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By Joseph C. McCaskill

The writer assumes that this volume is not intended to serve as a source of statistics on international trade and that the reader is not interested in wading through a lot of statistical tables copied from the various reporting agencies. Generalizations therefore are made whenever possible and not always is the source of the information meticulously cited. The United Nations regularly publishes trade data on mineral commodities. E. J. Gealy, and C. L Kimbell, of the U S Bureau of Mines (USBM), work with these data and estimate that they cover approximately 78% of total mineral commodities traded. In addition the General Agreement on Tariffs and Trade (GATT) publishes analyses of certain trade data The most complete report of production and trade in minerals 1s probably the international volume of the U.S. Bureau of Mines Yearbook The latest available edition is for 1968, and some of the data in this edition cover only as late as 1967. Unless otherwise stated, the source of data used in the chapter is this Yearbook Other staff members of the Bureau were most helpful and cooperative They are not to be held responsible for conclusions or points of view to be found in the chapter. THE NATURE AND SCOPE OF INTERNATIONAL TRADE The two and a half decades since World War II have witnessed an unprecedented growth international commerce The end of the war found the world economy seriously crippled. Many countries had suffered severe war damage; international trade was disrupted and nations had to resort to exchange controls and bilateral trading arrangements. The postwar recovery, however, was remarkably rapid Within two decades, world Income more than doubled, and world trade which was less than $60 billion in 1948 exceeded $200 billion in 1968, 8 and reached $278 billion in 1970.18 The growing world trade contributed to world prosperity which in turn fostered growth of trade. This dramatic growth of international commerce was made possible by the progressive liberalization of trade and capital movements by the major trading nations of the world which began immediately after the War and has not yet completely lost its steam. The modern-day stimulus of the expanded trade movement was the enactment by the Congress of the United States in 1934, of the

Jan 1, 1976

By A. S. Callen

These iron mines of Spain are located on the mountain ridge forming the boundary between the Teruel and Guadalajara provinces, called Sierra Menera. They form a property of 25 mines extending over an area of 1,677 hectares (4,140 acres) situated at a height varying from 1,200 m. (3,940 ft.) to 1,500 m. (4,920 ft.) above sea level. The deposit follows the direction north to south; huge masses of ore are being found both on the slopes and at the summit of the Sierra. The ore occurs among quartzites and magnesite limestone, in some places overlaid by quartzite 15 m. (50 ft.) thick; in some others (and this is more general) the ore is overlaid by earth and boulders of quartzite origin; this layer is about 8 m. (26 ft.) thick. The ore beds occupy the geological horizon of the Superior Trias or Muschelkask, which are here in direct contact with the Silurian quartzites. The lime-stones have been more or less transformed. There is ample evidence to show that these mines were worked in very ancient times—objects and tools employed in mining by the ancient Romans and Arabs are to be found plentifully in old workinigs which extend down into the deposits. It has been estimated that more than 10,000,000 tons of ore were mined in the old days in this district and carried to the primitive forges in the vicinity where iron of much renown in Spain was extracted. Remains of more than 20 of these forges are found in the neighborhood of Sierra Menera and are usually situated near waterfalls and forests. Much investigation has been carried on for the purpose of determining the quantity of ore to be found in these mines, but no exact calculations can be made at present. When the investigation is completed it will surely be found that the deposit contains a much larger quantity than the 100,000,000 tons indicated by the present workings. The mines are now worked as open quarries and this method can and will be followed for a long time, probably until the deposit is worked out. Figs. 1 and 2 give some idea of the quarries in operation and the reserves, the iron-ore stocks, screening installation and general arrangement. From these quarries 1,000,000 tons can be mined annually (987,000

