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By J. L. Wyatt

J. W. Tomlison—It seems probable that the author's conclusion, that the conductivity of the slags decreases with increasing content of FeO, is erroneous due to the method of plotting the data. Thus, the results of other workers2,3,13,14 show that the conductivity of molten oxide slags increase with increasing temperature, indicating that the trend of the curve shown by the authors is due to the fact that the data for the slags containing relatively small amounts of FeO are at higher temperatures than those for the slags containing relatively large amounts of this oxide. In this connection the work of Wejnarth2 may be mentioned in which in an investigation of a series of iron silicate slags, the conductivity was found to increase with increasing content of FeO; the fact that the author's slags contained TiO2 probably does not affect the issue since it has been shown15,16 that, at least as far as conductivity is concerned, this oxide behaves essentially the same as silica and that mixtures of the oxide with silica have a very low conductivity of the order of 10-4 mhos at 1750°C. In connection with the experimental technique it may be noted that bubbles of carbon monoxide would probably be produced at the surface of the graphite electrodes in contact with the melts thus rendering the accuracy of the measurements somewhat open to question. J. L. Wyatt (author's reply)—Dr. Tomlinson makes reference to works by Martin and Derge, which indicate that slag systems containing no TiO2 are charac-terized by an increase in conductivity with an increase in temperature. Further, I have cited his examples, which indicate a drastic increase with small temperature change. The results of Dr. Derge's work have no bearing whatsoever on the results of this paper, since the slags under study here contained up to 70 pct TiO2. One cannot generalize on slag systems as a whole on the basis of any one family, for there are definite compounds of ionic nature formed in each system, and the ionic mobilization of these is something that cannot be determined without actual experimentation. Dr. Tomlinson makes reference to an unpublished work which, he claims, shows that titanium dioxide behaves the same as silica in regard to conductivity. Since I have not had 'an opportunity to see the paper I cannot make any comments, but unless the same slag system was studied there can be no specific comparison of results. If the decrease in conductivity of the slag was due entirely to temperature phenomena, as Dr. Tomlinson indicates, then one is without an explanation of the values shown in the paper for slags containing from 10 to 20 pct FeO. I cannot agree that the deviation in findings was appreciably related to temperature change; further, I believe this point was completely covered in the paper. References 13 Endell and Hellbrügge: Glasstech. Ber. (1942) 20, 277. 14 Bockris, Kitchener, Ignatowicz and Tomlinson: Faraday Society. Discussion (1948) 4, 265. 15 Tomlinson: Thesis, London 1949. 10 Bockris, Kitchener, Ignatowicz, and Tomlinson: Unpublished work.

Jan 1, 1951

By J. P. Witherow

The plant of Messrs. Oliver Brothers and Phillips, the only one in operation until January, 1886, has not been available for any further experiments since those of Mr. R. W. Hunt, described in his paper on the subject, at the Chattanooga meeting. Continuous working has, however, led to important improvements in plant, and furnished valuable results in practice. The difference between the converter and plant of 1884, as illustrated in our Transactions, vol. xiii., p. 759 and following pages, and those of 1885, may be observed in Plates 1. and 11. accompanying this paper. Plate I. gives the elevation and plan, in half-section, of one of our latest 3-ton converters. Plate 11. gives a plan of the general arrangement of a plant adapted to turn out slabs, blooms, and billets for the general market. The letters on Plate I. refer to the following parts :

Jan 1, 1886

By Joseph J. Yancik, Leonard L. Felts, George B. Clark

Little information has been published concerning the actual or useful amount of energy obtained from explosives when they are used for blasting. To provide more data on this subject, 8-in. neet cement cubes were blasted in a steel plate box and the breakage energy evaluated by comparison with drop crusher results using Rittinger's," ' Kick's,%nd Bond's' theories. Theories by Bond and Wang," Lineau,' Hatch,' Roller," and others were not considered applicable. Those used in this investigation may be expressed mathematically as follows: [ ] The above equations were employed to determine values of KK, K for particle size distributions similar to those obtained from the blasting curves. These values were in turn used as a means of approximating the specific energy of the blasted material. The efficiency of crushing by blasting was then determined by dividing this specific energy by the maximum available work of the explosive per gram of cement.

