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By R. M. Goldhoff, J. W. Spretnak, R. Speiser

IT has been observed by Grange and Garvey' that the homogenization of boron-treated steels could lead to complete elimination of the hardenability effect caused by boron. The experimental conditions leading to this conclusion involved the heating of steel specimens with and without boron at 2350°F for 24 hr. To prevent oxidation and decarburization, the specimens were encapsulated under vacuum in silica tubes. This observation of permanent deterioration of boron effect was noted in both a 0.63 pct plain carbon steel and a 0.25 pct C low alloy steel, both of which had been treated with ferroboron and homogenized at 2350°F for 24 hr. In another series of boron-treated steels which had been homogenized for shorter times, the effect was to reduce, but not completely eliminate, the boron effect. Under these circumstances, it was presumed that longer heating times would cause permanent deterioration of the boron effect in this series of steels also. Since the characteristic grain boundary constituent could not be formed in any of these steels after homogenization, it was concluded that possibly boron was being converted into an ineffective form through chemical combination resulting from prolonged heating at high temperatures. Assuming the validity of this observation, a series of experiments to establish the relationship between temperature of homogenization and kinetics of deterioration was contemplated. Initially an attempt was made to reproduce the results just described. For this purpose commercial lots of AISI 8640 and AISI 86B40 steels were used. The analyses of these steels appear in Table I. Hardenability evaluation was on the basis of the hardness of normalized sections. Grange and Garvey' pointed out that these steels are air hardening to some extent and such a technique can be used. For these tests the specimens were held for 20 min in a salt bath at 1600°F and then cooled in still air. Several evacuated silica capsules containing pairs of the test steels were made up and heated for 24 hr at 2350°F. A number of failures occurred among these capsules, but evaluation of the specimens successfully treated indicated a complete deterioration of the boron effect. However, examination of the surface of the treated specimens showed that some reaction, probably with the silica tube, had taken place, since none of the specimens was bright. One further test was made at 2350°F for 12 hr, using a pair of specimens wrapped in tantalum foil prior to encapsulation. These specimens appeared bright after treatment, and their hardenability evaluation showed that no deterioration had taken place. Since these steels are extremely sensitive to de-boronization at high temperatures and particularly at long times of holding, the experimental observations raised some doubt as to the real occurrence of the permanent deterioration effect. To resolve this question an experiment was undertaken in which the high temperature portion of the treatment was completed in vacuum. For this purpose a molybdenum wound resistance furnace capable of maintaining good vacuum was used. All the pertinent accessories to this furnace were machined from molybdenum stock in order to withstand the high temperature involved in the experiment. With this equipment a temperature of 2400 °F was obtained and held under a pressure of 5x10-" mm Hg for 24 hr. A specimen of each of the two test steels was suspended in the furnace and both were heated simultaneously. Temperature was measured with a standardized Pt—Pt-13 pct Rh thermocouple, whose millivoltage at 2400°F was extrapolated from the standardization equation, good up to 2200°F. The complete evaluation of these specimens is shown in Table 11. The hardness values attained by each steel after normalizing, both before and after the prolonged high temperature treatment, remain the same. A microscopic study of the decomposition products present in the microstructures of specimens at various points in the heat treatment correlated with the hardness values observed. It seems that no permanent loss of boron hardenability effect occurs, at least in these Grainal-treated steels, when deboronization is circumvented. Acknowledgments This work was conducted under the sponsorship of the Aeronautical Research Laboratory, Wright Air Development Center, under Contract No. AF 18(600)-94, and their support and permission to publish is gratefully acknowledged. A note of thanks is also extended to the Republic Steel Corp. for supplying the materials used in the work. References ' R. A. Grange and T. M. Garvey: Factors Affecting the Harden-ability of Boron Treated Steels. Tro.ns. ASM, 1946, vol. 37, p. 136.

