoretical work which has been carried out on temperature increases has been aimed at the prediction of mean temperatures, and no account has been taken of fluctuations around this mean. It is questionable whether this approach will, on its own, be sufficient, particularly when temperature increases in stopes are considered. The fluctuations in air temperatures underground arise from two causes. The first of these would be the fluctuations in surface conditions, and here one could list random, diurnal and seasonal fluctuations. The second cause is the multitude of things which vary in a mine and here one could list variations in air flow quantity, sources of evaporation, heat transfer from pump and compressed air columns and, particularly in the stope, variations in air flow patterns. Fluctuations arising from surface temperature variations should be amenable to calculation, and here one envisages figures relating the decay of temperature variation with distance to factors such as air flow quantity. Fluctuations resulting from changes in the mine are perhaps more difficult to tackle theoretically and the best approach could well be to analyse underground observations. In this connection, there is a good case to be made for the increased use of statistical methods in the analysis of underground temperature measurements, and it might be of value to look at current air-conditioning practice. When carrying out cooling load calculations for a particular location it is customary to use design wet bulb

Jan 11, 1969

By John V. Beall

Monotonous flood planes flanked either side of the road as we drove in the embassy car from the airport to downtown Seoul. We crossed the brown waters of the Hann River, meandering over mud flats. A great, gnarled tree bore beautiful fall colors of gold. "That is a Ginko Tree, the oldest living fossil, probably a hundred million years old;" said Jean W. Pressler. Compared to other cities of the Far East, the traffic in and around Seoul was sedate. Few motorcycles or bicycles, and little superfluous horn tooting. "This is the best season in Korea. We have long beautiful springs and falls," said Pressler, chief of the mining branch of USAID, and he continued with a briefing on the country.

Jan 8, 1969

By R. S. Warfield

Several reconnaissance-type surface and drill core samples of Arctic Northwestern Alaska coals were taken during the summer field seasons of 1964 and 1966 for coking studies. Surface samples were taken from the Kokolik River and the Cape Beaufort areas; core samples were obtained from the Kukpowruk River and the Cape Beaufort areas. Only one Kokolik River surface sample possessed coking properties. This sample, representing an 11.6-ft coal seam, made coke approaching metallurgical quality when a 30-pct portion of selected blending coals was added. Four Kukpowruk River core samples, each representing the same 19-to 20-ft coal seam, were all of about the same coking quality. No differences of coke quality attributable to depth of permanently frozen overburden were found, but the data confirm previously reported information that the 19- to 20-ft coal bed is a potentially satisfactory base coking coal. In the Cape Beaufort area, a core sample with appreciable coking properties was taken at depth from a coalbed determined noncoking in a surface sample.

Jan 1, 1969

By J. H. Swisher

The solubility of graphite in CaO-S2O2-Al,O3 slags was measured by equilibrating slag samples with graphite crucibles and CO gas. Carbon contents as high as 2 ut pct were obtained in CaO-saturated, CaO-A1,O3 slags, and 1.3 wt pct in slags of the composition CaO.Si0,. Although the observed conditions for Sic formation were in agreement with those predicted from thermodynamic data, CaC, was found to form at a lower temperature than predicted frotn thermodynamic data. From measurements of the equilibrium carbon content as a function of CO Partial pressure, it was found that carbide ions dissolve in CaO-A12O3 melts with a valence of minus two. The carbon content increased with CaO concentration in Ca0-Al,O3 melts and increased with SiO, content along the CaO'AlO3-CaOSi0 join in the ternary system. When solid CaC2 was added to CaO-A12O3 and CaO-SiO2-A12O3 slags, it was found that one of the oxides in the slag was reduced by the carbide (Al2O3 in the forrner and SiOz in the latter). In electric furnace steelmaking, a double-slag practice is frequently used to meet alloy specifications. Initially a flush slag, which is oxidizing in nature, is used to remove phosphorus and carbon from the steel bath. Later in the refining period, the flush slag is replaced by a highly reducing carbidic slag. When calcium carbide is formed in or added to a finishing slag, the slag is effective as a desulfurizing agent and also permits alloying elements such as chromium, vanadium, and tungsten to be added to the slag in the form of oxides. The oxides are readily reduced by calcium carbide, thereby minimizing the use of expensive ferroalloys. More work has been done on the thermodynamics of silicon carbide in slags than on calcium carbide. Baird and alor' and Kay and alor' determined the free energy of formation of Sic by measuring the partial pressure of CO in equilibrium with solid silica, silicon carbide, and graphite. Using a similar technique, they determined SiOz activities in CaO-SiOz and Ca0-Si0,-A1203 slags. Rein and chipman3 also determined the free energy of formation of Sic using slag-metal equilibrium measurements. A literature survey has uncovered only one experimental study of the behavior of CaC, in slag systems. Shanahan and cooke4 report the results of some preliminary experiments on the solubility and stability of CaC, in a CaO-A1,03 and a Ca0-Si0-A1,03 slag at a temperature of about 1500". The carbon solubility as CaC, in a slag containing 50 pct CaO and 50 pct A1203 was reported to be 0.6 pct. They also review earlier work on the binary CaO-CaC, system. A eutectic exists in this system, but various investigators disagree on the eutectic temperature and composition. eal has given an explanation for carbide furnace erruptions in terms of the thermodynamic properties of CaC,; his analysis is not based on experimental data, but on compiled data for the free energies of formation of CaC, and CO.' , These data for steel-making temperatures are all extrapolated from the results of low-temperature measurements. In the experiments described in this paper, slag samples were equilibrated with graphite crucibles and with mixtures of CO and argon or with CO gas at 1 atm total pressure for measurement of the carbon solubility. Most of the work was done on Ca0-A1203 binary slags, although in some experiments CaO-SiO, and Ca0-Si0,-A1,03 slags were used. EXPERIMENTAL Slag samples of the desired composition for the solubility measurements were obtained by blending pre-fused master slags. The master slags were prepared by fusing mixtures of reagent-grade CaC03 with either A1,03 or Si0, in a graphite crucible. The master slags were crushed, then decarburized in air in a muffle furnace at 1200O C. A schematic diagram of the apparatus is shown in Fig. 1. The source of carbon for the solubility meas-