Mar 1, 1956

By C. DeWitt Smith

"It just looks like everything is doing fine but humans," wrote Will Rogers fifty years ago. "Animals are having a great year, grass was never higher, flowers were never more in bloom, trees are throwing out an abundance of shade for us to loaf under. Everything the Lord has a hand in is going great, but the minute you notice anything that is in any way under the supervision of man, why, it's cockeyed." Do these words from two generations ago apply to oil shale? The United States has been blessed with deposits that can yield synthetic crude oil at a cost competitive with natural crude oil-under present economic conditions and with existing technology. Yet, the oil shale program is cockeyed because of the artificial obstacles that have been placed in its path "under the supervision of man." But more about this later. For the moment, let's focus on...

Jan 10, 1974

By W. G. Matteson

IN 1915, the State of California passed a law of great scope and importance. This law has been in successful operation for., year and may be briefly described as an act "establishing and creating a department of. the State Mining Bureau for the protection of the natural resources of petroleum and gas from waste and destruction through improper operations in production; providing for the inspection of petroleum and gas wells; requiring all persons operating petroleum and gas wells to make certain reports" and providing the necessary officers and assessments-to carry out the provisions of the act. The statute provides for a separate department of the State Mining Bureau, under the general supervision of the State mineralogist, with a staff composed of a "state oil and gas supervisor" and four deputies. It rules that all petroleum and natural gas wells shall be drilled, operated or abandoned under the supervision of the State supervisor, who shall order such tests or remedial work as seems to him necessary to protect the interests of property owners and the general public. It also provides for a board of arbitration to consider orders given by the supervisor which are not acceptable to the well owner. Section 18 of the, act, which is the provision that is directly related to, this paper, requires "the owner of any well referred to in this act to keep a careful and accurate log of the drilling of such well;" and further requires that this log shall show the character and depth of the formations passed through or encountered in the drilling, particularly the location and depth of the water-bearing strata; the character of the water encountered (so far as ascertained); whether the water was shut off, and, if so, at what point; that it shall show completely the amounts, kinds and size of casing used; the depth at which oil-bearing strata are encountered; the depth and character of the strata, and whether all water was successfully and permanently shut off so as to prevent percolation or penetration into the oil-bearing strata. -

Jan 2, 1917

By Joseph Jensen, F. W. Hertel

Many fields have been zoned by nature with shales and intermediate waters between oil zones. Limitations thus imposed have been the basis on which a field was developed. In contrast thereto, in the Ventura Avenue field, nature proved more generous. Always expecting to find such similar limitations, operators drilled deeper and deeper into the oil zone without finding any distinctive shale bodies other than the Gosnell shale and only one intermediate water, which became the point below which the final water shut-off of each well was made. Thus, on top of the structure, about 3300 it. of oil-bearing zone has been penetrated below this intermediate water—a distance of 4000 ft. below the Gosnell shale. At first it seemed that the greater penetration in the zone, the better the well. The error of this assumption became evident as time passed. Other pressing attendant problems requiring consideration also developed. In the spring of 1929, the Associated Oil Co., still having a large undrilled area, adopted a method for developing this land by dividing the oil formation into zones, so as to drill two classes of wells and to prepare for others, if conditions in the future justified or required such action. Wells now completed are considered as permanent completions in the zone or class for which they are drilled, and are not looked on as a ready means for deepening or accepted as a temptation for deepening to get some flush production quickly. Provision has also been made to avoid future water problems. The most striking demonstration resulting from such work is the fact that the top of the structure is far from being the point at which the largest oil recovery is made. Wells on the flank of the structure invariably produce with lower gas-oil ratios and secure much larger oil production. Zoning of Oil Sands The Gosnell shale separates the upper light 50 gravity oil from the lower 30 gravity oil below. As the light oil zone is of practically no importance at present, it is not being exploited. The development pro-

