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By Allen Rogers

THERE are few natural monopolies comparable with the nitrate industry. Perhaps the only other one is, curiously enough, also an essential fertilizer material, viz., potash, of which the Germans have heretofore held practically a-monopoly due to the existence in their territory of the most important known deposits of potash salts. And although nitrates in minute amounts are found in many desert regions, the only deposits callable of being worked commercially exist in Chile. Combined nitrogen in the oxidized form is an essential for plant life. Nature provides it mainly through the agency of nitrogen-fixing bacteria. But where lands are cropped artificially this supply is too small; and gradually the nitrogen supply becomes exhausted. In order to continue farming, it is necessary to furnish a supply of nitrogenous plant food, and this is clone by putting on various substances containing combined nitrogen. These consist of various animal wastes, ammonium sulphate, the ammonia of which is obtained in the destructive distillation of coal, and Chile saltpeter. The latter is immediately available as a plant food, the nitrogen being in the required form. The other substances must oxidize before they are available. Besides its use as a fertilizer, Chile saltpeter is the source from which the bulk of the nitric acid of commerce is derived. The use of nitric acid in the manufacture of almost, all modern explosives is, of course, well known.

Jan 2, 1918

By Hallet R. Robbins

Korea, the ancient" Hermit Kingdom," is a peninsula jutting out from the coast of eastern Asia. By the natives it is called " Chosen," nfhich, translated, means " Land of the Morning Calm." It lies between the Yellow sea and the Sea of Japan. On the north it is separated from Manchuria and the Russian province of Primorsk by the Yalu and Tiumen rivers; on the south the Korcan straits interpose a rough voyage of 120 nliles to the nearest point in Japan. The entire country is situated between the parallels of 34O and 42O N. latitude. The surface of the country is made up of successive ranges of ul~glaciated mountains, separated by narrow, fertile, and more or less densely populated, valleys. Through all the obscure centuries of its history, Korea has succeeded in maintaining a monastic seclusion, over which, from time immeniorial until the late Chino-Japanese war in 1894, China exercised a shadowy sovereignty. Although Korea had been forced into slight foreign contact previously, her first forcign treaty was signed with Japan in 1876. Under the restraining guardianship of China, the Japanese treaty bore but infiignificant innovations for Korea; but when, in 1883, a treaty was made with the United States, the first of the western nations, a decade after the American gunboats, under Commodore Rodgers and Lieutenant Schley, forced their may up the Salee river, Korea awoke from her sleep of 4,000 years. The Eorean peninsula suddenly became the arena where the enterprises and individuals of many foreign nations met in fiercest rivalry. Out of this struggle grew two singularly successful American enterprises, both of which have played an important part in developing the natural resources of the country. The first, and best known of these, is the Oriental Consolidated Mining Co., which was organized by Lcigh Hunt

Jan 1, 1909

By J. W. Cunningham, W. A. Tiller, D. H. Lane

The effect of ultrasonic vibrations on ingot solidification has been considered both theoretically and experimentally. The theoretical section elucidates the mechanisms by which the ultrasonic vibrations might refine the ingot structure. The experimental section describes a very efficient means of introducing the ultrasonic vibrations to the freezing interface. The application of this technique to the consumable-electrode arc melting process shows that the columnar mode of freezing may be effectively suppressed yielding an ingot structure consisting predominantly of equiaxed grains. The results support the contention that the ultrasonic vibrations increase the nucleation frequency in the layer of liquid adjacent to the freezing interface. CERTAIN structural characteristics of as-cast ingots are undesirable since they create considerable difficulty for subsequent processing and often produce defects in the finished product. These structural defects are illustrated in Fig. 1(a), and are: 1) planes of weakness where columnar grains growing from the different mold faces meet, 2) strength anisotropy due to the preferred orientation of the columnar grains and 3) inhomogeneity due to segregation at dendrite boundaries within the columnar grains and at the columnar grain boundaries. The type of ingot structure that eliminates 1) and 2) and diminishes 3) is the fine-grained equiaxed structure illustrated in Fig. 1(c). Many attempts have been made to produce the desirable ingot structure illustrated in Fig. 1(c) by inoculating, casting with varying superheats, vibrating or stirring, or by irradiation with ultrasonic vibrations. These attempts have met with various degrees of success, the ingots generally having the structure illustrated in Fig. 1(b). All four methods have been the subject of numerous investigations,1"4 the latter producing the most erratic behavior and inconsistent success. The method of ultrasonic irradiation during ingot solidification has shown considerable promise on small-scale ingots (diam 2 in.) but has not yet been successfully adapted to large-scale operation. The present paper considers the application of ultrasonic radiation to ingot solidification both theoretically and experimentally. The purpose of the paper is to elucidate the mechanism by which ultrasonic energy refines the ingot structure and to describe a method for producing the desirable ingot structure in both laboratory scale experiments and in ingots of commercial size. THEORY Conventional Casting—Before discussing the possible effects of ultrasonic radiation upon ingot structure let us first briefly review the reasons for the breakdown of columnar crystallization to equiaxed crystallization during ingot solidification. The following is a slightly oversimplified description. In the conventional method of casting, the alloy having a certain degree of superheat, T, is poured to fill a cold mold which is at room temperature, Tc,. Due to conduction of heat through the mold wall the outer rim of liquid metal cools rapidly to the liquidus temperature and begins to supercool. At some degree of supercooling, nuclei of solid form at random in this supercooled layer at the mold surface. The grains in this chill layer begin to grow inwards producing a solute build-up, thus lowering the freezing temperature at the interface as illustrated in Fig. 2. As growth proceeds, the temperature gradient in the solid conducts away not only the latent heat of fusion evolved during growth but it also conducts away some of the superheat of the melt so that the temperature

