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By W. J. Carlson, I. lwasaki

Manganese and silica in nonmagnetic tailings from the direct reduction-magnetic separation step were so closely associated that no physical concentration methods were effective. Dilute sulfuric acid dissolved manganese and iron rapidly; manganese in the form of silicates was virtually insoluble in sulfuric acid solutions, thereby governing the maximum extraction attained by leaching. Autoclave leaching at elevated temperatures and at high oxygen pressures reduced the iron extraction to less than one tenth without affecting the manganese extraction. There was an indication that autoclaving solubilized the manganese silicates appreciably. Elimination of iron from leach solutions was carried out by aerating the solution in the pH range of 6.5-7; a platinum-calomel electrode pair provided a reliable indicator for the end point of iron removal. The purified leach solutions were free of interfering impurities for the recovery of manganese as metal, dioxide, or carbonate. Manganiferous iron ores of the Cuyuna Range, Minn., are too low in iron content to be directly useful as iron ores, and too low in manganese content to be termed manganese ores. Common methods of physical beneficiation such as gravity concentration and flotation have not been successful in upgrading this material. The R-N process, when applied to manganiferous iron ores,1'2 produces sponge iron by direct reduction of iron oxides, while leaving manganese as manganous oxide. From fine grinding and magnetic separation of the reduced ore, a tailing is produced which is relatively rich in manganese and low in iron content. The nonmagnetic tailing can readily be leached with acids and then further processed to recover manganese in various forms. In this way, two processes, neither of which would be an economic solution to the Cuyuna ore problem by itself, may be combined to produce two marketable products, thereby rendering the over-all process economically more attractive. This article reports on the results of a leaching study on the nonmagnetic tailings, both in a batch agitation vessel and in an autoclave; on the problems involved in the purification of leach liquors by aeration; and on the recovery techniques used to produce manganese metal by electrolysis, manganese dioxide either by electrolysis or by autoclaving, and

Jan 1, 1968

By M. E. Lombardi

ThE Coalinga oil field is located on the west side of the San Joaquin Valley, California. The structure is in general a monocline, the edges of the oil horizon resting on the foot hills and dipping gently toward the east. One prominent anticline occurs plunging southeast. The earlier drilling was done in the foot hills comparatively near the outcrop and the wells were shallow. The sands were followed eastward and, in the case of the anticline, along the plunge, the wells becoming deeper and deeper until the depth of 4,000 ft. was reached and passed. There is nothing to show that the oil will not be found in quantity at still greater depth. In fact, some of the best producers have tapped the sand at close to 4,000 ft. The recovery of oil still farther to the east, and therefore at greater depth, seems to be mainly a question of drilling. In this territory the formations drilled through are chiefly sands and shales; they will not "stand up" in an open drilling hole; the casing has to be carried close to the bit, and it is always difficult to keep the casing free for any considerable distance. Ability to carry casing of comparatively large diameter without conductor pipes for distances of 2,000 or 3,000 ft. or over is desirable in such territory chiefly for two reasons. It makes it possible to enter the oil sand with a pipe of ample diameter; it eliminates one or more expensive strings of casing which act only as conductors for the water string, and furthermore, in territory where waters are encountered which corrode steel rapidly, it makes possible the construction of a rust- and alkali-resisting water string. It is always desirable to shut off top waters, which may lie within 100 ft. or less of the oil sand, with 10-in. pipe. Where the depth is so great that a practical weight of 10-in. pipe will not withstand the probable collapsing pressures, 81/4 in. at least is desirable. About the limit of rotary drilling to date in California seems to be the setting of the 10-in. string at 3,200 ft., although the rapid advance in rotary work during the past year seems to indicate that this depth may soon be increased. It is my purpose now, however, to treat only of cable-tool drilling. The problem is to reach a depth of 4,000 ft. or more with a string of

Jan 1, 1915

By Robert W. Hunt

HAVING devoted considerable time to the investigation of the Clapp-Griffiths converter and the metal produced in it, it may perhaps be of interest to the Institute to learn the conclusions which I have formed. Of course, it is well known that the stationary converter of small size is the very oldest type of vessel used in the pneumatic process. Hence it will be only necessary to call your attention to the points which are special features of the Clapp-Griffiths. This converter has a slag tap-hole, situated at such a height in relation to the metal under treatment that, when the cinder is formed and boils up as the blow progresses, it can run off and thus be removed from contact with the iron, and will also be out of the way when the decarbonized metal is tapped into the casting ladle and the manganiferous alloy added. The manner of shutting off the blast, when the process is completed and the metal is being tapped, is another distinctive feature. The tuyeres are situated around the sides of the vessel, and enter the interior some little distance above the bottom; they are provided with plugs through the centers of which there are small openings. When the blow is completed, these plugs are forced forward into the outer orifices of the tuyeres, thus shutting off the blast, excepting the small quantity' entering through the passages named. While this is sufficient to keep the metal from running into the tuyeres, it reduces to the minimum the action of the blast while the metal is being tapped. Of course, this is of great importance, as in an ordinary stationary converter any delay in getting open the tap-hole means overblowing, and even while the first part of the charge is running out the oxidation is in frill force. Duplicate or movable bottoms are used, thus more than doubling the possible output of the plant. The pressure of' blast is quite light, never ex-

