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By William P. Blake

The numerous and copious reports of geological surveys made in the lead and zinc region of Wisconsin leave, perhaps, but little room for any original work, or for descriptive details of the nature and origin of the deposits not already given in the exhaustive memoirs of Percival, Whitney, and Chamberlin and their associates. HOWeyer, since the completion of the last survey, in 1879, much more attention has been given than before to the exploration of the ores of zinc, especially of late years, since the region has been better opened up by railways and the zinc industry of the country has assumed large proportions, giving a constantly increasing demand for zinc-ores. A residence of more than a year in the region, and the active direction during that time of mining operations over a considerable area, have familiarized me with the forms and peculiarities of many of the deposits; and it appears probable that some observations upon them, especially from the mining and commercial standpoint, may interest the members of the Institute. A few notes on the structure of the deposits from the mineralogical and chemical standpoints have already been presented by me to the Wisconsin Academy of Arts and Sciences." The presence of lead-ore in the soil at many points along the Mississippi river was well known to the aborigines, and early attracted the attention of the frontier traders, who purchased from the Indians the ore and even lead smelted out by the squaws. The demand for the lead-ore soon increased, and it became one of the early and potent factors determining the settlement of southwestern Wisconsin, and the development of its mining and agricultural resources. The mines of that section, together with those of Missouri and the Mississippi valley, may be said to have been the cradle of mining in the western United States. The deposits of ore being at or near the

Jan 1, 1894

By A. Phillips, H. J. Fisher

The influence of temperature and composition on the viscosity of high-purity liquid metals and alloys of the Pb-Sn and Sb-Cd systems was investigated by the logarithmic-decrement method. The variation of viscosity with temperature above the liquidus followed the equation: n = AeE/RT No large increase in viscosity was found just before normal freezing of any of the metals or alloys investigated. Certain alloys, supercooled below their stable liquidus, however, did show a marked increase in viscosity. Experimental activation energies for viscosity were determined for the metals investigated. Liquid-metal density values were obtained by a modified Joeger's method. IK an investigation of the properties of molten metals, the study of viscosity as a suitable means for studying the physical nature of the metallic liquid state has been utilized. Although interest in the relationship of the liquid to the solid-metal state holds promise of broadening the knowledge of metals in general, much information that is available regarding the influence of temperature and composition on viscosity, especially near the freezing point, is still controversial. The purpose of this paper is to present the results of recent work on this subject. Although interest in factors influencing the fluid behavior of metals and alloys has arisen from theoretical as well as applied studies of liquid-metal properties, the development of a comprehensive theory of the mechanism of viscosity has been handicapped because so little is known about the liquid state. Several theories of viscosity have been proposed and among the more recent are those of Andrade,1 Bernal,2 Frenkel,3 Eyring,4 and Gutmann and Simmons.5 Athough these contributions have helped to establish a basis of approach for studying the nature of viscosity, the fundamental aspects of the variation of viscosity with alloy composition have, in general, been neglected. Experimental Metals and Alloys Investigated: The Pb-Sn and Sb-Cd alloy systems were selected for investigation because they form constitutional features of theo-