Jan 1, 1969

By F. D. George, M. J. Salkind

Al3Ni whisker-reinforced aluminum was found to exhibit good Charpy impact toughness and little notch sensitivity even though its room-temperature tensile elongation parallel to the whiskers is only 2 pct. This impact behavior was maintained d liquid nitrogen temperature (-196"C). It is postulated that this behavior is due primarily to the presence of the continuous aluminum matrix which provides sufficient 10calized ductility in the vicinity of the crack tip to absorb considerable energy from the advancing crack. The impact behavior of Al-Alni was found to be quite anisotropic. Of six orientations studied, the transverse orientation having the notch normal to the whisker axis was found to exhibit the lowest impact energy, whereas the transverse orientation having the notch parallel to the whisker axis was found to exhibit the highest impact energy. A significant differnce was noted between the impact behavior of material containing needlelike whiskers and that containing bladelike whiskers. Only two of the six orientations studied exhibited complete fracture for the material containing needlelike whiskers. On the other had, most of the specimens containing bladelike whiskers exhibited complete fracture. It was postulated that the bladelike whiskers block transverse flow, thus reducing the amount of plastic deformation ahead of the crack tip. One of the more significant advantages of composite materials is the prospect of combining high strength with toughness. In general, toughness is associated with materials which exhibit considerable ductility and can deform plastically in the presence of a stress concentration. Very strong materials which resist plastic deformation generally exhibit low toughness. At first glance, then, it would appear as though strength and toughness are mutually incompatible so that useful engineering materials would have to be a compromise between the two. One approach to the problem of combining the high intrinsic strength of ceramics with the toughness of metals was to mix them together to form a cermet. Unfortunately, the toughness of cermets was found to be rather disappointing. Whisker reinforcement of metals, however, appears to be a more promising approach. It has been demonstrated that whisker-reinforced metals produced by unidirectional solidification exhibit enhanced strength due to the presence of high strength nonmetallic whiskers. The total strain capacity of these composites in the direction of fiber alignment is limited to that of the fibers, the matrix being unable to carry the load once the fibers have failed. A characteristic, then, of whisker composites is low ductility in the direction of whisker alignment, on the order of a few percent elongation. This low elongation, which is usually associated with brittle behavior, should not be taken as an indication of low toughness. Such a material can exhibit significant ductility in directions other than parallel to the fibers7 and can therefore possess significant intrinsic toughness. Toughness in a fiber-reinforced metal is derived from several mechanisms. The first is due to the toughness of the matrix itself. A continuous ductile metal matrix can act as an effective crack arrest medium by undergoing localized plastic deformation. Cracks initiated from the surface of the composite or from a brittle fiber failure must travel through the matrix before reaching another brittle phase particle. A second crack arrest mechanism peculiar to fiber composites is due to the fact that, as a crack travels through the matrix and approaches a fiber, the plastic deformation ahead of the crack tip will result in loading of the fiber. This causes the matrix shear strength in the plastic zone to be apparently higher, thus extracting more energy from the crack and diverting the crack at an angle to the original direction of propagation. A third crack arrest mechanism occurs in fiber composites which exhibit a weak bond between fiber and matrix. The idea was proposed by Cook and Gordons that if a crack propagating transversely in a fiber composite were made to turn and run along the fibers by decohesion of the fiber-matrix bond, then toughness would be imparted by the blunting of the crack tip and the creation of new surfaces. The last mechanism, interfacial decohesion, is commonly noted in naturally occurring fiber composites such as wood, bone, and bamboo, and has been observed in man-made composites such as glass fiber-reinforced resins,g silica fiber-reinforced aluminum," laminated steel," and tungsten and silica fiber-reinforced electroplated copper.'' The first mechanism, crack arrest by plastic deformation in the matrix, has been noted in tungsten wire reinforced cast copper." The purpose of this investigation was to quantitatively assess the toughness of a whisker-reinforced metal as a function of orientation. Previous investigation considered only cracks propagating nominally perpendicular to the reinforcement. In this investigation, crack propagation in three mutually perpendicular directions as well as three intermediate orientations was investigated. The system chosen for study was the unidirectionally solidified A1-A13Ni eu-tectic alloy which has a microstructure consisting of 10 pct by volume of A13Ni whiskers in a matrix of aluminum This material exhibits two different kinds of whisker morphology, depending upon the rate at which it is solidified.' At low rates of solidification (less than 2 cm per hr) the whiskers are bladelike, whereas at higher rates of solidification they are