Jan 1, 1931

By Nelson W. Taylor

With the extensive deposits of potash minerals which have been discovered in the southwestern states, and their rapid development, a permanent American supply of potassium compounds is now assured. The 325-year history of the potash industry in this country has been told by H. I. Smith1, of the U.S. Geological Survey, and the more recent activities of the Survey and of American potash companies were described last year by the same author2. In fact, it may be stated that so great is the productive capacity that two mines in New Mexico and one in California are able to supply more than half a million tons of crude and refined salts over and above that produced for agricultural purposes. The era of scarcity has given way to an era of superabundance. This situatiori makes it desirable for the potash producer to look for other applications for his product, and it is with this in mind that the writer presents some information pertaining to present and possible future uses for potassium compounds in the ceramic industry. Ceramic Products Ceramic products are essentially solid materials containing one or more oxides such as SiO2, Al2O3, CaO, MgO, FeO, K2O, Na2O, TiO2, which are the oxides of greatest abundance in the earth's crust. The typical ceramic process is that of firing or burning the batch, and the product may be glassy, crystalline or mixed. In the glassy or vitreous group come glass, porcelain enamel and glazes; in the crystalline group, refractory materials such as silica brick, or chromite or magnesia; and in the mixed group, porcelain, chinaware, stoneware, tile, brick, etc., which contain both a vitreous and a crystalline phase, in variable proportions. The ceramic industry of the United States is a billion dollar industry, and is important not only because of its magnitude but also because of the key position occupied by certain ceramic products in the whole manufacturing structure. From the standpoint of use of potash, the field of refractories is of no great interest, since K2O lowers the melting point of a refractory oxide and

Jan 1, 1938

By Nelson W. Taylor

With the extensive deposits of potash minerals which have been discovered in the southwestern states, and their rapid development, a permanent American supply of potassium compounds is now assured. The 325-year history of the potash industry in this country has been told by H. I. Smith1, of the U.S. Geological Survey, and the more recent activities of the Survey and of American potash companies were described last year by the same author2. In fact, it may be stated that so great is the productive capacity that two mines in New Mexico and one in California are able to supply more than half a million tons of crude and refined salts over and above that produced for agricultural purposes. The era of scarcity has given way to an era of superabundance. This situatiori makes it desirable for the potash producer to look for other applications for his product, and it is with this in mind that the writer presents some information pertaining to present and possible future uses for potassium compounds in the ceramic industry. Ceramic Products Ceramic products are essentially solid materials containing one or more oxides such as SiO2, Al2O3, CaO, MgO, FeO, K2O, Na2O, TiO2, which are the oxides of greatest abundance in the earth's crust. The typical ceramic process is that of firing or burning the batch, and the product may be glassy, crystalline or mixed. In the glassy or vitreous group come glass, porcelain enamel and glazes; in the crystalline group, refractory materials such as silica brick, or chromite or magnesia; and in the mixed group, porcelain, chinaware, stoneware, tile, brick, etc., which contain both a vitreous and a crystalline phase, in variable proportions. The ceramic industry of the United States is a billion dollar industry, and is important not only because of its magnitude but also because of the key position occupied by certain ceramic products in the whole manufacturing structure. From the standpoint of use of potash, the field of refractories is of no great interest, since K2O lowers the melting point of a refractory oxide and

Jan 1, 1938

EVERY dry thing that burns easily and multiplies or maintains fire by its own intrinsic nature can be put into an incendiary composition and various effects are produced. Some of these things are mineral combinations, like sulphur or its oil; some others, [163v] hot, dry, and subtle substances, like saltpeter; and some are. unctuous things, like fats and oils of any kind; while some serve because of dryness, like pith and wood. Some of these things are natural and some artificial But now I set aside the search for these differences in their composition. This is what I have found among all the ancient and modern things that I have been able to seek, and first, back in the time of Alexander the Great. Marcus Graecus, who was perhaps the inventor or a great experimenter and practicer of such things, writes of many of them. I have chosen some among these, and one* is this: In order to make it, he took Grecian pitch, alchitran, live sulphur, tartar, sarcocolla, niter, and petroleum oil, one part of each, and, in addition, a double amount of quicklime. He mixed it all with oil of egg yolks. Having put it in a well-covered and closed vessel of glass or glazed earthenware under warm manure, he left it for a month. Then, having liquefied it over a slow fire, always keeping the vessel well closed, he finally put this liquor in hollow sticks, in little pots, or in vessels expressly made, all with a little fuse fitted in the middle. If I should have to do this, I would say that a little gunpowder should be put in, which should give beginning to the fire so that it would ignite more easily. I have also found that another fire is made. For this sulphur is taken, or oil of sulphur if it is possible to obtain, petroleum oil or some rock oil, juniper oil, very well-refined saltpeter, and for one part of each of these five parts of asphalt; in addition, take goose or duck fat, pure black pitch, varnish, pulverized dove's dung, and enough aqua vitae to cover all the aforesaid things.. Then it is put in a glass vessel under warm manure for