Jan 1, 1957

By H. T. Kennedy, S. G. Dardaganian, J. L. Clanton

This paper presents equilibrium ratios measured on oil and gas samples taken from the Kelly-Snyder field at the reservoir temperature of 128°F. From these data smoothed curves were constructed for the reservoir fluid up to the bubble-point, 1,874 psia. A material balance calculation, based on the use of equilibrium ratios instead of the usual solubility and shrinkage meayr~rements is made on the field and compared to the con\.entional method. DETERMINATION OF EQUILIBRIUM RATIOS The equilibrium ratios, or K values were obtained by recombining separator samples of oil and gas taken when the reservoir was above its bubble point, and thus represented the reservoir fluid before any change had occurred due to the evolution of gas. The well sampled had a gas-oil ratio of 617 cu ft of high pressure sepalator gas per barrel of separator oil. and a bottom-hole temperature of 128°F. Samples were brought to equilibrium by agitating for 24 hours in a thermostat, maintained at the proper temperature within 0.2ºF, mercury being added when necessary to maintain the pressure constant. Samples of oil and gas were then taken by constant pressure displacement, and analyzed by low temperature frac-tionation. Equilibrium ratios were determined at 128°F and 500, 800, 1,000 and 1,400 psig. At the latter pressure, there were indications that the gas samples were contaminated with small quantities of oil, and only data taken at the first three pressures were included in Fig. I. This figure has been extended to higher and lower pressures by the use of the Fluor charts for 3,000 psi convergence pressure, on which the experimental points fit well. MATERIAL BALANCE EQUATIONS The possible errors involved in conventional material balance equations have been analyzed by Muskat1. Where the errors occur in field measurements, or in obtaining effective averages from variables such as gas-oil ratio and pressure, they will evidently be involved in any attempt to estimate the content of the reservoir. On the other hand, substantial errors may be introduced in conventional material balance calculations by: (1) the neglect of the amount of oil dissolved in gas at high pressures and temperatures in the reservoir, but which condenses under separator conditions; (2) the assumption that the separation of oil and gas in the reservoir may be duplicated by a differential liberation in the

By H. O. Hofman

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, FeS. They arrived at this inference from the observed fact that a matte containing Cu,S, 90.4, and FcS, 9.6 per cent. (or, in round figures, Cu2S, 90, and FeS, 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 five 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 ferrous sulphide-cuprous sulphide series, 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, 1908

By AIME AIME

DATA in this report enable comparisons to be made within the bituminous coal industry and comparison as well with copper and steel in respect to capacity and overdevelopment. The conclusions reached from the data will tend to correct numerous current misconceptions. The data have been prepared by various members of the Coal and Coke Committee of the A.I.M.E., from the most authentic sources avail¬able, and cover the period 1913-1924 wherever possible. CAPACITY AND OVERDEVELOPMENT Table 1 shows statistics for the industry, mainly from the U. S. Geological Survey sources, but partly from the U. S. Coal Commission reports. The mine capacity with equipment and labor as of given date is calculated for each state by obtaining the total man days worked as reported by the operators, and dividing this figure into the total production, getting the production per man day; this figure times the number of men employed times 308 (a theoretical full working year) equals estimated full-time capacity. Two major objections are made to this method-one that the total number of men employed is used instead of the number actually working, and the other that the number of days used only deducts Sundays and five holidays. Covering the first, the same number of men is used in estimating capacity as is used in actual production, and this condition exists at all times. Regarding the second, the opinion is general among coal men that 280 days is as great a figure as should be used, as it is practically impossible to keep any mine working full time at the same daily rate as when it is working part time. The capacity, as estimated on this basis, is much more nearly the true capacity, although even with present railroad efficiency this amount of coal could not be moved.

