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By AIME AIME

THE meeting" of the Rare Minerals and Metals Committee was held Monday afternoon, Feb. 17; Donald M. Lidclell, chairman, presiding. The first paper (T. P. 279), "Progress in the Use of Tantalum," by George W. Sears, was read by Mr. Smyth. Dr. Sears' paper contains an interesting summary of the uses, alloys and ores of tantalum and a resume of present method of reduction. The uses of tantalum is based on its extreme rise to the reaction of even the strong mineral acids, its great avidity for the common gases and its capacity for transforming alternating to direct current. Tantalum, as an alloy material, has received considerable study and many alloys have been reported. Among them three types appear to .be most prominent, alloys of high melting point, hard alloys and acid rising alloys. As the estimated quantity of tantalum in the earth's crust is less than that of gold, it must be looked upon as n rare metal. Australia is the greatest producer and the Black Hills of South Dakota produce minor amounts. As the one type of mineral available contains both tantalum and columbium, the extracting and metallurgy of tantalum are difficult chemical processes. Greater simplicity in this and the development of a market for columbium would undoubtedly be of great benefit to the tantalum industry, andl make for a greater use of tantalum produced.

Jan 1, 1930

By D. H. Newland

New York has a small but not insignificant place in the oil and natural gas industries of the United States. It has had a continuous record as an oil producer since 1872, with an aggregate yield of about 104,000,000 bbl. The reported output for 1935 was 4,237,000 bbl., a gain of more than 10 per cent for the year and a total that has been exceeded only in the early period of flush production half a century ago. The industry has been steadily building up since 1920 with the successful practice of the water drive, which has given a new lease of life to pools that had been practically drained of oil recoverable by pumping. An additional output of 2000 bbl. or more per acre is being procured by this method. Altogether the fields in New York State cover about 55,000 acres. Their limits are well defined and it is unlikely that they will be extended in the future, although there is some prospect of finding additional supplies by deeper drilling. The oil from New York is all classed as Pennsylvania grade, for which the recent price has been about $2.50 a barrel. It is refined at Olean, Wellsville and Bolivar, in the oil district, and partly in Pennsylvania refineries. Exploration for natural gas, outside of the established districts, was considerable during the year. Altogether 59 wells were drilled, distributed over 13 counties, of which 33 were listed as producers and 26 were dry. At the close of the year, 13 wells were in process of drilling. The 33 producing wells had a combined estimated flow of 278 million cubic feet per day. The best results were obtained from exploration in Allegany County, where out of eight wells drilled to the Oriskany sandstone five were successful and showed a combined open-flow capacity of 107 million cubic feet. The Oriskany sandstone was encountered at a depth of 4500 to 4900 ft. In Steuben County, next east of Allegany County, two out of seven wells to the Oriskany proved productive, and one of these, in the town of Greenwood, on the Watkins structure, was probably the largest that has so far been opened in the state, with a reported yield of 35 million a day. In the central part of New York interest was awakened by the activity shown in exploring for gas in the Trenton limestone, in Camden, Florence and Rome townships, Oneida

Jan 1, 1936

By D. H. Newland

New York has a small but not insignificant place in the oil and natural gas industries of the United States. It has had a continuous record as an oil producer since 1872, with an aggregate yield of about 104,000,000 bbl. The reported output for 1935 was 4,237,000 bbl., a gain of more than 10 per cent for the year and a total that has been exceeded only in the early period of flush production half a century ago. The industry has been steadily building up since 1920 with the successful practice of the water drive, which has given a new lease of life to pools that had been practically drained of oil recoverable by pumping. An additional output of 2000 bbl. or more per acre is being procured by this method. Altogether the fields in New York State cover about 55,000 acres. Their limits are well defined and it is unlikely that they will be extended in the future, although there is some prospect of finding additional supplies by deeper drilling. The oil from New York is all classed as Pennsylvania grade, for which the recent price has been about $2.50 a barrel. It is refined at Olean, Wellsville and Bolivar, in the oil district, and partly in Pennsylvania refineries. Exploration for natural gas, outside of the established districts, was considerable during the year. Altogether 59 wells were drilled, distributed over 13 counties, of which 33 were listed as producers and 26 were dry. At the close of the year, 13 wells were in process of drilling. The 33 producing wells had a combined estimated flow of 278 million cubic feet per day. The best results were obtained from exploration in Allegany County, where out of eight wells drilled to the Oriskany sandstone five were successful and showed a combined open-flow capacity of 107 million cubic feet. The Oriskany sandstone was encountered at a depth of 4500 to 4900 ft. In Steuben County, next east of Allegany County, two out of seven wells to the Oriskany proved productive, and one of these, in the town of Greenwood, on the Watkins structure, was probably the largest that has so far been opened in the state, with a reported yield of 35 million a day. In the central part of New York interest was awakened by the activity shown in exploring for gas in the Trenton limestone, in Camden, Florence and Rome townships, Oneida

