Search Documents

By H. J. Struth

Conditions in the gasoline market undoubtedly influence the oil industry's general economic situation to a greater degree than perhaps any other single factor. No matter how efficiently the oil industry manages to conduct its producing operations, a drop in the price of gasoline exerts definite pressure upon the posted price of crude oil in the field. Efforts of the recent past have shown that profits from the producing division of the industry are closely tied in with the course of the gasoline market. When refinery gasoline prices are depressed, as they have been during recent months, it is utterly impossible for purchasers to maintain a crude market that is commensurate with the cost of production, regardless of how well balanced the producing situation may be. In fact, the producer can no longer regard his operations in the light of an independent unit of the oil industry, since his financial well-being is directly dependent upon the well-being of the refiner. Because gasoline is the principal constituent of crude oil, it is obvious that profitable refining operations can only be maintained through profitable gasoline markets. Likewise, when the price of gasoline influences a profit for the refinery it also influences the prosperity of the producer, through the advent of higher and more profitable posted prices for crude oil in the field. Financial results for 1932 showed material improvement over the preceding year, primarily because the price of gasoline was maintained at levels somewhat above those of 1931. Consequently, the producer was able to record improvement in the crude market, through a somewhat higher level of posted prices. While effective methods of prora-t,ion of crude production are given credit for the advance recorded in the crude market last year, it is also a fact that the advent of higher prices for gasoline had a direct influence upon the posted prices of crude oil. For example, when gasoline was sold in Group 3 at 2 3/4 a gallon in June and July, 1931, the price of 36-gravity Mid-Continent crude was down to its lowest point of only 18c a barrel. As refinery prices advanced, however, there was a corresponding advance in posted prices of crude oil. Thus, when Group 3 gasoline commanded a price of 5c a gallon

Jan 1, 1933

By Sterry Hunt

The American Institute of Mining Engineers, and American science in general, have sustained a great loss in the death of Prof Benjamin Silliman, deceased at New Haven, Connecticut, on the 14th of January, 1885, at the age of sixty-eight. But a month has passed since, as one of the pall-bearers, I paid the last tribute to the remains of my old friend and honored master.

Jan 1, 1885

C. M. Bishop (Aircraft Div., A. V. Roe Cnnada Ltd., Toronto)—Reference is made to the coherency hardening of ß due to ß' and also to the hardening of ß due to a coherent precipitation of the a phase. What is meant by the term "ß'?" Would not the coherency hardening of ß during cooling be due to precipitation of a sub-microscopic dispersion of a, as is the case during reheating a ß-quenched alloy? I feel that these two phenomena are essentially the same mechanism, i.e., precipitation of a from unstable or supersaturated ß. From the text, it would appear that Tables III and IV are intended to show the effect of the martensite transformation on the properties of Ti-Mn alloys. Referring to Table 111, the ß-quenched alloys would contain a greater proportion of retained ß than would the equilibrated alloy. Could not the increase in properties be attributed to this, along with possible coherency hardening of the ß? In the same way, the structures referred to in Table IV contain ß from which they could derive their hardness. It would appear to be difficult, if not impossible, to assess the role of the martensite transformation from the data contained in these tables. F. C. Holden, H. R. Ogden, and R. I. Jaffee (authors' reply)—In reply to the first question raised by Mr. Bishop, the term "ß"' designates an apparent retained-p structure which is harder than it is after the most rapid cooling from the ß field. It is thought to be the result of a coherent precipitation of a. The mechanism by which hardening takes place is undoubtedly the same as that involved in the early stages of aging of a re-tained-p structure, and we are in agreement with Mr. Bishop on this point. The term "ß'" to designate the anomalously hard retained-ß structure was agreed upon at a symposium in 1953." The authors do not agree that the quantity of retained ß and/or ß' in the ß-quenched specimens of Table III is necessarily greater than that of the 600°C equilibrated specimens. The ß-quenched specimen has a structure which appears to be completely a' formed by the martensite reaction. It is recognized that there could be some retained ß (or ß') between the a plates if the M, temperature is below room temperature. This is unlikely for the 3.4 pct Mn alloy where the M, is known to be at about 640°C. Therefore, the increase in strength cannot be attributed to the presence of a greater quantity of coherency-hardened ß, but, rather, the increase in strength must be attributed to the transformation products formed, e.g., a' (martensiti-cally formed a). Concerning the data in Table IV, we agree that it is difficult to estimate the role of the martensite reaction, since the 6.4 pct Mn alloy was retained ß in the quenched condition.