Jan 1, 1961

By C. G. Black

THE purpose of this paper is to present data obtained from an investi-gation conducted on the grindability of coal by the American Society for Testing Materials Tentative Standard ball-mill method. This investiga-tion has been conducted over a period of a year, during which time several hundred tests were run on a wide selection of different coals coming from Pennsylvania, Ohio, West Virginia and Kentucky. The data herewith presented tend to show that the tentative standard ball-mill method might give results that are misleading and that a volume measure might be more indicative of the true grindability 'of materials of varying specific gravity. A means whereby the time element might be reduced has been studied and other phases of this work such as preparation of samples, mechanical screening, reporting results and duplicating tests have been investigated. It is hoped that all criticism offered in this paper will be taken as constructive, with the purpose in mind of perfecting the method now tentative to show the true conditions and of making optional the manner in which certain parts of the test might be conducted to meet diversified laboratory conditions.

Jan 1, 1936

By B. M. Larsen

AN increasing amount of attention is being paid to the possible influence of oxygen, in its several modes of occurrence in steel, upon some of the properties of the metal; but clearly investigations along this line are unlikely to yield significant results until reliable analytical methods for the determination of oxygen have been established. This paper presents some results of a study of an improved Ledebur method which aims to determine a definite portion of the oxygen; namely; that which presumably is present in diffusible form in the. solid steel. These more or less preliminary results lead us to believe that the oxygen so determined has some significance; their presentation at this time will, we hope, stimulate discussion of, and focus attention upon, certain rather neglected aspects of the problem. Considerable work has been done recently on methods of estimating inclusions and on the vacuum-fusion method for oxygen; with results which, however, are of somewhat questionable significance. It is commonly presumed that the oxygen in a bath of molten steel in a furnace is present partly as a separate phase consisting of suspended particles of oxides or silicates, partly in solution, the latter being probably the more important. Upon addition of a deoxidizer, it reacts with some portion of the dissolved oxygen and precipitates it as additional suspended particles; the oxygen not eliminated in this way, which remains in solution in the liquid steel, may be regarded indifferently either as dissolved oxygen or as dissolved FeO. When the steel is poured, some of the suspended particles rise towards the surface, others remain trapped in the finished steel, appearing as nonmetallic inclusions in amounts corresponding usually to about 0.01 to 0.03 per cent 02 in the steel. The dissolved oxygen may be partly eliminated as CO during freezing of the ingot, but some remains either in solution or in part precipitated as FeO. Finished steels may thus contain oxygen in several forms: (1) In non-metallic inclusions which are probably quite insoluble in the solid metal at all temperatures; (2) in solid solution which at lower temperatures may be supersaturated; (3) in FeO particles produced by relief of this