Jan 1, 1955

By David R. Mitchell, R. M. Fleming

MANY trends were evident in the coal industry during 1951. Some were favorable for the industry; others were not. Probably those having the most far-reaching consequences are those affecting coal's markets. The rapid dieselization of many railroads and the continued trend toward oil and natural gas for home heating has caused serious dislocations in various mining districts. Mines have been forced to close down or to work on a reduced time basis. Conversely the increased activity in the metallurgical industries has increased the demand for coking and special purpose coals, and the growing production of electric energy has increased the demand in certain areas for steam coals. The increased demand for metallurgical coal and for steam raising by the large utilities is more than equal tonnage-wise to the loss of coal to railroad dieselization and conversions to oil and gas in the domestic market. Since much of the expansion is at captive mines of large corporations, many commercial operators supplying railroad and domestic users have had their markets curtailed without any compensating demand from other sources. Feverish activity was in evidence in many areas by commercial operators attempting to find new markets. The Norfolk and Western Railway is the, only major American railroad committed to the burning of coal. It has an exceptionally good cost record. During 1951, fifteen additional modern coal-burning steam switching locomotives were authorized for construction in the company's Roanoke shops at a cost of about $1,450,000. When the new order is completed the road will own a total of sixty locomotives of the modern-switcher type, including thirty acquired by purchase last year. The Norfolk and Western today is the only American railroad building its own motive power. All of these locomotives burn coal. Production Coal production in the year 1951 will approximate 570 million tons of anthracite, bituminous coal, and lignite. Of this, approximately 7 pet is anthracite. Total production is approximately 30 million tons more than in 1950 and reflects the increase in general industrial activity. Exports are expected to be close to 50 million tons. The industrial stockpile is close to 75 million tons, the highest it has been since 1943. With the exception of the usual local stoppages the year 1951 was unmarked by labor disputes. It was a year of good labor-management relations with a negotiated wage increase unmarred by a work stoppage. This may be the beginning. of an era of sensible negotiations to find agreeable settlements of disputes without the usual protracted bickering and industry-wide strike. The United Mine Workers of America has condemned wildcat strikes, stating that in nearly every, instance proper grievance procedures have not been instituted. Government defense organizations, perhaps profiting by their experiences during World War II, are pursuing a more enlightened program with regard to the fuel requirements of the nation. Many prominent officials have stated that wherever possible coal should be considered the primary source of fuel in all defense expansion. With the increased consumption of steel by defense projects, approval of transportation facilities for liquid and gaseous fuels have been refused where these fuels would enter a coal producing area. Liquid and gaseous fuel producers also have failed to provide satisfactory evidence that they have sufficient reserves and are capable of supplying their product in adequate amounts for the periods of time required. Realization has at last become prevalent that the hydro-electric power installations in several areas are insufficient to handle increased demands.' Steam generating plants are being constructed in these areas and equipped to burn coal. Most notable of these, is the TWA area whose supplemental steam power plants are expected to consume 10 million tons of coal per year when completed. The Pacific Northwest is another area which is expected to follow the same pattern. Nearly all new steam-power generating plants are being equipped to burn coal either as a primary fuel or as an emergency measure. Metallurgical Coal The steel and other metallurgical industries are expanding rapidly to meet increased industrial demands and defense orders. Since these industries are dependent on coke, coke has had a year of high production and can be expected to break all existing records when steel-plant expansions are completed. Most notable of the expansion projects is that of the Delaware River area where the iron ore will be received by ship from Canada and South America. U. S. Steel is only one of several steel corporations that are planning on putting integrated steel producing units in this area. The Defense Solids Fuels Administration announced in December that through. November 30, 1951. 29 projects in eight states, with a total cost of

Jan 1, 1952

By Frederic Dewey

IT IS common to blame irregular assay results upon volatilization and much has been written upon the subject, but there is no. real evidence that, in a properly conducted assay, the loss of either gold or silver by volatilization is sufficient to affect appreciably the result, even when, arsenic or antimony may be present. Bulk assays of flue dust from assay muffles have been published, but the data given are totally insufficient to even approximate the volatilization from a single assay; and such figures as we have indicate the volatilization to be extremely small. Diligent search in the literature and wide inquiry among assayers and instructors have failed to produce a single case where the litharge volatilized in making an assay has been collected and assayed for gold and silver. Having attempted to do this, with most indifferent success, I am not surprised that this has not been done. While various textbooks give volatilization as a cause of loss in cupellation, it may safely be said that in the rare cases where this volatilization is sufficient to affect appreciably the result it is due to excessive temperature. Percy1 says "The loss of silver by volatilization during cupellation is very slight (unless the temperature has been much too high), and may be disregarded." This statement is repeated by the Beringers2 and Smith,3 who includes gold with silver. Mitchell4 says the litharge fume rarely contains over one ten-thousandth of silver. Campredon5 says that at a proper temperature no silver is lost by volatilization.