Jan 1, 1955

By George Kenzy, Charles B. Manula

This paper introduces a philosophy of dynamic modeling. Here, the development of a simulation model of a coal mining system is described for the purposes of: (a) system design and selection of equipment for a new operation; (b) analysis of existing operation' for possible alterations, additions, or general improvements.

Jan 1, 1976

There were present eleven Directors, the Institute's Legal Counsel, the Secretary, the Assistant Secretary, and twenty-three guests. The Report of the Committee on Nominations (listed elsewhere) was presented and ordered to take the statutory course. The appointment of a Committee on Mine Taxation was approved. An Advertising Manager was appointed. E. G. Spilsbury and A. S. Dwight were appointed as representatives of this Institute on the Franco-American Engineering Committee. The Transactions were presented to the University of Louvain, and the monthly Bulletin to the French Technical Index. Permission was given to publish in full the argument of William H. Shockley on simplified spelling. A committee was appointed to have charge of the publication of the Raymond Memorial Volume. There were elected 70 members, 15 associates, and 1 junior associate. Three members were reinstated and the resignations of two were ac-cepted. The clues of 10 members who had been in active service with the allied armies were remitted. An extension of time for the payment of dues was granted to the 11 members.

Jan 12, 1919

By F. W. Osterwald, C. R. Dunrud

Coal mine bumps are a serious hazard to life and property in the mines of east-central Utah. Research into geologic factors associated with these bumps indicates that the bumps are spatially and genetically related to structural and stratigraphic features. Some bumps are directly related to stress accumulation along faults, either from natural causes or as a result of mining. Frictional properties of bedding planes between coal and roof rock, and between some rock units within the roof, directly affect the deformation of coal ribs, and hence the incidence of bumps. These frictional properties are related to the lithology of the roof rocks as well as to the sedimentary structures within the rocks. Commonly a sequence consisting of 1/3 ft of carbonaceous silt-stone, about 2/3 ft of rider coal, and several ft of massive siltstone or sandstone overlies the main seam. The sequence causes difficult roof conditions in the mines, difficult mining conditions and, directly or indirectly, many bumps. The U. S. Geological Survey has studied the relationships between geological features and coal mine bumps at Sunnyside, Utah, for about six years. The work, which was originally undertaken at the request of and in cooperation with the U.S. Bureau of

Jan 1, 1965

R. W. Raymond, New York, N. Y.: Mr. Bain's introductory statement that there is a growing disposition on the part of the public " to change emphasis " in government from political equality " to " social justice " is somewhat vague; but I gather from his argument that he approves the growing disposition to which he refers, and that the " emphasis " which it demands involves a radical change in the policy hitherto pursued by the United States—the policy under which the Pacific States and Territories have been developed thus far. I do not understand how "social justice" is to be furthered by the sacrifice of " political equality," or how the change is to be effected by "emphasis." But I fancy that the beneficent and necessary

Jan 1, 1913

By R. W. Raymond

CHARLES WILLIAM HENRY KIRCHHOFF was born March 28, 1853, at San Francisco, Cal., where his father, Charles Kirchhoff, was at that time employed in the consular service of his native country, Germany. A few years later, the family moved to Hoboken, N. J., in the public schools of which city the son received his preliminary education, proceeding later to Germany, where he was graduated in 1874 as mining engineer and metallurgist at the Prussian Royal Mining Academy of Clausthal, in the Harz. Upon his return to the United States, he became chemist of the Delaware Lead Refinery at Philadelphia, and retained that position for three years. But in 1877 he began what was to be an almost uninterrupted life-long association with David Williams, the publisher of The Iron Age, of New York, who established in that year, and continued for a brief period, a journal entitled the Metallurgical Review, on the editorial staff of which Mr. Kirchhoff received a place. The enterprise was doubtless an attempt to cover a wide metallurgical field outside of that which properly belonged to The Iron Age. But it was soon abandoned, and Mr. Williams wisely concentrated his energies upon the older journal, which, under his vigorous and skillful management, and the labors of the able editors and correspondents whom lie selected, became one of the greatest institutions off its class in the world. From 1878 to 1881, Mr. Kirchhoff was assistant editor of The Iron Age. From 1881 to 1884, he was managing editor of the Engineering and Mining Journal; in 1884 he returned to The Iron Age, to become for five years its associate editor, and in 1889, on the retirement of James C. Bayles, editor-in-chief. This list of dates and employments, without further comment, sufficiently indicates, at least to the eye of an expert, that Mr. Kirchhoff had found his congenial career in trade journalism. His qualifications for this profession were somewhat exceptional. He possessed the scientific training, the knowledge of foreign languages and literatures, and the power of making and keeping friends, which enabled him to get early notice of technical novelties; he had the taste for statistics which made him both industrious and intelligent in their collection and use; and to these traits he added a mastery of the meaning of such accumulated data, and a