Jan 1, 1885

By N. E. Grosvenor

Several methods have been proposed for determining the tensile strength of rock. These have been tried out over the past several years, but the results have been erratic and of doubtful value. The tensile strength of rock is its weakest property, and this property apparently enters into all failure phenomena, whether underground or on the slope of an open pit. Therefore, it is essential that detailed quantitative information is known about the tensile strength of rock if the design engineer is going to select the proper pit slope, pit orientation, or orientation of underground workings so as to give the most economical and safest mining condition. This quantitative information may be used to orient the pit in such a manner as to allow steep slopes along two sides. This information possibly may be used to orient the direction of either underground workings or open pits so as to decrease powder consumption and to increase blasting efficiency. Hence it is of prime importance that a method of determining accurately the tensile strength of rocks be developed. The U. S. Bureau of Mines states' that no standard methods have been proposed by the ASTM for testing the tensile strength of rock. The method described in the Bureau publication is said by them to be unsatisfactory. A similar test that has been used in our laboratory in place of the USBM test is shown in Figs. 1 and 2. h this test the core is placed in a set of grips that has been designed for one particular size core. The grips are designed to distribute the stress around the core if they are tightened correctly. A universal joint or a flexible cable may be used in conjunction with the apparatus to prevent bending or twisting of the specimen. The main difficulty encountered with the system shown is the failure of the specimen within the grips. The possible cause of the failure within the grips may be due to a stress concentration set up by the uneven tightening of the grips. This method can be used only for tests on cores, and even then has been found to be totally unsatisfactory because of the failure within the grips. The U. S. Bureau of Reclamation has been using a test similar to the sketch shown in Fig. 3. Sulfur is cast around each end of the specimen to form a bearing surface and then a ring grip is used to apply a tensile stress. The grips are in contact with the sulfur cast and do not touch the specimen. This method is unsatisfactory, apparently because a large number of the specimens appear to break within the sulfur cast. Professor Wuerker of the University of Illinois uses the test shown in Fig. 4.' Professor Wuerker states2 that this method has given definite and reproducible results with the weakest as well as with the strongest rocks. The test is a supplement in all cases where cores cannot be obtained. The principle and equipment are the same as for the test for tensile strength of hydraulic-cement mortar. Soft

Jan 1, 1961

By J. K. Edgar

FOR a number of years the production and use of super-purity aluminum (better than 99.99 pct) has been steadily increasing. High-grade lots of such aluminum show certain outstanding characteristics not found in lower grades containing principally silicon, iron and copper as impurities. One such characteristic is the so-called "self annealing," that is, the recrystallization of the heavily cold worked metal at room temperature.' Interest therefore is aroused as to the effects of the impurities. It is well known that the amounts of silicon and copper which occur in aluminum of better than 99.95 pct are completely soluble, at least at elevated temperatures (above 200°C). Iron, on the other hand, is known to be fairly insoluble in solid aluminum. Thus, a knowledge of the limits of this solubility would be of considerable use in studying the characteristics of the high purity metal. All investigators have agreed that iron has very low solubility in solid aluminum. Rosenhain, Archbutt and Hanson2 reported traces of an aluminum-iron phase in the "purest samples of aluminum obtainable." Gwyer and Phillips3 reported that an iron constituent was visible under the microscope in metal containing ".0088 per cent iron." Roth1 found that in the solid state the solubility of iron in high purity aluminum was 0.01, 0.01, 0.017 and 0.022 pct at 225, 320, 500 and 600°C respectively. Dix5 working with alloys containing less than 0.03 pct impurities, concluded from microscopic and chemical analyses of eutectic areas that the eutectic composition was close to 1.7 pct iron. Dix placed the eutectic temperature at 655°C'. Archer and Fink,6 using high purity aluminum-iron alloys, found that the hypoeutectic liquidus intersects the eutectic horizontal at 1.7 pct. This is in fair agreement with the investigation of the aluminum-iron system by Gwyer and Phillips who placed the eutectic at 1.89 pct iron with a freezing point of 653° PREPARATION AND CHEMICAL ANALYSIS OF ALLOYS Electrolytically refined aluminum (99.991 pct aluminum) and a high purity aluminum-iron alloy (11.45 pct iron) were used in the preparation of the alloys for this investigation. To aid in controlling the iron content of the experimental alloys, an alloy of lower iron content was prepared first from these materials. The high purity aluminum was melted and heated to about 700°C in a plumbago crucible coated with alundum cement and the aluminum-iron alloy was then added. The alloy was thoroughly stirred, fluxed and skimmed and then chill-cast into notch bars. The analyses of the three materials are given in Table I. The alloys for the determination of the solid solubility of iron in aluminum were prepared by melting 600 g total of the aluminum plus the required quantity of the aluminum-iron alloy (No. 92531). These

