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By Paul Tyler

THE ferroalloying elements are connecting links between the steel industry and the nonferrous metal industries. Although ferroalloys are distinctly nonferrous themselves, they serve the steel industry either in the manufacturing process or in modifying the product-in some cases so that it may compete in the markets with nonferrous metals. Of the 92 elements generally accepted by chemists as constituting the primary building blocks of matter, all but the very rarest have been investigated with a view to employing them in steel manufacture. The surprising thing is that so few have been found commercially acceptable. Despite the relatively small number of elements involved, the employ-ment of alloys in steelmaking is one of the most complicated and probably one of the least well understood of modern industrial enterprises. A great deal has been written regarding the action of individual elements and a profuse and somewhat acrimonious literature covers pretty much the whole field of ferroalloy ore supplies. In the middle ground between the miner and the steelmaker developments are less carefully watched by most observers, and except for an occasional description of the technique of some conversion process or the tariff hearings in Congress, very little is said about them. The purpose of the present paper is to describe in relatively nontechnical terms this highly complex industry and to study its relations to our national progress.

Jan 1, 1933

By M. C. Fuerstenau, J. D. Miller

The response of calcite to flotation with saturated fatty acids and alkyl sulfonates of various chain lengths is presented. The amount of collector re-quired for flotation is shown to decrease systemati-cally with increasing carbon content from 8 to 12-carbon atoms per molecule. This systematic flotation response is correlated with the solubilities of the calcium-collector salts, which were established with a nephelometer. The 14-carbon collectors deviate from this systematic behavior, and no flotation is possible with the 16-carbon homologs. As determined by infrared analysis, the mechanism of collector adsorption involves a specific chemical reaction be-tween the collector and the surface. A reaction of the form CaCO3(s)+ 2 RCOO"=*=Ca(RCOO)2(s) + C03= is suggested. The pH of the system is also shown to be a most important parameter as it controls the carbonate, calcium, and collector ion concentrations in solution and thus controls flotation response. The importance of hydrocarbon chain length of collectors was recognized early, and various studies have been made on this aspect of flotation. Wilkinson, ' for example, noted that as the chain length of alkyl xanthates is increased, the amount of collector required for flotation of sphalerite is decreased. The same effect has been shown in the flotation of galena.2 Similar results were obtained when malachite3 and calcite4 were floated with various fatty acids. DeBruyn5 has shown that a similar phenomenon occurs when quartz is floated with amines at constant pH. Recently, Fuerstenau, Healy, and Somasundaran6 correlated this phenomenon with the van der Waals cohesive free energy of association of the hydrocarbon chains. It seems unlikely, however, that chain association could be involved in the sulfide and carbonate systems with the collector additions employed, especially with the short-chain xanthates. Rather, it would seem that the decrease in collector concentration with increase in chain length noted for flotation is related to the solubility of the metal-collector salt. The purpose of this investigation is to verify this premise and also quantify this phenomenon if possible. Calcite was selected for study with both alkyl sulfonates and saturated fatty acids as collectors. EXPERIMENTAL MATERIALS AND METHODS The collectors used in this investigation ranged from 8 through 14 carbon atoms per molecule. The fatty acids had a reported purity of greater than 99%. The sodium alkyl sulfonates were provided by the Marathon Oil Cot, Littleton, Colorado, and had the

Jan 1, 1968

By Frank R. Barnako

Coal mining is a hazardous occupation, but tremendous progress has been made in reducing accidental injuries and deaths in the mines. Let us take a look at the hazards in coal mining and the accident record. COAL MINE SAFETY TODAY Underground coal mining creates underground open areas, rooms, and haulageways. The roof (top) and ribs (sides) become highly stressed, and because coal and slate are very weak in tension or compression they frequently fail and fall from the roof and ribs unexpectedly. This is the most hazardous condition miners must cope with underground, and it has consistently produced the greatest number of fatal injuries in the coal mining industry. Only very sophisticated equipment, but which is not yet practical for use underground, is able to detect the buildup of stresses that may eventually lead to a roof or rib fall. Today's miner still looks for fresh cracks in the roof or rib, listens for the "drummy" sound, and feels vibrations from loose material in the roof, when tapped with a sounding stick, in order to find material which may fall. Once located, it is barred down, but if this is not possible, it is then secured to prevent it from falling. The next great& hazard is the equipment used to mine or haul coal. It is large, heavy, reacts quickly to its controls and is operated in con- fined areas with low lighting levels. The record of the last few years shows that fatalities attributable to mining and hauling equipment are about equally divided. Thorough training as part of a complete safety program is necessary to teach employees the hazards of loose roof, rib, and machine operation in order that they can work in the safest way possible. Unless there is such a program, the trade is learned by trial and error with a resulting tragic.