Jan 10, 1916

By P. Somasundaran, D. W. Fuerstenau

The length of the collector is found to influence the flotation of the mineral even at incipient conditions, which are below the concentration at which interaction at the solid-liquid interface begins to take place to form hemi-micelles. To study this dependence, concentration for incipient flotation of quartz was determined as a function of pH with collectors of various chain lengths. The observed effect of chain length on flotation is ascribed to that of collector adsorbed on the bubble surface. In previous studies, it was shown that at low concentrations the alkyl collector ions adsorb at the solid-liquid interface as individuals.''2 At higher concentrations, the collector ions adsorbed at the solid-liquid interface associate with each other to form two-dimensional aggregates called hemi-micelles. Above the hemi-micelle concentration, the length of the hydrocarbon chain is extremely important since the hydrocarbons are in effect removed from water during the association, making the energetic conditions more favorable for adsorption at the interface. Because of this enhanced adsorption, one observes a very rapid increase in flotation associated with the hemi-micelle formation at the solid-liquid interface. However, a dependence of flotation on the chain length at concentrations below that required for hemi-micelle association was also observed,' and this cannot be explained by the above mechanism which postulated hydrocarbon chain interactions only at the solid-liquid interface. This prompted an investigation into other possible reactions of the hydrocarbon chains and an examination of the conditions at the bubble surface involved in the flotation system and how these observations might explain the reactions at the solid-gas interface which cause the particle-bubble attachment required for flotation. To obtain more information on chain length effects, flotation, under incipient conditions, was tested by vacuum flotation techniques. The collector-concen-tration-pH relationships for flotation of quartz with alkyl ammonium acetate collectors was delineated by observing the pH at which quartz particles begin to float to the liquid surface. By investigating flotation as a function of pH, it was also possible to study the effect of neutral molecules on incipient flotation conditions, since the aminium ions hydrolyze to amine molecules at higher pH values. EXPERIMENTAL WORK Brazilian quartz specimens were crushed and sized, and the 270 x 400 mesh fraction was used for flotation studies. The samples were leached with concentrated hydrochloric acid until no coloration of the acid occurred. The leached material was washed free of chloride ions and stored in distilled water. The vacuum flotation technique developed by Schuhmann and prakash3 was used to determine the critical pH-concentration curves. This method, which can be used to delineate conditions for incipient flotation, is fairly simple and rapid. About 0.5 gm of 270 x 400 mesh quartz was placed in a 100 ml graduated cylinder which was then filled to the 100 ml mark with the collector solution made from high-purity alkyl ammonium acetate salts. The water used for the test was conductivity water saturated with air that had been passed through a cleansing train consisting of Drierite, Ascarite, a water wash bottle, and a trap. After the pH was adjusted, the cylinder was then conditioned for thirty minutes. In the tests where an acid pH was desired, sufficient acid was added before the collector solution to avoid any effect due to slow desorption of collector from the quartz surface. After conditioning, vacuum was applied to the system and the flotation or nonflotation of the quartz was noted. The pH at which the quartz particles began to float to the liquid-gas interface was taken as the critical PH. Critical pH curves were thus determined for different concentrations of the various collectors. Hallimond tube flotation data were taken from the authors' previous publication1 for correlation with that from the vacuum flotation. RESULTS AND DISCUSSION The results of vacuum flotation studies for determining critical pH-concentration curves, i.e., curves which delineate conditions for incipient flotation, are shown in Fig. I. In generaI, all the curves exhibit an upper and lower pH limit between which flotation will