Jan 1, 1948

By G. D. Arsdale

This paper describes a series of experiments leading to the development. of a method for leaching the mixed ores of the Inspiration Consolidated Copper Co., containing chalcocite and silicates of copper, by the use of solutions acidified with sulfuric acid and carrying ferric sulfate. Iron is added to the solutions and ferric iron is regenerated electrolytically to a percentage high enough to act as an efficient solvent. The decreased yield is partly compensated for by a higher current density. AN IMPORTANT problem in modern copper metallurgy, particularly in the Southwest, has been to obtain good recoveries from what are commonly known as mixed ores; that is ores in which the copper occurs partly as oxide and partly as sulfide compounds. The dividing line between mixed ores and ores commonly accepted as concentrating is not definite. In other words, much ore now being concentrated carries considerable copper in non-sulfide form, on which recoveries are hot so good as on ores carrying less of these constituents. While treatment by concentration may be commercially profitable, on ores carrying oxide copper within certain limits, there are large deposits for which the application of con-centration could not be considered, and yet which have not been considered amenable to leaching because they carried too much sulfide. The Inspiration Consolidated Copper Co. has large amounts of such mixed ores, and this paper is an account of the experimental work by which a method was developed for their treatment, and for which a large plant is now being erected by the Inspiration Co. It is not claimed that the method is a general solution of the problem of mixed-ore treatment but it is apparently well adapted for leaching the ores of the Inspiration Co., for which it was designed. The work done has covered preliminary laboratory and test-plant investigation, and .a pilot-plant run, extending from March to the middle of December, 1923. Thoroughly consistent and satisfactory results, were obtained continuously for more, than six months in the pilot plant; and it is believed that the results; and probable costs that can be had on a large scale have been definitely, proved. The method, however, was designed for local conditions; and while the basic principles are general, there are ores on which it will not work and other ores for which considerable modification may be required.

Jan 10, 1925

By M. B. Willey

The Louisiana Continental Shelf is a submarine area extending offshore as much as one hundred miles. The Gulf bottom in this region varies considerably in extent, profile and composition and consists largely of sedimentary deposits, predominantly those of the Mississippi River. It is very young in a geological sense. Up to the present time few major structures have been erected offshore in the Gulf and no comprehensive preliminary tests have been carried out. Results of pile driving tests are of little value as actual bearing capacities far exceed the dynamic resistance to driving as measured by conventional formulas. Soils encountered are, with few exceptions, cohesive and piling consequently develop their supporting power through surface friction. Because of the time required and relatively high costs, no complete load tests have been made. The results of those tests which have been made, and information obtained from pulling piling in one structure, indicate that design loadings could be considerably increased, and it is contended that comprehensive preliminary investigations including an actual load test, combined with borings and examination of materials encountered by competent soil experts, would effect economies in design far in excess of their cost. The Louisiana Continental Shelf—General The Louisiana . . . continental shelf is a submarine area which extends seaward for as great a distance as one hundred miles off the present shoreline. The Gulf bottom in this region is characterized by low slopes and its outer margin is outlined by the fifty fathom (300 ft.) contour. South of the margin of the shelf the slopes steepen abruptly in the continental slope zone and plunge into the deeps of the Gulf of Mexico.l The engineer who is called upon to design a structure on this shelf is concerned only with the uppermost portion to a depth generally not to exceed Ioo to 150 ft. This layer is very young in a geological sense, and it has the characteristics usually associated with infancy. A few of these are lack of strength, lack of uniformity, and high water content. It consists of the sedimentary deposits of the various rivers and streams entering the Gulf. These streams are all heavily burdened in quantities sufficient to fill the areas at their mouths, were it not for the fact that continual subsidence, equal or greater in amount and acting directly opposite, prevail over the sedimentary workings of the streams. This subsidence has been estimated by geologists to be at the rate of at least one foot per century. Influence of Mississippi River The Mississippi River, which has been the predominant factor in the formation of practically all the Louisiana continental shelf, is one of two rivers flowing into the Gulf that have been able to build protruding deltas. The Mississippi has done so because of its enormous size and load. It deposits sediments in amounts sufficient to replace and actually gain on the amount of subsidence.