Jan 1, 1973

By Charles N. Bell

The Telluride mining district of southwestern Colorado is defined by the 37" 45' and 38" parallels of latitude and 107" 45' and 108" meridians of longitude. Telluride was never a boom camp, but has had a steady growth. In recent years, notwithstanding the business depression of 1920, the business has been the same as in normal years. The first prospector is said to have appeared in 1875, in which year locations on the Smuggler vein were made. Shipments were made in 1877 and 1878, and in 1879 milling the ores was attempted. While the district produced high-grade ores, it did not become important until 1890, when the Rio Grande Southern R. R. was completed from Ridgway to Telluride. The railroad has since been extended to Durango. In the fall of 1896, 400 stamps were in operation, and the annual production was $3,000,000.00, two-thirds of which was gold. The total production from 1875 to 1923 was: gold $58,274,527; silver 41,-830,920 oz., valued at $31,016,893; copper 15,258,866 lb., valued at $2,533,291; lead 166,056,484 Ib., valued at $8,324,910; zinc 18,141,182 Ib. valued at $1,323,787; or a total production of $101,473,408. All claims are held in fee. Most of them are 1500 by 300 ft. but claims located within the last few years are 1500 by 600 ft. General supplies are obtained at Telluride, Denver, and Salt Lake. The largest mines are within 6 miles of the town of Telluride. Denver is 422 miles and Salt Lake is 439 miles, by rail, from Telluride. One-half of the distance to Denver and one-sixth of the distance from Telluride to Salt Lake is by narrow-gage railroad. The labor is efficient. The best miners are Italians and Austrians, then Slavs, Greeks, and Mexicans follow in the order mentioned. There are no labor unions. There are no serious mine pumping problems, the drainage being through adits. The Tomboy and Smuggler companies pump water from their reservoirs, the former for milling and domestic purposes and the latter for milling, power, and domestic purposes. BIBLIOGRAPHY A partial bibliography of the Telluride District is: Geologic Atlas Telluride No. 57; Preliminary Report on the Mining Industries of the

Jan 1, 1925

By H. Y. Yancey, B. M. Bird

During the past four years the experimental work in coal washing carried on by the U. S. Bureau of Mines and the University of Washington has been devoted mainly to the development of special methods for the tabling of fine sizes of coals that are difficult to wash. One important outgrowth of this investigation has been the application of hindered-settling classification to coal tabling. Although used for many years in ore dressing, the term "classification" as used here may be new to many readers. It may be defined as the separation obtained when a bed of particles is held in a uniform state of suspension in an upward current of water, either continuous or pulsating, just sufficiently strong to keep the bed in a mobile condition. A common example of this type of separation is a jig in which there is no suction stroke. When the hindered-settling classifier is used with the coal-washing table, the fine-size raw coal, instead of being fed direct to tables, as is the prevailing practice, is first fed to the classifier and grouped, according to the rate of settling against the upward current of water, into perhaps six separate products. After dewatering, each of these except the sixth, a refuse product, is elevated to a seperate feed bin arid washed on a separate table. This paper gives a brief discussion of the basis for the use of hindered-settling classification of a table feed; a description of the experimental work; a comparison of the results obtained with and without classification; and a discussion of the application of the classifier in commercial coal washing. Basis for Use oF Hindered-settling Classification of Table Feed Although theoretical reasoning might be used to justify treating a table feed by hindered-settling classification,l the simplest method of demonstrating the need of such a step before tabling is to show the