Jan 1, 1969

By E. S. Machlin, S. Weing

GRAIN boundary stress relaxation has been the subject of several investigations in recent years, but as yet the phenomenon is not well understood. One of the major difficulties has been the lack of a sufficient amount of data with which to evaluate any proposed mechanism. Little information is available on the effect of small amounts of substitutional solutes on grain boundary stress relaxation. It is with this important phase of the problem that this investigation is concerned. The influence of substitutional solutes on grain boundary stress relaxation has been recently investigated in copper by Pearson: and in aluminum by Dorn et al.' Pearson studied the effect of zinc, gallium, germanium, and arsenic on the relaxation peak of OFHC copper.* The pure OFHC copper decreased the peak intensity and a second peak appeared at a higher temperature. This latter peak was termed the alloy grain boundary peak. At the lowest binary concentration studied, approximately 1 atomic pct, the primary peak was almost completely obliterated. Pearson found that the activation energy calculated from the alloy grain boundary peak for all solutes, irrespective of the concentration, was 44,000 cal per mol. Pearson concluded that the increase in activation energy from 33 to 44 kcal per mol is not continuous but abruptly changes from the lower to the higher value. As no attempt was made to investigate the intermediate range of concentration and hence calculate the possible variation of the activation energy for the initial grain boundary peak, this conclusion is hardly valid. In contrast to these results, Dorn et al. studied the effect of zinc, silver, copper, germanium, and magnesium on the grain boundary stress relaxation of aluminum. No change in the energy of activation was observed for binary alloys of the flrst four solutes, but a linear increase was found for increasing concentration of magnesium. Saturation was not found up to the maximum of 1.6 atomic pct. The energies of activation were obtained by plotting the horizontal displacement of the dynamic modulus curve vs temperature for two vibrational frequencies. As the modulus is proportional to the square of the frequency, this requires the measurement of the torsional frequency over a range of temperature. However, the technique does not lead to an unambiguous interpretation of the grain boundary

Jan 1, 1958

By J. W. Rutter, K. T. Aust

In previous studies of grain boundary migration in zone-refined lead, the authors used bicrystal specimens consisting of a striated crystal which was grown from the melt, and an adjacent striation-free crystal, introduced by artificial nucleation and growth.1 While this method permits the study of the motion of individual grain boundaries, it does not provide control of the relative orientations of the grains. The present note will describe a technique for controlling the orientations of the two crystals in this type of specimen. The technique consists essentially of placing a striated crystal and a striation-free crystal of controlled orientations end-to-end in a graphite trough, then melting a short zone at the junction of the two crystals and allowing it to freeze to form the desired grain boundary. The apparatus used to carry out this process is illustrated in Fig. 1. It consists of a trough milled from high-purity graphite,with grooves in the underside for the placement of thermocouples. The graphite piece fans out on one end at the level of the bottom of the trough; the sides of the trough are completed in this region by the attachment of a mating plate with a slot cut at any desired angle to permit reorientation of the crystal placed at this end of the assembly. The joint between the crystals is made at or near the point where the slotted plate joins the rest of the trough. The thermocouple slots are deepened in this region so that the thermocouples are separated from the melt by only 1/32 in. of graphite. An induction heater, with suitable temperature control, is used to obtain the molten zone. The two single crystals used are first chemically polished in a solution consisting of eight parts glacial acetic acid and two parts 30 pct hydrogen peroxide. They are then placed in the trough with the ends to be joined at the position of the thermocouples. Next, cooling is applied to the two crystals by means of air

