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By Yinchang Wang

1. INTRODUCTION 1. Subject, and Scope The formation of the oxidized ores of zinc has been recognized as a subject of great importance in economic geology. For many years these ores have been much sought, partly because they are more desirable for metallurgical treatment and partly because they are apt to be freer from gangue than is the sulphide of zinc. Up to very recent years the oxidized ores were the principal source of the metal and at present they still furnish a large portion of the commercial production. . The oxidized ores of zinc include six minerals, as shown in the-following table

Jan 9, 1915

By H. A. Wheeler

That lead and zinc deposits are the result of prolonged,, slow deposition is the idea of most students of ore deposits, and in many cases, where the ore-bearing solutions have been very weak or the precipitating conditions have been very feeble, the ore accumulations have undoubtedly taken a long period of time. As these two vital conditions have been subject to great variations in the different mining camps, the following example is highly interesting in showing that deposition can be very rapid under favorable conditions, geologically speaking, and also extremely recent. In fact, the writer is inclined to regard most, if not all, of the Mississippi Valley deposits of lead and zinc as probably being very young, at least not older than Tertiary, if not Quarternary, in age. The extensive Joplin lead and zinc district, in southwestern Missouri, which is about 60 years old and has numerous mines that were abandoned from 1 to 50 years ago, shows that the lead and zinc today are in an active condition of solution and redeposition, although these two metals occur in the predominant form of sulfides. The mine waters from the older and more or less abandoned portions of the district are frequently so acid, mainly from the oxidation of associated pyrite, as to necessitate the use of wooden pipes and pumps. The first boom in the Oklahoma zinc fields, which is the southwestern extension of the Joplin district, occurred when ore was accidentally struck in drilling a water well. Among the mines then opened up was the Mission mine, at Lincolnville, Ottawa County, Okla. This mine was opened in 1903 in lean "sheet ground," or a flat blanket formation of chert carrying disseminated zinc blende, or "jack," and galena. Theore-body was very free from iron pyrites and the concentrates were very high grade, the "mineral," or lead concentrates, assayed 80 to 85 per cent. lead and the jack, or sphalerite, assayed 60 to 65 per cent. zinc. The orebody was very shallow, occurring at a depth of 76 to 95 ft. (22 to 28 m.) and very wet, requiring three or four pumps to handle the water. The mine was operated until 1914, when it was closed by litigation and immediately filled with water. The second Oklahoma boom, five years ago, opened up the large, active camps of Picher, Tar River, and Century, which are located 2 to 5 mi. west of Lincolnville. They are considerably deeper, being farther down on the westwardly dipping monocline that emanates from the Ozark