Jan 2, 1920

By Joseph E. Pogue

THE period of new oil discoveries in Illinois began in February 1937, when The Pure Oil Co. found the Clay City field the forerunner of a number of limestone pools. The importance of the area was emphasized greatly in December of the same year with the discovery of excellent sand production by The Carter Oil Co. at Louden and in June, 1938, with the discovery by The Texas Co. of the Salem field producing from two sands and one lime- stone horizon. By September, 1939, new discoveries in Illinois were estimated to have added, under prevailing production practices, some 500,000,000 barrels to the crude oil reserves of the United States and to have produced to that date some 63,000,000 barrels with daily production passing the 300,000-barrel mark by Sept. 1.

Jan 1, 1939

By AIME

TURMOIL has been rampant in the lead producing industry during 1946. The chronic labor shortage was aggravated by various work stoppages in mines, smelters, and refineries, while shortage of materials was widespread. Price uncertainties helped to confuse the situation in many countries and particularly in the United States until the removal of price control in the latter part of the year. At the end of the first year of peace, lead, which had been comparatively plentiful during the war years, was a scarce and high-priced metal throughout the world. It is the hope of the industry that the law of supply and demand, if allowed to operate without interference, will bring about a satisfactory balance between production and consumption. Under these circumstances it is not surprising that there have been few important developments in the metallurgy of lead, though a number of items of general interest to the industry have been reported. An ore body which may prove to be of considerable importance has been discovered at Mpanda, Tanganyika. The scarcity of lead ore is illustrated by the announced reopening of the La Manche lead mine in Newfoundland, idle for 56 years. A new lead producer came into production when Rhodesia Broken Hill started up its new smelter. Lead concentrate of 75 per cent grade is smelted in Scotch hearths and the lead is refined to market grade by the Harris process without desilverizing. Production is about 1000 tons per month. One Australian lead producer, Mount Isa, has returned to lead production after having operated its lead plant for the production of copper during the war. The East Chicago plant of the International Smelting and Refining Co. has been sold to the Eagle-Picher Co.

Jan 1, 1947

By Paul Torrey

IN his recent article, Stanley C. Herold described some of the principles involved in oil-field rejuvenation. The purpose of this paper is to present certain facts, based upon observations of systematic water flooding of oil sands in the Bradford and Allegany fields of northwestern Pennsylvania and southwestern New York, which, it is believed, will partially substantiate Mr. Herold's opinions. The writer gratefully acknowledges his obligation to the Forest Oil Corpn., the Kendall Refining Co., the Petroleum Reclamation Co., W. J. Healey, of Bradford, Pa., and the Producers Oil Corpn., of Olean, N. Y., for information included in this article; and he is especially indebted to Jerry B. Newby, of the Petroleum Reclamation Co., for helpful suggestions and criticism in the preparation of the paper. It is obvious that, in the calculation of mathematical formulas for the prediction of oil recovery, uniform conditions must be assumed; otherwise, the applicability of the results of such work will be, by necessity, restricted to the area or individual property for which they were designed. Geologic and physical conditions are so variable throughout the fields where water flooding is practiced that it is difficult to devise methods that can be universally applicable. However, it is believed that there are certain fundamental principles which, when applied with specific modifications designed to meet the conditions existing in local areas or individual properties, may yield considerably greater recoveries of oil.