Jan 1, 1962

By W. B. Vietz, C. W. Hill, T. P. Thomas

FLUXES, in general, may be classified according to their use as soldering, foundry or casting, and metallurgical and the chemistry of their action follows quite closely this division. The term foundry or casting fluxes, as used here, refers to the substances added to molten metals, preparatory to casting into molds or ingots, with the object of removing small amounts of impurities that have been introduced in handling or melting the metal, which was placed in a fair state of purity by the previous refining or metallurgical processes. The sources of these impurities are the oxide coating on the surface of the ingots, material extracted or mechanically removed from the crucible or furnace wall, and those formed by the reaction of the molten metal with the heating gases or furnace atmosphere. As commonly used, the term fluxes is applied to such materials as ammonium chloride, zinc chloride, salt, borax, and boric oxide. A second class of materials, usually called deoxidizers, includes substances such as metallic phosphides, sub-oxides, carbides, and bo-rides, that reduce the metallic oxides present in the metal. A third class includes various compounds that arc molten and non-volatile at the temperature of the molten metal and are used primarily to protect the surface of the metal from the action of the furnace or exterior atmosphere; to this class belong such mixtures as lime and fluorspar, lime and soda ash, various minerals, etc. In some cases these protective layers may act in a manner similar to the metallurgical fluxes and dissolve or unite with the oxide impurities of the metal, but as generally employed this latter action is negligible since there is little opportunity for the coverings to come into contact with more than the surface of the metal, and hence they arc without action on the body of the molten mass. The use of fluxes is the result of factory experience and tradition, but an extensive study has not been made of the chemical and physical actions that occur or the effects of these actions on the properties of the metal. It would seem necessary in any successful study of metal fluxes to determine not only what impurities are present in metals melted under

Jan 1, 1921

By D. H. Newland

Certain observations from the field and laboratory suggest the need for recasting some of our ideas about gypsum as a rock-forming mineral and in relation to supplies for industrial use. Until about 25 years ago, the use of gypsum was confined almost entirely to agriculture. During the past quarter century, though, its usefulness has been greatly developed, particularly in the building trades, which now absorb most of the gypsum produced. In 1919, according to the U. S. Geological Survey, the output of crude gypsum was 2,240,163 tons, a gain of 912 per cent. in 25 years. About one-half of this production was mined in New York, Ohio, and Michigan, where the proved supplies can hardly be regarded as over-large when viewed in relation to the rapid expansion of industrial requirements. The occurrence of gypsum in the United States is treated by R. W. Stone and others.' The deposits of Canada are described by L. H. Cole. Several states, including Kansas, Oklahoma, Iowa, Michigan,and New York, have made special surveys of their gypsum deposits, but the reports, as a rule, refer to conditions as they existed from 15 to 20 years ago. Association of Gypsum and Anhydrite The two calcium sulfate compounds, gypsum (CaSO4.2H2O) and anhydrite (CaS04), are the more stable forms of a series which includes at least two other members, so-called half-hydrate (CaSO4.1/2H20) and soluble anhydrite (CaS04). Each of the latter readily takes up water to recrystallize as gypsum and consequently is incapable of existence under ordinary geological conditions; also each can be prepared from gypsum by the application of heat within certain temperatures, the process on which is based the manufacture of commercial plasters. If the temperature limitations are not observed, the result of the calcination process will be insoluble anhydrite which, compared with the soluble form, takes up water very slowly so as to be of no practical use, although actually it is soluble and in time is convertible into gypsum like the other forms.

Jan 1, 1922

By Paul T. Allsman, E. W. Newman

Trenching, sampling, and core drilling in Stillwater and Sweetgrass Counties, Mont., by the Bureau of Mines have delimited over 5,000,000 tons of chromite ore containing more than 20 per cent chromic oxide. The Benbow and Mouat-Sampson mines have been developed and are fully equipped for mining and milling 500 tons and 2000 tons a day, respectively. Introduction The Montana chromite deposits were the first to be explored under the Strategic Minerals Act of 1939. In June of that year, the Bureau of Mines started exploration by trenching, test pitting, sampling and diamond drilling, and completed the project in March 1943. The U. S. Geological Survey cooperated by mapping the geology and logging the cores. The project was to determine the extent and grade of the chromite ore and to indicate sufficient reserves to justify development and exploitation of the deposits for the national emergency. Exploration has indicated that the district contains the largest and most important reserve of chromite ore in the United States. The Benbow and Mouat-Sampson mines have been developed and a 500-ton concentrating mill has been constructed on the Benhow property and a 2000-ton mill on the Mouat-Sampson property. Concentrates were produced from the Benbow mill three months after the attack on Pearl Harbor, when the nation's major chromite supplies from foreign sources were cut off. History It has been known for 50 to 60 years that some chromite deposits existed in an east-west belt along the north escarpment of the Beartooth Mountains about 25 miles north of Yellowstone Park, but nothing was known of their size and extent until the war demand of 1917 and 1918 stimulated the search. In those years two properties in the Stillwater region were actively developed, but no shipments were made. The Benbow property was located in 1918 by a local group. The property comprised seven claims along the strike at the east end of the belt. An adit was driven several hundred feet on the Eclipse claim. The seven claims were sold to the Chromium Products Corporation of Livingston, Mont., and were subsequently patented. In 1929, an eastern group obtained an option, installed some equipment, and erected several log cabins. The "crash" in the market in 1929 caused the operators to drop their lease, and the property remained inactive until 1939, when the Bureau of Mines began its exploration. Fourteen claims were located on the Boulder River in 1918 and subsequently patented by the U. S. Chrome Corporation.