Jan 1, 1920

By Leonard B. Gulbransen, John R. Lewis, W. Martin Fassell, J. Hugh Hamilton

T. E. Leontis (The Dow Chemical Co., Midland, Mich.)—This paper is of particular interest to me because of my own work with F. N. Rhines on the oxidation of magnesium and magnesium alloys a few years ago. The authors are to be complimented on their development of an accurate and reproducible technique for measuring ignition temperatures and on their comprehensive study of the many variables that affect the ignition temperature of magnesium. It is indeed gratifying to see that they have obtained a good correlation between ignition temperatures and the oxidation rates reported by us. The correlation is valid not only with composition within one alloy system but also between alloy systems; that is, alloying elements which effect the greatest increase in oxidation rate also produce the greatest decrease in ignition temperature. There are a few points upon which I would like to comment. In attempting to correlate ignition-temperature data, one must be sure that the same definition of this quantity is used by all investigators. It does not appear to me that such is the case in the authors' comparison of their data with the theoretically calculated values of Eyring and Zwolinski. The equation derived by these investigators defines the ignition temperature, To, as the temperature at the gadoxide interface, whereas the present authors use the metal temperature as the criterion for ignition. The contradiction in the effect of oxide-scale thickness on ignition temperature between the predictions of the Eyring-Zwolinski equation and the observations reported in this paper indicate that some variable has not been taken into consideration. Could that be the geometry and size of the specimen? There is a marked difference in the type of specimen used in this investigation and that used in our work which formed the basis of Eyring and Zwol-inski's theoretical treatment. Another factor which plays an important role in ignition is the vapor pressure or the rate of vaporization. Combustion can safely be assumed to take place in the vapor phase by the reaction between vaporized magnesium and oxygen. Thus, a more accurate theoretical analysis may be made on the basis of the rate of vaporization which may be the controlling rate of the process. The effect of a large number of alloying elements on the ignition temperature has been reported in this paper, but beryllium was not included. Practical experience dictates that beryllium markedly decreases the burning tendency of magnesium. I was wondering if the authors plan to study the effect of beryllium in their future work. The authors predict that concentrations of sulphur dioxide in the furnace atmosphere greater than 5.8 pct would be expected to increase the ignition temperature to values still higher than those they measured. I would like to mention that large concentrations of sulphur dioxide markedly increase the rate of combustion of magnesium once ignition has started. Although it has been shown in the paper that the ignition temperature of magnesium in oxygen increases with increasing sulphur dioxide content up to about 1 to 2 pct, in practice relatively low-melting commercial cast alloys (AZ63A and AZ92A) are being continuously heat treated at temperatures just below the melting point in air containing 0.5 to 0.75 pct SO*. In regard to the change in color of the oxide scale observed on magnesium and magnesium alloys just prior to ignition, I would like to mention that in our work alloying elements were found to color the usually white magnesium oxide even though ignition did not occur. For example, the oxide formed on Mg-A1 alloys was gray, increasing in intensity with aluminum content in the alloy. Finally, I might suggest that the authors indicate their source of the value of 0.8 g per cc for the density of MgO as it is formed on magnesium upon oxidation at elevated temperatures. W. M. Fassell, Jr. (authors' reply)—The comments by Dr. Leontis are very excellent ones and I will attempt to answer them in order. First, the problem of ignition of magnesium is a rather difficult one since many factors are involved. Concerning the comparison of the To in the Eyring-Zwolinski equation, eq 4, with the experimentally determined values, it will be noted that the calculated and experimental values of the ignition temperature in Table I are not self-consistent. In the case of the 1.78 pct A1-Mg alloy the calculated value is 49°C below the experimental value; for the 3.81 pct A1-Mg alloy, 122°C below the experimental value; for Mg with 5x10-' cm film, 19°C above the experimental value; for Mg with 2x10-I cm film, 28 °C below the experimental value. Thus, if it were merely a matter of difference of location of temperature measurement the calculated ignition temperature would always be below the experimental value, the difference being due to the thermal gradient through the oxide film. The possibility of a thermal gradient in the magnesium metal must be considered. From Carslaw and Jaeger,'Y t can be shown that the maximum temperature gradient that could exist between the oxide-metal interface and the center of the sample is of the order of O.Ol°C. The geometry and size of the specimen could certainly have some effect on the ignition temperature. The equation for ignition that has been proposed in reference 14 is of the following type containing terms to account for this and other factors: M dT AHv(T) =Cp--------------\-J(.T—TB) + ZAHl-M A dx where AH is the heat of reaction, v(T) is the velocity of the reaction at temperature, Cp is the heat capacity of sample, M is the mass of sample, A is the area of sample, t is time, J is the total coefficient of heat transfer outward from the reaction zone, TR is the temperature of the bath or furnace, and AH,, is the heat associated with any phase change involved. Prior to the instant of ignition, the vapor pressure of magnesium is of no special significance. After ignition, neither eq 4 nor the above equation is applicable. The actual combination of magnesium cannot safely be assumed to take place in the vapor phase. While experimental data is lacking to support a hypothesis that ignition does or does not occur in the vapor phase, some observation on the pressure ignition experiments may be of interest. At high oxygen pressures, once ignition has occurred, the reaction of magnesium with oxygen approaches near explosive violence, the entire sample being consumed in probably less than 1 sec. At atmospheric pressure it usually requires 15 to 20 sec. Thus it appears that the oxygen concentration becomes the rate determining factor. Further, if burning magnesium is observed through darkened glass (Lincoln Super-visibility Shade No. 12) the magnesium sample is very much hotter than the "smoke" and the outline of the sample is retained perfectly. No "flame" is visible above the metal. No work was done on Mg-Be alloys. We do, however, intend to study this problem in the near future.