Jan 1, 1949

By Henry Drinker

The Institute has lost a valued member by the death of Eckley B. Coxe, Jr. He bore the name of one who was largely instrumental in founding the Institute, and to whose support and guidance as active member, Vice-President, and President, the Institute owes. much. Eckley B. Coxe, Jr., was the nephew of the late Eckley B. Coxe. He held a large interest in the coal estates owned and developed by his family, and he was thus naturally led to take a continuing interest in mining matters, and for years and up to the time of his death was a full member of the Institute. He died at his residence, Drifton, Pa., on Sept. 20 last, aged 44. He was a member of the class of '93 of the University of Pennsylvania,. of which great institution he was a devoted alumnus. His educational and charitable activities were numerous, but his chief life-work and interest was in archeological investigation and research in Egypt, carried on through the Museum of the University of Pennsylvania of which Museum he was President. The discoveries made by the various expeditions financed and directed by him, and the notable publications issued by his direction and at his expense, chronicling the results, are among the most important researches ever made of buried Egypt. Mr. Coxe was a member of the International Historical Society and of many educational and charitable organizations. By his will, among other bequests, he left $500,000 to the Museum of the University of Pennsylvania and $100,000 to the University, the income of the latter fund to be applied to increasing the salaries of the professors of the Institution. He also left $100,000 to the Children's Hospital of Philadelphia, of which he was a manager, and in addition thereto $10,000 of which the income is to be applied in providing Christmas presents for .the child patients, and in providing an annual dinner for the patients and attendants of the hospital. He bequeathed $50,000 to Leonard Hall, an associate mission of the Episcopal Church, at South Bethlehem, Pa., $25,000 to the Epileptic Hospital and Colony Farm (Philadelphia) ; $50,000 to the Philadelphia Orthopaedic Hospital and Infirmary for Nervous Diseases; $15,000 to the United Charities of Hazleton, Pa., the income to be applied to the salaries of nurses; and $25,000 to the Mining and Mechanical Institute of the Anthracite Coal Region of Pennsylvania, founded by his uncle, Eckley B. Coxe, and of which Eckley B. Coxe, Jr., was an active trustee up to the time of his death. This Institute is known as one of the best preparatory schools for technical education in Pennsylvania, and is mainly devoted to extending an opportunity for education by day and night schools to the boys and young men of the Anthracite Region. Its principal is an alumnus of Lehigh University; it has an able local Board of Trustees, and an Advisory Board consisting of the Provost of the University of Pennsylvania, the President of Lafayette College, and the President of Lehigh University, all three of which institutions have established prize scholarships in the institute. Mr. Coxe carne of a distinguished ancestry, the record of which is fully given in the biographical notice of his uncle, Eckley B. Coxe, by Dr. R. W. Raymond, in Vol. XXV of the Transactions.`

Jan 12, 1916

By F. J. Meringer, C. W. MacGregor

Various investigations have been carried out to determine the effects of cold-rolling on the common physical properties as represented by the yield strength, tensile strength, percentage of elongation and ordinary reduction of area. Very little information is available in the literature with reference to the effects of cold-rolling on the true stress-strain properties. Since the ordinary physical properties base both the stresses and the strains on the original dimensions of the test piece, which are greatly changed during the test, they are essentially empirical values and do not represent physically either true stresses or true strains. Consequently, they do not give an accurate picture of the effects of different conditions, both mechanical and metallurgical, on the strength and ductility of the material. It is not, however, the purpose of this paper to review the various advantages accruing from the use of true stress and true strain values, since these have been shown elsewhere,1-l2 but to utilize them in representing the various effects considered. The true stress S and true strain (e = q') values mentioned above for the tension test are defined by1 S =1/A and where P, A, Ao are the axial load, the instantaneous area and the original area of cross section, respectively. From simultaneous readings of the axial load and the dimension or dimensions determining the instantaneous area of cross section, the true stress-strain curve is constructed by using the relations given in Eq. I. It is then the object of this paper to discuss the general effects of cold-rolling on the true stress and strain values for a low-carbon steel together with the effects of age-hardening and directionality on these properties. Preliminary Investigations The material considered throughout the paper is a low-carbon steel of the following chemical analysis: C, 0.19 per cent; S, 0.118; P, 0.092; Mn, 0.85; Si, 0.01. The stock was received in bars, 7 by 3/4 in., and was first annealed for one hour at 1650°F. followed by a furnace cool. Photomicrographs of this material showed considerable directionality even in the annealed condition. In view of the possible effects of the nonhomogeneity and directionality in this material, it was considered important to investigate their influence on the true stress-strain diagrams. In addition, the effect of strain-aging in this steel was also made the subject of a preliminary study. Effect of Aging on True Stress-strain Properties Since a certain time element would elapse between the cold-rolling operation and the final tension tests, it was determined to investigate the aging character-