Jan 1, 1949

By J. G. Bradley

On February 1, 1971, United States Steel Corporation, Lorain Works began operation of its first BOP facility equipped with a partial combustion gas cleaning system.- This shop consists of two 220 ton vessels. Figure I schematically describes this partial combustion gas cleaning system and highlights the necessary features for it-s safe and efficient operation. Waste gases are drawn into the membrane hood by a 2250 H.P. induced draft fan and are first quenched by the six inch bull nozzle at the top of the hood. Larger solid particles are separated from the gas in the quencher venturi and final scrubbing takes place in the P-A high energy venturi scrubber before the cleaned waste gas is burned in the flare stack. Scrubbing water is routed through a cyclone separator and then cycled into one of two 100' diameter thickeners. Underflow sludge which averages 20% solids is dewatered by 100 H.P. centrifuges. The clear overflow from the thickeners is recycled first to the P-A venturi and then to the quencher before returning to the thickeners.

Jan 1, 1972

By Eugene McAuliffe

IT is not possible to include in this paper, limited as it is in scope, the many diverse steps toward the reduction of mine accidents that are taken in the mines that produce the nation's coal. Every coal-producing state has enacted laws covering proper mining practices, and the major portion of these are directly related to the safety of the mine employees. The United States Bureau of Mines, the American Institute of Mining and Metallurgical Engineers, The American Mining Congress, a number of national, regional and state organizations, as well as the coal technical press, have covered time and time again all of the "do" and "don't" phases of mine operation that bear on the important question of mine and employee safety. Within the past 15 years The Union Pacific Coal Co. has attempted to put into practice in its mines in southern Wyoming these many good recommendations, finding some value in all, and yet, to secure substantial results, the management found it necessary to resort in the end to what might be referred to as "extra-territorial" methods. It is the writer's purpose to show in this paper that marked and even extraordinary betterment can be brought about when employer and employee work together with due sincerity. In presenting our own experi-ence, one that has been duplicated in so far as results are concerned on numerous other properties, no theory of perfection of management exists; on the other hand, our organization feels that as long as our record of accidents remains as shown by even our latest and best performance we still have far to go. Safety work in some form has been carried on in and about the mining properties of The Union Pacific Coal Co. since the first mine was opened at the now long-abandoned town of Carbon, Wyo., in 1868. On June 30, 1903, an explosion and subsequent mine fire occurred in mine No. 1 at Hanna, taking 169 lives, and a second explosion occurred in tile same mine on March 28, 1908, in which 59 additional lives were lost. Looking back with impartiality on the causes leading up to these two unfortunate disasters, we can only conclude that shooting from the solid, the absence of adequate ventilation, rock dusting, the use of water at the face to allay

