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By J. E. Lawver, R. R. Beebe, J. L. Wright

This paper describes a separation coefficient Ks useful as a "measure of goodness" to be used in factorial and response surface methodology. The use and limitations of the separation coefficient is discussed, and a computer program for calculating the coefficient is presented (in Fortran). The application of the coefficient is illustrated in terms of electro-dynamic separation of Mesabi semitaconites. Present Mesabi wash ores and gravity concentrates with an iron to silica ratio of only 5 or 6 to 1 are no longer readily salable, for the steel industry now demands concentrates with an iron to silica ratio of at least 10 to 1 and a structure comparable to pellets. THE ELECTRODYNAMIC-FLOTATION PROCESS Wash ores and gravity concentrates consist largely of hematite, goethite, and quartz. Several methods of beneficiation are being tested at the University of Minnesota Mines Experiment Station with a view to improving the salability of these materials. A process that looks particularly promising from an economic view is the combination electrodynamic-flotation process shown in Fig. 1. This process is designed to upgrade gravity concentrates to a 5% silica content and to provide fines — from the flotation circuit —to permit agglomeration. Although electrodynamic concentration of specularite is an established and well-understood process, the electrodynamic concentration of Mesabi goethite-hematite gravity concentrates presents interesting and enigmatic problems. The gravity concentrates are by no means assemblages of clean, free mineral particles. Instead, the concentrates to be retreated consist of a great variety of middlings. More or less complete liberation would require grinding to minus 325 mesh, at which size only flotation could be expected to function, and even then grades and especially recoveries would not be satisfactory. A close examination of the gravity concentrates shows that grinding to 100% minus 48 mesh will produce a product which is approximately 70 weight % plus 325 mesh (see Fig. 1). The remaining 30 weight % can be deslimed and floated by conventional methods, but the resulting iron concentrate is

Jan 1, 1964

By N. W. Shed

The specifications for bridge-steel are usually not severe. The main difficulty is to secure a material which will roll easily, without showing signs of cracking on the corners of the blooms or on the flanges of the beams. In many mills sulphur has been deemed the most harmful constituent in this respect. It has been thought hazardous.to roll steel containing over 0.07 per cent. of sulphur. Yet, in making steel for the Phoenix Iron Company, I have produced from stock running as high as 0.13 per cent. of sulphur a material which rolled very satisfactorily. It is reasonable to infer that the injurious effect of sulphur can be neutralized, to a great extent, by proper treatment in the open-hearth furnace; and the following notes from my usual practice here may be of interest to those obliged to use high-sulphur stock. The steel made at Phoenixville in the 20-ton furnaces has about the following composition : Per cent. Carbon,...0.15 to 0.20 Manganese,.........0.50 to 0.60 Sulphur,..........0.11 to 0.13 Phosphorus,.: .0.04 to 0.06 Silicon,.......... 0.01 to 0.02 The best running heats were made with a small amount of pigiron. In using large proportions of pig the quantity of ore is also increased. This not only cuts the bottom, but also lengthens the time required to bring the charge down. Up to 50 per cent. of pig may be used, but 25 per cent. is much better. A 40,000-pound charge, containing 10,000 pounds of pig and 30,000 pounds of Bessemer butts or beam-scrap, works very well.

Jan 1, 1890

By John W. Cabot

The following series of analyses, which may, be of interest to Bessemer-steel makers, is submitted as a contribution to the muchvexed discussion of manganese in Bessemer steel. They were made by the writer in the spring of 1881, at the works of the Pittsburgh Bessemer Steel Company Limited, during a' period of about eight days, part of. which time the rail-steel showed great variation in rolling qualities. During the first part of tile time in question, it rolled well; later on it began to roll wome until, finally, it cracked very badly, reaching its worst stage. After this it rapidly improved until it again rolled smoothly. During this time of transition from good rolling to bad, and hack to good again, the course of the manganese was followed quite closely. It is the striking correspondence between these varying manganese contents and the differences in rolling which is here presented as worthy of notice. The other ordinary elements were determined occasionally, but showed no. unusual variation: The steel, in question, was ordinary rail-steel of about the following compusition : C=35. P - .08. Mn - .98. Si = .08. 8 = .06. The samples for manganese determinations were taken at first from an average of two days' work, and later on, when the steel