Jan 1, 1936

By John S. Crandall

Occurrence: small crystals in alluvial sands from the eroding Belt Series mica schists. Flowsheet: dragline, trommel screen, jigs, drier, crusher, screens. Value: ground, $2.50 per cu yd, garnet sand gross $60. per ton. Costs: production and sales $48. per ton. Uses: blasting sand in aircraft plants, monumental works, foundries. Efficiency comparison: superior to silica sand. Future: possibilities only touched upon, research continuing.

Jan 1, 1950

By Geo. H. Ashley

The following paper is intended to be suggestive only, and to open the way for discussion and further observation. Its preparation was requested only two days before the time limit set for the submission of the papers comprising this symposium. Thus no time existed for detailed studies, so it is largely a memorandum of such facts as have come incidentally to the notice of the writer in the study of coal in the field. The field study of sulfur in coal has received very little special attention or description from coal student's. The presence of sulfur concretions is noted in hundreds of descriptions, and certain benches of a coal bed may be described as "sulfury" or the presence and position of sulfur bands may be noted in coal sections in connection with sampling. It may be accepted that some sulfur is present in all coal. The amount varies greatly in different regions, in different beds, and in the same bed in different areas. The anthracite of Rhode Island comes the nearest of any coal known to the writer of being free from sulfur, several analyses of that coal showing less than 0.1 per cent. Subbitumi-nous coals in Colorado in a few places have close to 0.2 per cent. of sulfur on the dry-coal basis and in other states subbituminous coals approach this lower limit. Bituminous coals seldom run under 0.4 per cent. of sulfur on the dry basis, though in a few places dry bituminous coals in Colorado and Washington have between 0.3 and 0.4 per cent. The better known bituminous coals have almost everywhere over 0.4 per cent. The best of the Pocahontas and New River coals run close to 0.4 per cent., but there is very little commercial coal in Pennsylvania, Ohio, Indiana, Illinois, Kentucky, or the other states, that runs under 0.5 per cent. on the dry basis. From these minimum figures, the amount will range up to 5 or 6 per cent. or higher if visible sulfur is not excluded. It must be remembered that the usual analysis of a coal bed is not intended to give the total proportion of sulfur in the bed but the amount in the coal after the removal of the more obvious and larger sulfur masses. Professor Parr has already pointed out that, chemically, sulfur occurs in several forms: as pyrite, organic sulfur, sulfates, and possibly as un-combined sulfur. Sulfur in the form of sulfates is commonly the obvious result of the weathering of pyrite and may be found in the coal within .

Jan 1, 1920

By Thomas Varley

IN THE congressional act establishing the Bureau of Mines one of the functions outlined was "to assist I the industry in the prevention of mineral waste." This had not only to do with the waste in mining but in milling and metallurgical practices, including smelting. The organization of the Bureau of 'Mines includes many divisions, each working in a particular field and charged with certain investigative work. The metallurgical division has the above duties under its immediate supervision, and the station located at Salt Lake City is directed by the chief of this division: There are ten experiment stations of the Bureau of Mines, located in various parts of the country, most of them being housed at state universities under cooperative agreements. Considerable care was exercised in locating the stations and in choosing the particular type of work to be investigated at each place. Inasmuch as the Bureau was designed to serve and cooperate with the industry it is only natural that the investigative work be of interest and importance to the territory immediately adjacent to the respective stations.