Jan 1, 1916

By W. H. Hough, P. B. Leavenworth

Development in the Upper Texas Gulf Coast during 1943 resulted in the discovery of 11 new fields as compared with 12 discovered in the same area during I942. Of the 11 new fields, eight are classed as oil and/or condensate and three as gas fields. In addition to the new discoveries, several more or less important new horizons and extensions were encountered in some of the older fields, as noted in the text under the heading "New Pays and Extensions.'' Drilling During the year, 418 wells were drilled, as compared with 356 drilled during 1942. Of these, 323 were field wells, of which 188 produced oil, 21 were gas wells and 114 were dry holes. The remaining 95 viere wildcats, 12 of which produced oil, 4 produced gas and 79 dry holes. Distribution of themwildcats with respect to the various trends may be summarized as follows: over the 91,340,492 bbl. produced in the same area during 1942. The production statistics in the text and the accompanying tables include condensate or distillate as oil production, because many Gulf Coast fields produce oils with a wide variation of specific gravities, all of which are commingled in pipe lines. Table 3 shows by counties all of the drilling and production" data applicable to this particular area. Outstanding Fields of 1943 The Upper Texas Gulf Coast covered in this report has 178 more or less active oil and gas fields, including the 1943 discoveries. Of these Table 4 lists those that were most important from the standpoint of production. Each of these fields pro duced in excess of one million barrels of oil during 1943. Some of the interesting facts to be noted from this list of some 26 oil fields are: (I) four of the fields— namely, Conroe, Hastings, Friendswood and Thompson—each produced more than 10 million barrels during 1943, whcrcas Conroe and Hastings were the only fields that produced 10 million barrels during 1942; (2) some of the older fields (discovered prior to 1920), such as Barbers Hill, West Columbia, and Hull, are still producing in excess of one million barrels annually; (3) some of the fields more than doubled their 1942 production—e.g., Anahuac and Friendswood. The large increase in production in practically all instances is the result of increased allowables from wells drilled prior to 1943 and

Jan 1, 1944

By W. H. Hough, P. B. Leavenworth

Development in the Upper Texas Gulf Coast during 1943 resulted in the discovery of 11 new fields as compared with 12 discovered in the same area during I942. Of the 11 new fields, eight are classed as oil and/or condensate and three as gas fields. In addition to the new discoveries, several more or less important new horizons and extensions were encountered in some of the older fields, as noted in the text under the heading "New Pays and Extensions.'' Drilling During the year, 418 wells were drilled, as compared with 356 drilled during 1942. Of these, 323 were field wells, of which 188 produced oil, 21 were gas wells and 114 were dry holes. The remaining 95 viere wildcats, 12 of which produced oil, 4 produced gas and 79 dry holes. Distribution of themwildcats with respect to the various trends may be summarized as follows: over the 91,340,492 bbl. produced in the same area during 1942. The production statistics in the text and the accompanying tables include condensate or distillate as oil production, because many Gulf Coast fields produce oils with a wide variation of specific gravities, all of which are commingled in pipe lines. Table 3 shows by counties all of the drilling and production" data applicable to this particular area. Outstanding Fields of 1943 The Upper Texas Gulf Coast covered in this report has 178 more or less active oil and gas fields, including the 1943 discoveries. Of these Table 4 lists those that were most important from the standpoint of production. Each of these fields pro duced in excess of one million barrels of oil during 1943. Some of the interesting facts to be noted from this list of some 26 oil fields are: (I) four of the fields— namely, Conroe, Hastings, Friendswood and Thompson—each produced more than 10 million barrels during 1943, whcrcas Conroe and Hastings were the only fields that produced 10 million barrels during 1942; (2) some of the older fields (discovered prior to 1920), such as Barbers Hill, West Columbia, and Hull, are still producing in excess of one million barrels annually; (3) some of the fields more than doubled their 1942 production—e.g., Anahuac and Friendswood. The large increase in production in practically all instances is the result of increased allowables from wells drilled prior to 1943 and

Jan 1, 1944

By William Kelly

THE objeet of this paper is to describe the electric equipment at the iron-ore mines of Penn Iron Mining Co., Vulcan, Mich. and of Republic Iron Co., Republic, Mich.; to give the result's of tests; and to discuss the methods in use from an operating as well as from an efficiency standpoint. Electricity was introduced at the Penn mines for pumping, hoisting, and compressing air in the spring of 1907, upon the completion of a hydro-electric plant built by that company on the Menominee river about 4 miles from the mines. This plant was described in a paper1 presented before the Lake Superior Mining Institute. A paper2 presented at a meeting of the same Institute describes some of the operating features, and the safety devices of the electric hoist at the Curry shaft were briefly described in the Proceedings of the First Co-operative Safety Congress held under the auspices of the Association of Iron and Steel Electrical Engineers at Milwaukee, Wis., Sept. 30 to Oct. 5, 1912.