Jan 1, 1926

By M. Mortada

Nonsteady-state flow of slightly compressible liquids in porous media of non-uniform properties has been the subject of a number of recent studies. Most of these studies considered one-dimensional flow in systems with cylindrical geometry and with the properties of the porous medium varying with radial distance only. A. Houpeurt' studied the problem in its general form by examining the solutions of the differential equation, In Eq. 1, the permeability k and the porosity + are arbitrary functions of radial distance. Houpeurt concluded that, except for special forms of the functions k and the problem is not well suited for mathematical treatment, but lends itself to high-speed digital computation. Carslaw and Jaeger' discussed the solution of Eq. 1 for the case in which the permeability varies as a power of the radial distance. P. Albert3 studied analytically the pseudo steady-state solutions in systems of finite radial extent and non-uniform properties. He also obtained some numerical solutions for nonsteady-state flow using a high-speed computer. William Hurst4 examined the interference pressure drop due to a point sink located in an infinite system consisting of two permeability regions in series. In this case, the permeability changed at a radial distance r from the point sink. INTERFERENCE BETWEEN OIL FIELDS IN A NON-UNIFORM AQUIFER The interference pressure drop for oil fields located in an extensive aquifer of uniform properties is discussed in a number of places in the literature. This work considers the interference pressure drop for oil fields located in a non-uniform extensive aquifer comprising two regions of different properties as shown in Fig. 1. Region I of the aquifer extends from which is the radius of Oil Field A, to ar,,, where a>1. It has permeability k,, porosity +, and effective compressibility c,. Oil Field B is located in Region II which extends from ar, to infinity and has different properties from those of Region I, but the same formation thickness h. Region II has permeability k2, porosity and effective compressibility c2. The choice of this type of aquifer should not imply that it is of frequent occurrence. It is chosen primarily to illustrate the effects of non-uniform aquifer properties on oilfield interference. It is of interest to point out that a non-uniform radial aquifer in which both the permeability and the porosity are inversely proportional to the radial distance can be treated in a manner similar to a linear aquifer of uniform properties. The situation where only the permeability varies as the inverse of the radial distance is also amenable to analytical treatment. Both aquifers behave quite differently from a radial aquifer with uniform properties so far as the water influx and the interference pressure drop are concerned. METHOD OF SOLUTION The expression for the interference pressure drop in Oil Field B due to a constant rate of water influx in Oil Field A is developed in the Appendix. This is accomplished by the simultaneous solution of two partial differential equations describing the pressure in Regions I and 11. The two differential equations are solved subject to the following conditions: (1) at r,, the pressure gradient is constant; (2) at ar the pressure and

By C. E. Van Orstrand

An intrusive body is a mass of igneous rock that has migrated upward, presumably from great depths. Great variations in form, composition and depth of burial occur. It is not proposed in this paper to go into all of the details of the problem. Instead, it mill be assumed here that the intrusive has the form and characteristics represented in Fig. I. According to W. 11. Emmons minerals are not deposited in appreciable quantities below the "dead line." Important amounts of ores of virtually all metals may be found around summit cupolas, but only gold, copper and zinc (in limited quantities) are usually associated with trough cupolas. Most students of ore deposits agree that temperature changes are largely instrumental in precipitating many ores in the "hood" and that the difference in temperature between the intrusive and that of the country rock may be the chief factor in determining the mineralogy of a deposit. A problem then of some interest is to correlate the principal physical features of the intrusive with the phenomena of heat conduction as evidenced by the cooling curves and the isothermal surfaces. Mathematical Theory In order to show the possible application of heat conduction to the interpretation of the processes of metalliferous deposition associated with intrusives, it will be as- sumed that the intrusive is a large par-allelopiped of dimensions, 2l, 2m, 2n. The equation that represents the flow of heat from the parallelopiped into country rock (v = o, 1 = o), which has the same thermal properties as the intrusive, is2,3 l-x v I FT 2 [2 2 — l-x m — y — m — y n — z In this equation, the origin, x = o, y = o, z = o, is at the center of the parallelopiped. v = temperature at point x, y, z, time 1. v, = initial temperature throughout the intrusive, 1 = o. k = coefficient of thermal diffusivity. a, ß, y are variables of integration. Put n = m in Eq. I, and we have v I [2/5 [2I-x 2 — l-x m — y 2 2 2 kt 2 20xt e-a2da ebrdß

Jan 1, 1946

By C. E. Van Orstrand

An intrusive body is a mass of igneous rock that has migrated upward, presumably from great depths. Great variations in form, composition and depth of burial occur. It is not proposed in this paper to go into all of the details of the problem. Instead, it mill be assumed here that the intrusive has the form and characteristics represented in Fig. I. According to W. 11. Emmons minerals are not deposited in appreciable quantities below the "dead line." Important amounts of ores of virtually all metals may be found around summit cupolas, but only gold, copper and zinc (in limited quantities) are usually associated with trough cupolas. Most students of ore deposits agree that temperature changes are largely instrumental in precipitating many ores in the "hood" and that the difference in temperature between the intrusive and that of the country rock may be the chief factor in determining the mineralogy of a deposit. A problem then of some interest is to correlate the principal physical features of the intrusive with the phenomena of heat conduction as evidenced by the cooling curves and the isothermal surfaces. Mathematical Theory In order to show the possible application of heat conduction to the interpretation of the processes of metalliferous deposition associated with intrusives, it will be as- sumed that the intrusive is a large par-allelopiped of dimensions, 2l, 2m, 2n. The equation that represents the flow of heat from the parallelopiped into country rock (v = o, 1 = o), which has the same thermal properties as the intrusive, is2,3 l-x v I FT 2 [2 2 — l-x m — y — m — y n — z In this equation, the origin, x = o, y = o, z = o, is at the center of the parallelopiped. v = temperature at point x, y, z, time 1. v, = initial temperature throughout the intrusive, 1 = o. k = coefficient of thermal diffusivity. a, ß, y are variables of integration. Put n = m in Eq. I, and we have v I [2/5 [2I-x 2 — l-x m — y 2 2 2 kt 2 20xt e-a2da ebrdß