Jan 1, 1927

By Howard I. Smith

THE mineral trona was discovered on Government land in 1938, about 18 miles west of the town of Green River, Wyo., in the core of the John Hay, Jr., well, a test well drilled for oil by the Mountain Fuel Supply Co. in sec. 2, T. 18 N., R. 11o W., sixth principal meridian. Although no oil or gas was reported, the drilling led to a discovery of great potential economic importance and exceptional scientific interest. Trona is a relatively rare mineral found at various places in playa deposits but not previously found at any great depth. It is composed of hydrous sodium carbonate and sodium bicarbonate (Na2CO3.NaHCO3.2H2O). Pure trona contains the equivalent of 70.35 per cent of sodium carbonate. Total sodium computed to carbonate times 1.42 equals the percentage of trona in the absence of other sodium carbonate minerals in the sample. ANALYSES Two short pieces of core sent to the author a few days after the completion of the Hay well were analyzed by R. C. Wells† and found to be exceptionally pure trona. A brief article on this discovery has already been published.1 Arrangements were then made through W. T. Nightengale‡ for the author to inspect and sample the core. The company log of the well included notations of sodium salt crystals from a depth of 1190 to 1820 ft. Not being able to identify all the minerals present, the author selected several specimens of the core for petrographic examinations and sampled the sections of trona for analysis. J. J. Fahey, of the Geological Survey, examined the specimens and reported most of the crystals to be a new anhydrous sodium carbonate and calcium carbonate mineral (Na2CO3.2CaCO3), which he named shortite,2 after Maxwell N. Short.* He analyzed the samples of trona, with the results shown in Table i. [ ] In addition to the 10 ft. I in. of trona in the first section, it is reasonable to assume that the 9 ft. 8 in. for which no core was available for sampling is either mostly trona or some other soluble salt, but it should not be included in calculating reserves. In the part of the core between 1590 ft. 3 in. and 1600 ft. 4 in. the material insoluble in cold water, amounting to about 5 per cent, was estimated petrographically to contain 70 per cent clay, 25 per cent shortite, and 5 per cent pyrite. ACCOMPANYING MINERALS Fahey later secured about 600 ft. of the core for a detailed examination and study

Jan 1, 1942

By B. B. Gottsberger

A NOTABLE feature of the practice of the American mining engineer is the fact that 'his field has been world wide, and the results of his work may be found in all countries. For this reason, the mining engineer is particularly interested in any legislation tending to restrict his freedom in this respect. In their zeal to improve the status of the professional engineer, those responsible for the enactment of the registration laws now in effect in various of the United States may have introduced a practice that will result very much to the detriment of the American mining engineer. He is preeminently interested in the maintenance of the professional "open door," and fame may be the reward of him who calls the first "International Conference for the Limitation of Restrictive Legislation." There is no reason why these United States should be the only country to regulate the practice of professional engineering and, in fact, the movement is spreading beyond its borders. Already, it is necessary for the mining engineer to be thoroughly conversant with the various state laws in order to insure his right to pursue his calling. It may soon be necessary for him to make sure of his status in foreign countries before undertaking work in them.