Jan 1, 1969

By D. A. Rice, M. C. Fuerstenau

Flotation data indicate that sulfonate and amine adsorb physically on manganese oxide; oleate also adsorbs physically if the zero point of charge is sufficiently high. Chemisorption of oleate occurs on pyrolusite between pH 8 and 9, and possible mechan- isms of collector adsorption involving metal ion hydrolysis are discussed. The flotation characteristics of most metal oxides1-15 have been examined with standard collectors such as fatty acids and sulfonates. From these studies it would appear as though electrical phenomena are important when shorte r-chained collectors are involved. For example, Iwasaki, Cooke, and Choi9 have shown that dodecyl amine and dodecyl sulfate float iron oxide above and below the zero point of charge, respectively. In another system, D.W. Fuerstenau and Modi10 have shown that dodecyl sulfate, dodecyl

Jan 1, 1969

By C. A. Komar

The Bureau of Mines conducted oil-displacement tests in the laboratory with three water-in-oil and five oil-in-water emulsions that were created with ultrasonic energy at a frequency of 20 kHz and an acoustic intensity of approximately 100 watts per cm2. Emulsions of either crude oil or kerosine, brine, and 112 to 2 percent emulsifier were formed during 30 seconds of acoustic irradiation. Results indicate that ultrasonic energy induces greater and more uniform dispersion of one liquid in another in the presence of small amounts of chemi¬cal emulsifiers. When the emulsions were injected as a buffer slug before waterflooding, recovery of the oil-in-place was 8 to 22 percent greater than with conventional waterflooding in the test specimens, regardless of the con¬tinuous phase (oil or brine). The emulsions do not appear to be applicable to the Appalachian area; however, because the oilfields are too "tight," the clays in the formation remove the emulsifier from the displacing fluid, and not enough additional oil is produced, compared with recovery using conventional waterflooding, to warrant the increased operating costs.

Jan 1, 1969

By Ronald P. Hollenbeck

Samples of clays, shales, and slates from 29 locations in the Appalachian Region of Alabama and Georgia were tested and evaluated to determine their suitability as raw material for the manufacture of lightweight aggregate by the rotary-kiln method. Samples from 11 locations in Alabama (one each in Etowah, Lawrence, and Morgan Counties and two each in Colbert, Cullman, Tuscaloosa, and Walker Counties) and one location in Walker County; Ga., produced satisfactory lightweight aggregate.

Jan 1, 1969

By N. G. W. Cook

The conventional cyclic system of deep-level mining by drilling and blasting gives rise to an inadequate degree of stope sorting when mining thin reefs. This results in poor utilization of the capital facilities of a mine in the form of shafts, haulages, airways and associated equipment. Continuous and controlled removal of the thin gold-bearing portion of the reefs would permit better stope sorting and hence greater utilization of capital facilities. Results of experiments to develop hard rock cutting machines for mining are reported and the benefits which could be derived from their use are discussed.