Jan 1, 1946

By W. A. Krivsky, R. Schuhmann

Jan 1, 1962

By A. T. Miesch, L. B. Riley

Distribution of minor elements in sandstone-type uranium deposits of the Colorado Plateau is being studied by the USGS on behalf of the A EC. A primary objective has been to provide basic data which could be useful in geo-chemical exploration for new deposits. The basic statistical measures — similar to those used in sedimentary petrology—are described. The underlying principle is that the frequency distributions fit or approach the log-normal form. Since 1952 the U. S. Geological Survey on behalf of the U. S. Atomic Energy Commission has conducted a study of the distribution of minor elements in sands tone-type uranium deposits of the Colorado Plateau. A primary objective in this study has been to provide basic data which could be useful in geo-chemical exploration for new deposits. Among the basic data considered important are estimates of the abundance and habit of each element in the ore and in the host rocks. It has been found that a few basic statistical techniques, and variations of these techniques, are useful in this type of study. Some of the basic techniques have been used to advantage by researchers in geochemistry and in other fields of geology, especially sedimentary petrology; others have been used to only a limited extent. Among the latter is the linear correlation coefficient, which has proved useful in assessing the element associations in a particular rock type without analysing individual mineral separates. In computing the basic statistical measures a scale has been used which is, in some ways, similar to the phi ($) scale used by sedimentary petrol-ogists in grain-size studies.' FREQUENCY DISTRIBUTIONS It has been recognized for some time that the results of analyses for a given minor element in a suite of samples of rocks or ores yield frequency distribution curves which are approximately normal when the curves are plotted on logarithmic or geometric scales. In other words, the analytical results give an approximate lognormal frequency distribution. A classical example is given by D. G. Krige2 in the study of the distribution of gold values from a mine on the Witwatersrand. Another example is shown in Fig. 1, the distribution of barium concentrations in samples of uranium ore from the Chinle formation. The geochemical data are analogous to grain-size data gathered by the sedimentary petrologist. Both types of data, after simple logarithmic transformations, may be treated by conventional statistical methods based on the normal distribution. This is not to say that other types of transformations may not serve equally well or better for particular element distributions.3 Spectrographers and other analysts are quite aware of the dependence of their precision on the concentration of the element present.4 For example, in the part per million range the variation may

Jan 1, 1961

A New Ingersoll-Rand Turbo Blower The Ingersoll-Rand Co. has added to its Turbo Compressors and Blowers a low-pressure machine t o handle volumes from 3,000 to 35,000 cu. ft. per minute at from 1-2 ½ lb. These are particularly adapted to such service as foundry cupola blowing, atomizing oil for oil burners, supplying blast to heating and annealing furnaces of various kinds, blowing air for water-gas generators, pneumatic conveying and ventilating. They are of the single stage, double flow type and are furnished either electric motor, steam turbine or water wheel driven.

Jan 6, 1916

By C. G. Wilson

DURING the course of some experiments on the plastic deformation of gallium a standard stereo-graphic projection was prepared with (001) at the center and it was felt that this might be useful to others working with single crystals of gallium. The stereogram, given in Fig. 1, was made using the following crystallographic data (Bradley, 1935):