Jan 1, 1932

By R. E. Gilchrist, R. R. Harvey, M. R. Dean

A simple and rapid three-component analysis procedure has been developed for use in fluid-flow studies. The method is based on refractive index measurements, combined with refractive dispersion measured between the Ha and H wave lengths. The procedure requires. calibration curves for the three-fluid system. The only restriction on the fluids employed is that only one be an aromatzc or olefinic compound. Individual sample measurements require only a few minutes. Composition results within the limits of accuracy required for fluid-flow analog studies are obtained. INTRODUCTION The simultaneous analysis of three-component mixtures is a problem often encountered in fluid-flow analog systems. In petroleum production research, the problem is usually encountered in experiments on the displacement of fluid from a porous medium. In the case of immiscible displacement, simple volumetric measurements of the produced fluids are usually sufficient, the analog fluids often being the actual reservoir fluids themselves — oil, water and gas. However, modern secondary recovery of petroleum sometimes involves production under miscible conditions, in which the oil is displaced by liquefied petroleum gas which, in turn, is displaced by dry gas. Since this type of displacement is done under conditions of pressure and temperature that are not easily reproduced in the laboratory, studies are often performed with analog fluids at essentially atmospheric pressure. Since the number of samples taken during one of these experiments is usually quite large, the time required for analysis becomes an important factor. In the past, the difficulty of conventional analysis has been avoided by the addition of various tracers to one or more of the components, or by the use of a tracer fluid as one of the components. With these techniques, a relatively large amount of analytical time is still required. Moreover, in the case of added tracers, the tracer material may migrate in part to one of the other fluids, may be adsorbed on the solid surfaces of the model, or may introduce side effects not characteristic of the prototype fluid. The substitution of a tracer fluid for one of the components can severely limit the choice of analog fluids. Optical refractometry provides a rapid and economical method of analysis of two-fluid systems or of monitoring small changes in composition of an essentially one-component system. Refractometric methods are capable of high degrees of accuracy, require only very small samples and can easily be adapted to automatic methods. They are not generally applicable, however, where three or more fluids are present over wide ranges of concentration. The method of three-component analysis described here has three essential characteristics. 1. It is based on refractometric measurements and thus preserves all of these desirable properties. 2. It does not make any stringent demands on the choice of fluids that can be analyzed. 3. It is capable of accuracy sufficient for fluid-flow analog studies. THEORETICAL The difference in the refractive index of a substance at two different wave lengths of light is known as its dispersivity. When the difference is taken between the specific refractions at the two wave lengths, the quantity is referred to as the specific dispersivity. Specific refraction was defined empirically by Gladstone and Dale1 as r = n-1/d....[1] where n is the index of refraction and d is the density. The definition is given more correctly by the expression r =n2-1/n2+1 1/d..........(2) 1References given at end of paper. MICIFTV OF PETROLEUM ENGINEER JOURNAL.

1913. FRANDKA WBONA DAMS Montreal, Canada. 1921. WILLIAM CUTHBERTB LACKETT Sacriston, Durham, England. 1923. GELASIOC AETANI. Rome, Italy. 1929. TAKUMAD AN Tokyo, Japan. 1920. HENRYS TURGISD RINKER. Merion Station, Pa. 1922. FEDERICGIOO LITTI. Torino, Italy. 1906. SIR ROBERTA . HADFIELD. London, England. 1928. JOHNHA YSH AMMON.D. New York, N. Y. 1921. FRANKW ILLIAMH ARBORD London, England. 1917. HERBERTH OOVER. Washington, D. C. 1906. HENRI LECHATELIER. Paris, France. 1900. WALDEMAR LNDGREN Cambridge, Mass. 1879. JOHNM ARKLE .New York, N. Y. 1921. C. MCDERMID London, England. 1913. EZEQUIELO RDONEZ Mexico City, Mexico. 1909. ALEXANDRPEO URCEL Paris, France. 1911. ROBERT H . RICHARDS Cambridge, Mass.

Jan 1, 1929

By H. S. Coe

ENGINEERS have long recognized the desirability of correlating the data obtained from small-scale slime-settling tests with commercial work as carried on in large tanks. This need, though most apparent in designing new installations, frequently arises also in existent plants, since a large range of experimental work can be performed without interfering with regular operation. GENERAL SETTLING PHENOMENA In order to develop rational methods of laboratory testing, it becomes necessary to study the general phenomena of settling. Since it was desired to give the public the benefit of these methods at as early a date as possible, together with the knowledge of the general principles of slime settling necessary for a clear understanding of the laboratory tests, we have ventured to discuss the subject in so far as brought out by the work which we now have under way. We realize that certain of our preliminary conclusions may be subject to modification, but it seems probable that, with but few exceptions, the general laws enunciated will cover the settling behavior of all pulps encountered in metallurgical plants. However, it must be recognized that there is still a vast amount of work to be done upon certain phases of the subject; therefore, at this time we will attempt only a discussion of the behavior of ore pulps during the process of settling or dewatering, under certain given conditions. The laws and principles controlling these conditions are not fully established, so that a complete discussion of them will not be attempted in this paper. In metallurgical practice, slime pulp consists of water, finely divided sand