Jan 1, 1952

By Oswald J. Heinrich

The responsibility resting upon the owners and managers of mines where fire-damp is generated, renders it a matter of imperative duty that a frill and correct statement of any explosion that occurs should be given to the public. But such a statement must be based on the testimony of impartial eye-witnesses or trained experts. Then a sad experience may result in the adoption of effective preventive measures. In the absence of any official and professional body of mining experts in the State of Virginia, the writer desires to submit to his professional brethren of the American Institute of Mining Engineers an account of an explosion which recently took place in a colliery under his management, and earnestly desires a thorough and impartial discussion on the Fats submitted. Description and Plan of the Mine.—The "Grove" shaft is situated at the nearest point 825 feet from the last old workings upon the Midlothian property, south of the old Pump shaft works. (See Plate 111.) The shaft was sunk by the former company, some thirty years ago, to the depth of 622 feet. An incline over 230 feet long, starting in a northwest direction at a depth of 105 feet above the shaft bottom, had been driven to explore the coal on the dip. A return of very small dimensions had been driven round the shaft on the south side, entering the upcast chamber. With the information obtained from the former company that a seam of coal about four feet thick, at a depth of 490 feet, had been found, and with the information obtained by the present proprietor, R. T. Burrows, of Albion, N. Y., by means of two boreholes on the dip west of the old shaft, in both of which workable seams of coal at various depths had been ascertained, the clearing out and thorough retimbering of this shaft were commenced in March, 1873. Borehole No. 1, at a depth of 4773 feet from surface, revealed a seam of coal. This borehole was afterwards carried to a depth of 1140 feet to the granite, without finding any other seam of coal. Borehole No. 3, at a depth of 608 feet, revealed the first coal-seam, 14 1/2 feet thick; at 633 feet, the second, 12 feet thick; at 662 feet the third, 1 foot thick, and at 692 feet the fourth, 43 to 5 feet thick. The borehole was stopped at a depth of 715 1/2 feet.

United Engineering Trustees, Inc. TAMES L HEAD, '50 E C MEAOHER, '52 R M ROOSEVELT, '49 The Engineering Foundation F F COLCORD, '50 E A PRENTIS, JR , '48 R M ROOSEVELT, '49

Jan 1, 1952

By R. D. Pehlke, J. V. Gluck

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult's law and obeyed Henry 's law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner's interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

By G. W. Toop, C. S. Samis

Jan 1, 1962

By W. M. Dressel, A. Visnapuu

The Bureau of Mines, U.S. Department of the Interior, has upgraded high-iron domestic chromite concentrate to high-chromium concentrate by a laboratory carbonyl process. The chromite concentrate product has a chromium-to-iron ratio in excess of 3:l compared with the starting concentrate ratio of 1.6:1. The high-iron chromite was first reduced to convert the iron oxides to the metal, and then treated with carbon monoxide at elevated pressures and low temperatures to convert the metallic iron fraction to iron pentacarbonyl. Carbonylation was accelerated by the addition of hydrogen sulfide in small quantities. A constant flow of carbon monoxide swept the iron pentacarbonyl formed in the reactor out through a pressure-reducing valve. The mixture of carbon monoxide and iron pentacarbonyl at atmospheric pressure was then passed through a heated section to decompose the iron pentacarbonyl to carbon monoxide and iron, whereupon the latter plated out on the heated surface. Carbon monoxide pressure, temperature, and promoter trends for enhanced carbonylation are presented.