Jan 1, 1942

By Chas Fettke

DURING the summer of 1916, while on a visit to the United States Agricultural Experiment Station at Mayaguez, Porto Rico, the writers were told by D. W. May, the director, that an occurrence of manganese ore had been reported from the mesa southeast of Mayaguez. A visit to the locality showed that the mesa is covered by a mantle of bright red soil resting upon serpentine. Here and there over its surface concretionary masses of limonite have been washed out of this soil. These were FIG. I.-MAYAGUEZ FROM NORTHWEST END OF MESA. apparently mistaken for manganese ore. On account of the similarity of this occurrence to the extensive iron deposits of northeastern Cuba, it was thought that a brief description based upon a two days' reconnaissance survey of the area would be of scientific interest. Mayaguez is on the west coast of Porto Rico, at Mayaguez Bay, which is the third in importance of the harbors of the island. The city itself is about ¾ mile inland on the low-lying plain at the mouth of the

Jan 3, 1918

By David J. Mack, Chin Bea Kim

The decomposition of the Ni-Zn eutectoid at 56 wt pct Zn was studied by isothermal transformation. Its progress was followed by metallographic, hardness, and X-ray diffraction methods. Three transformation products were found: lamellar pearlite at high temperatures; an intermediate temperature structure; and martensite at the lower temperaCures. No transition structu,ves were found. THE decomposition of the Ni-Zn eutectoid at 56 wt pct Zn was stuadied as part of a long-range program of study on the eutectoid transformation in alloy systems which do not have one or more components which exhibit allotropy. Available information on the Ni-Zn eutectoid transformation is limited to that presented in connection with the determination of the phase dilagram. No systematic studies of the eutectoid were found in the literature, alkhough the microstructures of the Ni-Zn eutectoid were reported by Tamuru.3 X-ray diffraction data exist for the ß, ß1, y , and y1 phases.' EXPERIMENTAL PROCEDURE The eutectoid alloy was prepared from "A" nickel shot and Bunker Hill super-purity zinc (99.998 pct).

Jan 1, 1962

By Louis A. Mattson, Winthrop A. Rowe, John T. Cumberlidge, Victor M. Mejia

The parent ultramafic of Nickel Mountain is an alpine-peri-dotite. Compositional layering and late stage dunites suggest the intrusive crystallized in the upper mantle or lower crust. The ultramafic mass was fault emplaced in the upper crust, probably during upper Jurassic time. Soil, saprolite and silica boxwork nickeliferous ores were formed over the Nickel Mountain peridotite during the development and later destruction of the Klamath peneplane. A complex fault pattern was produced by irregular gravity displacements along fault surfaces during the relative uplift of Nickel Mountain. The majority of the ores occur in the fractured hanging wall of these gravity faults. Consequently, structure mapping is important for mining purposes. Ore types at Riddle are classified on the basis of MgO, Fe, and Si02 contents as well as textures. The chemical, mineralogical and textural differences of the various ore types reflect differences in weathering histories. Satellitic ore bodies occur peripherally to Nickel Mountain. These are erosional remnants of landslides and large gravity fault blocks from Nickel Mountain.