Jan 1, 1882

By N. M. Parikh, T. J. Koppenaal

The strengthening mechanism of fiber-reinforced silver has been investigated as a function of fiber density and fiber material. Stress-strain curves were determined in the range 2 x 10-6 to 2 x 10-3 plastic styain and slip lines were examined. The yield strength at 0.2 pct permanent strain is markedly dependent upon fiber density but the stress necessary to initiate plastic deformation is independent of fiber density. The strengthening mechanism of the fibers is shown to be malogous to grain boundary strengthening in poly crystalline metals. The variation in strengthening with different types of fibers is also noted and discussed. In recent years, considerable progress has been made in the understanding of the mechanical properties of two-phase systems, particularly in the classical dispersed-phase alloys where the separation between the dispersed phases is 0.01-0.1µ. However, little work has been done on fiber-reinforced metals where the dispersed-phase separation is considerably larger than this. Parikh1 investigated the mechanical properties of many fiber-reinforced metals and found that two general relationships are always observed, as follows: 1) A fibrous network incorporated into a second weaker metal strengthens the latter, and the amount of strengthening increases with fiber concentration. 2) At a corrstant fiber concentration, the amount of strengthening in a given matrix can vary considerably, depending upon the type of fiber employed. The object of the present investigation was to examine the fuiidamental factors controlling these two observations. procedure: Fig. 1 shows the initial step in the fabrication of the specimens. The sieve is shaken so that the fibers fall into a mold with the longitudinal axes of most fibers in the X-Z plane. The fibers are then compressed to a predetermined density, thus forming a "felt", and the necessary amount of matrix metal is added to the top of the felt. The mold is heated, in vacuum or hydrogen, to above the melting point of the matrix metal; the molten metal flows into the felt, and the entire assembly is cooled. This produces a "composite" that is essentially free of voids. A number of composites were prepared in this manner using 1/4-in. kinked lengths of mild steel

Jan 1, 1962

By Don Coulter

OBSERVATIONS were made over a period of seventeen months to ascertain the economic value of a four-cycle Miller engine direct-connected to a Watts compressor, to determine whether this type of engine could compete suc-cessfully against the old type of two-cycle engine in general use. The accompanying tables show the data obtained. The first, over a period of seventeen months, compares the operating cost per hour and cost per horsepower-hour with

Jan 8, 1928

By C. A. Heiland

For a long time it has been known that it is possible to deduce conclusions about the physical constitution of the interior of the earth from the records of natural earthquakes obtained by stationary seismographs. In view of this fact it is surprising how late, relatively speaking, geologic prospecting by seismic methods has been taken up, although the first suggestion was made 40 years ago—that travel-time curves of artificial explosions might be used for the study of the change of the velocity of seismic waves as depth. Further suggestions of practical applications of artificial explosions for geologic purposes were made by Belar12 by von dem Borne,3 by Benndorf and by Galitzin,5 but it was not .until 1919 that Mintrop obtained a patent on the seismic prospecting method which he has applied commercially on a large scale ever since. Dr. Mintrop came to this country with his method at about 1923. Since that time, several American oil companies have developed seismographs of the mechanical type for the vertical component similar to that of Mintrop's (Humble Oil Co., Dr. Ricker). Other consulting geophysical companies designed other types of seismic devices, the simplest of them for the recording of the first impulse being the geophone (McCol-lum Geophone Co.). The galvanometric recording method as first proposed by Galitzin is being used (Geophysical Research Corpn.?) and use is being made even of the piezoelectric properties of crystals for portable seismographs (F. Rieber). There is such an enormous variety of all kinds of portable seismographs, vibrographs, accelerographs, etc., that it is difficult to decide just what kind is preferable. Unfortunately, nothing has been published as yet about American designs of portable seismographs, except the Wood-Anderson torsion-seismometer. After Mintrop's design of portable seismographs, other constructions were made

Jan 1, 1929

By J. C. Osler

The design of a tailings dam is a geotechnical engineering project of considerable scope. For the design, it is necessary to establish the engineering properties of the soil or rock strata which will support the dam and the tailings or other fill which will be used to construct the dam. The various field and laboratory investigations which are necessary to obtain the required design parameters are discussed in the paper and the use of these parameters to compute stability, settlement, and seepage are considered. The designer of a tailings dam can never assume an absolute knowledge of the properties of the foundation strata. Further, initial design assumptions are often approximate, particularly with regard to the distribution of pore pressures through and beneath the dam. Thus, the installation of performance monitoring instruments is recommended, since data obtained from such instrumentation can be used to check the stability of the structure both during construction and after its completion.