Jan 2, 1914

By W. R. Crane

DRAINAGE in these mines has been discussed in papers, on mining practice,1 but the fact that water, varying from 0.16 to 3.46 and averaging 1.43 times the amount of ore mined, has to be pumped from the mines daily, indicates the importance of the problem and the advisability of making a thorough investigation of the source of mine water, its mode of entry into the mines, its effect upon mining conditions; and consideration of means of improving the conditions. While conditions are not serious, yet there is danger that they may become worse if present mining practice is continued, owing to the presence of formations, known to carry large quantities of water, that overlie the ore bed worked. Much detailed information has been collected regarding: rainfall, and run-off in streams draining the district; the effect of different kinds of formations, porous and non-porous; the inclination of the surface; the condition of the surface above the mines, i. e., whether or not disturbed by ground movement; the occurrence of the ore and character of associated formations, particularly with respect to presence of jointing or slip planes, faults, etc.; failure of top rock in the old stopes; and the conditions under which water effects entrance into the mines, i. e., whether as a natural or forced flow. The study furnished fundamental data on the source of waters now entering the mines and that which may later enter due to collapse of top formations in. abandoned workings. The presence of jointing, or slip planes, has a pronounced influence upon the whole drainage problem. These present lines of least resistance to the water and, by weakening the top formations, cause fracturing of the overlying rock, allowing both surface and deep-seated waters to enter the mines.

Jan 1, 1927

By John N. Dew, William L. Martin, `

This paper describes the results of a laboratory investigation conducted to obtain data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. Air and fuel requirements, rates of advance, com-bustion temperatures, and coke and fluid distributions are presented. The mechanism of oil recovery by in stiu combustion is discussed. Five crude oils ranging in gravity from 10.9 to 34.2"' API were prodrrced from a semiadiabatic, uncon-.solidnted sand pack by in situ combustion. Experimental conditions were varied over a wide range in order to determine the inter-relation-.ships of process variables. The mini-mum air flux requirement for self-sustained combustion was found to he less than 10 scf/hr-ft'l. The rate of advance of a self-sustained combustion zone was found to be nearly proportional to the air flux at the combustion front. The effects of presrure and injected air flux were studied in a series of experiments using a 21.2" API crude. A minimum air require-ment was observed at an air .flux of 20 scf/hr-ft'. The oil saturation con-sumed as fuel averaged 5.5 per cent of pore volume. The effect of air pressure was, found to be .small for experiments having high combustion eficiencies. This study should promote a better understanding of the problems and mechanisms involved in labora-tory investigations and field applications of the in situ combustion pro-cess. The data presented will be use- ful in the interpretation of results of field tests. When tempered with volu-metric sweep efficiencies, the data can be used in making preliminary economic appraisals of the process as applied to reservoirs containing high porosity unconsolidated media. INTRODUCTION The purpose of this work was to obtain laboratory data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. In situ combustion basically consists of (1) injecting air into a reservoir through selected input wells to create an air sweep through the reservoir, (2) igniting the crude at the injection well, and (3) propagating the combustion front through the reservoir by continued air injection. By this means, oil is swept toward producing wells in the area. The fuel for combustion is supplied by heavy residual material (coke) which has been deposited on the sand grains during distillation and cracking of the crude oil ahead of the combustion front. Recovery of petroleum by a combustion or heat wave process is not a new idea. F. A. Howard was granted a patent in 1923 on a process in which air and a combustible gas were pumped into an injection well and ignited.' Russian engineers reported on field experiments with a crude oil gasification process in 1935'. Other known early field tests include those conducted near Bar-tlesville and Ardmore, Okla., in 1942." More recently completed field tests include an inverted seven-spot by Sinclair Oil Co. in the Delaware-Childers field, Nowata County, Okla.'; a three-well and an inverted five-spot test by Magnolia Petroleum Co. in Jefferson County, Okla."."; and a test by California Research Corp. in the Irvine-Furnace field in Kentucky. The Worthington Corp. has completed a test in cooperation with the Forest Oil Corp. in Clark County, 111.l Several field tests are now in progress. Sinclair has acquired a 600-acre lease in the Humboldt-Chanute field, Allen County, Kans., and is under way with a large-scale operation. Three field tests are under way in California. The General Petroleum Corp. is conducting an inverted five-spot pattern test in the South Bel-ridge field in Kern County under a cooperative agreement with 11 other companies, including Continental Oil Co. California Research Corp. is conducting a four-well pattern test in Midway-Sunset field near Maricopa, and Richfield Oil Corp. is under way with a test in the Ojai field in Ventura County. Although the published information is valuable concerning results of field tests, little laboratory data other than that reported by Kuhn and Koch5 are available to aid in appraising the tests from a technical or economic standpoint. Engineering data needed to evaluate the process include the amount of air required per barrel of oil recovered, minimum injection rates which will support combustion, rates of advance, air required per unit volume of reservoir cleaned, amount of oil recovered, and amount of oil consumed as fuel. The present laboratory investigation was undertaken to provide these data for that portion of the reservoir swept by the combustion zone. The first phase of this investigation was exploratory in nature and was conducted at injection pressures less than 100 psig. Data were ob-