Jan 1, 1925

By G. R. Love, M. L. Picklesirner

THE use of color adds a new beauty, power, and versatility to metallography. This has been amply demonstrated in a number of public exhibits and on the walls of corporate, government, and university metallographic laboratories around the world. Indeed, in a number of cases, the color not only is of esthetic value but is scientifically essential to the competent examination of particular samples and systems. Optical strain analysis,' determination of true grain size in U-A1 alloys: phase identification in Nb-base alloys,3 analysis of transformation rates in heat-treated Nb-Zr alloys,4 measurement of solidification segregation in cast Nb-Zr alloys,' study of the intermediate phases in Nb/Sn diffusion couples,6 investigation of the oxidation kinetics at various surface orientations in single crystals,7'8 and a number of other research efforts9'10 would have been vastly more difficult without the extra clarity and distinction introduced by color—either the colors resulting from particular polarized light techniques or the interference colors obtained by oxidation. It is unfortunate that the beauty of colored micro-structures cannot be shared more widely, but the economics of publishing a technical magazine apparently prohibits color plates except under extraordinary circumstances. It is doubly unfortunate that no convenient, general method exists for communicating the information available in colored microstructures to the scientific community. True, in some instances the color changes observed are dramatic enough that direct black and white photography is adequate. In photoelastic stress analysis, several orders of interference fringes may be produced and it is frequently desirable to suppress the color effects (use monochromatic light) to simplify interpretation. On the other hand, relatively minute color variations may be readily detectable by eye, be of considerable assistance in interpreting a structure, and yet be enormously difficult to reduce to an unambiguous black and white print. In order to illustrate a possible compromise or solution to the above problems, we wish to show three black and white photographs of the same region of an Nb/Sn diffusion couple whose interpretation depends heavily upon use of color techniques. These micro-structures were obtained from a section through a rod consisting of commercial-purity niobium tubing filled with 99.995 pct Sn (melt-filled in 10"6 Torr vacuum). The composite rod, measuring 500 mm long, was bent into a hairpin shape and inserted into water-cooled copper grips in a vacuum high-temperature furnace. The rod was outgassed for 2 hr at a furnace temperature of 800°C and was further heated by self-resistance using a 2.2-kva ac power supply. The rod was raised to 1910°C over a 4+-hr period, held for 15 min, slow-cooled to 1500°C over a -hr period, and free-cooled to room temperature (all temperatures were measured with W5Re/W26Re thermocouple). Throughout the heat treatment the ambient pressure was kept below 8 x lo-' Torr. Metallographic preparation of the sample was completely conventional except that it was necessary to extend the grinding steps to remove damage in the brittle NbsSn phase introduced by sectioning. No satisfactory chemical or electrochemical etch has been found for these diffusion couples; of those which have been tried, any that attack the niobium-rich phases at all attack the tin-rich phases disastrously. However, the final polishing steps did produce a slight relief effect and this, coupled with anodizing, yielded excellent clarity in the microstructures for direct observation. The anodizing voltage was chosen to give maximum change in color per unit change in composition. In this case, indeed normally, this maximum sensitivity occurred in the blue-to-red color range. The pure niobium tube wall anodized to a relatively bright blue

Jan 1, 1967

By Frederic Benard

PRIOR to 1936, the Ontario Refining Co. received all incoming blister copper from The International Nickel Company's smelter in the usual form of 460-lb. cakes, or slabs. These were received in open cars in lots of 250 pieces. At the refinery the cakes were unloaded onto narrow-gauge cars, for convenient handling and pickup by charging cranes. In March 1936, an investigation was started on the feasibility of trans-ferring converter copper in the molten state from the smelter to the refinery anode furnaces, a distance of 114 miles. Although common in steel practice, the transportation of blister copper in this form had not previously been attempted and a preliminary study of the various factors involved was therefore necessary. For this purpose, a series of experiments was made in which molten copper, removed at different stages during the furnace cycle, was held in a small portable holding furnace. This vessel was essentially a refractory-lined steel cylinder provided with ports for filling and emptying, heated by an oil burner. Dimensions of the steel shell were 3 ft. 10 in. diameter by 7 ft. 3 in. long, and thickness of refractories depended oil the design and combination used for the particular experiment. The vessel was filled with approximately 2 ½ tons of copper at a predetermined temperature, the lining having been preheated to a definite point by means of an oil burner. All openings were well luted and temperature readings were made every 15 min. by means of an immersion-type thermocouple. In this manner the rate of heat loss resulting with different refractory design could be developed. The ratio of exterior surface to weight of metal was taken into consideration in comparing the experimental results with what might be expected for a full-sized unit, and observations were also made on type and degree of slag accretion. It was not possible to get as much information on this latter point as desirable, but all evidence showed that the problem would be control of slag build-up rather than attack oil refractories.