Jan 1, 1972

By N. E. Norman, R. Stier

The mining industry is continually seeking out new and better underground mining techniques. One of the most recent-also, perhaps, the most significant-of the new concepts in underground mining is the use of mechanical rock-boring machines. And one of the problems that concerns us all in this matter is the cost of mechanical rock tunneling. To help answer the oft-quoted question "What will it cost me?" the following pages deal with the operating costs of so-called "medium to medium hard rock" boring machines-i.e., those designed to meet the drilling requirements in 8000 psi to 25,000 psi rock. A few machines are capable of drilling hard rock above 25,000 psi, but the economics of mechanical tunneling in rock that hard is limited at the present time. [ ] For mechanical rock tunneling, there are five main cost factors influencing the expense: Capital Investment, Cutters, Labor, Power Requirements, and Maintenance. These factors give us a good basic picture of the cost of excavation, although muck handling, erecting supports, and other costs directly related to conventional tunneling and mechanical boring enter into the final picture.

Jan 6, 1967

By Bai Shiwie, Li. Guangyu

This paper presents the study in situ on stress field of rock mass in a large dam site. By means of two different measure instruments and the method of stress relief, a lot of measure in situ has been done, including stress measurement of three dimensions at ten points and two deep-hole stress measurements in the perpendicular boreholes which are 59.4m and 53m deep seperately, and the basic accordant results corresponding two methods have been got. In the process of the deep-borehole stress measurement we got the stress value in critical state in which cylindrical core would become core-disking in the high stress area, which was first got in the world. The maximum principal stress was up to 650 kg/cm2. The stress value obtained by test and the thickness of rock disks all basically accord to the analysis by mechanical mechanism of core-disking The plane linear elastic finite element analysis has been completed. Results of inverse calculation all ac- cord to the measurement results in four different positions. The whole outline of the stress field of dam site was delineated clearly.