Jan 1, 1921

By Meguru Nagamori

DURING the smelting of the sulfide ores of copper, nickel, and certain other metals, a matte phase is formed. For a better understanding of the physico-chemical properties of mattes, binary systems such as Cu-S, Ni-S, Fe-S, and so forth, should be studied, especially in the vicinity of liquid compounds such as Cu2S, Ni3S2, FeS, and so forth. These compounds are relatively stable in the solid state although they can exhibit appreciable deviations from stoichiometry. With small deviations from stoichiometry there are large changes in the activity of both sulfur and metal this is a characteristic of both solid and liquid sul-fides near the stoichiometric compositions. In the vicinityof molten Cu2S,1 for instance, the activity of sulfur increases about 100 times for a 0.012 increase in the mole fraction of sulfur and, correspondingly, the activity of copper decreases greatly. In this sens the minor deviations from stoichiometry should be carefully taken into account in studies of such metal-sulfur melts. Metal-sulfur melts may be considered to have properties intermediate between metallic solutions and molten salts, i.e., neither entirely metallic nor entirely ionic. The radius of the ion sZ- is 1.84 as compared with 1.04? for a single bond covalent s.2 It is therefore inferred that when the sulfur is more ionic its partial molar volume is larger, although metal-metal, metal-sulfur, and sulfur-sulfur interactions may bring about further complexities. Thus, it is to be expected that the molar volumes, which are derived from density-composition relations, will help in resolving the structure of the melts. In this study the maximum bubble pressure method with bubbling gases of H2, H2S, and Ar, .was employed to measure the density. EXPERIMENTAL Materials. Silver of 99.95 pct purity was melted in an alumina crucible and hydrogen gas was then bubbled through the liquid for the deoxidation. In preparation of Cu2S, electrolytic copper powder (>99.9 pct Cu) was mixed with precipitated sulfur and heated to 1200°C in an alumina crucible under a hydrogen atmosphere. Mixtures having the approximate compositions FeS and Ni3S2 were prepared by heating reagent grade electrolytic iron or reduced nickel powder with precipitated sulfur under a hydrogen atmosphere. The H2S gas was of 98.5 pct purity, the impurities being mostly CO2 and CS2 which hardly contaminate the melts. Apparatus. The crucible system is shown schematically in Fig. 1. To minimize the variation of melt composition during a density measurement, the apparatus was designed in such a way that either Ar, H2, H2S, or mixtures of these gases could be used as the bubbling gas. When the melt had a high partial pressure of sulfur, H2S gas was used. When the partial pressure of sulfur was so low that oxygen might dissolve in the melt, the use of H2 was preferred. In intermediate cases, argon or mixtures of H2-H2S were used. Density of Dibutylphtalate. Dibutylphtalate was used as the manometer fluid. Relative to distilled water, the density of the dibutylphtalate, pdib g per cc, was measured and found to be: pdib (25°C) = 1.046 i 0.002. With the use of the temperature coefficient reported by Kemppinen and Gokcen,3 the following value was

Jan 1, 1970

While coal was mined in New Mexico in 1860, production was on a small scale during the period considered here, and Table 77 contains all the data found. [ ]

Jan 1, 1942

By AIME AIME

LIFE in few countries is dominated by geographic conditions to the degree that it is in Peru. The broad plateau of the Andes, bordered by lofty ice-clad ranges with deeply eroded flanks, imposes a pattern on the region to which most human activities must conform. On the Pacific side, desert conditions prevail, interrupted only by irrigated valleys along rivers that descend from the highlands. Above seven or eight thousand feet the rocky ridges become grass covered, and the central zone is one of high pastures with cultivation in the valleys or on terraced slopes except at altitudes over 15,000 ft. where glaciated landscapes prevail. Each of the three belts has its own distinctive resources and climate, and each its own special ways in which its inhabitant, must make a living. The Pacific region is one of the most arid regions in the world. Except for the irrigation, the country is an unmiti¬gated desert. The climate, in spite of the tropical latitudes, is mild with the heat relieved by air from the adjoining cold ocean. Fogs are prevalent throughout the winter months but precipitation is scarcely measurable. Ideal conditions exist for cultivation of sugar and cotton which are the dominant crops. Lima, the capital. situated in one of the most productive valleys, is an impressive city which in its modern development is well maintaining the high position it held when it was the

Jan 1, 1945

By Robert Bell

The regions to which this paper refers include the whole of the Dominion of Canada east of the 130 Rocky Mountains and north of the water-shed of the St. Lawrence. Very little exploration for economic minerals has yet been done in this immense country; but that little has already served to indicate great wealth in some localities. Having been engaged for a number of years in conducting government geological explorations in these vast territories, I shall endeavor to give the members of the Institute an idea of the prospective mineral resources of almost half a continent, as far as they are yet discernible. I purpose confining my observations to the economic minerals, and will not attempt a description of the geology of these territories; hut it will be necessary to say a few words about the rocks in order the better to explain the distribution of such minerals. The Laurentian nucleus of the continent is the principal feature of the geological map of the Dominion. It stretches from Lake Superior to Baffin's Bay, and from Great Bear Lake to the Straits of Belle Isle. Hudson's Bay itself, which is half the size of the Mediterranean Sea of the old world, lies in the center of this area. Its shores are bordered in places with newer rocks. On the west side of James' Bay (its southern prololigation) these extend inland over 200 miles, and consist of fossiliferous Devonian and Silurian strata. On the western and northwestern side of Hudson's Bay proper, altered rocks are met with, some of which resemble the gold-bearing strata of Nora Scotia, some the Huronian of Lake Huron, some the older Huronian, and others the crystalline series of the neighborhood of Sherbrooke in the Province of Quebec. Along the east coast (called the Eastmain)and among the islands lying off it, there is an interesting set of volcanic and sedimentary rocks which appears to be identical with the Animikie and the Nipigon series of Lake Superior. The area which I have characterized in a general way as Laurentian, includes tracts and belts, more or less extensive, of the Huronian series. Such areas appear to be most common, and have been best explored, in the country between the Great Lakes and Hudson's Bay.