Jan 1, 1938

By Ralph Arnold

WHILE much geological work and drilling have been done in Venezuela, the incompleteness of geological evidence obtainable and the restricted areas in which drilling has been done make any estimates of oil resources extremely speculative. Nevertheless, it is felt that the data given are justified, in the belief that the ideas of a geologist familiar with the region are better than those of a promoter. The oldest beds of interest to oil men are those of the Cretaceous, which are well developed in eastern Venezuela and about parts of Lake Maracaibo. In both cases, a hard massive limestone is overlain by a great thickness, most of which is shale. In the west, in places this shale is more than 2000 ft. (610 m.) thick, while in the east it may attain 3500 ft., (1067 m.). The limestone and parts of the shale are oil producing. In the east, the Tertiary where present is almost entirely covered by the Quarternary, but in the west it is well developed. In probable unconformity over the Cretaceous shales is found a series of sandstones and shales, which may beg called the lower coal series. It is well developed southwest of the lake, where it is the oil container, and is probably the lowest series exposed east of the lake. Above this is the Pauji shale, which is probably the point of origin of all the oil east of Lake Maracaibo and in the State of Falcon. It has a thickness of about 3000 ft. (914 m.) in the Mene Grande region. The upper coal series is developed as a great thickness of sands, shales, and clays, with some partly consolidated limestone. Its thickness may be as great as 10,000 ft. It is the oil container of the Falcon-El Mene region and a probable location for oil in some of the area about the lake. It may or may not include the so-called Maracaibo series in which the oil is found at Mene Grande. Over much of Venenzuela, the Quarternary is present in unknown thickness, which probably is not great. It obscures oil structure in all cases and presents the greatest hazard of oil exploration for the fields which probably exist below.

Jan 7, 1922

By MALCOLM FRASER

I was delighted to be invited to be patron of this Joint Conference, but the challenging task you have set yourselves, and your speakers' depth of expertise, deny anyone, even the patron, the opportunity to be patronizing. Australia's history has been inextricably linked with the fortunes of our great mining industry. That link will remain. Just as the gold rushes of the last century, and the discoveries at Kalgoorlie and Broken Hill changed the lives of generations, so the more recent development activity in iron ore, bauxite, nickel, coal, and uranium are having a significant impact on the lives of Australians today. The minerals industry has contributed to Australia's jobs and prosperity. Mining is not free of problems, but so long as safeguards are strong and appropriate the net benefits the mining industry brings Australia will continue to be enormous. We rely on our mining industry to find, prove, develop and sell our minerals profitably, and my Government is committed to maintaining a healthy mining industry. In the past year there have been positive signs of a resurgence in exploration and development. The North-West Shelf ventures are spending $50 million on a feasibility study to work out the extent of future investment in that project; exploration expenditure for minerals other than petroleum increased by 34 per cent in 1976-77 to $134 million; petroleum exploration increased dramatically last year almost doubling to $94 million-this year it is projected to reach $125 million.

Jan 1, 1978

By P. L. Allsman

A method of analyzing blasting action indicates that major cost savings are possible by revising practice and bringing the classical blasting formulas up to date; difficult problems such as taconite and throw-breakup can be attacked by engineering Denonation pressure — the peak pressure developed by the explosive reaction; "shatter blasting." Average detonation pressure — the average pressure over the time the reaction continues; "heave blasting." Radial presswe — the stress in a radially expanding sphere about the detonation. Corresponds to the diminishing peak pressure. Lateral stress - the stress in a circumferential direction, induced by outward movement of the rock away from the detonation. Limiting stress or Slim— the rock property at which failure will occur in the case at hand; may be tensile or compressive strength, or combinations. Recent developments in explosives technology, following the advent of nuclear explosions, have led to a rather complete understanding of their action. A survey was made for the purpose of uncovering any knowledge which might be applicable in the mining and quarrying industries, the principal users of explosives. Although no revolutionary techniques have become apparent, much basic data pertaining to blasting — fortunately not classified — have been developed by recent research, from which a good general understanding of the process can be derived. It is hoped this explanation of the scientific principles governing explosive action, together with a proposed analysis of blasting practice, will further the development of mining engineering. NATURE OF THE REACTION: The phenomenon of explosion, termed detonation, is in reality a rather complex chemical reaction, and as such is completely explainable by physical and chemical laws. Detonation is characterized by high temperature and pressure, extreme rapidity — often being complete within one microsecond — and most importantly by formation of a shock pulse which accompanies the reaction zone. As with any chemical reaction, there is a critical value of temperature and pressure below which detonation can not occur; this is termed the "critical point". Whereas an explosive substance will decompose slowly at ordinary temperature, with the formation of gases which readily dissipate; at elevated temperature the reaction is considerably speeded. If pressure is suddenly applied at some point in an explosive medium, adiabatic compression results, and the temperature is locally raised. When the temperature becomes high enough the decomposition will be so rapid that the gaseous products do not have time to dissipate, but contribute to a further build-up of pressure. This, in turn, furthers adiabatic temperature rise over a widening area, and with any heat generated by an exothermic reaction, causes a rapid increase in temperature. Both temperature and pressure are spontaneously built up in this manner until the critical point is reached, resulting in detonation. The values of pressure and temperature necessary to create detonation are established by the unusual nature of the process. If temperature alone is raised above the critical point, without sufficient increase in pressure, deflagration or "low-order detonation" occurs. In the true, or "high-order detonation", the shock pulse resulting from the violent decomposition becomes an integral part of the reaction, and itself aids in increasing the detonation