Jan 1, 1945

By Henry P. Ehrlinger, James C. Bradbury

Tripoli is a naturally occurring, very finely divided form of silica found chiefly in some midwestern and southeastern states and used commercially as fillers and abrasives. Definitions Tripoli is a microcrystalline, finely particulate, more or less friable form of silica that appears to be the product of leaching of siliceous limestone or calcareous chert. The term was originally applied to a deposit near Seneca, Mo., that resembled material of that name found near Tripoli in North Africa (Hovey, 1894). The two deposits were subsequently found to have different physical characteristics -the North African tripoli, now called tripolite, is a diatomite, composed of the siliceous skeletons of microscopic marine plants called diatoms, and the Missouri tripoli contains no diatom remains; the term tripoli, however, continued to be used for the Missouri material and is now applied in a general way to most silica deposits similar to it in characteristics and geologic origin. In commercial trade tripoli is commonly understood to designate material from the Missouri-Oklahoma field; silica from southern Illinois, the other major producing area, is referred to commercially as amorphous silica. Each term, however, may be used commercially for material, regardless of place of origin, that has the characteristics or uses commonly ascribed to the material from one or the other major producing area. For example, in the commodity price listings, Engineering and Mining Journal routinely lists under Tripoli, prices "f.0.b. Elco, III." and "f.0.b. Seneca, Mo., and Rogers, Ark.," and under Silica, amorphous, prices "f .o.b. Ill.," and "f .o.b. Dierks, Ark." Amorphous silica, the commercial designation given to southern Illinois tripoli, is, like the term tripoli, a misnomer. Mineralogically, the southern Illinois deposits are composed of microcrystalline quartz, and no amorphous material has been detected during X-ray and scanning electron microscope investigations (Leamnson, Thomas, and Ehrlinger, 1969; Thomas et al., 1970). Soft silica is another term that has been applied to Illinois and Tennessee tripoli, presumably to distinguish it from the more compact Missouri material. It has also been used in the ceramic trade to distinguish tripoli from "hard" silica, or silica flour, produced by pulverizing silica sand (Heinz, 1937). Rottenstone, produced commercially in Pennsylvania, is similar to tripoli in that a major constituent is finely particulate silica, and its uses are much the same as those of tripoli- as abrasives and fillers. The origin of rottenstone also is similar to that of tripoli-decomposition of a siliceous sedimentary rock. The parent rock is defined as a siliceous limestone (Gary, McAfee, and Wolf, 1972; Thrush, 1968) or as shale (personal communication). Heinz (1937) quotes a brief statement describ-

Jan 1, 1975

By Jay R. Burns

TWO magnesium sand-casting alloys are commonly favored in the United States. These are referred to as H and C alloys (Dow Chemical Co.) or 4Mz65 and AM260 alloys (American Magnesium Corporation). Both are of an aluminum-zinc-manganese type. H alloy contains 6 per cent aluminum and 3 per cent zinc and is characterized by relatively good toughness. C alloy contains 9 per cent aluminum and 2 per cent zinc and is employed where high yield strength and pressure tightness are required. Examination of magnesium castings poured in Europe and England,'J however, demonstrates that H and C alloys are replaced by .%8 and AZ~I, respectively. That is, A8 reprcsents a magnesiurn alloy having superior toughness while A291 is suitable for high yield strength and pressure-tight applications. The basic difference between the .Ameri-can and European alloys is that the foreign alloys employ a somewhat higher aluminum content and less zinc than is found in H and C alloys. The mechanical properties of the alloys, when divided into high and low-aluminum groups, are quite similar, as determined from separately cast foundry-control type test bars ,In this paper the decrease of mechanical properties caused by any given amount of microporosity is measured for H, C, A8, and AZ~I alloys. The relative susceptibility of each of the four alloys to microporosity is also determined. Typical mechanical properties and nominal chemical analyses are reported in Table I. The apparent similarities between the two alloys in each group have led to considerable discussion as to the relative merits of each of the compositions.2 Popular points for comparison between the alloys have been the relative susceptibility of each of the four alloys to microporosity6 and the effect of this microporosity on their mechanical properties. It is primarily intended, in this paper, to show the

Jan 1, 1946

By John L. Lamont, Walter Crafts

SELECTION of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of hardenability,1 as-quenched hardness,2,3 and tempered tensile strength.4 Ductility and toughness may also be estimated if the steel is completely hardened on quenching,5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In fine-grained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accompanied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to 4 in. in diameter. PROCEDURE The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1o30, 1040, 1340, 3310, 3316, 4320, 4330, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 9310, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.35. The bars were tempered as follows: ½ in., I in., and I 5/8 in., 2 hr; 2 ½ in., 3 hr; 4 in., 5 hr. All bars were air-cooled from the tempering tem-