Jan 3, 1916

By R. E. Cech

Particles -3 to 30 µ diam of a 29.5 pet Ni, 70.5 pet Fe alloy after being melted and solidified while falling through a hydrogen atmosphere were found to contain a distortion-free body-centered-cubic phase. In most particles, the amount of body-centered-cubic phase approaches or equals 100 pet. It was shown by a series of experiments that this phase forms directly from the liquid. It is pointed out that a mechanism previously suggested in recent papers on the theory of the liquid-solid transformation can account for the solidification of body-centered-cubic phase in a temperature range where face-centered-cubic is the stable phase. IN the course of an operation to produce powders for a study of the martensitic transformation in Fe-Ni alloys, an unexpected phenomenon was observed. Powders of a 29.5 pet Ni alloy, which has a subzero M, temperature, were found to contain considerable amounts of a body-centered-cubic phase at room temperature. The experiments to be described were designed to elucidate the mode of formation of this unexpected phase. Experiments and Discussion An alloy containing 29.5 wt pet Ni, balance iron, was vacuum melted from high purity electrolytic iron and carbonyl nickel shot and solidified in the crucible. The metal was converted to oxide, ground to 100 pet <37µ, pressed to a cake, and homogenized 20 hr at 1350°C. To insure homogeneity the grinding, pressing, and homogenizing heat treatment was repeated a second time. The oxide was then ground to 100 pct <37µ and hydrogen reduced at 500°C. The reduced powder was given a spheroidizing treatment to produce spherical cast particles. The treatment consisted of dispersing the particles in hydrogen and allowing them to drop through a vertical hydrogen furnace set to a temperature higher than the liquidus of the alloy. This operation, commonly known as shotting, has been described more fully elsewhere.&apos; The powder produced by this method was found to contain approximately equal parts of body-centered-cubic and face-centered-cubic phases. A magnetic separation technique, previously described,&apos; was applied, and it was found that particles were either completely face-centered-cubic or nearly completely body-centered-cubic. The microstruc-

Jan 1, 1957

By Anthony Folger, Charles E. Straub

Kansas produced 38,150,878 bbl. of oil in 1928 and 40,658,170 bbl. in 1929, thereby retaining its rank as fourth among the oil-producing states of this country. Production for 1928 was less than that for 1927 (Fig. 1) because of a decrease in the number of completions, but the average initial production per well (Table 1) shows an increase due to the completion of wells of comparatively large capacity in the new Valley Center pool of Sedgwick County. This increase in average initial production per well was further augmented during 1929 by completion of additional wells of comparatively large capacity in the Valley Center pool and the new Greenwich pool of Sedgwick County. Production for 1929 exceeded that for 1928 and threatened to exceed all records except that of 1918, however, production was prorated in

Jan 1, 1930

By Akira Ishizu, Nobuo Matsui, Hideo Yamamoto, Tatsuya Nagahama

At Kamioka Mine of Mitsui Mining & Smelting Co., Ltd., Japan there are three mills, treating a total of 6400 t/d of lead-zinc Ore. In the lead-zinc bulk differential flotation at Shikama Mill the addition of reagents is automatically controlled by the feed rate, the lead and zinc content in feed, froth and tailing, the pH and the concentration of cyanide ion in the pulp. As the zinc thickener overflow at Shikama Mill contains CU(CN)3--, ZnS, CdS, CN-, xanthate and frother, all the ingredients in the over- flow other than CN are floated by using the Nagahm flotation machine, and the water containing only CN- is effectively recycled to the lead- zinc differential flotation circuit. In the lead-zinc straight differential flotation at Mozumi Mill, the overflow of tailing pond is recycled especially to the cleaning flotation circuit by decreasing the pulp density. Thus the integrated recycling of wastewater greatly reduces environmental problem and in addition, it generates sizeable profit.