Jan 1, 1969

By R. R. Beebe

Marcona Corporation produces about 3.5 million long tons of iron ore pellets annually on its two travelling grate pelletizing machines at San Nicolas, Peru. During 1969, these pellets will be shipped to customers in four marketing areas--Japan, the United States, Europe, and South America. All of these sales are on the open market, and product quality is a major concern. Typical chemical, structural, and quality test results for Marcona pellets are given in Table 1. [ ]

Jan 1, 1969

By H. E. Cook

The Ising model for the internal energy of a binary alloy has been used to obtain a general equation for the critical resolved shear stress of partially ordered crystals. The equation expresses the stress in terms of the Warren "alphas " and can be used to estimate the variation in strength with order without the assumption, present in the original formulation of this problem in terms of domain size, that order is complete within each domain and that the domains are of ungorm size and shape. In addition, it is the general equation, according to the Ising model, for strengthening by short-range order. Two applications of the equation are considered: One is an estimate of the variation in strength of CkAu with long-range order. The other is an estimate of the variation in strength of FeCo with quench temperature. Reasonable agreement is found with the variations reported in the literature. When the internal energy of an alloy crystal depends upon the distribution of solute, the strength of the crystal will also depend upon it because a portion of the applied stress for plastic deformation will be: where V is the volume of the crystal and E(E) is the energy change associated with the solute redistribution caused by the plastic strain, E. We expect T to equal zero for a crystal having a random arrangement of solute because the arrangement would remain random after plastic deformation. Likewise, we expect it to equal zero when the crystal is perfectly ordered because the motion of paired dislocations found in such crystals does not disrupt order. However, when short-range order exists or when long-range order is incomplete, plastic deformation will decrease the amount of order and additional work, proportional to the ordering energy, will be expended. Fisher' estimated T for crystals having short-range order by assuming an interaction energy between neighboring atoms and estimating the change in the number of unlike neighbors as a dislocation moved through the crystal. (His analysis was limited and several workers2"6 have since given more complete ones.) Fisher minimized the importance of a strengthening mechanism of this type for paired dislocations in a structure having long-range order. ~ottrell,' however, pointed out that T could be appreciable for ordered crystals having antiphase domains. He attributed the strengthening to the increase in surface energy of the domains as they were cut by paired dislocations. Ardley,' in his test of Cottrell's theory, found that r for Cu3Au crystals obeyed the equation: for 1 > t where 1 is the domain size, t is the domain wall thickness, and y is the surface energy of an antiphase boundary. His experiments represent the classic confirmation of the strengthening mechanism proposed by Cottrell. However, the assumptions involved in using Cottrell's theory are valid only for large domain size in CU~AU,~"~ i.e., when Eq. [2] reduces to: For small domains, ~linn~ has questioned Ardley's assumption that order was complete, and, indeed, Stoloff and ~avies" fpnd it incomplete until a size of approximately lOOA was reached. Even when the order within a domain is complete, it is not obvious how one determines the appropriate value for I in a structure where domains vary in size and are irregularly shaped. The purpose of this paper is to estimate T without restrictions upon the degree of order and domain shape. Our major assumption will be the use of a generalization of the model proposed by Bethe" (the Ising model) for the internal energy. This will in fact allow us to combine the theories for strengthening by short-range order and by antiphase domains into a single, general formalism. We will use the results to estimate the variation in strength of Cu3Au crystals with long-range order8 and the variation in flow stress of FeCo crystals with quench temperature.12'13 INTERNAL ENERGY For simplicity, we restrict our considerations to those binary solid solutions which can be described as an arrangement of atoms on a Bravais lattice. An atom site will be indexed by three numbers (PI, pz, p3) determined by the vector: from the origin fixed at atom (0, 0, 0) to the atom site where a', an, and a, are the lattice translation vectors. We write: For the energy of the crystal where pi(p) is the probability (either zero or one) of finding an atom of type i (i = 1, 2) at site (p), which is shorthand for (pl, pz, p3) and pj(p + r) is that for an atom of type j (j = 1, 2) at the site (p + r), which is shorthand for (pl + rl, The coupling parameter, resents the energy associated with the pair Pi(p), Pj(p + r). The crystal is assumed large enough so that surface effects can be neglected; therefore, trans-lational and inversion symmetry require the coupling parameters to obey the relations

Jan 1, 1969

By Alton B. Cook

Data are presented to show oil vaporization resulting from the passage of natural gas through a sand-packed tube saturated with synthetic reservoir oils. The Bureau of Mines performed 13 experiments, using reservoir oils synthesized with base crude oils of approximately 22°, 35°, and 45° API, at 100°, 175°, or 250° F and 1,100, 2,600, or 4,100 psia. It has been determined that the amount of vaporization is significant if proper conditions exist. These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil, and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized.