Jan 1, 1961

By Paul A. Farrar, Felix Ermains, Harold Margolin

The systems Ti-Crand Ti-Vhave been reinvesti-gated in the region up to 40 wt pct alloying addition using both conventional and rapid quenching techniques. The Ti-Cr eutectoid temperature was determined to be at 667° & 10° C and 14.5 wt pct Cr. The solubility of the Cr in a Ti was found to be less than 1 pctat 700"C. The P transus of the Ti-V system was found to be depressed to 510°C at 40 wt pct V and the solubility of V in a Ti was found to be less than 2 wt pct at 700°C. Investigation by a. d. McQuillan1-3and m. k. McQuillan4 on the systems Ti-Co, Ti-Cr, Ti-Cu, Ti-Fe, Ti-Mn, Ti-Ni, and Ti-V has cast doubt as to the position of the ß/a + ß boundaries in many of these systems. Their investigations were carried out using hydrogen pressure and/or rapid quenching experiments, as opposed to the conventional quartz capsule techniques employed by most other investigator.'" By these methods, the ß/a + ß boundary was found to be lower than that obtained by conventional techniques in all except the Ti-Fe system. In the latter, the ß/a + ß boundary was essentially the same as the boundary obtained by conventional technique.7' On the basis of rapid quenching results in the Ti-Cr system, M. K. McQuillan4 placed the eutectoid temperature below 550°C whereas other investigations using conventional techniques had placed the eutectoid variously as between 650' and 700°C,5 between 675' and 700°C,6 between 650" and 675°C,7 at 670°C,8 and above 625"C.la9l3 In order to check these results, a reinvestigation of four of the systems was undertaken using both conventional and rapid-quenching techniques. The Ti-Fe and Ti-Mn systems will be dealt with in anoth er paper, with only the Ti-Cr and Ti-V systems being discussed here. EXPERIMENTAL TECHNIQUES Alloys employed for the delineation of the systems under investigation were prepared from iodide titanium sheet capsules containing the alloying materials,

Jan 1, 1962

By A. W. Fahrenwald

FLOTATION practice in Idaho is now about 13 years old. The advance has been steady during these 13 years. The operators have been alert to take advantage of the newest developments and they have themselves made a constant effort to improve their work. The metallurgical improvements are clue to the development of (1) better equipment, (2) better reagents, and (3) better understanding and control of the process. During the 8 years which the writer has been in this district, there has been continuous experimentation by several companies to improve the ore dressing by flotation methods. Gravity concentration has fought hard to hold its place, and although it is true that gravity processes have been improved during this period, nevertheless, in several of the important mills of the district the few tables that managed to hang on have finally given way. On the straight-lead ores, tables and jigs are still used; and, due to better classification, their hold on this job has been strengthened.