By Edwin B. Eckel

This paper, based on brief field examination and on data supplied by the operators, records the condition of the Italian mercury industry as of March 1945, not long after Italy's collapse. Except for the once-Italian but now Yugoslavian Idria mine near Trieste, virtually all the known mercury deposits are in the Monte Amiata district in Siena and Grosseto Provinces, 75 miles north of Rome. This district contains the Abbadia San Salvatore. the Siele. the Argus, and the Cerreto Piano mines besides numerous prospects and unproductive mines. Under pressure from Germany the principal mines were highly productive during the early part of the war, but production fell off long before its end. All of the mines were damaged in some way at the German withdrawal but by September 1944 the Abbadia had resumed production and several others were only lacking power by the early spring of 1945. The Monte Amiata district is characterized geologically by a thick series of sedimentary rocks that range from Triassic to Eocene in age . and are surmounted on Monte Amiata itself by a thick cap of extrusive trachyte. Bodies of travertine and of landslide detritus, younger than the trachyte, are rather widespread. The structure is complex and little known but most of the ore deposits seem to lie along or near a major, north-trending fault or on associated cross-fractures. Cinnabar is the only important ore mineral and clay minerals are by far the most abundant products of hydrothermal alteration. A southward increase in the amount of stibnite, relative to cinnabar, suggests horizontal zoning. The grade of ore ranges from 0.60 to 3.0 Pet and the reserves, as compared with those in American mines, are enormous. Even in the face of war-time scarcities, the mines are remarkably self-sufficient and labor is plentiful, but the costs of production are estimated to be not greatly below those of the better American mines. Notes on the principal mines, on the mining and metallurgical methods, and on the manufacture of synthetic cinnabar are included in the paper. Introduction With but few brief interludes, Spain and Italy, including the Idria mine near Trieste, which has passed from Austrian to Italian to Yugoslavian hands in the Past 3 decades, have led the world in the production of mercury, or quicksilver, for many centuries. Despite their enviable position with respect to the supplies of a metal so essential in both war and peace, there is a notable lack of up-to-date information in America on the mercury industry of either country. Duschak and Schuette' and Schuettez,3 give by far the best summaries in English known to the writer, but the latest firsthand report cited by them on the Italian mines was published in 1915.' Having been deeply interested in the geology and economics of mercury for several years, the writer naturally felt most fortunate in being the to obtain enough firsthand information on the Italian industry to fill at least a few of the gaps in our knowledge. The opportunity came during the war, soon after this industry, together with the rest of Italy, had capitulated to the Allies. Many of the facts presented here are thus definitely "dated," but others are of less transitory nature, and even the dated facts should be of interest in showing the strength and