Jan 1, 1984

By Samuel M. Brock

Problems related to strip and auger coal mining have grown with the development of the industry and the economy. New technology has produced equipment that has made mining by surface methods not only highly productive, but potentially highly destructive of water resources and natural environments. On the other hand, growth of the economy has produced an increased demand for clean water and created new demands for amenity values that natural environments provide. Thus, opposing forces have created conflicts in resource use. And these conflicts have made surface mining highly controversial. Resolving the controversy will require the solving of complex economic and social problems. The essence of the economic problem created by surface mining is that, in the absence of proper regulation, substantial costs resulting from the process are borne by the public rather than the mine operator. The major goal for the regulation of the surface mining industry is to provide controls which will promote the attainment of maximum social welfare. Deciding upon the type of controls required, and how to apply them to attain a social optimum, however, poses some very difficult problems. In a comprehensive article on this subject, David B. Brooks defined the problem and suggested that benefit- cost analysis might be helpful in providing guidelines for making decisions about surface mining regulations.1

Jan 5, 1969

By R. M. Brick, M. A. Williamson

Certain features of the response of copper and brass to deformation and recrystallization remain obscure. The textures obtained on rolled sheet are listed by Schmid and Boas1 as: No adequate explanation has been advanced for the presence of the secondary deformation texture of copper and its absence in brass or for the origin of the cubic recrystallization texture of copper.2 A recent publication3 attempted to rationalize the above empirically described annealing texture of brass on the basis of retention of the (110) [112] rolling orientation plus twinning about the central octahedral poles of the usual secondary (110) [115] orientation. The difierence in the textures of annealed copper as compared to 70-30 brass is also shown by the difference in the position of ears for drawn copper, at o° and go", as compared with drawn brasses, at 45o, for all compositions between oo-10 and 70-30.4 Data on indi- vidual crystals are as yet too few to permit of an analysis of these textures comparable to that of mild steel as made by Barrett and Levenson.5 Experimental Methods The materials studied included copper specimens cut from the central, equiaxed crystal portion of a tough-pitch wirebar; brass made from this copper and high-purity (99.99 per cent) zinc including alloys of 7 per cent, 15 per cent, 24 per cent, 29 per cent and 36 per cent Zn and large single crystals of 70-30 bras. Sections 1/4 in. thick of the cast polycrystalline copper and brasses were reduced 40 per cent by rolling, recrystallized to a common grain size of 0.045 mm. and then rolled directly to foil 0.002 in. thick. Hardness readings employing both the Vickers and Rockwell machines were taken at intervals during the reduction. For comparison, similar specimens were cross-rolled—i.e., turned through 90° for each pass—and comparable hardness data were secured. Finally sections from the single crystals of brass were cut to obtain the following initial orientations; these sections were rolled, hardness data secured and a complete micrographic record of structural changes obtained.

Jan 1, 1941

By W. M. Weigel

The rapid advance, during recent years, in the manufacture of articles that have been in common use for generations and the development of new materials entering into appliances and devices unheard of fifty years ago have created a demand for some of the more common non-metallic minerals. To supply this demand there has quietly developed a branch of the mining industry of which little is known by most mining engineers —the mineral-filler industry. In this paper, and generally in the trade, the term mineral filler is applied to a mineral used in its natural state after mechanical preparation only (such as grinding, milling and washing), without undergoing any chemical change and without exerting any chemical action on the substance with which it is incorporated. The consumption of mineral fillers is confined chiefly to large manufacturing centers in the Eastern and Northern Statcs. Where available, materials originating near the place of consumption are used, as most fillers bring a comparatively low price and, frequently, the freight may equal the cost of the finished filler at the mine. The Southern States have abundant deposits of non-metallic minerals suitable for fillers, which supply the manufacturing industries in adjacent states. Many of these deposits are equal to, or superior, in quality to those mined in the North, but they can not compete with them because of the freight rates. The mineral-filler industry has felt the present depression, but it has suffered less than most mining industries, for as a rule the mills are simple, the overhead expenses are low, and the labor is entirely local and can revert to farm work when the plant closes down. Many other deposits in the southern district will undoubtedly be developed when business revives and freight rates are adjusted. Most of the non-metallic mines are small and the tonnage handled is low in comparison with the tonnage involved in modern large-scale mining of coal, iron, copper, etc. On the other hand, at nearly all non-metallic