Jan 1, 1982

By A. E. Lee

THE Blackwell Zinc Co., Inc., a subsidiary of the American Metal Co., Ltd., operates a horizontal retort zinc smelter at Blackwell, Okla. The plant has 14 furnace blocks of 800 retorts each, fired with natural gas on a 48 hr cycle. Over 13,000 tons of zinc-bearing material, chiefly sulphide flotation concentrates, are treated monthly to produce slab zinc and high lead-cadmium fume. In 1942 a program of rebuilding and modernizing the smelter was started. By 1947 furnace smelting capacity had been increased to a point where roasting and sintering facilities were inadequate, and it was necessary to purchase oxidized materials to supplement sinter production. The seven 210 ft Ropp roasters and three 42 in. x 44 ft Dwight-Lloyd machines then in use had been in service at least 20 years and were in need of major rebuilding. Thus it was entirely practical to consider all new equipment and a change of method rather than rebuilding and repairing obsolete units. A study of the problem indicated that roasting as such could be eliminated and roasting and sintering accomplished in one step by a modification of the Robson process,' which had been used since the early 1930's by the National Smelting Co., Ltd., at their plants at Avonmouth, England, and Swansea Vale, South Wales. Francis P. Sinn, General Manager, Zinc Smelting Operations, The American Metal Co., Ltd., who was familiar with the practice in England, suggested the use of one large machine for the entire operation from concentrate to sinter. One step sintering appeared to best meet Blackwell's plant requirements and indicated substantial savings in labor, gas, coal, and repair costs. Choice of Machine Size The sinter machine size was set at 12x168 ft for a rated capacity of 540 tons per day. This tonnage, produced on a five day week, would meet the seven day requirements of the 14 furnace blocks. The one large machine was quoted at a lower cost than two or more 6 ft wide machines of similar total capacity. Further, the larger machine could be housed in a smaller structure and only one set of equipment for charge preparation and delivery and for disposal of sinter cake was needed. One machine on a five day week made possible a concentration of the skilled operating personnel and required less men than a plant including two or more machines and related equipment circuits. Fewer units of equipment meant less maintenance, and the two down days weekly allowed ample time to repair and, if necessary, to make up lost production. Experience had indicated better sintering quality and rates with larger masses of material, not only on wider machines, but also in deeper beds. The ratio of windbox perimeter to area for the 12x168 ft machine is 0.179, compared to 0.353 for a 6x102 ft machine and 0.617 for a 42 in. x 44 ft machine. This meant less air leakage with resulting fan power savings and less spoilage of charge along the pallet sides. Performance Initial operation of the new sinter plant was made in November 1951 and regular production attained late in December. The average product sinter output during 1952 and the first half of 1953 has been 18.2 tons per hr. The average for one month has been as high as 22.4 tons per hr. Considerable experimenting with varied operating conditions accounts in part for the below capacity — 24 tons per hr — average output, and work to further improve production rate continues. A typical sinter analyses is 66.0 pct Zn, 0.3 pct Pb, 0.1 pct Cd, 0.3 pct S, 8.0 pct Fe, 2.0 pct SiO,, 0.8 pct CaO, and 0.2 pct MgO. Use of this material has made possible increases in furnace burden and improved furnace operation over the former practice using sinter made from Ropp roasted concentrates. Better lead and cadmium elimination in sintering has permitted the furnace production of slab zinc lower in lead and cadmium. Anticipated economies of operation have largely been gained. The sinter plant is operated by seven men per 8 hr shift — one head operator, three equipment operators and three sweepers — plus one oiler on day shift only. While it has been necessary at times to operate seven days a week to produce the required sinter tonnage, the five day work week usually has been adequate. Consumption of natural gas for sinter bed ignition is 200,000 to 300,000 cu ft per day. Green Ore Sintering Practice The 30 to 31 pct sulphur content of the —200 mesh zinc concentrates is the fuel used to sinter the charge, no coal addition being required. In the feed to the machine, sufficient concentrates are added to crushed return sinter fines containing 0.3 to 0.5 pct sulphur to produce a charge averaging 5.0 to 6.5 pct sulphur. Since the return sinter used in Blackwell's practice is varied from — 1/2 to — 1/8 in., the actual sintering mixture of fine sinter and concentrates is somewhat higher in sulphur. The coarser sinter particles are too large to resinter and merely aid porosity in the sinter bed. The ratio of concentrates to return sinter in the charge ranges from about 1:4 to 1:5.5. Variations are based on the appearance of pried up bed sections, bed exit gas temperature trends, windbox suctions, and return sinter size. Sufficient sulphur must be used to obtain fritting of the charge into a soft sinter cake and to aid in the elimination of lead and cadmium. Excessive feed sulphur will result in partial slagging of the cake impairing porosity and prolonging sintering time.

Jan 1, 1954

By T. Sterry Hunt

I have in a previous communication called the attention of the Institute to the geognostical relations of the crystalline iron ores belonging to the Eozoic racks of North America, at which time I noticed (1) those associated with the gneisses of the Laurentian series, (2) those of the crystalline schists of the Huronian, as seen in Northern Michigan and in many localities along the Appalachians; (3) those of Southeastern Missouri associated with petrosilex porphyries and schistose rocks, and presumed to be nearly of the same age with those of the Huronian schists; and (4) the highly titaniferous ores of the Norian or Labradorian series from Essex County, N. Y., and from various parts of Canada. It may here be remarked that, although the presence of titanium is most marked in the Norian ores, this objectionable element is sometimes found in the schistose ores of the Huronian, and to a lesser extent in certain Laurentian magnetites. The ores of each of these geological divisions have their individual peculiarities, which serve to distinguish them to such a degree that the magnetites and specular ores of the Laurentian are as dissimilar to those of the Huronian as are the crystalline silicated rocks of the two series. As it happens that these mineralogical dissimilarities correspond to diflerences in composition and in adaptability to different processes of manufacture, which, in the present condition of the iron industry, are objects of special consideration to metallurgists, it will be seen that these geognostical distinctions become of great practical importance. During the past year I was desired by the Geological Commissioners of Pennsylvania to devote a few weeks to certain geological studies in the eastern part of the State, in the course of which I was enabled to make, with regard to its crystalline iron ores, some observations to which I desire to call the attention of the Institute. I may mention, in passing, that the great South Mountain belt, from the Schuylkill to the Delaware, is composed of Laurentian rocks, in which are found the characteristic ores of the series like those of the Highlands of New Jersey and New York, and of the Adiron-