Jan 1, 1977

By D. C. Shelton

This paper discusses the metallurgical testing procedures and their applications at the laboratories and mills of Pima Mining Co. The author shows, using discussions and case histories, that routine sampling and evaluation of daily and monthly data can be as valuable as thorough laboratory investigations and mill test work. A great deal of valuable information can be made available this way. This paper discusses laboratory and mill metal-lurgical testing procedures and their applications at Pima Mining Co., located about 25 miles southwest of Tuscon, Ariz. The Company, incorporated in 1951 (the year the orebody was found) in California to operate the Pima mine, is jointly owned by Cyprus Mines Corp., Utah Contruction and Mining Co., and Union Oil Co. Milling started in December 1956. The main Pima orebody is a contact metamorphic vein of copper-bearing hornfels with an average dip of 45° to the south with an east-west strike. The hanging and footwalls are quartzitic pyroclastics (arkosite) containing some sulfides. Barren igneous intrusions are also present. Conglomerates and alluvial wash cover the deposit to a depth averaging about 200 ft. The principal copper mineral is chal-copyrite. Native copper, chalcocite, and minor amounts of chrysocolla and other copper minerals are also present, together with sphalerite and some molybdenite. Generally, it has been noted that the ratio of chalcocite to chalcopyrite is higher in the lower grade ores, while as the grade increases, there are only minor amounts of chalcocite. Open pit mining is employed at Pima, using both trucks and an inclined skiphoist system. A detailed description of Pima Mining Co. operations was presented by Spaulding et all. More recently another orebody to the north and east of the present pit has been discovered and will be placed in operation within a few years. This ore is of a porphyritic rather than a lode nature since values are disseminated in both igneous and metamor- phosed sedimentary rocks. The new orebody is expected to be harder and cleaner than the present deposit. The views expressed in this article are those of the author and do not necessarily reflect those of Pima Mining Co. nor of the profession in general. PlMA MILL The following outline of milling practice is presented to furnish a background for later chapters of this report wherein specific problems will be detailed and analyzed. Run of mine ore is crushed in three stages, using conventional equipment to 85% minus 1/2-in. for feed to two 10 x l6-ft rod mills operating in open circuit. Each rod mill discharge is split between two 10% x 13-ft ball mills in closed circuit with three 20-in. cyclones. In addition, a 7 x 12-ft ball mill with one 20-in. cyclone receives part of the discharge from one of the rod mills. This equipment was manufactured by Allis Chalmers and Equipment Engineers. The cyclone overflows are combined, sampled and, after joining the regrind cyclone overflow, are distributed into 12 10-cell Fagergren 66-in. flotation machines. The primary rougher concentrate produced

Jan 1, 1965

By F. F. Poland

The purpose of this paper is to describe a new process for the refining of secondary copper-base metals and a specially designed high-temperature electric-resistor furnace used in the process for the distillation of zinc from these metals. The process was used for the conversion of nickel silver to cupronickel and to recover the zinc content in metallic form. It also proved applicable and economical for the treatment of scrap brass for separating and reclaiming the copper and zinc. The relatively large furnace developed for the distillation of zinc is described in detail, for it made economically possiblc the direct recovery of metallic zinc from scrap brass, which is a new step in the processing of such material. Considerable interest has been shown in the utilization of the distillation furnace for other metallurgical processes, where it is of advantage to operate in a controlled neutral or reducing atmosphere, or to avoid having the processed metal in contact with refractories other than carbon, or to operate at temperatures between 3000 and 4000°F. Purpose of Development It was recognized early in the war effort that nickel would become a critical metal. therefore all nickel stock and alloys containing relatively high percentages of nickel were frozen immediately. Among these alloys were considerable quantities of various grades of nickel silver, an alloy containing copper, nickel, zinc, and in some grades lead, also minor amounts of iron, manganese and other constituents. At the time there was no existing plant or process to eliminate the zinc, lead, and minor constituents so as to convert this metal to cupronickel, one of the important alloys needed by the U. S. Navy for condenser parts. Therefore the Bureau of Industrial Conservation of the War Production Board requested the executives of the leading nonferrous metal companies to have their metallurgical staffs study the problem of converting this metal to cupronickel conforming to U. S. Navy Specification 44T40. The composition specified therein is as follows: nickel, 29 to 32 per cent; zinc, 1.00; iron, 0.00 to 0.60; lead, 0.05; tin, 1.20; manganese, 0.00 to 1.00; total of other elemcnts (maximum). 0.50; copper, remainder. The problem in converting these alloys to cupronickel was the elimination of zinc, lead, iron, manganese, and other elements without appreciable loss of nickel to slags or other by-products. Revere Copper and Brass Incorporated, through its Research and Development Department, undertook to solve this problem. A Government-owned plant was built at Rome, N. Y., and there the conversion was made successfully.

Jan 1, 1949

By Doll. H. G.