Jan 1, 1976

By Harrison, Henry Fay

The study of an entirely new series of alloys may be undertaken from a desire to obtain knowledge applicable to the perfection of industrial alloys, or merely to test certain theoretical considerations. In the case of antimony-tellurium alloys, the theoretical side only is at present important; but it is hoped that the results of this investigation may have some industrial value, at least indirectly, by furnishing one more example for comparison when studying commercial alloys. The statement is found in various places that antimony is isomorphous with arsenic, bismuth and tellurium; but very little experimental evidence has been offered in support of this assumption. All four metals crystallize in rhombohedra, and the ratio of the axes a: c is approximately the same—which seems to indicate, but does not prove, their isomorphism. The close association of these metals in minerals also seems to indicate that they are isomorphous. There are, however, certain differences in their properties which render this coriclusion somewhat doubtful, and it is therefore desirable that inde-

Jan 1, 1902

By David S. Bolin

INTRODUCTION This paper is directed toward those companies or individuals who may be considering the possibility of tin exploration or development projects in South America. Although tin deposits are known in many countries of Latin-America including Argentina, Peru, and Mexico, the majority of the deposits are located in Bolivia and Brazil. These two countries also account for virtually all the current production. Many factors affect the economic decisions related to mining and exploration projects in this region including the following: 1) Types of deposits 2) Anticipated size and grade of deposits 3) Deposit geometry and ore distribution as it affects the selection of a mining method 4) Metallurgical amenability 5) Governmental policies 6) Taxation 7) Anticipated capital and operating costs 8) Marketing costs This discussion will be directed toward each of these points. The majority of the presentation will be concentrated on Bolivia as this country is the principal producer in the region, however, the potential for further tin development in Brazil is excellent. Due to the remote and previously almost inaccessible location of the stanniferous districts of Brazil, little is known with respect to size and type of non-alluvial deposits which may exist in this vast country. TYPES OF DEPOSITS Two major types of deposits are currently being exploited in Bolivia; alluvial, and hard rock or lode deposits. Bolivia produces substantial tin from both types of deposit whereas virtually all Brazilian production to date has been from alluvial sources. Alluvial Deposits Brazil: The alluvial tin deposits of Brazil are located in river channels and flood plains adjacent to low mountain ranges. The terrain containing the tin placers is flat, marshy, and generally jungle covered. The major controls of alluvial cassiterite concentration are the ancient and present stream channels. The average tin concentration in the placers varies from 500 grams to approximately 1.0 kilograms per cubic meter. Tin reserves in the Rondonia field of Brazil have been estimated at 600,000 tons of fine tin. A bucketwheel suction dredge went into production in the Rondonia district in 1979, and four others have since been ordered. Several other gravel pump, and hand mining operations are also in production in this field. In addition to the Rondonia district, tin occurrences are known from Xingu, in Para state, and in the state of Minas Gerais. Bolivia: The alluvial deposits of Bolivia are somewhat more complex due to the variable geomorphology and abrupt topography. Conventional placer accumulations of cassiterite are found in many stream channels and intermontane basins surrounding the major lode tin producing regions. In addition to stream and valley placers, a group of deposits locally referred to as "Pallacos" or "Llamperas" which consist of colluvium, landslide debris and glacial moraine material, contain substantial tin reserves in some areas. The stream channel and intermontane basins contain the only deposits which are presently being exploited by mechanized methods. One dredge is working the stream channel below Cerro Rico de Potosi and another is operating in an intermontane basin southeast of the city of Oruro. Both of these dredges are operated by private companies. The average grade for these operations varies from 250 to 500 grams per cubic meter. The largest of the intermontane basin placers known at present is the Centenario deposit located adjacent to the Catavi lode deposit. This deposit contains approximately 170 million cubic meters of material with an average grade of about 150 grams per cubic meter. The "Pallacos" deposits are found on the slopes of mineralized areas and in glacial moraine. The mineralized material is generally completely unsorted, with tin and sometimes tungsten values distributed erratically throughout the entire mass. Most of these deposits are worked by small leasors or cooperatives; however, at least one mechanized washing plant is in operation southeast of Oruro. The size of these deposits may reach up to several million cubic yards. Grades are very erratic, but may range from 200 to 500 grams per cubic yard. In addition to the formal mining operations, virtually every drainage surrounding the major mines is being worked by independent' miners utilizing hand mining and jig or pan concentration. The aggregate production from these operations is substantial. The