Jan 1, 1927

By Arvid E. Nissen, Knox Taylor, John H. Hall

Some months ago one of the authors was asked to write a paper on the heat treatment of steel castings that would be more comprehensive than other matter he had published; this is an attempt to present in condensed form the results of experimental work and actual practice carried out for the most part in 1907, 1908, and 1909. It is not a laboratory research and the work done was carried out for the express purpose of putting in practice the processes discovered as fast as possible. Most of the tests are the result of commercial practice and not of bars annealed in our laboratory; most of the micrographs were made for our own records and not for publication. Certain of the micrographs, therefore, are not as clear as we may wish but they were good enough for our purpose at the time they were made. The tests and micrographs are selected from several thousands in our files. All of these micrographs are magnified 60 diameters. These experiments were conducted almost entirely on steel made in a 3-ton bottom-blown converter, and most of the steel illustrated analyzes about 0.05 in phosphorus and sulfur. Unfortunately, a certain number of specimens are shown of which we do not have the complete analysis, but in most cases in which the phosphorus and sulfur vary much from the figure just given that fact is noted. For purposes of comparison, we have included a certain number of micrographs and tests of steel made in the electric furnace, some of which were from specimens made in other shops and some in our own shop, and some tests of acid open-hearth and tropenas steel. A brief examination of the tests in Table 1 shows that certain treatments of, for instance, 0.30 per cent, carbon steel are not represented by any test data. Had this been a laboratory research, this information would undoubtedly have been furnished, but as this work was done for commercial purposes the omissions are due to the fact that, at the time the work was done, we saw no advantage in trying every composition of steel with each treatment discussed in the paper.

Jan 1, 1920

By R. Simon, L. Yarborough

This paper presents a correlation for predicting the critical pressures of gas-solvent-reservoir oil systems of the type encountered in gas and solvent injection processes. Experimental data from 14 systems were used to develop the correlation which expresses critical pressure as a function of composition, C7+ mol weight, and C7+ characterization factor. Critical pressures predicted by the correlation for the 14 gas-solvent-reservoir oil systems have an average deviation of 2.8 per cent of the experimental values. The correlation war used to study a wide variety of other hydrocarbon mixtures reported in the literature whose critical conditions are in the range of interest in oil recovery work (100 to 280F and 2,000 to 6,000 psia). Critical pressures predicted by the correlation had an average deviation, expressed as per cent of experimental value, of 5 per cent for 20 miscellaneous mixtures from the literature, and 6.4 per cent for I7 methane-butane-decane mixtures reported by Sage and Lucey. INTRODUCTION Predicting critical points of hydrocarbon mixtures is an important part of phase behavior calculations. If the critical point can be predicted for a specific mixture, the separation between the bubble-point and dew-point regions will be defined, and physical properties of the mixture can be calculated by using the principle of corresponding states. Numerous correlations for predicting critical points of hydrocarbon mixtures have been published. Six of these correlationsl-8 were for light hydrocarbons, and two correlations7,8 ere for high boiling-point petroleum distillates. Organick9 And Eilerts" presented correlations which combined the published data from both light and heavy mixtures, and these correlations became the only available methods for predicting critical pressures for wide boiling range mixtures. In the course of the authors' work on secondary recovery by gas and solvent injection, experimental data were obtained for 14 mixtures of dry gas, ethane-propane-butane solvents, and various reservoir oils. The critical pressures and critical temperatures of these gas-solvent-reservoir oil systems were in the range of 1,900 to 4,800 psia and 180 to 265F. The critical pressures predicted for the 14 mixtures by the correlations of Organick and Eilerts had an average deviation from the measured values of about 13 per cent. The authors felt that it was necessary to develop a better correlation for engineering calculations and the resultant correlation, which is presented on Figs. 1 and 2, predicts the critical pressures of the 14 mixtures with an average deviation of 2.8 per cent. The validity of the correlation was tested by applying the correlation to other hydrocarbon mixtures reported in the literature. This subject is discussed later in the paper. The authors feel that there is also a need for an improved critical temperature correlation for gas-solvent-reservoir oil systems. However, developing a critical temperature correlation is a significant study in itself and is not included in this paper. EXPERIMENTAL DATA The compositions and critical points obtained by the authors for 14 gas-solvent-reservoir oil mixtures are shown on Table 1. The methane concentrations in these mixtures varied from 20 to 63 mol per cent. The intermediate hydrocarbon group, consisting of ethane, propane, and butane, varied from 20 to 64 mol per cent, and the concentration of the C,, fraction from 10 to 20 mol per cent. The physical properties of the C,, fraction covered the range from light, paraffinic, nonasphaltic (Mixtures 5, 6, 7, 8, 9 and 10) to heavy, aromatic, and asphaltic (Mixtures 13 and 14).