Jan 1, 1949

By Edwin B. Eckel

This paper, based on brief field examination and on data supplied by the operators, records the condition of the Italian mercury industry as of March 1945, not long after Italy's collapse. Except for the once-Italian but now Yugoslavian Idria mine near Trieste, virtually all the known mercury deposits are in the Monte Amiata district in Siena and Grosseto Provinces, 75 miles north of Rome. This district contains the Abbadia San Salvatore. the Siele. the Argus, and the Cerreto Piano mines besides numerous prospects and unproductive mines. Under pressure from Germany the principal mines were highly productive during the early part of the war, but production fell off long before its end. All of the mines were damaged in some way at the German withdrawal but by September 1944 the Abbadia had resumed production and several others were only lacking power by the early spring of 1945. The Monte Amiata district is characterized geologically by a thick series of sedimentary rocks that range from Triassic to Eocene in age . and are surmounted on Monte Amiata itself by a thick cap of extrusive trachyte. Bodies of travertine and of landslide detritus, younger than the trachyte, are rather widespread. The structure is complex and little known but most of the ore deposits seem to lie along or near a major, north-trending fault or on associated cross-fractures. Cinnabar is the only important ore mineral and clay minerals are by far the most abundant products of hydrothermal alteration. A southward increase in the amount of stibnite, relative to cinnabar, suggests horizontal zoning. The grade of ore ranges from 0.60 to 3.0 Pet and the reserves, as compared with those in American mines, are enormous. Even in the face of war-time scarcities, the mines are remarkably self-sufficient and labor is plentiful, but the costs of production are estimated to be not greatly below those of the better American mines. Notes on the principal mines, on the mining and metallurgical methods, and on the manufacture of synthetic cinnabar are included in the paper. Introduction With but few brief interludes, Spain and Italy, including the Idria mine near Trieste, which has passed from Austrian to Italian to Yugoslavian hands in the Past 3 decades, have led the world in the production of mercury, or quicksilver, for many centuries. Despite their enviable position with respect to the supplies of a metal so essential in both war and peace, there is a notable lack of up-to-date information in America on the mercury industry of either country. Duschak and Schuette' and Schuettez,3 give by far the best summaries in English known to the writer, but the latest firsthand report cited by them on the Italian mines was published in 1915.' Having been deeply interested in the geology and economics of mercury for several years, the writer naturally felt most fortunate in being the to obtain enough firsthand information on the Italian industry to fill at least a few of the gaps in our knowledge. The opportunity came during the war, soon after this industry, together with the rest of Italy, had capitulated to the Allies. Many of the facts presented here are thus definitely "dated," but others are of less transitory nature, and even the dated facts should be of interest in showing the strength and

Jan 1, 1949

By F. Lynwood Garrison

It is not intended to make in the present paper any deduction or to formulate any theories from the results obtained by experiments. The further expenditure of considerable time and labor would be required to obtain a sufficient basis for positive assertions as to the microscopic structure of the different varieties of iron and steel, and the structural changes which take place in them. It is therefore my purpose at this time to offer simply a synopsis of the general results arrived at in a few months' work, a brief description of apparatus used, and a few hints as to the preparation and preservation of the material which it is intended to investigate. The study of the microscopic structure of iron and steel is not altogether new. Some attention has been given it in both England and Germany. But the foreign publications on the subject have thus far been confined, so far as I am aware, to two papers, one by Herr Martens, of Berlin, contributed to the Verein zur Befoerderuny des Gewerbfleisses and the other a lecture by Dr. H. C. Sorby of Sheffield. Dr. Sorby, it seems, was induced to investigate the subject as bearing on the structure of meteoric iron ; and the results he obtained are certainly very interesting. At the Boston meeting of this Institute, in February, 1883, Mr. J. C, Bayles called attention to the subject in a neat and exceedingly interesting paper, in which the work of Messrs. Martens and Sorby was summarized,* and original suggestions were added. It is at present difficult to say what will he eventually the practical value of the microscope, thus employed, in the sciences of engineering. The role which it seems most likely to play is that of' an adjunct to the testing-machine, and not (as some have supposed) a rival to the chemical laboratory. That it will be a most valuable accessory seems, to say the least, highly probable. I need hardly go at length into the details of preparing the material for examination. Mr. Bayles has described the process in such a plain and comprehensive manner that if his instructions are