Jan 1, 1930

WITH the economic situation of the world what it is, we may expect important events in every month of 1922, and January showed us some-what of the nature of things that will happen. The Germans announced their inability to meet in full the reparation payments that were due Jan. 15. The Su-preme Council arranged a plan for them to pay some thing on account every 10 days, and called a conference at Cannes to talk things over. While this conference was in progress Premier Briand resigned and was suc-ceeded by Poincaré. This emphasized the growing differences between British and French policies and interests. The French want to exact the utmost from the Germans; so do the British. The latter think, however, that the French aims will so cripple the Germans that they can not work properly and hence can not trade. Great Britain, with a huge unemploy-ment problem, must have trade. The French thought that Briand was unduly deferring to the British and withdrew their support of him. The other important political developments of the month in Europe were the establishment of the Irish Free State, relieving the British of the vexatious Irish question; and the growing tendency to recognize the Soviet government of Russia and admit its representa-tives into international conferences. In the United States the great political event was the establishment of the dominance of the agricultural bloc in the Senate, which implies the passage of agrarian legislation that will probably be unwise. Economically, there was no progress in the United States. If anything there was probably some reces-sion in the physical volume of business. There were some further reductions of wages, but these were irregular, geographically, and moderate in amount. The great unionized trades maintained the jam. Events of great importance were the formal demand of the anthracite coal miners for increased wages on April 1 and the declaration of the bituminous coal miners that they would resist a reduction at that time. The attitude of these groups is believed to presage labor troubles in the spring. In the metal markets affairs were dull during Janu-ary, but prices were generally firm, save for a little further weakening in iron and steel. In the matter of production, however, there was some quickening of activity, especially in copper, zinc and iron.

Jan 2, 1922

Joseph Esrey Johnson, Jr., had already achieved rare distinction as an able metallurgist, clear thinker, brilliant author, and wise consulting engineer to bankers and operators; he had achieved the essentials of a great career when dcath cut short his activities on Apr. 4, 1919, in the forty-ninth year of his age. He belonged to a family of iron blast-furnace men and mine managers. His father, Major J. E. Johnson, after serving with distinction in the Army of the North, identified himself with the iron mines and blast furnace at Longdale, Va., with which he was connected during almost his entire business life. It is significant, that, during those troublous times of reconstruction in the South, he enjoyed always the affection and respect of his neighbors and associates alike. From him his son obtained not only a thorough training in blast-furnace practice and iron mining, but great personal courage and force of character. His mother, who survives both her husband and sons, possesses rare intellectuality, humor and a tenderness and human sympathy which those who were privileged to know well J. E. Johnson, Jr., recognized beneath his exterior of aggressiveness and will power. In a recently published analysis of the qualities which characterize the world's great men, three traits stand out preeminently; viz., independence, courage, and intellectuality. Each of these characteristics J. E. Johnson, Jr., possessed in extraordinary degree. His early education was obtained under a private tutor at Longdale, and this circumstance probably enhanced a natural tendency to independence of character and individuality which, however, under the control of his unusual power of straight thinking and clear analysis never allowed him to go far astray. It has been said of him that if once he set his mind to a problem, however knotty, he scored a bull's-eye before the subject was dropped. His manner of attacking a subject involved first mastering the details of the available knowledge; then, putting this acquired information to one side, with an untrammeled mind blazing out a path of his own, so clear, so well-defined, and expressed in such simple terms that he illuminated the whole subject without distorting the original data or discussion. His two books, "Blast-furnace Construction in America" and "The Principles, Operation, and Products of the Blast Furnace, "on the iron blast furnace together form the most comprehensive, the most enlightening, and the most useful treatise on the subject ever produced in any language. But his ability did not end with the mastery and elucidation of principles enunciated by his predecessors; his own

Jan 1, 1920

By E. A. Holbrook

Research, primarily, is finding out the truth. Research applied to enigeering opens the door to new principies and processes, the application of which benefits mankind in a material way. The engineer believes that investigation instituted with the primary view of making the results directly applicable to the industries is the highest type of research. Coal is essentially the basis of modern industrial civilization; therefore, any considerable research pertaining to coal must link itself to the industry by practical application of the results of the research. In other words, all investigational work connected in any way with coal leads to conclusions that permit a better understanding of the origin, nature of occurrence, composition, better and safer mining, more careful preparation, or greater efficiency in utilization of coal. Modern engineering research has been fostered essentially by universities and in the laboratories of institutions of learning. Coal problems that lend themselves to solution in the laboratories have been first attacked and are perhaps the farthest toward solution. For example, a great amount of research work has been carried out with the various phases of chemistry connected with coal. On the other hand, the equally important problems connected with methods of mining have received but little attention, primarily because their solution involves the continued use of a great and expensive laboratory, which is none other than the mine itself. As many of the problems already solved have had chemistry as their background, so many of the problems unsolved have physics as their background; there are also unsolved problems that deal in coal economics. Even psychology must be called upon in future coal-mining research as a basis for solving those great problems that deal with human relationships. 'In general, considerable advance has been made in coal research dealing with chemistry, not so much progress has been made with problems having physics and engineering as a background, while there is a tremendous range of untouched problems that deal essentially with business and psychology. Research in coal mining is not a new development. In the chronicles of the northern coal trade as published in the Transactions of the North