The notion prevails that writing is a knack, that the skilful use of the pen is a gift of nature. This is an error. Dogberry may be responsible for it; he said: "To be a well-informed man is the gift of fortune, but to write and read comes by nature". Because Dogberry said it, we may be sure that Shakespeare thought otherwise. Ability of any sort may be partly innate, but my own observation and experience lead me to conclude that most of the easy writers have become so by constant practice. As I recall the names of men successful with the pen, I remember that most of them have written a great deal and have taken particular pains to improve their style. The suggestion that proficiency in the difficult art is a happy accident provokes a sardonic smile. The larger part of the great writing in our literature is the result of persistent effort. An easy fluency has been the undoing of many; their flamboyant and fantastic scribbling has proved as perishable as froth. This criticism applies to technical writing also; in order that a technical description or discussion may hold the interest of the reader, at least long enough to cause him to read it to the end, the writing must be done carefully and systematically; otherwise it will fail in its purpose of conveying information. Clearness is absolutely essential. "It is not enough to use language that may be understood; it is necessary to use language that must be understood."* The purpose of writing, at least of that which is meant to be read by others, is not only to express ideas but to communicate them. Lack of perspicuity may prove as bad as

Jan 1, 1931

By Alfred H. Bell

The year 1936 in Illinois was marked by considerably increased activity in drilling, both wildcat and proved territory, in leasing, and in seismic and geologic exploration. Of the 92 oil and gas wells completed during 1936 in Illinois, 49 were oil wells, 3 were gas wells and 40 were dry holes. This compares with but 34 completions in 1935. The total of the daily initial productions of the new oil wells was 1755 bbl., or an average of 36 bbl. per well. One new field was discovered, the Bartelso field in Clinton County. The leasing of some large blocks of acreage in Clay, Marion, and other counties by the Carter Oil Co. in the late fall of 1935 was followed in 1936 by extensive leasing in southern Illinois by 10 major companies and many smaller companies and individuals. It is estimated that 2½ million acres were under lease by the end of 1936. Seismograph surveying has been carried on by about seven companies, and the number of seismograph parties operating in Illinois has varied from six to eight throughout most of 1936. It is estimated that approximately two million dollars has been spent in the state in seismic and geologic exploration and in leasing during the last quarter of 1935 and all of 1936. Production of crude oil in Illinois in 1936, according to the Bureau of Mines, was as follows: Barrels Barrels January...................... 325,000 July........................ 402,000 February..................... 294,000 August..................... 380,000 March....................... 396,000 September.................. 386,000 April......................... 347,000 October.................... 393,000 May......................... 389,000 November.................. 363,000 June......................... 383,000 December................... 387,000 4,445,000 This 4,445,000 bbl. was an increase of 3 per cent over 1935. Although this increase was due largely to the fact that production was not artificially curtailed, it also reflects some new production and some increases in production from repressuring and water-flooding, which offset the

Jan 1, 1937

By Carl F. Floe, Michael B. Bever

THE possibility that carbon may be soluble in copper to a limited extent has been recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are frequently used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. REVIEW OF LITERATURE In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of o.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.92 58 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been in prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as o.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1945