Jan 1, 1886

By B. Chalmers, S. Wojciechowski

THE structure of the equiaxed zone of several A1-Cu samples mechanically stirred during unidirectional solidification was examined. The stirring was produced by rotary oscillation of the mold about its vertical axis.' It was found that in Some samples the structure is not of the same type over the whole of the equiaxed zone; it consists of regions with two different etching responses. Fig. 1 shows this structure in a Al-1 wt pct ku sample. The lighter etching regions with a coarse structure form something like a network and the darker etching regions with a finer structure can be observed as the continuation of the coarse structure inside this network. The difference in size and shape of the dendrite branches (they are rounded in the coarser structure) is similar to that found by Williamson and Chalmers in ice crystals solidified in undercooled water: when the amount of undercooling was small, the ice crystals were more rounded and coarser than these solidified with a larger amount of undercooling.' It seems justified to conclude that the observed structure resulted from solidification under different thermal conditions: the coarser structure solidified first out of the "purer" liquid and with a smaller amount of undercooling and the finer was formed later out of solute-enriched liquid under conditions of much more rapid heat extraction. A considerable change in the heat flow conditions at the later stages of solidification can be easily understood by taking into account that the coarser crystals form a continuous network and the amount of trapped liquid is relatively small; hence the contribution of latent heat is much smaller in the later stages of solidification. The difference in structure and etching characteristic reflects a difference in composition between these two regions. It was found that the darker etching re- gions are harder (30.4 to 31.3 HV5) than the lighter etching ones (25 to 26 HV5). A similar type of structure was found in a A1-4 wt pct Cu sample grown by Czochralski method. Fig. 2 shows the structure in the lower part of a sample grown slowly and then decanted by a rapid removing of the sample from the melt. In a few places trapped liquid solidified in the same manner as in the sample shown in Fig. 1.

Jan 1, 1968

By Philip B. Bucky

[ ]

Jan 1, 1942

By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By W. L. Fink, H. C. Stumpf, L. A. Willey

VERY few studies of the aluminum-sodium system have been reported. Heycock and Neville1 were unable to detect any solubility of sodium in liquid aluminum. Mathewson2 prepared an equilibrium diagram consisting of two horizontal lines at the melting points of the two metals. He was unable to detect solubility at either end of the system. Scheuer3 first developed a method for the chemical determination of sodium in aluminum and then studied the solubility of sodium in liquid aluminum. His method involved heating aluminum with excess sodium under hydrogen until the two liquids were at equilibrium, chilling the melt, and analyzing the aluminum-rich layer. He reported the solubility to be 0.l0 pct sodium at 700°C, 0.115 pct at 750°C, and 0.128 pct at 800°C. This paper on the aluminum-sodium system is the twenty-first in a series from the Aluminum Research Laboratories describing equilibrium relations in aluminum alloy systems. MATERIALS The alloys for this investigation were prepared from electrolytically refined aluminum (99.99 pct) and sodium of reagent quality conforming to specifications of the American Chemical Society.4 Chemical analysis of the aluminum showed the following impurities: 0.002 pct Si, 0.002 pct Fe, 0.002 pct Cu, <0.001 pct Mn, 0.002 pct Mg and 0.001 pct Na. The sodium content of all alloys was determined by either chemical or spectrographic standard procedures5 No. IIA and No. SII respectively. DETERMINATION OF LIQUIDUS The boundary of the miscibility gap was determined by a modification of the method of Scheuer3 and of that used by Henry and Cordiano.6 As finally developed the method was as follows: A fused alumina crucible 25 mm id with 75 mm depth and 1.5 mm wall thickness was placed on the bottom of a container made from a 4-in. length of 1 ½ -in. iron pipe and pipe caps. The space around the sides of the crucible was filled with 40 mesh crystalline alundum. A charge of 60 g of aluminum and 10 to 15 g of sodium was placed in the crucible, the sodium first being trimmed and rinsed with iso-pentane to remove kerosene. The container was tightly capped, filled with argon (99.6 pct pure), and heated to the desired temperature (between 670 and 800°C). A positive pressure of argon (about 8 mm of mercury) was maintained through a small pipe to the upper cap. After soaking for from 2 to 5 hr, the container was quenched by directing a stream of water onto the base, so that solidification of the aluminum-rich layer was rapid and essentially unidirectional. Analyses were made on drillings taken from the bottom of the ingots after machining off the surface layers. Pre-