Jan 1, 1886

By AIME

IN the following pages are described the history and present operations of one of the country's great mining and metallurgical organizations-the United States Smelting Refining and Mining Company. Though the articles are largely of interest to the technical man, the success of the Company as a business enterprise should not be overlooked. Almost immediately following incorporation 42 years ago payment of dividends began and the total to date has been about $140,000,000, roughly half to preferred and half to common shareholders. Founders of the Company were Boston businessmen and financiers interested in such diverse enterprises as shoe machinery manufacture, banking, newspaper publications, and stock brokerage. The legal profession also was represented. The Company is one of the few, among the leaders in the mining industry, that has resisted the urge to move its home office to New York and has always remained in Boston. Perhaps for that reason it has been regarded as a "conservative" company. Conservative or not, it has certainly spread out geographically and it has certainly put its eggs in many baskets. In addition to the precious metals and the major nonferrous metals it has ventured into coal and recently in a small way into the field of oil and gas. It seems to have a predilection for the North American Continent; for in addition to Alaska, Canada, and Mexico it has had important operations in California, Arizona, Nevada, Colorado, New Mexico, and particularly in various districts in Utah.

Jan 1, 1948

By E. N. Doyle

Since the mid-1930's a number of plants, using the principles of heavy media separation, have been installed throughout the world. In cases involving lead, zinc or lead-zinc ores the reasons for the choice of this type of beneficiation process have fallen into four major categories: A) The economic recovery of additional distinctly separate products, such as dolomite limestone at the Mascot Plant (1) of the American Zinc Co., and the ferrosilicon produced by St. Joseph Lead Company. (2) B) The elimination of a large portion of run-of-the-mine ore prior to grinding and flotation, to allow increased throughput with low capital cost. Examples of this approach are the Levante and Ponente plants of the Montevecchio Company in Italy (3) and the frequent choice of the Sink-Float process by the Penarroya Company of Paris. C) The processing of a sedimentary deposit, in which the valuable mineral is contained in the matrix separating the boulders, as was the case at the St. Joseph Lead Company plant at Haydon Creek (4) and also at Bunker Hill Mining and Smelting, Kellogg, Idaho. D) The simplification of Around support programs in mines by allowing greater freedom of action in the extractive pattern. An example of this choice is Cominco’s Sullivan plant which came into being as part of an extensive proposal to update the mining, crushing, transportation, grinding and beneficiation processes. (5)