Jan 1, 1920

By J. C. Febles

HISTORY. THE use of iron for the precipitation of copper was known at least as early as the fifteenth century. Both Paracelsus and Basil Valentine refer to it in their writings, as early as 1500 A. D. It was used in Peru, for this purpose prior to 1637, and at Rio Tinto, Spain, as early as the sixteenth century. The statement has been made repeatedly that in the early history of the mining industry at Butte, the practicability of this method of recovering copper from solution was overlooked, and that enormous quantities of copper-bearing water were allowed to go to waste, the copper in which might easily have been recovered at small cost; and that this oversight on the part of the mine operators was due to ignorance of this method of recovering copper. As a matter of fact, very little copper-bearing mineral was encountered in the mines of Butte until a depth of 400 or 500 ft. bad been reached, and in many cases much greater depths were necessary to reach the copper-bearing zone. The water encountered in the upper levels (although in most cases quite highly mineralized) contained little or no copper, and it was only after considerable areas of copper-bearing ore had been uncovered and developed that copper sulphate began to. appear in the mine water in any considerable quantity. In fact, the first water that was observed to contain copper carried it in such small amounts as to be of little or no importance. It was only after years of underground work had opened extensive areas of stopes, drifts, and other underground workings, these being subsequently filled with waste, nearly all of which contained small copper values, which became oxidized by exposure to the air and were acted upon by the slowly percolating mineral water, that the recovery of copper from mine water became commercially important.

Jan 7, 1913

By W. M. Peirce, R. K. Waring

Zinc of high purity offers definite advantages in certain fields. A process by which zinc of 99.99 + per cent purity is produced by pyro-metallurgical methods is described in this paper. The process consists of a fractional distillation following the primary reduction; this fractional distillation employs the principles of rectification for the separation of lead and other high-boiling impurities and cadmium and other low-boiling impurities. Theoretical Considerations Involved in Production of High-purity Zinc by Distillation Fractional distillation, fractional condensation, and rectification are recognized methods of separating mixtures of liquids. In the field of organic liquids these methods are widely used but not commonly to effect as complete a separation of liquids as is done in the problem under consideration. Zinc boils at 905" C., cadmium at 778" C. and lead at about 1620" C. Zinc may contain from several hundredths of one per cent to over one per cent each of cadmium and lead, and the problem is to reduce these impurities to a few thousandths of one per cent. For lead and zinc, the spread in boiling points is substantial, 715° C., while for zinc and cadmium it is only 127" C. The basic limitation of any separation by distillation may be found from the relation between the equilibrium composition of the vapor and the liquid for all mixtures of the two substances involved. If a mixture of constant boiling point is found, or if a stable compound that vaporizes without dissociation occurs, there is a definite theoretical limit to the degree of separation that is possible when operating at atmospheric pressure with respect to that mixture. Otherwise, any degree of separation is theoretically possible. The equilibrium composition of vapor in contact with liquid mixtures of zinc and cadmiurn at the boiling point has been determined experi-

Jan 1, 1937

E. E. THUM,* Salt Lake City, Utah (written discussion?).-While the present paper is confined exclusively to the microstructure of fusion welds, it may be of interest to draw attention to certain appearances existing in resistance welds such as spot or butt-welded joints produced by the Thomson process. For instance, a butt weld between two pieces of carbon tool steel (carbon about 0.90 per cent.) will show concentric ellipsoids of the various materials from pearlite to martensite. The surfaces of demarcation are quite well defined, the center of the ellipsoid being at the intersection of the axis of the piece and the plane of the weld. Often these unannealed welds show a troostitic center; evidently this core was not quenched as rapidly as the surrounding shell. Such specimens are beautiful samples for instruction purposes. An annealed butt weld of this kind will show a very well defined central ellipsoid of decarburized, materials. It is interesting to consider the reason why this change takes place. It must be understood that the heat is on the metal for a very short time, possibly 30 sec. It is therefore evident that the decarburization, or migration, of the carbon takes place with extreme rapidity. Since no blowholes are evident in a well-made butt weld, the deoxidizing air and the products of combustion must migrate with the highest speed; second, the carbon might migrate back into the stock; or, last, a large proportion of the pearlite may be extruded with the hot metal, which forms a fin at the plane of weld. Examining these possibilities in detail, it is not probable that such deep-seated decarburization, extending with maximum effect to the very center of a 2-in. round bar, is done by reaction with the oxygen of the air. This would postulate entrance of oxygen and egress of carbon oxides in large quantity without leaving behind traces in the form of oxides or