Jan 1, 1923

The primary purpose of the Institute is to advance the technologic and engineering arts embraced by it through interchange of knowledge. This can best be clone by the presentation and discussion of technical papers by its members. Short practical papers are especially welcome. An author should always satisfy himself that his material is of a quality that will he a credit to him and to the Institute. The preparation of a good paper frequently leads to a reorientation of the author's thoughts, and publication contributes much to the professional standing of the author. Members are urged to submit papers presenting the results of their work. Attention to the following suggestions will greatly further the prompt and efficient handling of manuscripts. 1. SUBJECTS: The subject must be within the field of the Institute. Original work, the results of field, plant, laboratory or theoretical investigations, new views on old but important problems and occasionally reviews of timely and important subjects of wide interest to our members may constitute the basis of a paper. The mere fact that the work is original does not necessarily justify publication: it must be of a substantial nature, of value to a reasonable number of our members and worthy of permanent record. It is seldom desirable to subdivide the results of a single research for publication in a variety of journals. Previous publication is usually a bar to acceptance. If any part of your paper has been published elsewhere and you regard repetition as absolutely necessary please so state in your covering letter. 2. CONSTRUCTION: Papers should be clearly and concisely written in good English. Care in this regard ensures wider reading and the saving in space permits the Institute to publish more papers. It is the experience of the Papers and Publications Committee that most papers can he improved by condensation. "Readers" who are asked to recommend acceptance or nonacceptance put particular emphasis on the length of the paper and the elimination of unnecessary or any extraneous material. The terminology and units employed should be those current in the particular field. An examination of Institute publications will afford useful guidance in such matters. Webster's New International Dictionary, 1935 edition, is the Institute's authority for spelling and style. Various abbreviations are used habitually; for instance, lb., pound; bbl., barrel or barrels; ft., foot or feet; hr., hour or hours; in., inch or inches; Fig. 1 but Figs. 2 and 3.

Jan 1, 1946

By Charles H. Hopkins, J. M. Lohr

A COMMERCIAL development requiring a suitable alloy or alloys for sealing into various grades of glass made it desirable to have a more exact knowledge' of the expansion characteristics of the nickel-iron alloys than appeared in the published literature. The expansion of the more common [ ] types of glass under consideration varies from 2.7 to 10.4 X 10-s per degree Centigrade, over the range 20° to 400° C. For reference, the thermal expansion curves of several types of glass used for sealing by the lamp and tube industries are given (Figs. 1 and 2). This paper covers a detailed investigation of the thermal expansion of a series of nickel-iron alloys in which the nickel content varies from 30 to 70 per cent. Particular stress is laid on the alloys that contain between 40 and 55 per cent Ni.

Jan 1, 1938

By H. P. Allen

THE Achotla mill of the Cia. Minera de Peñoles is of special interest in that it is one of the few still employing the chloridization process. The ore milled comes from the Suriana mine and consists of both oxide and sulphide, from neither of which can the gold or silver be extracted by a simple cyanide treatment. The mill was built in 1927, after several years of study in the development of the process1, and operated from December of that year until October 1930. Operations were resumed in February 1935, and have been continuous since, treating approximately 5000 tons per month, while the mine is getting up to full tonnage of 6500 tons per month.

Jan 1, 1937

The Naval Consulting Board is asking the aid of all the members of the Institute in its effort to help solve the submarine problem. Probably every member of the Institute has some suggestion, and while each one of these may be of only slight value in furnishing the remedy, the aggregate may be of great service. Every member of the Institute will soon receive a pamphlet known as Bulletin No. 1 of the Naval Consulting. Board of the United States in which full information and instructions will be given to all of those who are willing to assist. It is hoped when this information is received the members of the Institute will give it their prompt attention and write as soon as possible to the Secretary of the Naval Consulting Board, 13 Park Row, New York, N. Y.