Jan 1, 1970

By R. T. Hukki

This paper presents a preliminary analysis of the fundamental relationship between the net energy used and the respective product size throughout the entire range of sizes covered by crushing and grinding, and an attempt to find a sensible correlation between the existing theories. Walker, Lewis, McAdams, and Gilliland' have given the following differential equation of a general form for comminution: dE = -C§ [1] where E is the net energy required per unit weight in a certain process of comminution; x is the factor indicating the fineness of the product; n is the exponent indicating the order of the process, and C is a constant related with the material, units chosen, etc. H exponent n in the above equation is replaced by numerical figures 2, 1, and 1 1/2, the integrated form of the general equation leads to the well known fundamental theories represented by the law of von Rittinger,' law of Kick, and the third theory of comminution by Bond, respectively. The total net energies (E) from infinite feed size to a product of size x are as follows: The net energy required in a certain process of comminution is proportional to the new surface developed according to the law of von Rittinger, to the weight or size of the bodies treated according to the law of Kick, and to the length of the new cracks formed which initiate breakage according to the theory and explanation by Bond. On a logarithmic paper, where particle size is presented on the abscissa and energy consumption on the ordinate (see Fig. 21, all three relationships are represented by straight lines. The slope m of the line according to the law of von Rittinger is equal to -1.0; of Kick, 0; and of Bond, -0.5. Experimental evidence in favor of the law of Rittinger has been presented, e.g., by Gross and zimmerley5 on quartz crushed in a drop weight crusher and evaluated for surface by the method of dissolution, by Dean on magnetite crushed by a similar method and evaluated for surface by the determination of coersive force, by piret7 and co-workers on a group of minerals crushed again by a similar method as well as by compression and evaluated for surface by permeability and gas adsorption methods, and by schellinger8 on a group of minerals ground in a calorimetric ball mill and evaluated for surface by gas adsorption. Experimental evidence in favor of the law of Kick seems to be scant in the field of comminution. On the other hand, in the field of mechanical engineering Kick's law seems to be of fundamental nature in processes such as cutting, pressing, shaping, and rolling of metallic substances. Experimental evidence in favor of the third theory has been provided by Bond." To a large extent, data are based on the vast amount of grindability tests performed in the laboratories of Allis-Chalmers Manufacturing Co. In addition to the devoted proponents of one or the other of the basic theories listed above, certain investigators have indicated that one of the theories might be applied for a certain range of sizes, while another theory might be used for other sizes. In a discussion of a paper by Bond," Dobie" presented a statement at the International Mineral Dressing Congress in London (1952) indicating that 1) for large particles, the law of Kick was approximately correct; 2) for finer particles, von Rittinger's suggestion was nearer to the truth; and 3) Bond's new

Jan 1, 1961

By E. A. Gulbransen, K. F. Andrew

The vacuum-microbalance method was used to study the oxidation behavior of Zircaloy-2 and -3A over the temperature range of 300 to 850°C and at 0.1 atm pressure. The results fit in well with the authors' earlier studies on zirconium. Tin was found to increase the rate of oxidation and also the temperature at which the metal burns. Both the cubic-rate law and the parabolic-rate law gave imperfect fits to the rate data. Since the parabolic-rate law has been derived from accepted physical principles, this rate law was used to interpret the rate data. A heat of activation of 28,600 cal per mole was calculated. The transition phenomenon previously observed in hot-water and steam-corrosion processes was studied systematically for oxygen atmospheres. Observations on the rate of oxidation, color and properties of the oxide films show that the transition phenomenon was associated with a failure in the adherence of the oxide to the alloy. ZIRCALOY-2 and -3A have found important uses in the field of reactor metals due to their low neutron adsorption, good strength and good resistance to corrosion. One feature of the corrosion reaction in steam or hot water is the sharp transition in the rate of corrosion to a higher value after a certain amount of reaction has occurred. This paper presents a study of the reaction of Zircaloy-2 and -3A with oxygen including a study of the transition phenomenon which has been found to occur also in oxygen atmospheres. A comparison will be made between the oxidation behavior of these alloys and the pure metal. It was hoped that a study of the details of the oxygen reaction would lead to a better understanding of the reactions occurring in hot-water and steam atmospheres. Literature Kinetics-—The reaction of Zircaloy-2 and -3A with hot-water and steam atmospheres has been studied by Thomas.' Goldman and Thomas,' Thomas and Forscher," and Thomas and Kass.' Empirical equations for the kinetics of the reaction have been given by Thomas and Forscher." The change from the initial slow rate of reaction to the final rapid rate of reaction has been termed transition with the post-transition corrosion kinetics following a simple linear equation in time. The corrosion behavior in high-temperature steam was similar in many features to the corrosion in high-temperature water. Goldman and Thomas' and Pray and Peoples' have shown that the addition of tin, while increasing the rate of corrosion, counteracts the deleterious effect of nitrogen. The beneficial effect of iron, nickel and chromium was to improve the adhesion of the oxide to the metal as well as to counteract the deleterious effect of nitrogen. Mallet and Albrecht" have studied the oxidation of two zirconium-tin alloys. The cubic-rate law was found to fit the oxidation data for the 1.5 pct tin alloy while the parabolic-rate law was found to fit the data for the 2.5 pct alloy. Kendall' in a recent paper has studied the oxidation of Zircaloy-2 containing 1.5 pct tin in air atmospheres. Transition Phenomenon—In steam atmospheres Thomas' has observed fora 1.8 pct tin alloy containing small amounts of iron, nickel and chromium that transition to a more rapid rate of corrosion at 400°C