Jan 5, 1919

By J. D. Wright

INTRODUCTION The Endako deposit was first explored in 1926, but development waited until the early nineteen sixties. It first came under the control of Placer Development in 1963, and early in 1964 a decision to bring it into production was reached. The deposit is located near the geographic center of British Columbia, and is served by an east-west communication system including a paved highway, mainline railway and good telephone, teletype, and computer facilities. The plant area is shown in Figure 1. The operation is known as the Endako Mines Division of Canex Placer Limited of Vancouver. First production was achieved in June, 1965, at a nominal rate of 10,000 tons per day, but it soon was closer to 15,000 tons per day. In 1967, two new grinding and flotation, sections brought capacity to the present rate of approximately 27,000 tons per day. With mill heads of around 0.15 percent MoS2, production is about 14,000,000 pounds of molybdenum per year. A flowsheet of the operation is given in Figure 2. A legend for this flowsheet is given in Table 1. Published ore reserves are estimated at 214,500,000 tons at an average grade of 0.143 percent MoS2. PRIMARY CRUSHING The 85 or 100-ton haulage trucks dump over a grizzly into a 42 inch x 65 inch C.A.C. (Canadian Allis Chalmers) gyratory crusher. The

Jan 1, 1976

By W. M. Weigel

SALT production in Louisiana and Texas at the present time is entirely from salt domes of the interior and coastal groups. Before and during the Civil War salt was recovered from numerous salines and salt springs by evaporation in open 'kettles. The location of these in nearly every instance was near what is now known to be a salt dome, and the source of the salt in the salines and spring waters was that in the salt core. The tops of many of the shallower domes have been subjected to erosion1. The discovery that the salt occurred as large masses of rock salt in the form of domes was made in May, 1802, at Avery Island, La., by John Marsh Avery, grandson of the original owner, John C. Marsh, who built the old salt works in 18122. The first shaft for mining was sunk on the Avery dome in 1867 by Chouteau and Price. It was 90 ft. deep, about 58 ft. being in solid salt. It was abandoned in 1870. There are three general groups or fields of salt domes; interior Louisiana in northern Louisiana, interior Texas in northeastern Texas, and the coastal domes nearer the Gulf Coast and extending from the Mississippi River to the Rio Grande. This last group contains by far the greatest number of domes. As many of the coastal domes especially are prolific producers of petroleum and a few of sulfur, their geology has been intensively studied and fully covered in the literature. The depth to the top of the salt varies from near the surface, where shallow ground waters have dissolved the salt to just below recent deposits, to several thousand feet, where the depth has been estimated only by geophysical methods. The diameter of the salt core varies from less than ½ mile to over 2 miles. Only domes where the salt is compara-tively near the surface have been developed for commercial salt. Three deeper domes, which will be described later, have recently been developed or are in process of development, as a source of brine for chemical use.