Jan 1, 1982

By W. H. Emerson

In the summer of 1894, a specimen of corundum from Acworth, Ga., which mas reputed to be of markedly inferior quality for the manufacture of corundum-wheels, was received by the Geological Survey of Georgia, with the request that it be analyzed, in order to ascertain whether this inferiority was associated with any peculiarity of composition. In its appearance there was nothing uncommon, though it seemed to be rather easily scratched with a knife, while, at the same time, it scratched agate easily. An analysis gave the following results: Alumina, 94.58; silica, 1.77; magnetic oxide of iron, 0.69; calcium oxide, 0.44; and water, 2.51 per cent. There is nothing unusual in this composition, except the amount of water, which is usually, in southern corundum at least, from 0.3 to about 1 per cent. Concerning this corundum, the Mineral Resources of the United States, 1893, pp. 676 and 677, Bays: "It is supposed that this variety of corundum contains a little water, as it is

Jan 1, 1900

By Franc R. Joubin, D. H. James

Uranium exploration in the North Shore area of Lake Huron goes back to 1847 when J. L. LeConte, a distinguished American geologist, identified a pitchblende-like mineral which he called coracite from specimens sent from a locality north of Sault Ste. Marie. In 1948 a search for the LeConte occurrence resulted in discovery of the Camray field, some 70 miles north of Sault Ste. Marie. Prospecting the Camray field yielded about 30 pitchblende occurrences spread over approximately 200 sq miles. Almost without exception these discoveries consisted of narrow, short, pitchblende-filled fractures, within or along the contacts of diabase dykes cutting pre-Cambrian Archean granite and gneiss. Eight discoveries were diamond drilled and three were explored underground, but none proved to be of economic value. Uranium prospecting at this time spread far afield, and it was in 1949 that radioactive conglomerate was discovered in Long Township of the Algoma district midway between and 90 miles from Sault Ste. Marie and Sudbury. F. Joubin examined this discovery at that time but could not interest capital in its development.

Jun 1, 1956

By J. S. Jacobi

Treating copper ores by heap-leaching and similar hydrometallurgical means is a time-honored practice, which was well known even in the 19th century. Later the method lost ground to better ore dressing processes, particularly selective. flotation. More recently there has been a distinct reversion to leaching techniques, particularly for scavenging operations in old mining stopes, in connection with LPF systems, irrigation of tailings dumps and similar situations. These hydrometallurgical techniques will gain further ground because processing is simple and permits better extraction of copper, particularly from low-grade or partly oxidized ores. In the lixiviation of primary ores at some major operations, copper-bearing liquors may undergo re-circulation in heap-leaching arrangements or the ores may be subjected to systematic percolation treatment. The liquors resulting from this source usually are quite strong (above 10 gpl copper) and copper would normally be reclaimed by electrowinning or cementation. These processes fall out- side the scope of this paper which is concerned with recovery of copper from weak 1iquor.s containing from 0.1 to about 3 gpl copper.