By D. J. Schmatz, H. I. Aaronson, H. A. Domian

Diffusion kinetics in disordered hcp Cd-Mg alloys have been investigated by means of the Kirkendall effect and concentration-penetration curves determined with an electron-microprobe analyzer. Self-diffusion coefficients of both species were determined at the three marker compositions obtained, averaging 27.6, 46. 7, and 78.1 at. pct Mg, by means of the Darken analysis. These coefficients were then corrected for the unequal and concentration-dependent partial molar volumes of the two elements with the Balluffi analysis, and for the vacancy flux effect by the Manning analysis. The latter correction reduced the Balluffi correction produced larger changes in the self-diffusiv-ities; neither, however, produced statistically significant changes in the Do's or the H'S. The most striking result of this investigation is that at all three compositions and at all temperatures studied both the uncorrected and corrected self-difjusivities of magnesium are higher than those of cadmium. The Cd-Mg system is the first one found in which the higher melting, lower vapor pressure element diffuses more rapidly. Both an empirical correlation due to Toth and Searcy and considerations of the atomic mechanism of diffusion indicate that this anomaly is probably due to a comparatively low value of the activation energy required for a magnesium atom and a vacancy to exchange sites, perhaps occasioned by the higher compressibility of magnesium atoms. KIRKENDALL effect studies have been previously reported for only two hcp solid solutions: the E phase of the Zn-Cu system1 and the a phase of the Cd-Hg system.' In neither investigation were the marker-movement studies supplemented with the concentration-penetration curve determinations necessary to evaluate self-diffusivities by means of the atano and the Darken analyses. The present program was undertaken to obtain both types of data on a hexagonal solid solution in order to provide more detailed information relevant to the mechanism of diffusion in this type of lattice. The Cd-Mg system was chosen for this study because the disordered solid solution extends across the entire phase diagram at temperatures above 253"c5 and the substantial difference in the melting points of the component pure metals promised that marker movements would occur at reasonably rapid rates should the diffusivities of the two species be as unequal as might be anticipated. The experimental convenience of the relatively low melting points of cad-miun and magnesium and the availability of extensive and accurate activity data6 (required for application of the Darken analysis) were additional reasons for selecting this alloy system. Since the anisotropy of diffusion is not large in either pure cadmium7 or pure magnesium,' the diffusion couples were prepared from polycrystalline components. The presence of a well-defined texture in the couples—the c axis of individual crystals tended to be normal to the diffusion direction— however, provides a fair degree of crystallographic definition to the data obtained. The principal (and entirely unexpected) finding of this investigation, that magnesium, the high-melting low-vapor pressure element, diffuses more rapidly than cadmium, in contradiction to a broad range of results in fcc and bcc alloys, as well as in the previously studied hcp alloys,172 makes the self-diffusivity determinations of immediate interest in understanding the origin of this anomalous result. EXPERIMENTAL PROCEDURE The cadmium (Belmont Smelting and Refining Co.) and magnesium (Dow Chemical Co.) used in this study were both of 99.99 pct purity. Alloys containing 51.0 and 65.6 at. pct Mg were prepared from these materials by melting under a MgC12-base flux in a high-purity graphite crucible. These alloys were subsequently hot-worked and then homogenized in a helium atmosphere at temperatures close to their solidus points. Sandwich-type diffusion couples of the type g/d/g were prepared from the pure metals by solid-state diffusion. Two-piece alloy couples of Mg/65.5 at. pct Mg (Mg/gCd) and Cd/51.0 at. pct Mg (Cd/CdMg) were welded by a liquation technique. The individual components of both types of couple were initially cylinders 1.27 cm in diam and in length; the ends of these cylinders were machined accurately flat and parallel. For both welding techniques, the pure cadmium cylinders and the alloys were chemically polished in a mixture of 40 pct ethyl alcohol, 40 pct hydrogen peroxide (30 pct conc), and 20 pct nitric acid,g while those of pure magnesium were polished in a solution of 10 pct nitric acid in ethyl alcohol.' Immediately afterwards, both metals were rinsed in freshly distilled acetone, and then in similarly purified methanol.' The Mg/Cd/g couples were assembled in a carefully cleaned stainless-steel welding fixture, in which a screw operating through a self-centering arrangement permitted a controlled pressure to be exerted upon a couple prior to welding.'' Tungsten marker wires 0.005 cm in diam were placed at the d:g interfaces of some of these couples, and imbedded in the couples during the application of pressure. As soon as a couple had been assembled, the welding fixture was inserted into a Pyrex capsule containing a packet of zirconium chips at each end. The capsule