Jan 1, 1959

By W. R. Purcell, C. S. Brooks

The internal surfaces of rocks which are in contact with interstitial fluids are known to influence in some degree the recovery of hydrocarbons from pay zones. Despite the admitted importance of the influence of solid surfaces on hydrocarbon recovery, little information is available concerning the extent of surface of reservoir rocks. In this paper a description is given of the apparatus and procedure employed in the determination of the surface areas of sedimentary rocks, and values are reported for a variety of sandstone and limestone cores. In addition, consideration is given to the Kozeny equation, which relates surface area to porosity and permeability. A colliparison is made between the surface areas as calculated from this equation and the geometrical areas of a series of packs of spherical glass beads. Also, for a group of sandstone cores. Kozeny areas are compared with surface areas as determined by the gas adsorption method employed in this investigation. INTRODUCTION It has long been recognized that many processes which are of importance to hydrocarbon production are controlled in some degree by the extent of the surface of the reservoir rock through which the hydrocarbons move. For example, the recovery efficiency that is obtained in a given reservoir is certainly determined in part by the action of interfacial forces between the reservoir fluids and rock, and this action is influenced in turn by the extent of solid surface. Despite the admitted importance of surface effects to problems of petroleum recovery, little information is available concerning the extent of surface of reservoir rocks." It is the purpose of this paper to describe an apparatus which has been employed for the measurement of the surface areas of rock samples and to present the values which have been obtained for a variety of sandstone and limestone cores. In addition, the relationship of surface area to permeability and porosity, as given by the Kozeny equation, will be discussed. METHOD OF MEASURING SURFACE AREA The method of determining surface areas as employed in this work has previously found wide use in studies of porous solids such as catalysts. The method involves the measurement of the amount of physical adsorption of an inert gas, such as nitrogen or argon, on the bare surface of the solid at reduced pressure and constant temperature near the normal liquefaction temperature of the gas. With the aid of the theory of isothermal adsorption as developed by Brunauer, Emmett, and Teller,' it is possible to ascertain the amount of gas (and hence the number of molecules) which is required to cover the solid surface with a single layer of molecules. From a knowledge of the covering area per molecule the total surface ares of the solid can be computed. Since the Brunauer. Emmett, Teller (BET) theory has been adequately discussed elsewhere: it will suffice here merely to present their final equation as ordinarily employed for surface-area calculations. This equation relates the volume of gas, V, which is adsorbed at pressure, P, to the liquefaction pressure, Po, of the gas, and to the volume of gas, V.,, that is required to form a monomolecular layer: In this equation C is a quantity which is related to the heats of adsorption and liquefaction of the gas; for a particular solid-gas system at Constant temperature, C is considered to have a constant value. The basic adsorption data can be presented in the form of Equation (1) by plotting the quantity P/V(Po- P) as a func-

Jan 1, 1952

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and It is now thought1' that the "{0,1,13)" habit reported for the Fe-Ni-C alloys'' is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove. The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics and reduce to the unit tensors and j so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and "{2,3,10)" or "(127)". (It is now thought1' that the "{0,1,13)" habit reported for the Fe-Ni-C alloys'' is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove.' The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and tj2 = vi (i = 1, 2, 3), the Kz qd 771 elements are given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics cij Iand cij reduce to the unit tensors 6ij and 6ij so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and 77~ are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963