Jan 1, 1948

Jan 6, 1976

By M. G. Corson

THE theory of hardening by interference with slip which has been so clearly developed by Jeffries and his co-workers requires that an alloy to be amenable to age or heat hardening should contain among its components some that will stay in solid solution at high temperatures and precipitate as a secondary phase on cooling. This secondary phase may be either a more or less pure individual element (chromium in the case of copper, anti-mony in the case of lead), or some intermetallic com-pound. Those cases of hardening which depend on the precipitation of a compound are not only the most frequent, but are also far superior in the efficiency of hardening obtained. However, the slip interference theory as stated in its most general form is not sufficient to foretell new cases of this type of hardening and also will not explain some phenomena of a more intricate nature. It is not sufficient that a secondary phase might be absorbed by the main one at high temperatures and precipitated at the lower ones. The kinetics of this precipitation and the accompanying. physical phenomena of dimensional changes play independent and highly important parts. These kinetics, while not yet sufficiently studied to he formulated in the shape of physicochemical equations, might find their expression-in a qualitative systema-tization of the phenomena of precipitation according to two different viewpoints. To begin with, we encounter the question as to the velocities of the precipitation and of the growth of the phase precipitated. To harden a metal in an efficient manner we must be able to control the precipitation on one hand and also to bring the total of the secondary phase to such a number and size of the particles pre-cipitated as, will produce a desirable hardening effect under commercially feasible conditions of. age or heat hardening. From this viewpoint six different cases may be dis-cerned.

Jan 7, 1928

By L. E. Mannion

Sodium carbonate (soda ash) is one of two principal commercial alkalis. Its principal competitor is sodium hydroxide. The use of sodium carbonate is recorded in ancient Egypt, where naturally occurring brines and solid salts provided impure soda for early glassmaking. Until the 19th century, soda ash (as well as potash) was recovered mainly by leaching wood or other plant ashes. In 18th-century Europe, for example, leaching seaweed ash with hot water produced a brown laundry lye. One of the better grades of this material was a Spanish product, barilla, which analyzed 24 to 30% Na2CO3 (Hou, 1942). The modern chemical industry was born in 1691 with the LeBlanc process for making sodium carbonate from salt, sulfuric acid, and lime. English industry used this process extensively in the 17th and 18th centuries. The next major advance was in 1863, when Ernst Solvay devised the ammonia-soda, or Solvay process. The first of many Solvay plants was built in 1874. These supplanted the LeBlanc method and dominated worldwide soda ash production until 1974, when mined sodium carbonate became predominant. Although considerably less important until recently, natural sodium carbonate deposits historically have supported small soda ash operations throughout the world. Shortages during World War II stimulated production of "natural" soda ash from such deposits, particularly at Searles Lake, CA and Lake Magadi, Kenya. More spectacularly, increased production from the vast trona deposits in Wyoming has virtually supplanted the Solvay process in the US. Principal producers of natural soda ash as well as the character of the source deposits are listed in Table 1. [ ]