Jan 1, 1935

By Nicholas J. Grant, William H. Ferguson, Bill C. Giessen

Ta-lr alloys have been examined over the complete range of compositions using metallographic and X-ray techniques. The terminal solid-solubility limits, solidus temperatures, and intermediate phases were determined. There are four inter-mediate phases: o, tetragonal, analogous to a (Fe-Cr); 0,. orthorhombic; az, tetragonal; and a TaZr,, cubic, AuCu, structure. Of these, o and a, melt peritecticaLly, a, decomposes peritectoidally, and a TaIrs has a congruent melting point. Three peri-tectic and one eutectic reactions occur. 1 HE Ta-Ir phase diagram has not been treated in the literature. Intermetallic phases and terminal solid solubilities have been described and estimated.'-4 The previous findings have been confirmed in this work. A complete diagram with additional phases and solidus curves is presented. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by the National Research Corp., Cambridge, Mass., and iridium powder of 99.9 pct purity, supplied by the Bishop Co., Malvern, Pa. Both powders were -200 mesh. Table I lists the analyses as given by the suppliers. A standard procedure was employed in making the alloy buttons, which was described in detail in Refs. 5 and 6, and which included repeated arc-melting of powder compacts and determination of the composition by the weight-balance method. This is especially justifiable due to the similar vapor pressures of tantalum and iridium. In the critical parts of the diagram, a spacing of 1/2 at. pct was used, based on premelted master alloy material. The observed structures and X-ray spectra were consistent with the composition sequence of the alloys. Table II lists the final alloy atomic percentages with the calculated percent error of composition. Cross sections representative in grain size and composition were selected for the study, as described in Ref. 5. Based on prior experience, no contamination from the tungsten electrode was considered. Temperature measurements were obtained using a Leeds and Northrup optical pyrometer and have been described extensively in Refs. 5 and 6. All heat treatments were made in the high-vacuum tantalum tube furnace mentioned in Ref. 5. Samples annealed in tantalum containers cooled from 1800" to 1000"~ in 5 sec; those annealed in ceramic crucibles cooled over the same range in 15 to 30 sec. The thermal treatments are listed in Table 111. All specimens were homogenized at 1735°C for 24 hr. Tantalum-rich compositions were treated in tantalum buckets. Iridium-rich compositions were annealed in tantalum buckets below the eutectic temperature of 1950°C; up to 2200°C, tungsten-lined tantalum baskets were used; and above 2200°C thoria crucibles were used. It was found that refractory oxides (in early stages of the investigation alumina crucibles were used up to 1800°C and thoria crucibles were used to 2400"~) give off minute amounts of oxygen and thereby influence the microstructure considerably, or react directly with the alloys.

Jan 1, 1963

By H. Ries

Introduction BODIES of pyritic ore in schistose rocks have long been known in different parts of the world. The several occurrences resemble each other in being usually of more or less lenticular shape, inclosed in walls of schist or gneiss, and carrying pyrite, chalcopyrite, and pyrrhotite in varying proportions, as the chief ore minerals. The deposits differ, however, in that sometimes one, sometimes another, of the three sulphides mentioned may predominate. The orebodies in general are more or less closely conformable with the schistosity of the wall rocks, although in cases this may not hold true. The boundaries may or may not be sharp, but in general are fairly distinct. The lenses vary in size, may occur singly, or in groups; in the latter case they may be in line, overlapping, or occasionally parallel. Pinching and swelling of individual lenses is not uncommon. The genesis of these pyritic bodies has provoked much discussion, and they have been variously classed as sedimentary, igneous intrusions, hydrothermal replacements or impregnations, etc. Indeed, in some cases different geologists have most positively assigned widely diverse origins to the same deposit, as in the case of Rio Tinto 1 and Rammelsberg.2 It is true that in the light of modern criteria, we have been able in a few cases to decipher clearly the process of origin and so there seems no doubt now regarding the genesis of the deposits at Rio Tinto, Spain;3 Rammelsberg, Germany ;4 Ducktown, Tenn.;5 southwestern Virginia;6

Jan 8, 1917

By P. Marier, T. R. Ingraham

When cylindrical powder compacts of nickelous oxide (NiO) are heated in an equilibrated stream of SO3, SO,, and 02, in the temperature range 500°to 800°c, tlickelous suljate (NiSO4) is formed as an adherent layer on the oxide. The reaction is diffusion-controlled, with an activation energy of 13 ± 3 kcal per mole. When cylindrical powder compacts of NiSO4 are heated in a stream of dry nitrogen in the temperature range 1000 0to 11500C, NiO is formed at a well-defined interface between the sulfate and oxide. The interjhce migrates into the sulfate at a constant rate at a constant temperature and gas flow. The reaction rate increases with increasing gas flow and decreases with increasing partial pressure of SO3 in the gas stream. Resolution of the partial-pressure data with a Lang-itzliir Adsorption Isothern suggests that about 80 pct of the NiO interface is covered with SO3. The heat of adsovption is about 68 kcal per mole. The activation energy of the decomposition process is 61 ± 3 kcal per mole. MOST of the work reported on the formation and decomposition of nickel sulfate is related to thermodynamics.1-3 No quantitative work has been reported on the decomposition process. The only kinetic work reported on the formation is that by Fletcher and shelef.4-6 whose main purpose was to study the effects of alkali metal sulfate additions on increasing the rate of nickel sulfate formation. They found that, in the absence of an additive, only small amounts of sulfate were formed and the kinetic data were difficult to interpret. However, they suggested that the sulfa-tion of nickel oxide is a diffusion-controlled process for which the activation energy is approximately 17 kcal per mole.6 In this paper, both the formation and decomposition reactions will be examined; and based on the effects of temperature, flow rate, interfacial area, and partial-pressure of sulfur trioxide, mechanisms and activation energies will be suggested for both processes. EXPERIMENTAL Material. The nickel source material used in all experiments was Baker and Adamson Reagent Grade NiSO4. 6H2O, for which the following analysis was supplied by the manufacturer: C1, 0.001 pct; NO3, 0.005 pct; Co, 0.02 pct; Cu, 0.005 pct; Pb, 0.002 pct; Fe, 0.001 pct: insol, 0.005 pct. The anhydrous sulfate was prepared by heating the hydrate at 420°C in a muffle furnace for 5 hr. Nickel oxide was prepared by decomposing the sulfate at 950°C over a period of 10 hr. Method. The technique used for measuring the rates of formation and decomposition was developed earlier in these laboratories.7-8 The method is based on the observation that the kinetic parameters of a reaction can be established in a flow system, with specimens prepared by compacting powder to a uniform pellet shape. The results are identical with those established with solid polycrystalline specimens or single