Jan 1, 1969

By G. W. Weems

The Bureau of Mines used the Burnett method and apparatus to determine the compressibility factors for helium and carbon dioxide mixtures at 0°, 10°, 20°, 23°, and 35° C and to pressures of 900 psia. Tables of compressibility factors and approximations of the virial coefficients are presented for seven binary mixtures as well as for helium and carbon dioxide. The results compare favorably with existing data.

Jan 1, 1969

By S. R. B. Cooke, S. W. Clark

Adsorption of calcium and magnesium by quartz was determined over a wide pH range using flame photometry for solution analysis. A parallelism was noted between calcium adsorption at alkaline pH and flotation of activated quartz by means of various fatty acid collectors. Abstraction of calcium from 100 ppm solutions increased above pH 10.5 until all of the calcium was removed at pH values between 12 and 12.5. Calcium was desorbed from the quartz over the pH range 12.5 to 13.0 and returned to the solution. Precipitation of magnesium hydroxide prevented measurement of magnesium adsorption above a pH of 9.9. A calcium adsorption isotherm determined at pH 9 matched measurements of barium adsorption by other investigators over the range where adsorption corresponded to the equation of a Freundlich adsorption isotherm. In accordance with the Gouy-Chapman theory for adsorption in the diffuse layer, adsorption of the divalent cations under these conditions was four times the adsorption of monovalent sodium. Activation of quartz by multivalent metal cations in flotation using anionic collectors has been studied by many investigators. The occurrence of activator cations in the water of flotation mills makes depression of silaceous gangue very difficult. Alternatively, in some flotation systems it is practical to cause activation of quartz so that it is floated from the desirable mineral values. The present study was initiated to investigate the activation of quartz by measuring adsorption of calcium and magnesium ions as a function of solution pH. Early empirical tests showed that quartz would be activated to flotation using anionic collectors if any of a number of divalent or trivalent metallic cations were present in the pulp.1*2 Subsequent studies by Clemmer,3 Cooke and Digre,4 Cooke,5 Schuhmann and Prakash,6 and Cooke, Iwasaki, and Choi,7-8 showed that flotation depended strongly upon the alkalinity of the flotation pulp, the concentration of the activating cations, and the chain length and structure of the organic collectors used. The concept of the electrical double layer has been applied to the case of the quartz-aqueous solution interface by Gaudin and Fuerstenau,9-10 and by de Bruyn 11 to explain the activation of quartz by multivalent metal cations. Studies of the surface of quartz by Gaudin and Fuerstenau9,10,12 and by Li " using the streaming potential technique contributed much information on the electro kinetic condition of the surface of quartz in the presence of various organic and inorganic ions. Measurement of adsorption of ac-

Jan 1, 1969

By N. G. W., Cook

When an excavation is made underground the original rock stresses are removed from the surfaces of the excavation. These surfaces converge to partially close the excavation and the superincumbent rock mass moves down towards the excavation. If the convergence of the surfaces of the excavation were controlled, energy generated by their motion against the controlling forces could be extracted. Since the total forces in the rock mass are not significantly affected by the excavation, stress concentrations arise around the excavation, which compensate exactly for those stresses no longer transmitted through the excavation. These phenomena give rise to two general principles which provide the basis for analyzing the effects of making any underground excavation. The first of these is that the total force resulting from the stresses across any plane in the rock, including any plane through the excavation, must be the same before and after the excavation is made. The second of these is that energy must necessarily be released as a result of making an underground excavation.

Jan 1, 1969

By L. K. Weaver

Bureau of Mines investigated the progressive impact that petroleum (crude oil and condensate) operations in the Gulf of Mexico have had on onshore operations and the expected effect of increasing activities in this area on future petroleum supplies from domestic sources. The data analyzed include capital expenditures, number of wells drilled, success ratio for exploratory wells, daily production per completion, annual producing rates, and oil reserves. The report compares offshore and onshore data and ascertains trends in petroleum industry operations. Observed data and trends indicate that in the near future Gulf of Mexico development and production will continue to increase relative to total U.S. petroleum activity. By 1975 annual oil and condensate production from the Gulf of Mexico is expected to be in the range of 750 million bbl to 1,150 million bbl, and account for approximately 20 to 30 pct of the estimated total domestic production.

Jan 1, 1969

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525'C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine' and LOW.' Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468'C, hold 72

Jan 1, 1969