Jan 1, 1947

By B. M. Larsen

IN endeavoring to put the art of the steelmaker on a more scientific basis, as a means of securing closer control of the product, we must be severely critical of the basis of any theory we use. In particular, we must be careful to distinguish between factors that are primary and those of only secondary importance. The concentration relations that determine the slag-metal equilibria, which are usually more or less closely attained, are of course of primary significance, but a clear picture of the whole process requires that the actual rates of the several reactions be taken properly into account. At the high temperature of the steelmaking furnace, all reactions might be thought to be very rapid, but some of them in fact are not; the essential causes of this condition are important to a proper understanding of the process. This paper aims to present, and to justify, the viewpoint that the most significant reaction is the oxidation of carbon in the metal, the progress of which determines the oxygen pressure levels in slag and metal and produces stirring effects, all of which influence the course of the process as a whole. REACTION RATES AT STEELMAKING TEMPERATURES General experience in reaction rates makes it almost certain that at steelmaking temperatures equilibrium is attained practically instantaneously when the reactants are well distributed in a single liquid phase -that is, in the so-called homogeneous reactions. The actual slowness of some of the reactions in the open-hearth furnace must therefore be attributed to a relatively slow rate of diffusion within the slag or metal phase, which limits the rate at which the reactants can meet each other in the liquid steel or at its surface. That the reactions can be made to go with great rapidity, by proper mixing and stirring of the reacting phases, is indicated by the following illustrations: I. In the Bessemer process there is intimate contact between air and the whole mass of metal, and the reactions are complete in a few minutes. 2. Perrin1 has demonstrated that by pouring liquid steel into slag contained in a deep ladle, and thereby producing almost a slag-metal emulsion, the phosphorus or oxygen content of the steel is adjusted immediately. 3. Barret, Holbrook and Woods observed a quite rapid rate of desulphurization when powdered calcium carbide was stirred vigorously into liquid iron. 4. When a spoonful of liquid steel is poured into a mold containing aluminum wire, the formation and precipitation of alumina occurs in the fraction of a second required to freeze the surface layer of the tiny ingot. The first three examples all show that any means of increasing the effective surface between slag and metal and promoting intimate mixture of the reacting phases, thereby obviating the limitation imposed by diffusion, will enhance the speed of the steelmaking process.

Jan 1, 1941

By Raymond Mancha

A TEST of any fan requires the determination of such data as fan pressure, air volume handled by the fan, and power input to the fan shaft. When testing operating mine fans of the centrifugal type, test methods have been employed, for the sake of convenience, that permit great latitude in detail of procedure resulting in wide variance in results by different investigators. Some controversial aspects of field fan testing are the result of past failure to define dearly the various forms of fan pressure and to a lack of understanding of the accurate procedure for the measurement thereof. Also, the anemometer for air-volume measurement, although convenient, if carelessly used and maintained is subject to a wide error range with variation in method of application and in instrument accuracy. The appearance of the axial-flow type of mine fan offers the possibility of refinements in field testing that were impractical with the centrifugal fan. First of all, the fan inlet and outlet are more sharply defined, giving loser agreement as to just where the fan begins and ends; thus there is less disagreement as to the proper location for measurements of fan pressure. The area of passage into the inlet of an axial-flow mine fan usually constricts, causing high air velocities with accompanying steadiness of flow. Thus the fan inlet offers an ideal location for accurate air-volume measurements with the Pitot tube, the proper use of which is well established by code. Thereby the controversial aspects of such measurements are eliminated. Use of the Pitot tube also facilitates a more accurate measure of fan pressure, since the individual pressures measured can be properly weighted, as will be explained later. Determination of power input to the axial-flow mine fan operating in the field is subject to the same inaccuracies as with the centrifugal fan if the axial-flow fan is also belt driven. However, because of the higher rates of rotation usual with axial-flow fans, direct-driven units are more numerous and it is unnecessary to assume a drive efficiency, thus eliminating one possible source of error. It is the purpose of this paper to define and explain the various types of pressure measurements involved in a field test of an axial-flow mine fan, and to further explain the proper use of the Pitot tube when measuring pressures and volumes. DEFINITION OF FAN PRESSURES The two fan pressures most commonly discussed are fan total and fan static pressure, each of which has the same meaning regardless of whether the fan is blowing, exhausting, or blowing and exhausting, as in the case of a fan with ducts connected to both outlet and inlet. Fan total pressure is the amount by which the total pressure of the air delivered by the fan exceeds the total pressure of the air received by the fan. This pressure is a measure of the maximum amount of the work done on the air by the fan that is available for external use.