Jan 1, 1938

By James R. Holden, Frederick E. Wang

Through both single-crystal and powder X-ray diffraction methods, ten A6B23-type compounds have been confirmed to exist between lanthanides (A) (plus scandium and yttrium) and manganese (B); A = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. The formation of a compound of this type is shown to he extremely atomic size-sensitive; hence it can be classified as a "size-factorH compound. The "enveloping effect", a geometrical consideration observed in its crystal structure, is proposed as the reason for the A6B23-type compound being size-sensitive. The approximate ideal geometrical ratio of the radii R/r is 1.31 while experimentally A6B23-type compounds have a radius ratio lying within the range 1.2 to 1.4. FLORIO t al.' characterized the structure of Th6MnZ3 as fcc, space group Fm3m, with 116 atoms in the unit cell. Since then, a number of isotypic binary compounds, and recently Gd n,,' have been confirmed to exist. The fact that strontium and barium form A6Bz3-type compounds with magnesium strongly suggested the possible existence of Ba6Liz3. However, investigation3 showed the compound Ba6LiZ3 to be absent. Since both strontium and barium are group 11-a elements and are therefore "open metals",6 the nonexistence of Ba6LiZ3 can hardly be explained satisfactorily by valence-electron considerations. On the other hand, the consistent atomic-radius ratio, (R/r),* observed for the known A6Bz3-type compounds,3 strongly suggests that the formation of compounds of this type is atomic size-sensitive. Therefore, one is tempted to explain the nonexistence of Ba6LiZ3 entirely on the basis of the atomic-size difference between strontium and barium. However, this approach is not entirely without objection. Atoms are not rigid spheres and are known to vary in size within certain limits.7 Since the atomic-radius difference between strontium and barium (0.07 to 0.09A) is within these limits, it is reasonable to assume that the size difference would have a negligible effect on the formation of Ba6LiZ3. This view is further supported by the fact that the radius ratio, R/r, in other known "size-factor" compounds is observed to range widely—for example, from 1.08 to 1.45 for ABz-type compounds (C15, MgCuz type)' and from 1.37 to 1.58 for AB5-type compounds (D2d, CaZn5 type).g The present investigation was undertaken in order to find a more satisfactory explanation for the non-existence of Ba6LiZ3 and, consequently, a better understanding of the nature of the A6Bz3-type compound. The primary objectives are to confirm the previous conclusion3 that the A6B23-type compound is indeed a "size-factor" compound and subsequently to determine the atomic-radius ratio range in which the A6Bz3-type compound can exist. In order to achieve these objectives, stoichiometric A6Bz3 alloys, where manganese (B) was alloyed with various lanthanide elements (A), were selected for investigation. The atomic-radius ratios of lanthanide elements with manganese range from 1.26 for Lu/~n to 1.46 for Eu/Mn. This radius ratio range includes and exceeds the range of all previously reported A6Bz3-type compounds—1.32 for Th/Mn' through 1.38 for Sr/Li. Furthermore, the atomic-size difference between successive elements of the lanthanide series in order of atomic number) is of the order of 0.01A (europium and ytterbium are exceptions). The series of lanthanon-manganese alloy systems is ideally suited to a precise determination of the limits of allowable atomic-radius ratio for A6Bz3-type compound formation. EXPERIMENTAL PROCEDURE The lanthanide metals, in ingot form, supplied by Michigan Chemical Corp. (St. Louis, Mich.) and Nuclear Corp. of America (Burbank, Calif.), were guaranteed by the suppliers to be at least 99.9 wt pct pure (traces of silicon, calcium, and other minor constituents present on occasion, not to be more than 0.05 wt pct) as shown by spectrographic analysis. Manganese metal, in polycrystalline form, was redistilled from the commercial, chemically pure grade and was analyzed to be at least 99.95 wt pct pure. In all cases, the atom ratio between the two elements in each charge was A (rare-earth meta1):B (manganese) = 6:23 and a constant weight, 3 g, of

Jan 1, 1965

By R. W. Culbertson, S. Kasper

During the 1920's, approximately 11,000 small gasifiers were in operation in the United States. They converted about 15 million tons (13.6 Mt) of coal per year into low Btu gas. In some cases, hot raw gas was used for applications such as firing open hearth furnaces or brick kilns. In other cases the gases produced in the gasifiers were cooled, cleaned and desulfurized for various utility and industrial purposes. The steel industry was by far the largest user. The most important fact was that the conversion of coal to a usable fuel gas was demonstrated to be commercial. During the late 1940's and early 1950's, this form of energy was largely replaced by natural gas as the pipeline net work was expanded. Producer gas was no longer economically competitive. Over the past 25 years, government controls on the interstate price of natural gas have maintained this situation. At present only three commercial small coal gasifier plants are still in operation in the United States. These facilities are operated