Jan 9, 1963

By Paul Gordon

The distribution coefficient, k, of interest in zone refining is generally defined as the ratio of the solid to the liquid solubilities of one element in another at the normal melting point of the solvent. In practice, distribution coefficients are frequently calculated from solubilities at temperatures well below the melting point of the solvent, e.g., at a eutectic temperature. This is done because of the general lack of accurate data on the liquidus and solidus curves in most phase diagrams. The practice is equivalent to assuming that the liquidus and solidus curves are straight lines in the temperature range between the melting point of the solvent and the temperature at which data for the solubilities are known. It is recognized that the k values so derived may be in serious error; we have found evidence in recent zone-refining operations that a case in point is silicon in aluminum. The phase diagram found in the literature for silicon in aluminum indicates a eutectic on the aluminum-rich side at 12.5 at. pct Si and at 577°C,1 and a solid solubility of silicon in aluminum at this temperature of 1.59 pct.2 It also shows the liquidus and solidus as nearly straight lines from 577°C to the melting point of aluminum (660°C)1,2 The k value obtained from this data is 0.13. This is almost exactly the same as the k value (about 0.14)' obtained in a similar way for copper in aluminum. Yet we have found by mass-spectrograph analyses* of three bars of zone-refined aluminum that copper is efficiently removed from aluminum by zone refining but silicon is not. Two of the three bars of aluminum were zone-refined in our laboratories, the other in the laboratories of AIAG Metals, Inc. The former two bars, designated bars PG2 and PG3, were 30 in. long by 1 in. in diameter during refining; each was processed in a high-purity graphite boat* and kept under refining stage of the process consisted of thirty unidirectional zone traverses at rates of about 1 to 2 in. per hr, with a zone length of 1 to 2 in. At approximately the middle of the refining period a 6-in. piece of the impurity-laden finishing end of the bar* was cut off and replaced with new start- ing material. Following refining, the purest 20-in. section of the bar (obtained by discarding approximately 2 in. of the starting end and 8 in. of the finishing end of the bar) was leveled and then analyzed. The AIAG bar was 16 in. long and about 1.2 in. in diameter; it was purified by eight passes of a 2-in. zone at a rate of 1.6 in. per hr, the bar being contained in a sintered alumina boat lined with loose alumina powder of the highest purity. Data for the silicon and copper contents of the three refined bars are given in Table I. Derived data for the efficiencies of the zone-refining operations are listed in Table 11. It is clear from these two tables that the copper is removed much more efficiently—by a factor of 10 to 50 times—from aluminum during zone refining than is silicon. For example, in bar PG3 the thirty zone passes reduced the copper content from 10 to 0.02 ppm, i.e., by 500 times, whereas the same treatment lowered the silicon content by only a factor of about 16. It seem virtually certain, therefore, that the distribution co efficient, k, for silicon in aluminum is well above that for copper and is very likely not much below unity. This also implies that the solidus line on the aluminum-rich side of the A1-Si phase diagram is very probably appreciably curved near the aluminum melting point since the phase-diagram data indicate such curvature is unlikely in the liquidus.

Jan 1, 1965

By Walter Crafts, D. C. Hilty

The liquidus diagram for the iron field of the Fe-S-O system has been derived experimentally. The solubility of oxygen in molten Fe-S alloys has been measured at several temperatures and found first to decrease slightly and then increase rapidly with increasing sulphur content. IT is well-known that the types, distribution, and amount of inclusions in any given steel are closely allied with the oxygen and sulphur contents of the metal, so that the term "deoxidation" as conventionally applied in steelmaking refers not only to the control of oxygen and oxide inclusions but to collateral modification of sulphide inclusions as well. Inclusions commonly occur in steel as mixtures of oxides and sulphides, sometimes closely associated and sometimes apparently completely divorced. Their effects on the properties of the metal may vary widely depending on their types and distribution as well as on their quantity. The mechanism by which inclusions form, however, and the means for controlling it are exceedingly complex and not well understood. Nevertheless, as described by Benedicts and Lofquist' and by Wentrup' all oxide and sulphide inclusions, excluding mechanically entrained matter, must result from specific modifications of the basic equilibria of the Fe-S-O system. In an investigation of the mechanism of deoxidation and inclusion formation being carried out at the Union Carbide and Carbon Research Laboratories, it became evident that quantitative data for the fundamental Fe-S-O system were essential to a better understanding of the problem. Consequently, the liquidus surface of the portion of the Fe-S-O diagram of interest in steelmaking has been determined, and the solubility of oxygen in liquid iron containing sulphur has been measured. Fe-S-O Diagram The portion of the Fe-S-O diagram of specific interest in steelmaking is the Fe-FeS-FeO corner. Of the contiguous binary diagrams for this partial system, only those for Fe-FeO and Fe-FeS are known with reasonable certainty.3 Several attempts to derive the FeO-FeS diagram have been made, chief among them being the work of Giani as reported by Oberhoffer,4 and, more recently, that of Vogel and Fulling." Although both Giani and Vogel and Fulling published diagrams for the FeO-FeS system, their observations indicated that the oxide component approximated Fe3O4 rather than FeO, so that there is doubt whether the system is truly binary. Benedicts and Lofquist and also Wentrup published qualitative sketches of the ternary diagram based on the assumption that it was of the type described by Marsh for a ternary system in which two of the contiguous binary systems are simple eutectic systems and the third exhibits a solubility gap in the liquid. Apparently, however, the only previous effort to establish the diagram experimentally was that of Vogel and Fülling whose results are reproduced in Fig. 1. Although defining approximately the limits of the miscibility gap and the location of the ternary eutectic, point E in Fig. I, Vogel and Fülling's diagram must be considered only semiquantitative. It was derived from a limited number of observations mainly along two quasi-binary sections, and the directions of the tie-lines and the location of the critical point, K in Fig. 1, were estimated by computation. Experimental Procedure The experimental technique employed for the present investigation involved melting mixtures of ferrous sulphide and ferric oxide in contact with iron. Since it was considered that in this part of the system the vapor pressures of sulphur and SO, are so low that they would not affect the results significantly, the melting was carried out in a current of argon to sweep out products of any initial re-