Jan 1, 1942

By Wei-Kao Lu

A general rate equation is derived for gas -solid reactions in metallurgical processes by considering the contributions of chemical reaction at inter-phase boundaries and diffusion through the solid product layer simultaneously. This equation takes care of the whole range continuously from purely diffusion control to purely chemical reaction control. The parabolic law,' McKewan's equationa derived with the assumption of interface area control and the equation derived by Kawasaki et al. with the assumption of purely diffusion control are found as the limiting cases of the corresponding forms of the general rate equation. Many metallurgical processes involving gas-solid reactions have been extensively studied. The common examples of these processes include the reduction of oxides to metallic products, the roasting of sulfides to oxides or chlorides and the oxidation of metals. Gas-solid reactions consist of at least two kinds of steps; one involves the transport of reactant and product to and from the reaction zone and the other is the chemical reaction taking place at the interphase boundaries. In the limiting cases one or the other of the above mentioned steps will be much slower than the other and is then rate controlling. For example, the oxidation of metals is diffusion controlled and obeys the parabolic law.' On the other hand, if the diffusion rate is much larger than the chemical reaction rate then it will be controlled by the chemical reaction rate. This latter case occurs for the reduction of iron oxides studied by McKewan. If the rate of diffusion and of the chemical reaction have the same order of magnitude, a more detailed analysis is necessary. Thus at the beginning of the reaction when the solid and gaseous reactants are in direct contact, the reaction should be chemical reaction rate controlled as no diffusion process is involved. At the other extreme as the reaction zone moves further into the solid, the diffusion distance becomes greater and the diffusion rate continuously decreases. Eventually, therefore, for a sufficiently large sample the rate must become diffusion controlled. As the transition from one controlling step to the other must be continuous, we cannot describe this transition period by either of the two limiting cases. In this paper the author attempts to derive a general rate equation for gas-solid reaction systems. This is effected by considering the rates of diffusion and chemical reaction simultaneously from the state of pure diffusion control to pure chemical reaction control. I) DERIVATION The system under consideration is made of at least three phases, namely the gaseous one, the solid reactant, and the solid product as shown in Fig. 1. The notations are listed at the end of the paper. The mass transfer process involves the diffusion of reactants and products across the solid product layer. It is reasonable to consider that no chemical reaction will take place in the solid product layer with respect to both gaseous reactant and product. For the characteristics of local equilibrium of the system, the diffusion process is really in a quasi-steady-state. It will be proved in the following paragraphs. Then we can invoke the law of conservation of mass valid for all chemical species passing through the layer. The solid reactant sphere has an initial radius, ro, after a fraction of completeness of the reaction, the unreacted core has a radius ri, where r, is in the solid product region. Let Cg be the activity of gaseous reactant in the

Jan 1, 1963

By H. L. Gilbert, C. T. Anderson, W. J. Kroll

In a previous paper,' the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.% When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8 in. in diameter. The supply of direct current of high amperage for producing the desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flcxible tubing of the movable electrodc, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decsed to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 19oo"C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica accortling to the reaction: SiO² + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1949

By Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.' This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

By W. T. Cardwell

This paper presents a theory for estimating the rate of gravity drainage of a liquid out of a sand column. Account is taken of the variation in permeability to the liquid as the saturation in the upper part of the sand becomes less than 100 pct. The theory is confirmed by previously published experimental data. Introduction Petroleum engineers have expressed the need for 4 theory of gravity drainage. Brunner,' in particular, has pointed out that some type of mathematical theory is necessary to begin the application of laboratory data to field problems. Muskat and his associates2'3-4 have recently made contributions to the theory of gas-drive behavior and have indicated an intention to apply their methods to water-drive systems. No theory of gravity drainage rates has been developed, however, and it seems desirable to formulate one at this time. Differential Equations of Capillary Flow The flow of liquids in partially saturated porous media has been studied by many investigators.6-10 Richards6 presented derivations of fundamental differential equa- tions governing two-phase capillary flow; and used simplified forms of those equations in solving a steady-state problem. Muskat and Meres6 presented and used equations different from those of Richards. Their equations did not explicitly involve capillary pressure gradients; but included, on the other hand, terms expressing the effects of the evolution of gas from the liquid phase during flow. Leverett8 stated in 1940 that "previous work on the flow of fluid mixtures in porous solids [had] failed adequately to account for all of the three influences that cause motion of the fluids: capillarity, gravity, and impressed external pressure differentials." Leverett's basic equations, however, were specialized forms of the general equations of Richards,5 which had actually taken account of the three influences mentioned by Leverett, but had not been used in a problem involving all three. The fact is that our knowledge of capillary flow and our ability to express this knowledge in differential equations exceed our ability to solve the equations except in a few cases. General differential equations have usually been of little more than formal value. In solving practical problems, it has been necessary to develop specific equations, preserving terms that involved the factors important in those problems, and purposefully neglecting other terms that were not of predominating influence. This is the method followed here. It is believed that the solution of the particular problem and the scheme of the solution itself are new.