THIS paper discusses a method and apparatus for determining the dip of formations traversed by a drill hole, by means of electrical measurements in the hole. The process consists in recording the Spontaneous Potentials present along three oriented generatrices in the hole, By comparison of the three curves thus obtained, after application of a correction factor to compensate for any deviations of the hole, the dip angle and the dip direction are determined. Excellent accuracy is obtained for dip angles over 10°. Because the method is simple and the apparatus rugged, the measurements are rapid and reliable; consequently, they can be made at all the levels that are of interest at any time after the well has been drilled. Mechanical cores are not needed to evaluate the dips. A convenient, time-saving procedure is to perform the dipmeter survey at the time the electrical log is taken, using for both operations the same cable and truck. Actual examples of results obtained in wells of the Gulf Coast area are given.

Jan 1, 1942

By L. A. Panek

During the past three years, USBM has developed an apparatus and technique for direct measurement of existing pressure and change of pressure in mine rock. This relatively simple and inexpensive monitor is reliable for months after being installed. It is used to determine shift of ground pressure created by different sequences of mining, to ascertain the cause of rock failures, and to evaluate the need for artificial support. The technique has been employed to measure pressures in limestone, greywacke, concrete, diabase, and soft iron ore. When rock is subjected to a load it is deformed. Ordinarily this is observed in a mine as the displacement of one point with respect to another—the deflection of the roof, which may be observed as a convergence between roof and floor; or the extrusion of material from the rib, which may be observed as a decrease of the distance between the rib and the post of a timber set. The effect of excessive pressure may be a rockburst if the rock is strong, or it may be squeezing ground if the rock is soft. Some desirable effects of high stress (high in relation to strength) are the caving of roof in a longwall mining operation, the caving of ore in block caving, and the decrease in mechanical energy required to break down the mineral seam in a retreating pillar-robbing operation. In any case, whether the observable effect of rock load is desirable or undesirable, it is a displacement, and depends on the following four factors: 1) The structure—the size and shape of openings, pillars, and linings, the geologic bedding and jointing. 2) The mechanical properties of the rock—prin-cipally the strength, modulus of elasticity, and flow characteristics. 3) The load or applied stress—primary sources are the weight of superincumbent rock, which increases with depth, and unrelieved tectonic stresses; secondary sources are redistributed pressures caused by other nearby openings, especially large mined out zones (rock pressure depends partly on the rock structure created by mining). 4) Duration of load, related to the length of time the opening is exposed. CONTROL OF ROCK DISPLACEMENT Rock displacement can be controlled by control of these four factors. Consider now the means of exercising such control over these factors. Control of the structural features is obviously possible to a great extent, as such control is exercised largely by choosing the method of mining and the methods of natural and artificial support. Rock properties vary, even within a particular mine, but they are controllable only in the limited sense that control may be exercised by choosing the beds or zones to be mined so that rocks with undesirable properties will not occupy critical positions within the rock structure created by mining. Rock pressure is the most complex of the four factors through which ground control can be achieved because it is invisible, difficult to measure, and poorly understood. Rock pressure is controllable only to the extent that control is exercised on the rock structure created by mining. Considering openings within a particular mine, time of exposure varies, and is readily controllable because it is easily measured and easily understood — the longer an opening stands, the greater the likelihood of failure or excessive convergence. Control is exercised by choice of an appropriate sequence of driving openings of different classes, such as haul-ageways and rooms, which are required to remain well supported for different lengths of time under different conditions. Again, control is exercised through the method of mining. All controllable factors can be controlled by proper design of the mining method. The orientation and relative positions of the mine workings and the sequence of their excavation are likely to be much more important to ground control than is the design of artificial support. This implies that the major decisions in regard to ground control are made, knowingly or not, at the time the mining method is chosen. WHY MEASURE ROCK PRESSURE In addition to restrictions on the several factors, control implies the measurement of these factors in some sense, whether only qualitatively by visual observation, or by actual quantitative determination with a measuring instrument. Rock pressure is the most difficult of these factors to measure, largely because of the interaction between the measuring device and the rock. Nevertheless, the quantitative