Jan 1, 1953

By D. C. Hilty, W. Crafts

A qualitative pseudoternary solidification diagram for the Fe-S-O system modified by manganese is proposed and supported by experimental derivation of an isothermal section at 1475°C and substantially 1 pct Mn in the solid-metal phase. The solubility of oxygen in liquid iron containing 1 pct Mn and sulphur contents up to 0.9 pct has been measured at 1600°C and found to increase as the sulphur content exceeds 0.15 pct. AS has been pointed out previously,' all oxide and sulphide inclusions in steel, excluding mechanically entrained matter, result from modifications of the basic Fe-S-O system. Therefore, one method of attack on the problem of the mechanism of deoxida-tion and inclusion formation is to examine the influence of deoxidizers on the Fe-S-O liquidus diagram. This approach has been adopted in work on the subject being carried out at the Metals Research Laboratories of the Electro Metallurgical Co. and has resulted in the postulation of types of solidification diagrams for the Fe-S-O system modified with common deoxidizers. This method has been of considerable assistance in interpretation of the factors affecting the formation of inclusions.' For the most part, however, these diagrams have been highly speculative. They were constructed primarily by inference from the pertinent binary and ternary systems and from the appearance of inclusions produced by specific deoxidizers. Moreover, since the systems contain four or more components, simplifying assumptions and qualifications were necessary in order to permit their representation as modifications of the Fe-S-O diagram. Consequently, experimental confirmation of the type of construction employed for these diagrams is desirable, and the present paper is concerned with such evidence. The addition of manganese to the Fe-S-O system was selected for initial investigation. Manganese is an important component of practically all steel and is, therefore, of fundamental interest. Because of its great affinity for sulphur, manganese has a more profound effect on the sulphide side of the Fe-S-O diagram than any of the other common deoxidizing eletments. In addition, more quantitative information pertaining to the contiguous binary and ternary systems involving iron, manganese, sulphur, and oxygen is available than for the other deoxidizers. Fe(Mn)-S-O Solidification Diagram Many of the side diagrams of interest in connection with this system are known. The Fe-Mn binary has been well established by several investigators;% the Fe-O system has been clarified by Darken and Gurry;' and FeO-MnO diagrams have been published by Herty,5 Andrew, Maddocks, and Howat,6 and by Hay, Howat, and White.7 The Mn-O diagram does not appear to have been derived experimentally, but the portion of 'it that is of interest can be visualized easily from a consideration of the melting points of Mn and MnO and the fact that a broad miscibility gap must exist between them. The ternary Fe-Mn-O diagram has been discussed by Benedicks and Löfquist,8 Wentrup,9 and by Körber and Oelsen.10 Experimental study of the Fe-Mn-O system has been carried out by Körber and Oelsen and to a lesser degree by Chipman, Gero, and Winkler,11 Hilty and Crafts," and others. On the basis of published information, then, an outline of the Fe-Mn-O liquidus diagram can be constructed as illustrated by Fig. 1. In this, as in all succeeding diagrams, transformations such as the ?-? reaction in iron have been ignored for purposes of simplification. The arrows denote falling temperature. The distinguishing feature of this diagram is the broad region of liquid immiscibility extending

Jan 1, 1955