Jan 1, 1949

By H. Cecil Spicer

The results described in this article are based on field work conducted during the periods APril-May, 1939, and MaY-JulY, 1940. The United States Potash CO. is mining potash on Government land under a permit from the Department of the Interior and the geophysical investigation mas completed under a cooperative arrangemerit made between that company and the Conservation Branch of the Geological Survey. The writer, a member of the Section of Chemistry and Physics of the Geologic Branch, was assigned to this investigation. Four definite objectives were in mind for the geophysical work in the studies over the salt deposits. The first was to determine the measure of success that could be attained in this type of work with the resistivity methods that were to be employed. These methods had been introduced into the work of the Conservation Branch by Benjamin E. Jones for the investigation of dam sites, and have been used under his direction by the author for such work. If the method proved to be applicable, an l was to be made to contour the top of the salt beds and also the other formation boundaries known to be present in this area. Salt-water aquifers were to be studied in an effort to determine their boundaries, and an attempt was to be made to delineate the potash-bearing beds. Others have made, and reported, resistivity studies over saliferous deposits in different areas. Friedell and Messrs. Schlumberger2 reported geophysical work performed in the disrovery of the salt domes of Alsace; Carrette and Kelly3 described the geology of the same area. Leonardon and Kelly4 published a resistivity curve obtained over the Hettenschlag dome, and a further discussion of this same area was given by the Messrs. Schlum-berger5 in a communication. Messrs. Alty6 described studies 0" salt deposits in which the sing[e-probe method was used. Sinerez7 mentions that electrical methods were tried over salt deposits in Spain. Geoffrey and Charrin8 show a resistivity curve obtained over marl, gypsiferous marl and salt which is similar to that obtained over the New Mexico salt deposits. Kelly9 reported resistivity work performetl with the ground comparator of Zuschlag over the salt deposits near Syracuse, N. Y., where the Salina formation is at a depth of 700 to 800 ft. Some structural studies on the potash basin of Alsace are described by Poldini.10 Another single-probe resistivity study, made over salt deposits in New Mexico, is briefly described by Heiland,ll through the courtesy of Harry Aurand, of the Midwest Refining CO.

Jan 1, 1942

By A. C. England, William F. Haney, Paul B. Crawford, Bobby L. Landrum

The creation of unsymmetrical vertical or horizontal fractures in a producing well will result in a unique distortion of the normal shut-in pressures existing at the four surrounding wells. An electrical model study has been made to show how the shut-in pressures at the wells surrounding the fractured producing well may he used to estimate the size and orientation of vertical or horizontal fractures. The pressure differences at the four surrounding wells are recorded during production from the fractured well. The resulting pressure dato are matched from a table of several hundred possible fracture combinations. The table refers to the figure showing the effective size and orientation of the commercially created fracture. INTRODUCTION The creation of commercial fractures about oil and gas wells has led to considerable speculation as to the size and shape of the fractures. It is important that the size and shape be known in certain instances, especially when pressure maintenance programs are to be initiated. It was shown that if knowledge of a vertical fracture could be found that such information may be utilized in planning a waterflooding or gas cycling program and that in some cases the fractures might be utilized very effectively.' Other work showed that it may be desirable to create "pancake" fractures in certain reservoirs but that they should exist in a desirable range.' If the fractures are too large, they should be plugged prior to initiating a pressure maintenance program. If an irregular shaped "pancake" fracture is created, it is desirable to know the orientation of this fracture because similar but unreported studies have shown that "pancake" fractures may or may not substantially affect the sweep efficiencies and performance of the flooding or cycling program. Consequently, it may be desirable in some instances to estimate the effective size and orientation of the fracture. ANALOG An electrical model was used in making this study. The electrical model consisted of a circular reservoir approximately 8 in. in diameter, 1 in. thick and was filled with a dilute salt solution. A copper band formed the periphery of the reservoir. A vertical fracture was simulated by a copper strip soldered to the wire well located in the center of the reservoir. Vertical copper strips of various lengths and orientation were soldered to the wire well to represent vertical fractures in the reservoir. In studies reported here on vertical fractures it was arbitrarily assumed that two fractures originated at the well and extended out into the reservoir. An electrical potential was imposed between the wire well and the periphery of the tank. Plots of the iso-potentials are shown in Figs. 1 through 9. This model provides the steady-state isopotentials existing in a uniform, homogeneous circular reservoir having a vertically fractured well at its center. The permeability of the fracture is much greater than the permeability of the matrix proper. The effects of gravity are neglected. In preparing Tables 1 and 2, four symmetrically located unfractured wells were assumed to exist around

Jan 1, 1956