Jan 1, 1961

By H. H. Podgurski, F. N. Davis

In silver alloys containing less than 0.2 wt pet Cu. the reaction 9 + 1/2 0, = CuO(s) was found to proceed to equilibrium between 700o and 808oC. From measurements of the equilibrium dissociation pressures of the CuO at several temperatures, the differential heat of solution and the activity coeflicients for copper in silver were calculated. These values were found to be in reasonable agreement with those calculated from data appearing in the literature. A metastable "copper oxide" with an atom ratio of oxygen to copper as high as 1.7 was formed by internal oxidation at 300°C of these same dilute Ag-Cu alloys. No anomalous behavior was noted in the temperature dependence of oxygen solubility in silver. The solubility minima between 300" and 800°C reported several years ago can be accounted for, at least in part, by reactions with trace impurities, such as copper. Cold-worked siloer exhibits an enhanced permeability to oxygen. THIS investigation was undertaken because of our interest in interactions between solute and lattice defects in metals. The reason for the choice of the O-Ag system for study is the anomaly in the solubility of oxygen in silver reported by Steacie and Johnson1 in 1926, specifically that isobars between 100 and 800 Torr show solubility minima at 400°C. It was also claimed that the copper impurity in the silver was not responsible for the minima. Recently, Eichenauer and Müller2 proposed that surface adsorption might have been responsible for this solubility anomaly, but no adsorption isotherms are available to check the pressure and temperature dependence observed at the low temperatures. Surface-tension measurements on silver made by Buttner, Funk, and udin3 suggest that a considerable fraction of a monolayer of oxygen exists on silver at 922°C and at an oxygen pressure of 150 Torr. To account for the pressure sensitivity reported by Steacie and Johnson1 at 300°C, the oxygen bound to the surface at 922°C cannot be considered relevant; the existence of a surface layer at 300°C characterized by a lower energy of binding would be required to explain the effect. All of our attempts to detect an interaction of this type with surface sites have failed. In this investigation we have not been able to associate the dissolution of oxygen in silver with a dislocation interaction. Evidently, severely cold-worked silver does not contain a sufficient number of trapping -sites for oxygen. Indeed, our work shows that oxidation of trace impurities in the silver was probably responsible for Steacie and Johnson&apos;s results. In addition, we have been able to establish the nature of the reaction with copper impurity in silver by thermodynamic considerations. EXPERIMENTAL PROCEDURE Measurements of both the internal oxidation rates and the solubility were made volumetric ally in a system equipped with a gas burette, a mercury manometer, a McLeod Gage, and a mass spectrometer. The silver and the silver-alloy samples were protected from contamination by mercury vapor from our pressure gages by suitably placed refrigerated (-78°C) traps. Silica reaction vessels were employed for experiments performed above 500°C. Spectroscopically pure gases were used in this investigation. The highest-purity silver used in the solubility measurements was 99.999 pet. By chemical analysis 2 ppm of Cu were found in this silver. The two Ag-Cu alloys used in this research were made up to 0.14 and 0.15 wt pet Cu starting with 99.999 pet Ag. An unexpected source of error was discovered in the course of the work. At temperatures near 800°C silver distilled from the hot silica reaction tubes into cooler regions of our system. Although the weight loss of silver from the sample was not important in itself, oxygen was being consumed by the silver distilled into the cooler part of the system to form a stable oxide phase from which the oxygen was not recovered. In a separate experiment conducted to determine the necessary correction, losses between 0.2 and 0.3 cu cm (stp) of 0, in 24 hr were measured at 810°C. On the assumption that the flux of silver from the vessel to form Ag2O de-