Jan 1, 1962

By Daniel T. Brian, O&apos

Exploration targets and results in the mining industry are commonly summarized in terms of tonnage and grade. Business appraisals require, as additional information, the expected profit or loss implied by the physical summay. The early incorporation of knowledge gained through financial analysis computations can provide a means for economically resolving many common exploration and development problems. Examples of such applications from the activities of exploration planning, reconnaissance, land acquisition, and development planning are presented. While prospecting for mineral deposits, geologists are frequently asked what they hope to find or have found. The response is usually descriptive, such as "50 million tons of 1% copper," and the economic implications are deferred until a capital investment decision is required. At that time, a financial analysis integrating the four analysis components is completed. These components are: 1) Tonnage and Average grade above cutoff grade 2) Capital and operating costs 3) Product value 4) Appropriate profit or loss accounting Close examination of these components reveals that there is no intrinsic reason for avoiding financial analyses at earlier stages in exploration, as long as the uncertainty of the estimate is realized. Tonnage and average grades are commonly estimated at early stages in exploration. For this component, the appropriate cutoff is the major uncertainty. Capital and operating costs are difficult to estimate before detailed quantitative information is available, but estimates useful for the types of applications pertinent to earlier exploration stages are possible. Product value estimates may or may not be difficult, depending on the pricing structure of the particular commodity. A simplified accounting procedure usually may be adopted without introducing any significant loss of validity. This paper describe some of the financial analysis applications which are pertinent during mineral exploration and deposit development. These applications lend additional insight during exploration planning, land acquisition, physical exploration, and development. The examples are oriented toward a hypothetical management investment policy which is based on a single criterion, a minimum 15% discounted cash flow rate of return. In reality, managements use multiple criteria. This simplification is convenient for purposes of presentation and does not invalidate the examples. Computers are useful, but not a requirement, for the applications described. The use of computers provides the results on a more timely basis at costs lower than equivalent manual computations. UNDERLYING PRINCIPLES AND ANALYSIS METHODS Data estimates are subject to uncertainty. The analyst may choose to assess this uncertainty by using one of two principles. Each principle has some advantages. The principle most commonly employed is "assumed certainty." Each financial analysis is based on one set of selected data, which may represent the average estimates, minimum expected conditions, etc. The critical data is identified by making successive calculations, varying the values used. Such studies, called sensitivity analyses, isolate the economic effect of various uncertainties, and guide the allocation of future efforts toward improving the overall accuracy of the analysis. A second principle, "assumed risk," examines the interactive effect of the current uncertainties by qualitatively assigning probability distributions to each data element. These probability distributions indicate the currently appraised chance that a given numerical value will prove to be true. The corresponding procedure, risk analysis, consists of processing many individual financial analyses, each analysis being based on randomly selected numerical values from the probabilistic distributions. The result is a numerical presentation of the uncertainty, but care must be exercised in the interpretation of results. The advantage of this procedure is the direct measurement of economic uncertainty caused by the interaction of uncertain estimates. Kennecott Copper Corp. has developed computer systems for accomplishing sensitivity and risk analyses.

Jan 1, 1970

By Carroll Forbes

INTRODUCTION MANY different shapes of drill bits are in use with hammer drills, but little definite information is available whereby to judge which one of these shapes is the best. The following investigation was undertaken in order to determine what effect, if any, the shape of the cutting edge has on the cutting speed and wearing qualities of drill bits. The bits tested were those in common use, namely, the 4-point or cross bit, the 6-point bit, the Z bit and the "Carr" bit. The rock in which the tests were made was the red granite from southeast Missouri. It is a coarse crystalline granite containing an unusually large amount of quartz and is extremely hard, and on account of its uniform texture is admirably adapted to this work. While tests in other rocks might show somewhat different results, nevertheless it is the opinion of the authors that the relative cutting quality inherent in the shape of the bits would be the same in all rocks. Other qualities, such as mudding freely, freedom from fitchering, etc., might make one bit more desirable than another in softer rocks. DESCRIPTION OF BITS TESTED The 4-point bits were the usual shaped bits commonly made on the Leyner sharpener with 14° taper on the wings and a 90° angle between cutting edges. Some tests were run at 85 lb. pressure with a 4-point bit made with a 5° taper on the wings. This was made by using the Carr bit die. The 6-point bits were the usual shaped hits made on, the Leyner sharpener. The Carr bits were made with a 5° taper and an angle of 100° between cutting edges.

Jan 8, 1917

By M. F. Trice

PYROPHYLLITE is a hydrous aluminum silicate (A12Si4010(OH)2)1 that occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mobs' scale.1 The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey,2 contain pyro-phyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, "are noticed in but small quantities to the extent they might occur as accessory constitu-ents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 percent and the alumina from 22 to 33 percent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent.