By Henry M. Howe

Jan 1, 1909

By Tomek Ulatowski

INTRODUCTION In 1974, Industrial Miners Mexico, S.A. (IMMSA), agent for the borrowers, was the largest privately-held mining, smelting, and refining company in Mexico (accounting for 32% of Mexico's nonferrous metal and coal production in 1974), the fourth largest company in terms of sales, and the second most profitable company in Mexico, excluding government wholly-owned and operated industries. The company was engaged in the mining, smelting and refining of coal, copper, fluorite, gold, lead, silver, zinc and related by-products for domestic consumption and export. A combination of favorable factors led IMMSA to propose an investment plan amounting to US$286 million for 1974 through 1978, of which US$150 million was to be financed. These factors included: Substantial profits in 1973 and 1974 Positive near-term outlook for metal prices Success of the reinvestment program in increasing productivity Substantial additions to proved reserves during 1973-1974 and Fiscal incentives provided by the Mexican government to stimulate investment in the mining industry. The primary purpose of the investment program was to construct a new electrolytic zinc refinery and to expand and modernize many of the company's existing mining and refining facilities. THE BORROWER Company History Compania Miners Mexico, S.A. was incorporated in the city of Monterrey in 1918 as a wholly-owned subsidery of ASARCO Inc. (formerly American Smelting and Refining Company, New York) for the purpose of mining and processing non-ferrous metals and related products. In compliance with the Government's Mexicanization program, ASARCO Inc. divested itself of 51% of its equity in Compania Miners Asarco, S.A. on June 30, 1965. Subsequently, ownership in the divested share was apportioned as follows: 15% ownership in Compania Miners Asarco, S.A. to a group of private investors, and 36% in trust for subsequent public sale. The company's name was changed to Asarco Mexicana, S.A. in 1965. Mexican ownership in Asarco Mexicans, S.A. was increased to 51% in 1967, following the purchase of the 36% share ownership held in trust, and then to 66% in 1974 when ASARCO Inc. divested itself of an additional 15% of its holdings in Asarco Mexicans, S.A. Following its 1974 divestiture of 15% of Asarco Mexicans, S.A., ASARCO Inc's ownership in Asarco Mexicana, S.A. was reduced to 34%. In 1974, the company changed its name for the second time to Industrial Miners Mexico, S.A. (IMMSA). Fiscal Agreement IMMSA entered into a fiscal agreement with the Mexican government in 1969. The agreement, which was renewed in 1974, provided for 100% of the production and export tax corresponding to the federal government with a minimum of 50% of the amount refunded to be reinvested in fixed assets. Further, the agreement permitted the company to

Jan 1, 1985

By S. J. Rothman, A. L. Harkness, L. T. Lloyd

Self-diffusion in Y uranium has been measured using U235 as the tracer isotope. The diffusion coefficient fits an Arrhenius-type equation D = 2.33 x 10 -3 exp (- 28,5000/RT) cm2/sec The values of Do and Q are unusually low and are not consistent with the values expected from theories based on a simple vacancy mechanism of diffusion. CYLINDRICAL samples, 1 cm in diam and 1/2 to 1 cm long, were prepared from high-purity uranium containing 0.0343 pct u235, Table I. The samples were water quenched from 690°C (the a-ß transformation is at 668°C) to remove preferred orientation, and annealed at 450 "C to minimize residual stresses. One end of each cylinder was polished on a 1-µ diamond lap and electropolished in a phosphoric acid solution. After a final cleaning by cathodic sputtering, a 1- to 3-µ thick layer of the tracer isotope, uranium containing 93 pct u235, was sputtered onto the sample.' To prevent contamination during the diffusion anneal, the diffusion couples were placed in a tantalum cup and covered with another piece of uranium, and the whole assembly was sealed off in an evacuated quartz tube. Annealing temperatures were constant within +2.0°C. The samples were heated and cooled slowly between room temperature and the ß-? transformation (774°C) in order to minimize distortion of the sample surface that might arise from aniso-tropic thermal expansion and density changes during phase transformations. After machining off 1/16 in. from the radius to