Jan 1, 1964

By W. O. Philbrook

An engineering analysis indicates that the coke rate in present blast-furnace practice is set not by chemical or thermal needs but to give adequate charge permeability for economical driving rates. An equation showing interrelations among pressure drop, gas flow, and charge characteristics has been derived. Flooding conditions and the location of the fusion zone are discussed. Maximum ore size is probably limited by chemical re-ducibility rather than by heat transfer. THE intention of this paper is to show that the ].imitations on the production rate and coke requirement of the iron blast furnace are not primarily chemical or thermal in nature but are related to characteristics of the burden and operation that govern gas flow, heat transfer, and stock movement. A semiquantitative analysis will be developed in terms of standard engineering principles to give a useful picture of the relative importance of physical and mechanical factors in contrast with the chemical features of the process that are more commonly emphasized. Most of the details of calculation have been omitted in the interest of brevity and to avoid submerging the rnain points in a sea of arithmetic. Numerical values have been arrived at by objective methods from reported operating data or by reasonable estimates of material properties where exact data are lacking and then tested to see how well they fit practice, rather than by working backward to find what assumptions are needed to give the desired answers. The analysis is oversimplified in many ways because exact engineering relations have not yet been studied for bed distributions as complex as are known to exist in the blast-furnace stock column. One objective of this paper is to show that the blast furnace, in spite of its complexity, can be at- tacked by engineering methods in the hope that this viewpoint will stimulate the kind of research needed for a more exact treatment. The basic ideas and many of the conclusions presented are qualitatively well known. A careful literature survey to credit the source of all observations not original to the author would indeed be voluminous, and such has not been attempted. T. L. Joseph&apos;s Howe Memorial Lecture&apos; gives an excellent background of what is known about the internal workings of a blast furnace. Other important reference works or sources of specific information will be noted. It is hoped that the present paper will contribute something new, in method of attack and interpretation, that will aid in a clearer understanding of how to operate the blast furnace to best advantage. Factors Limiting Production and Coke Rates The rate of combustion of coke in a blast furnace, as in any fuel bed, is exactly proportional to the rate at which air is supplied. It is axiomatic, then, that the production rate of a furnace is limited by the rate at which it will take wind, i.e., burn coke, and the amount of coke that must be burned at the tuyeres to make a ton of iron of suitable composition. These two possible limiting factors will be considered briefly in the order mentioned. One common restriction on wind rate is flue-dust production. Since the volume of top gas is nearly proportional to the blast volume (by a factor of about 1.35 on a dry basis), an increased wind rate causes a correspondingly increased linear velocity of top gas in the throat of the furnace. The higher

Jan 1, 1955

By W. J. Leas, L. A. Rapoport

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas&apos; which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy&apos;s law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy&apos;s law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By L. A. Rapoport, W. J. Leas

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas&apos; which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy&apos;s law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy&apos;s law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By James A. Barr

Phosphate rock is a natural rock containing one or more phosphate minerals usually calcium phosphate, of sufficient purity and quantity to permit its use, either directly or after beneficiation in the manufacture of commercial products.1 The principal minerals in phosphate rock have the apatite structure which may be represented by the type formula: Ca10(X2) (PO4)6 where X represents the hydroxyl group (OH), chlorine or fluorine, either singly or collectively. The calcium may be partly replaced by sodium, magnesium, and other positive ions such as manganese, strontium, lead, uranium, cerium, yttrium and other rare earths. The PO4 radical may be partly replaced by small quantities of UO4, AsO4, SiO4, CO3, SO4, or Vo4. A typical commercial rock is usually a calcium phosphate containing 3 to 4 pct fluorine, the major impurities being limonite or other iron oxides, clay, aluminum phosphates and silica as quartz sand. A little vanadium is present in most of the domestic rock deposits (except the Tennessee Brown Rock), according to Jacob, Hill, Marshall and Reynolds! A little uranium occurs in the Florida leached zone, as will be brought out later. The chemical analyses are reported as P205, or tricalcium phosphate Ca3(PO4)2, the latter often designated by the trade name BPL (bone phosphate of lime). Commercial analyses usually report iron and alumina as oxides, lime as CaO and silica or insoluble. Colony3 examined many samples of apatite, staffelite, dahlite and American phosphorites and concluded that all have identical X-ray diffraction patterns. The phosphates in the phosphate rock have very minute crystalline structures. The mineral apatite Ca3(F.Cl) (PO4) 3 is the principal primary source of the element phosphorus, and occurs widely distributed in igneous rocks but rarely in a minable mass. Only about 12 pct of the world production of phosphate rock comes from primary apatites; the remainder is derived from secondary phosphorites. These phosphorites have been formed by the alteration of sediments by solutions containing phosphoric acid. Such solutions have come from the weathering or leaching of igneous rock containing apatite, bone deposits of prehistoric animals, marine life or guano deposits. These phosphorites are mostly alterations of phosphatic limestones. The sedimentary phosphate deposits are of marine origin and may have been enriched by subsequent solution of the more soluble calcium carbonate by waters containing carbon dioxide, by physical concentration by wave action, and by redeposition of the dissolved phosphate ions. Uses of Phosphate Phosphorus is the spark of life and is the structure builder and one of the main elements of plant food (fertilizer). Without phosphorus, life cannot exist. A "complete" plant food[t] in addition to phosphorus compounds contains potash, which acts as a catalyst to convert nutrients to useful forms, nitrogen to supply the growth element and many minor elements. The cycle of supply of phosphorus is from the apatite to solution and soil, absorption of plant life, decay and return to the soil or by animal life feeding on the plants. With insufficient supply of phosphorus in vegetation, life is not prolific. If crops are removed from

Jan 1, 1960