Jan 9, 1917

Planning for a surface coal mine includes selecting the best means and equipment for uncovering the coal, loading it, and transporting it to the preparation plant. The machines and methods that will ensure optimum production will depend upon the location and characteristics of the seam to be mined. Stripping Techniques The choice of stripping units is influenced primarily by the system of mining, such as contour or out-crop mining as contrasted to mining in a region of rolling terrain with relatively flat upland surfaces. Factors such as the life of the mining operations production requirements, types of overburden, local and regional dip of coal, and land reclamation are other important considerations.

Jan 10, 1967

An ore search for commercial titanium-bearing ore deposits is in progress by the Crane Co., manufacturers of valves, because they expect this metal to be important in valve manufacturing in the future. The company will eventually be mining and making titanium sponge. At present they are buying titanium tetrachloride from the Stauffer Chemical Co, at Niagara Falls and making titanium by reaction with magnesium. Production from the Babbitt concentrator of Reserve Mining Co. is scheduled to begin in late 1951 or early 1952. The capacity is to be 300,000 tons of pellets per year made from magnetic taconite concentrates.

Jan 7, 1951

By A. D. Hughes

A relatively small area in Malaya, about 200 miles long by 40 miles wide, is the most important source of tin in the world. Some tin is recovered in other parts of the peninsula. Of the tin mined, 98 pct is recovered from alluvial deposits. From 1935 to 1941 the average annual world production of tin was 190,000 tons. The average annual production from Malaya during the same period was 62,000 tons or about one third of the total. Other producing countries, in order of importance, were the Netherlands East Indies 34,000 tons, Bolivia 30,000, Belgian Congo, Nigeria, Siam, Burma, China, and a few others with smaller amounts. The serious shortage of tin during the war period was due to the fact that the Japanese were occupying Malaya, Netherlands East Indies, Siam, Burma, and China which, together, formerly were producing 65 pct of the world supply. Because of the importance of tin in the world economy, and because of the fact that little is generally known in this country regarding the methods of recovering the tin in Malaya, it is believed that a short description of the industry, as carried on there, may be of interest to many of the readers. In addition you may be interested in the effect of the Japanese occupation, subsequent recovery of the properties and conditions existing at that time. The Malay Peninsula lies at the southeast tip of Asia. Singapore, a British colony, is situated on a small island at the southern end of the peninsula. It is a city of nearly a million population, an important world port, the site of a large British naval base and of one of the tin smelters. The Federation of Malaya consists of nine states, plus Penang, Malacca, and other small areas formerly part of the Straits Settlements, and it now covers the entire peninsula. The civil administration is controlled by the British. A constitution was adopted recently after reaching agreement with the Malay Sultans of the various states, who retain control of religious matters. The Capital is at Kuala Lumpur, a city of about 200,000 population, 250 miles north of Singapore and about half way to Penang. The country covers an area of 51,000 square miles, an area about equal to that of Florida and about one third that of California. It has a population of about seven million consisting of Malays, Chinese, East Indians, and a relatively small number of Europeans. The principal products are tin and rubber. There are over three million acres of planted rubber. The country is not self-supporting agriculturally as about one third of the necessary food supplies is imported. Rice is the principal food of the Asiatic population and some of the recent unrest is caused by a shortage of rice and the consequent high price. Good highways have been built through the settled part of the country. A railway, Government owned, extends from Singapore northward through the entire peninsula. The climate is tropical but health conditions are good for a tropical country. I was in Malaya from 1939 until January 1942, during the time of the simultaneous air attacks on Pearl Harbor, Manila, Hongkong, and Singa-