Jan 1, 1961

By W. C. Leslie, R. M. Fisher, K. G. Carroll

A nitride, believed to be Si3N, has been separated from three nitrided silicon steels. Germanium nitride, Ge3N4, has been prepared from pure germanium. Comparison of the diffraction patterns indicates that the two nitrides are isomorphous; on orthorhombic structure is suggested in place of the rhombohedral structure previously reported for Ge3N4. THE possibility that a nitride of silicon may, under appropriate conditions, precipitate in silicon steels or in steels killed with silicon makes it desirable to have some positive means of identifying such a compound. One such means is the X-ray or electron diffraction pattern of the nitride. A review of the meager data in the literature indicates that the nitride most likely to form is Si3N4, a conclusion supported by the results of a study of nitrided silicon steels to be published shortly by L. S. Darken and R. P. Smith, of this Laboratory. Unfortunately, there is available no diffraction pattern for this nitride. Data have been reported, however, for Ge3N4 which, judging from the similarity between germanium and silicon, might be expected to be isomorphous with Si3N4. An effort was made, therefore, to form such a silicon nitride, to determine its composition and diffraction pattern and, if possible, its structure. To this end a series of three silicon steels was nitrided under controlled conditions with the resultant formation of nitride particles which yielded an electron diffraction pattern in situ. The particles were then extracted from the steel and an attempt was made to determine their chemical composition. X-ray and electron diffraction patterns were also obtained from the extracted particles, which indicate that the nitride is isomorphous with Ge3N4, although a complete determination of the structure has not been possible. These results show that a silicon nitride with a well-defined diffraction pattern can form in silicon steels, and they suggest that this nitride is Si3N4. Materials and Procedures The sillicon steels investigated were In the form of thin sheet or strip and had the composition shown in Table I. The 0.58 and 1.21 pct Si steels were nitrided by holding them at 1110°F in an H2-NH3 atmosphere containing 3 pct ammonia for 48 hr. The nitride particle size was increased by subsequent heating at 1500°F for 13 1/2 hr in helium. The resulting microstructure is shown in Fig. 1. The steel containing 3.20 pct Si was nitrided at 1200°F for 16 1/2 hr after which it was held in helium at 1500°F for 4 hr. Its structure as seen under the electron microscope is illustrated by Fig. 2. As would be expected from the higher silicon content and the shorter holding time at 1500 °F, the nitride particles are smaller and more numerous than those in the 1.21 pct Si steel. The ammonia-hydrogen treatment reduced the carbon content of the steels to a very low level, so no interference was encountered from carbon or carbides. In the case of the 3.2 pct Si steel, the carbon was reduced to 0.003 pct before nitriding by heating in dry hydrogen. Attempts to obtain an X-ray diffraction pattern from polished and etched surfaces of the 1.21 and the 3.20 pct Si steels were unsuccessful. However, an electron diffraction pattern was obtained from the surface of the steels. The interplanar spacings obtained from these patterns arc shown in Table 11, col. 5. The nitride particles were then extracted from all three steels by dissolving the ferrite matrix in bromine-methyl acetate, the solution used in the Beeghly method for the extraction of aluminum nitride from steel. X-ray diffraction patterns of these residues, obtained by means of a spectrometer and by a 57 mm Debye-Scherrer powder camera using filtered cobalt or chromium radiation, are given in Table II along with the pattern obtained by

Jan 1, 1953

By R. W. Gurry, L. S. Darken

The solubility of cementite in austenite is computed by thermodynamic methods from the observed solubility of graphite. It is found that the solubility of cementite is greater than that of graphite in the entire austenite temperature range. Thus the prior discrepancy between this portion of the phase diagram and the observed metastability of cementite is partially resolved. FOR several years it has been apparent that a serious discrepancy exists in certain observations pertaining to the Fe-C system. Direct experimental data indicate: 1-That the curve representing the solubility of graphite in austenite'" crosses that for cementite4 at about 945°C as shown in Fig. 1. 2— That graphite and austenite saturated therewith are stable1 relative to cementite at all temperatures between the eutectoid, about 723°C, and the eutectic, about 1153°C. These observations are mutually incompatible in view of a well-known consequence of the second law of thermodynamics, namely, that the stable phase (presumably graphite at all temperatures) has a lower solubility than the metastable phase (presumably cementite). Hence either 1 or 2 above must be in error; either the measured solubility of graphite or of cementite, or the observation as to the stability of graphite, is in error. Our present purposes are: 1—To collate the available data on cementite and prepare a table of HO — HO° and of (Fa— HO°)/T. This tabular method seems the best and most convenient way to represent the heat and free energy of formation. 2—To determine whether the measured solubilities of cementite and graphite in austenite are in accord with the above table and the measured thermodynamic properties of austenite, in order to resolve, if possible, the existing paradox of these two solubilities. Enthalpy of Cementite The enthalpy of cementite at 273 °K, H279 — HOcem, was computed by integration of the low temperature heat capacity as measured by Seltz, McDonald, and Wells" 68" to 298 °K) and as given by the Debye functions recommended by them (0" to 68°K); the result is included in Table I. At higher temperature HCem — H,,"" is given by Kelley who used the data of Naeser7 (298" to 1037°K) and of Umino8,9 (273° to 1923°K). We have recalculated Hcem — H273 cem from the data of UminoO in the following way. In the equilibrated alloy at temperature the weight fraction of cementite Pct c -Pct cr is PctC -PctCr designated f(C), and the

Jan 1, 1952