Jan 1, 1940

By K. C. Mills, E. T. Turkdogan

A number of investigators1 6 have noted the presence of a liquid miscibility gap in the Fe-Sn binary system. However, the first attempt to measure the

Jan 1, 1964

By Martin G. Castro, Renato G. Bautista, Morton Smutz

During the last 25 years, multistage mixer-settlers have been used extensively for liquid ion exchange work. The mixer-settler has the advantage of being a compact device in which a large number of stages can be assembled in a relatively small area. They are particularly advantageous for the separation of rare earths. Most of the adjacent rare earths have separation factors which are near one, which means that a large number of stages are needed to produce a good separation. When two elements (m, n) are extracted simultaneously, the separation factor (ßm, n) is defined as: [ ] where Ym, Yn are the molarities of the respective elements in the organic phase and Xm, Xn, are their molarities in the aqueous phase at equilibrium. The industrial consumption of rare earth oxides rose to over 6800 tons in 1968, an increase of 33% over 1967.1 The increased production and demand for rare earth and lanthanum chlorides for petroleum cracking catalysts was one of the principal factors in this increased consumption of rare earths. In 1968 approximately 59% of the rare earth oxides produced were used for gasoline cracking catalysts in the form of rare earth and lanthanum chlorides. There was also an increase in the sales of lanthanum oxides for use in optical lenses and in fiber optics. The future looks good for the rare earth industry. The rare earths can be expected to be used in many new products which are being developed. Until the late 1950's tributyl phosphate (TBP) was the principal solvent used in rare earth liquid ion exchange. In 1957 Peppard3 reported the use of di (2-ethyl-hexyl) phosphoric acid (D2EHPA) as a solvent for separating the rare earths. Rare earth separation factors of up to 2.5 were obtained in nitrate and chloride systems while the maximum separation factor using the

Jan 1, 1972

By H. J. Modi, D. W. Fuerstenau

pH effectively regulates the flotation of corundum through its control of the surface charge. Since collector ions function as counter ions in the double layer, the collector must be anionic when corundum is positively charged and cationic when it is negatively charged. Even a long-chained xanthate will float positively charged corundum. Association of the hydrocarbon chains of the adsorbed collector ions gives rise to increased adsorption and increased rate of flotation. Because of this phenomenon, neutral organic molecules aid flotation although the unionized collector cannot promote flotation independently. Na2SO4 was found to depress the flotation of corundum with animic collectors through ionic competition whereas the same salt activates corundum for flotation with cationic collectors. A close connection between ion association, electrokinetic behavior, and floatability is suggested. As part of the increasing interest in the physical chemistry of flotation, strong experimental evidence has been obtained which indicates that organic ions are adsorbed as counter ions by non-metallic oxide minerals mainly because of the electrical forces which exist at interfaces(1-3). Thus flotation of such minerals without activation should then be appreciable only when the mineral and the collector are oppositely charged. Since only limited work has been reported on the effect of surface charge upon flotation behavior(3) this general hypothesis on the flotation of insoluble oxide minerals has not been tested thoroughly. Investigating the flotation of a mineral for which extensive electrokinetic data exist yields a way to test this hypothesis more extensively. The electrokinetic behavior of corundum in solutions containing both organic and inorganic electrolytes has been studied quite thoroughly' Electro-kinetic measurements have shown that in the case of corundum, simply by controlling pH the solid surface can be charged either positively or negatively. For this reason corundum was chosen for study. The object of this paper is to present a study of the flotation of corundum and to explain the results in the light of our knowledge of adsorption mechanisms gained from streaming potential investigations. This paper is concerned mainly with the effect of surface charge on flotation with anionic and cationic collectors, but in addition such flotation phenomena as collector hydrolysis, Van der Waals attraction between hydrocarbon chains, ionic competition, and activation are discussed. While the present paper is confined to a reporting of the data obtained and some of the more immediate conclusions, it will be seen that the results, in combination with those on other systems, do promise a