Jan 1, 1980

By K. P. Gupta, A. K. Pal, L. Chandrasekaran, U. P. Singh

The Mn-Sn binary system, investigated at the high-manganese end and between 500° and 1000° C, shows four phases at temperatures below 727"C, namely the u Mn, the p Mn, the Mn3 Sn, and the Mn, Sn phases, while at higher temperatures only the last three phases remain stable. The solubility of tin in a Mn is very small and the maximum solubility of tin in P Mn phase appears to be abollt 10 at. pct Sn. The solubility range of the Mn,Sn and the Mn, Sn phases is 23.0 to 26.0 and 37.0 to 40.0 at. pct Sn, respectively. The lattice parameter of the 13 Mn phase increases with increasing tin content. The Mn, Sn thase is hexagonal with and appears to be basically of the Ni3 Sn type structure except that for quite a few X-ray diffraction lines the calculated and observed relative intensities do not agree well. The Mn-Sn binary system has been studied by several investigators.''~ Their results indicate that three intermediate phases, namely, the Mn3Sn, Mn,Sn, and MnSn, phases, exist at high concentrations of tin. However, so far the proper phase equilibrium has not been established at the manganese-rich end and very little data is available for the composition range between pure manganese and Mn3Sn. Moreover, earlier investigators differ in their opinion about the exact composition range at which the Mn3Sn and Mn,Sn phases appear and some doubt has been cast by some investigators3 regarding the structure of Mn3Sn phase which has been reported to be isotypic with Ni3Sn (Mgscd type) structure. In this investigation an attempt has been made to establish the proper phase equilibrium between pure manganese and Mn + 50 at. pct Sn composition in the temperature range of 500" to 1000°C. PROCEDURE The raw materials used were from three different sources. For exploratory work five alloys containing 5, 10, 15, 20, and 25 at. pct Sn were prepared using 99.9 pct pure manganese and tin supplied by E. Merck & Co., Germany. The rest of the alloys and one more 25 at. pct Sn alloy were prepared using 99.9 pct Mn supplied by Gallard Schlesinger Chemical Mfg. Corp., U.S.A., and 99.999 pct Sn supplied by Semi Elements Inc., U.S.A. Weighed amounts of manganese and tin were melted in recrystallized alumina crucibles in an inert gas (argon) high-frequency induction melting furnace. By careful control of temperature and time of melting the losses were reduced to below 0.2 pct in all cases. Since the losses were very small, no attempt was made here to analyze the samples chemically. Alloys were wrapped in molybdenum foil and sealed in small evacuated fused silica capsules. The alloys were annealed at different temperatures, controlled within + l°C, for sufficiently long periods to attain proper phase equilibrium, and subsequently quenched in cold tap water. The annealing periods used at different temperatures were 15 days at 500°C, 7 days at 600°C, 5 days at 700" and 750°C, 3 days at 800°, 850°, and 900°C, 2 days at 968"C, and two alloys annealed at 968°C were reannealed for 10 hr at 1000° C. From each annealed specimen, a part was utilized for metallographic study while another piece was used for X-ray diffraction study. 1.0 pct HNO, solution and oxalic acid solutions of concentrations 0.05 to 1.0 pct were used for etching Mn-Sn alloys above and below the MnsSn composition, respectively. Since all alloys were brittle, X-ray specimens were prepared using the as-crushed -325 mesh alloy powders. Only one 25 at. pct Sn alloy powder was reannealed in an evacuated silica capsule at 800°C for 5 min and water-quenched. X-ray diffraction patterns . for the Mn3Sn phase with the as-crushed and the reannealed powders did not show appreciable change. Un-filtered iron radiation at 25 kv, 15 ma was used with either Norelco 114.6-mm-diam Debye Scherrer Camera (for phase identification) or Norelco 12-cm-diam symmetrical focusing camera (for lattice parameter determination of the 6 Mn phase). The estimated accuracy of lattice parameter determination for the focusing camera was * 0.001A. RESULTS AND DISCUSSIONS The results of metallographic and X-ray diffraction study made with different alloys are shown in Fig. 1. The variations in lattice parameter with composition for the p Mn and the Mn3Sn phases are given in Tables I and 11, respectively, and the lattice parameter as a function of composition for the p Mn phase is shown in Fig. 2. The lattice parameter of the p Mn phase increases with increasing tin content while for the Mn,Sn phase the data obtained from two two-phase alloys and one single-phase alloy indicate increase in a,, and decrease in c, parameters with increasing tin content. The results, Fig. 1, indicate that the solubility of

Jan 1, 1969

By P. R. Kalischer

IN the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more components that tend to form very stable oxides Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken If, however, it s required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible Since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets All of the pertinent properties of the magnets could be accurately and delicately measured by density measurements and magnetic tests of sufficient scope to give a complete demagnetization curve From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties NATURE AND REMOVAL OF SURFACE BARRIERS The early work of the present investigation was based upon published processes In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 per cent Fe, 50 per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200ºC or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics However, this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen Both the iron and nickel powders sintered

Jan 1, 1941