Jan 1, 1967

By A. S. Michaels, R. S. Timmins

A study of the effect upon oil recovery from an un-consolidated porous medium of chromatographic transport of selected reverse-wetting additives during water displacement is described. Flow tests were performed on hydrocarbon oil-saturated sand columns (containing connate water) into which small volumes of short-chain aliphatic amine solutions were introduced during water flooding. Concurrently, meusurements of oil-silica contact angles, oil-water interfacial tensions and oil-water distribution coefficients were measured us a function of additive concentration. Certain treatments were found to cause a slight reduction in oil recovery, while others produced a significant increase (up to 50 per cent of the normtzl irreducible rninimum oil saturation). Recovery eficiency was correlated most satisfactorily with the maximum degree of reverse wetting produced during additive transport; conditions which resulted in only mild oil wettability of the sand reduced recovery, while those favoring strong oil wetting increased recovery. A mechanism of reverse-wetting additive action during chromatographic transport is developed which ascribes the results to transient changes in oil-solid contact angle during flow, with consequent release of oil trapped by capillary forces. Implications of these observations with regard to improved waterflood efficiencies are discussed. INTRODUCTION The need for finding improved methods of oil production is amply illustrated by the large volume of oil considered economically unrecoverable by existing production practice. Water flooding has long been an excellent method of secondary recovery. However, even in those areas of a formation which are well swept by a water flood, 20 per cent or more of the oil remains trapped within the formation and is not recovered. This trapping of oil within the pores of the rock structure results primarily from interfacial forces. If these interfacial forces were altered, it is possible that the trapped oil could be released and recovered. The addition of surface-active agents to a water flood to alter the interfacial properties of the oil-water-solid system has received considerable attention as a method of increasing oil recovery. Studies of surfactant treatment have yielded varied and, in some cases, apparently conflicting results. Increased oil recovery using surface-active agents has been reported by a number of investigators. Others have found that use of surfactants in a water flood either has no effect upon oil recovery or decreases it. Since surface-active agents tend to alter the formation wettability and oil-water interfacial tension simultaneously, several investigators have tried to determine the role these two factors play in oil recovery. Data have been presented which indicate that the most desirable condition for the solid surface is strongly water-wet. Other results indicate that, although breakthrough recovery may be less, the greatest ultimate recovery is obtained when neutral wettability prevails.", " The desirability of low interfacial tension seems to depend upon the wettability of the formation. Reports of higher recoveries, when the interfacial tension is high in a water-wet system and low in an oil-wet system, are at odds with reports of increased recovery in water-wet systems when surfactants which decrease the interfacial tension are added to the water flood. A review of previous work studying the effects of using surface-active agents in a water flood shows that these agents produce widely different effects and that opinions as to the role of the various interfacial properties are diverse. The consensus, however, is that the interfacial properties are quite important in the displacement of oil from a porous medium by water. Even in those investigations where appreciable increases in oil recovery resulted from treatment with a surface-active agent, economic considerations generally made practical application of the treatment unattractive because surfactants tend to be adsorbed within the formation. This adsorption would necessitate using large quantities of surfactant if all of the flood water were treated to contain a given surfactant concentration, even if this concentration were quite low. Preston and Calhoun suggested that the principles of chromatography could be applied to the use of surface-active agents as a means of increasing oil recovery. A small volume of surface-active material is injec-