Jan 1, 1961

By H. E. Lee, D. Ingvoldstad

AT Bunker Hill the original charge storage and preparation system was installed in 1917 to accommodate lead-silver gravity mill products. Only minor tonnages of wet fines such as vanner and flotation concentrates were received. Charge flux and diluent requirements were provided by an ample supply of siderite middlings and coarse lime-rock. While oversize material was crushed through %-in., the use of roll crushers in series resulted in a more or less granular, free-running charge of adequate porosity. Under such conditions, receipts could be proportioned directly from receiving bins, and suitable blending was obtained by passing the resultant layered composite through a small Stedman disintegrator. This elementary system served well for production and smelting of an extremely lead-rich sinter, in the low column blast furnace. Here sinter physical quality is less critical, and appreciable quantities of raw flux and oxidized ore may be charged directly to the blast furnace without seriously impairing furnace capacity. Prior to 1938 the relative proportions of zinc receipts were low and extraneous flux requirements at a minimum. However, subsequent war-inflated zinc demands brought marked increase in fine concentrate and slimy zinc leach residue receipts and an abrupt introduction to smelting a more refractory zinciferous charge. The higher temperature demands of the more refractory zinciferous charge required a higher smelting column and the higher column, in turn, rendered the blast furnace less receptive to improperly prepared feed. Inadequate presinter processing facilities prevented the production of acceptable sinter, and blast furnace production declined to 50 pct of former capacity. In view of a prevailing contention among lead metallurgists as to the deleterious action of high zinc slag on blast furnace capacity, it was natural to overstress this factor and to concentrate on possible changes in furnace design. Another interpretation was that primary correction should be sought through expanded sintering facilities. This divergence of opinion, together with the extreme material shortages of the 1940's, delayed corrective

Jan 1, 1957

Jan 1, 1967

By T. C. M. Pillay, John Chipman

The Si-0 equilibrium in liquid iron was investigated in some detail by Gokcen and Chipman1 who reported equilibrium constants of the following reactions: In each case the thermodynamic equilibrium constant K was obtained by extrapolating K' to infinite dilution. Their results on reaction [I] were consistent with those of earlier observers, and there seems to be little doubt as to the approximate validity of the equilibrium product determined. On the other hand, the results on reactions [2] and [3] indicated unusual curvilinear relationships between the activity coefficients of silicon and of oxygen and the silicon concentration. Since a linear relation is observed in all other similar instances, it was concluded that some source of error had affected the gas-metal equilibrium relationships. Recently the authors undertook a restudy of these equilibria with the view especially to establishing the equilibrium constant of reaction [2]. Their experiments, however, were discontinued before a tbroughly satisfactory answer had been obtained and consequently have remained unpublished until the present time. Quite recently Matoba, Gunji, and Kuwana2 published the results of a very thorough study of these equilibria. It is the purpose of the present note to Compare these three sets of experimental data, a comparison which leads to Confirmation of the results of Matoba and coworkers. The experimental arrangements described by Dutilloy and Chipman were employed. A controlled mixture of Hz, H,0, and argon was led into the induction furnace over the surface of the Fe-Si melt contained in a silica crucible. On account of the slow approach to equilibrium, runs were continued for at least 8 hr and, in some cases, as much as 12 hr. Samples were taken by means of silica tubes at the start and during the final 4-hr period of each run. Out of twelve runs only seven appeared to have approached equilibrium with sufficient certainty to be reported here. The results of these experiments, all at 1600°c, are shown by the triangles in Fig. 1. Equilibrium was approached from both oxidizing and reducing conditions and the direction of approach is indicated by the shape of the triangle. Attempts to extend the study to higher silicon concentrations were unsuccessful on account of the transfer of silica from the metal bath to the upper portions of the crucible by means of a silicon-monoxide mechanism. Matoba, Gunji, and Kuwana used similar methods and approached equilibrium from both sides. Their results at three temperatures are shown by the solid lines of Fig. 1. A line corresponding to 1600 deg is interpolated from their equations and is shown by the dotted line. The results of Gokcen and Chipman at 1600 deg in the range 0.02 to 2.0 pct Si are also shown. At concentrations up to about 0.6 pct Si, these investigators approached equilibrium from both directions, and their results in this range appear to be trustworthy. Above 1 pct Si, however, all of their experiments involved oxidation only, as shown by a decrease in the silicon content of the bath. It now seems certain that they failed to reach equilibrium at these higher silicon concentrations and that the curvilinear relation shown by their results is incorrect. It is evident that their results in the lower silicon range are in good agreement with those of Matoba and coworkers. In fact, a straight line drawn through their results would parallel the dotted line and would differ from it by only 0.05 in log K. The new data also lie close to that line. It may thus be concluded that the three sets of data are in good agreement and that the equations proposed by Matoba and coworkers for reaction [2] are satisfactory . They take the limiting value of log K', at 0 pct Si as log K ,. The slope of each line gives the value

Jan 1, 1962