Jan 1, 1950

By W. K. Hardy, H. H. Stadelmaier, L. J. Huetter

The ternary system Co-Sn-C was studied in the cobalt-rich region. The liquidus projection ulas established and two fonr -phase reactions were found. An isothermal section at 950°C was worked out. In the region studied the following phases were observed: cobalt-rich solid solution, graphite, binary compound y -cobalt-tin, and a ternary compound. As a result of the limited solubility of carbon in liquid cobalt-tin alloys, the investigation was limited to the cobalt-rich region. Tin contents up to 32 at. pct were studied. Cobalt of 99.99 pct purity, tin of 99.97 pct purity and synthetic graphite of 99.93 pct minimum purity prepare the alloys. Carbon determinations of all alloys were obtained by gas volumetric analysis. Samples were investigated microscopically and by X-ray diffraction using CoK, and FeK, radiation. Cooling curves were obtained with a number of alloys to determine the temperature of the four-phase reactions. The thermocouple was calibrated with the melting points of high-purity silver and copper. In the region studied the following phases were observed: Cobalt-rich solid solution (face-centered cubic) Graphite. Binary compound y (solidifies congruently at composition Cop~n)'. Ternary compound k which is face-centered cubic with superlattice and nonferromagnetic.' In Fig. 1 the fields representing the projections of the liquidus surfaces were determined by microscopic investigation and are labled by their primary phase. In the field labled C graphite is the primary phase. During solidification in this field much of the primary graphite was expelled through the surface of the melt. It could not always be established microscopically whether the remaining graphite was primary or purely eutectic. Therefore it was not possible to determine accurately the boundary curve which drops from the binary eutectic el at 1309 "~~ to the point of the four-phase reaction at F. The ter-nary carbide is the primary phase in the field labled k. To the right of this field the primary graphite is consistently nodular whereas flake graphite is observed at tin contents somewhat below F. The ternary carbide does not appear to solidify congruently. The graphite is attacked in a peritectic reaction along the boundary between k and C. Thus no graphite is observed in alloys in the k field. In alloys right of the boundary between k and C the graphite nodules are located in the center of the k crystallites, further documenting the peritectic nature of the reaction with the graphite. A four-phase reaction was found at F and 1120 &3"C. The most likely reaction is L+ CY-Co + C — k. Below the temperature of the binary eutectic ez at 1112" a second four-phase reaction was observed at E and 1100 lt3"C. It is the ternary eutectic L — CY-Co + k + y. Figs. 2(a ) to (e) show microstructures of the ternary alloys in the as-cast condition. Fig. 2(a) shows the eutectic a-Co + C (with some primary graphite) with the carbide k in the grain boundaries. Fig. 2(b) shows primary cobalt (dark areas) and the eutectic a-Co + k which is formed along F-E.

Jan 1, 1961

By C. W. Mason

TIN has long been cited as offering a classic example of polymorphism, second in repute only to the allotropy of sulphur. The notorious "tin disease," which Cohen1 has studied so exhaustively in terms of the enantiotropic transformation of tetragonal white 0 tin to cubic gray a tin, has apparently encouraged the expectation that one or more addi-tional polymorphic modifications might exist. The search for confirma-tion of this idea has, as might be anticipated, led to the accumulation of a body of miscellaneous evidence, much of which would probably never have been sought, or taken seriously even by its discoverers, but for previous assumptions. The ball apparently was started rolling in 1880 by Trechmann,' who reported a new modification of tin (y tin), which was brittle and found in "hard head," a highly arsenical, slaggy material produced in a certain stage of tin smelting. A mixture of two kinds of crystals was obtained from a Cornish tin furnace, and those thought to be y tin were studied crystallographically. The results indicated that these crystals were rhombic and of different density from the tetragonal tin prepared electrolytically by Miller.3 Their analysis was given as 98.7 per cent Sn, 1.3 per cent Fe, and traces of As, Sb, Bi and S. In 1881 von Foullon4 obtained similar crystals from a Bohemian tin furnace. Headden5 examined crystals similar to those of Trechmann and von Foullon and reported them to be monoclinic, but of analysis corresponding to stannous sulphide. Later, Stevanovic,6 by goniometric measurements, proved that these crystals of SnS were really rhombic. Groth7 pictures and describes both "rhombic tin" (Fig. 9, vol. 1) and stannous sulphide (Fig. 84, vol. 1); their faces and angles correspond within the accuracy of measurement. Spencer3 in 1921 examined the above evidence critically; he found similar crystals from Cornish tin furnaces, proved them to be SnS, and even was able to analyze some of Trechmann's original specimens, finding high sulphur content. (Apparently Trechmann's analysis had been based on a second lot of crystals, not described crystallographically.)

Jan 1, 1939