[ ] DISCUSSION F A LORIA*-The method of testing gun steel for resistance to surface cracking described in this paper was restricted to the examination of small, rod-shaped specimens The writer would like to point out the importance of other factors in producing defects in forged and bored gun tubes which would not be apparent in this investigation because of the nature of )he test Actual section size would accentuate the possibility of internal wall (bore) defects arising from unequal expansion between the internal and external wall surfaces on firing, resulting in internal tearing Checks and tears on the inside walls arise from internal tensions and nonuniformity on cooling, but the internal tearing can be reduced by using alloys of low expansion and of good thermal conductivity so as to reduce the difference between the outer and inner wall surfaces Also, the possibility of the location of inclusion segregates within a machined gun tube becomes more likely than in a small test specimen The effect of these nonmetallics on gun life and performance is evident when one realizes that the inclusions are soft yet brittle They reduce the amount of plastic deformation which can take place before cohesive failure occurs Once localized fracture has occurred at the position of a chain of these inclusions, a sharp notch (crack) is formed which produces stress conditions more favorable to cohesive failure than to plastic deformation These cracks aid erosion by providing channelways for the explosive gases, eventually leading to the tearing out or spalling of blocks of metal Oxidation of the surface may be partly responsible for the change in the surface of gun steel during firing observed by the author The appearance of burn on the surface is an indication that high temperatures were reached on firing, resulting in a slight oxidation of the surface Since the color of the oxidized film depends on both temperature and time, a higher temperature is required for a given color to form when it is caused by explosive heat, which acts for only an extremely short time at a given spot, than when it is caused by ordinary tempering The cross section of the gun steel specimen, Fig 16, illustrates that the repeated firing temperatures were high enough to cause

Jan 1, 1948

By L. F. Mondolfo, B. E. Sundquist

The undercooling associated with the nucleation of the secondary phase from the liquid by the solid primary phase was studied in sixty binary alloys by means of a hot-stage microscope. It was found that in a system of a and ß, a usually nucleates ß at low undercoolings, but ß does not nucleate a, except possibly at undercoolings approaching homogeneous nucleation. This behavior can be explained in terms of relative interfacial energies and shows that crystallographic disregistry is only a minor factor in heterogeneous nucleation from metallic liquids. PREVIOUS experimental work1-6 on nucleation of solids from liquids has shown that normally nucleation is heterogeneous, and that small solid particles present in the liquid are responsible for the nucleation. These experiments and the theory that has evolved from them have made apparent that there is a "characteristic undercooling" associated with the nucleation of the solid from a given liquid by a given impurity. Little is known, however, about the chemical and structural relationships between the nucleating agent and nucleated solid that control the effectiveness of the nucleating agent in catalyzing the nucleation, as measured by the required undercooling. A review of the literature has yielded seventeen undercoolingsL-6 for the nucleation of solid from liquid metals by "known" nucleating agents. All values come from experiments in which the metal studied was divided into a number of particles (10 to 300 pin diam.) much larger than the number of extraneous impurity particles so as to obtain a large number of particles free of foreign nucleating catalysts. Known nucleating agents are then introduced by coating the droplets with particles or a thin film of the catalyst. Six of the seventeen undercooling values referred to cases where, for various reasons, the identity of the nucleating species was not at all certain. Another six cases involved nucleating agents with a crystal structure that was not known. Four other cases involved undercoolings listed as greater than or equal to undercoolings which were very likely those for homogeneous nucleation. One investigation3 involved adding to droplets powdered oxides, carbides, and so forth that were doubtlessly covered with adsorbed oxide or nitride films. The highly variable nature of these films resulted in highly variable undercooling (as was also found in preliminary work in this investigation). It is apparent that the information on heterogeneous nucleation in liquid metals is too limited to give rise to any definite conclusions on the nature of the catalytic process. With these problems in mind a new method was

Jan 1, 1962

By Richard A. Sheppard

Zeolites-crystalline hydrated aluminosilicates of the alkalis and alkaline earths-are important rock-forming constituents in sedimentary rocks and are potentially valuable industrial minerals. They have a framework structure that encloses interconnected cavities occupied by the relatively large cations and water molecules. The cations, chiefly sodium, potassium, and calcium, and the water have considerable freedom of movement within the structure and give the zeolite their cation- exchange and reversible-dehydration properties. Some zeolites have essential contents of barium, strontium, or magnesium. The basic structure

Jan 1, 1975