Jan 1, 1983

By Robert M. Grogan, Gill Montgomery

Fluorspar, the commercial name for fluorite, is a mineral composed of calcium fluoride, CaF,. Its valuable properties are due to its content of fluorine, and it is the principal commercial source of that element. The name is derived from the Latin word "fluere," to flow, because the mineral has a low melting point and is used in metallurgy as a flux. Cryolite is a sodium aluminum fluoride, Na,AlF,. It is a rare mineral which has been found in commercial quantities in only one place in the world, Greenland. Small amounts of it are shipped from stock in that country, and its place in industry has been taken over almost completely by synthetic cryolite. Because of the relative unimportance of cryolite, discussion of it has been relegated to a short section at the end of this chapter, which is principally concerned with fluorspar. History Fluorspar was used for ornamental purposes by the Greeks and Romans, who fashioned such things as vases, drinking cups, and table tops from it. Various peoples including the Chinese and the American Indians carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola (1564), who wrote about it in 1546. Mining began in England about 1775 and at various places in the United States during the period 1820 to 1840. Production became substantial following the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage were stimulated by growth in the steel, aluminum, chemical, and ceramic industries and were accelerated by World Wars I and II. Fluorocarbons entered the picture in 193 1 and the use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920s, a differential flotation scheme for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low grade ores in the 1940s were outstanding technological contributions that enabled increased production of fluorspar concentrates. In recent years the development of pelletizing and briquetting processes for making flotation concentrates into gravel-size particles for use in steel furnaces and the development of more efficient and selective flotation schemes for treating crude ores containing abundant dolomite and barite have been major improvements in the industry.

Jan 1, 1975

By D. J. Carney, E. Van Meter, J. J. Oravec

A study was made of combustion-air temperatures and factors affecting air temperatures in the open-hearth regenerative systems. Air-temperature surveys in the regenerative system revealed marked thermal gradients in the air above the checkers. The design of the fantail-uptake region plays a prominent part in increasing the heat recovery of the regenerative system. THE efficiency of the open-hearth regenerative system is one of the most important factors affecting open-hearth performance. Until recently, this factor has not received the attention in the literature given to many other items affecting performance, such as the type of charge, speed of charging, and the mechanical equipment of the open hearth. J. S. Marsh&apos; emphasized the importance of the flame temperature and its dependence upon the combustion-air temperature. By means of measured air temperatures in open-hearth furnaces, data were presented which showed a remarkable degree of correlation between production rate and combustion-air temperature. This correlation was extremely good in view of the numerous factors, other than air temperature, which affect open-hearth production rates. In Marsh&apos;s work, a 100°F increase in air temperature reduced the heat time by approximately 45 min. Realizing the importance of combustion-air temperature, it is desirable to know which factors control the regenerative efficiency of the open-hearth furnace. B. M. Larsen recently discussed this subject.&apos; The present paper illustrates a few of the more important items that affect regenerative efficiency and combustion-air temperature. In the latter part of 1951, a study of open-hearth combustion-air temperatures was begun at the South Works of the United States Steel Corp. In the initial work at open-hearth shop X, which produces low carbon steel products, temperatures were measured in the uptake in a manner similar to that used by Marsh&apos; and the results obtained were very similar to the Bethlehem data. When it was decided to expand the study of combustion-air temperatures, open-hearth shop Y was selected because of the greater variety of furnace-design features, types of steel produced, and firing rates used. With the use of aspirating thermocouples, continuous gas analyzers, thermocouple and optical pyrometers, a study was made of: 1—effect of combustion-air temperature on open-hearth production rate, 2—thermal gradients present in various zones of the regenerative system, 3—effect of furnace-design variations on air temperature and heat recovery, 4-—effect of furnace-operating variables on heat recovery, and 5—variation in heat recovery with furnace age during the normal furnace campaign. Data collected on individual heats at 15 min intervals included air-flow rate, firing rate, checker temperature, combustion-air temperature, and furnace pressure. These data were collected on approximately 230 heats of steel. In addition, information was obtained at random on air infiltration and combustion-gas compositions. The data gathered have shown the desirability of closer control of open-hearth firing practices, a need for reducing air infiltration in the uptake zones, and a need for further study of design of checkers and of uptake-fantail areas. Equipment Air is practically a nonradiating medium. Consequently, in the measurement of air temperatures, the principle of heat conduction must be used rather than heat radiation. For this reason, aspirating-type thermocouple pyrometers normally are used to measure air temperatures. With these devices, air

Jan 1, 1956