Jan 1, 1967

By N. A. DeCecco, H. M. Meyer

IN the early stages of a titanium brazing investigation, binary titanium systems partially or completely known and fundamental metallurgical data were surveyed to select the pure metal most likely to be satisfactory for producing a ductile high strength joint. The phase diagrams for the purpose of this survey were classified into two groups: 1—systems with large solubility in ß titanium, but negligible solubility in a titanium, and 2—systems with large solubility in a titanium. Those metals with melting points believed to be too high or too low for titanium brazing (Tim = 1730°C) were eliminated from consideration. The melting points of vanadium, tungsten, tantalum, hafnium, zirconium, and the platinum group are too high and those of zinc, lead, cadmium, and tin are too low. The remaining metals were grouped as follows: 1—large ß solubility: Cr,¹ Mn,² Fe;³ CO,4 Ni,5 Cu,6 Be,' Si." —large a solubility: Al.9

Jan 1, 1954

By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967

By S. R. Seagle, R. Schuhmann, N. A. Parlee

Rates of CO evolution and CO absorption were measured for liquid-iron alloys containing from 0.15 to 4.4 pet C, using a modified Sieverts apparatus. The alloys were held in alumina crucibles, so that both crucible-metal and gas-metal reactions occurred simultaneously. The data are interpreted on the hypothesis that the C-O reaction rate is controlled by oxygen diffusion across the boundary layers at the gas-metal and crucible-metal surfaces. CARBON-monoxide evolution from liquid Fe-C-0 alloys is a key reaction in steelmaking processes, both in the steelmaking furnace and in the ingot mold. Also, this reaction probably is an essential step in the desulfurization of iron under blast-furnace conditions, for which carbon is the principal reducing agent or deoxidizer present in the iron. The thermodynamic properties of the solutions of C and 0 in Fe and the equilibria of these solutions with gaseous CO and CO, have been investigated in some detail and are reasonably well understood. However, while these equilibrium data have accumulated in the laboratory, other data have accumulated to show that equilibrium conditions are often not achieved under plant operating conditions. Thus, an understanding of the rate and mechanism of the carbon-oxygen reaction not only has theoretical interest, but ultimately may assume considerable practical importance. Reaction Mechanisms and Rate Equations The over-all reaction under consideration is C (in liquid Fe) + 0 (in liquid Fe) + CO (gas) [I] Although this appears to be a straightforward heterogeneous reaction, involving just two phases (liquid metal and gas), a wide variety of reaction mechanisms has been proposed. Different authors have expressed divergent views as to the nature of the rate-controlling steps. Accordingly, a brief discussion of the possible reaction steps will be given. 1) Homogeneous Reaction Within Liquid Iron— Feild' and Jette2 have applied chemical reaction-rate theory as if the C-0 reaction were a homogeneous, second-order reaction occurring within the liquid-metal phase. This mechanism necessarily produces CO "molecules" dissolved in liquid iron. In order to yield CO gas, the dissolved CO must nucleate CO gas bubbles, and the dissolved CO also must be transported to the bubble surface where it enters the gas phase. However, this mechanism is inconsistent with present concepts of the structure of liquid-metal solutions. 2) Reaction at Gas-Metal Interface—At the surface of contact between gas and metal, a second-order reaction between dissolved C and 0 may occur to produce a CO molecule which enters the gas phase. This reaction presumably involves an "activated complex" structure in the interface. Some such surface mechanism appears essential because the carbon and oxygen do not occur in the same species in the two phases and therefore must react in some way at the surface. At liquid-iron temperatures, calculations based on reaction-rate theory indicate that the surface reaction must proceed extremely rapidly and thus cannot be a rate-determining step in the C-O reaction under ordinary conditions.3 ccordingly when the over-all reaction is measurably slow, the surface reaction may be considered at equilibrium; that is Cc* Co* = m'Pco [2] in which Co* and Co* are the concentrations of carbon and oxygen (weight per unit volume of metal), respectively, in the liquid-metal phase at the interface, Poo* is partial pressure of CO in the gas phase at the surface (atmospheres), and m' is the mass-action constant for Reaction [I]. Since activities of C and 0 are not strictly proportional to concentrations, m' is not a true thermodynamic equilibrium constant but varies with carbon content.' 3) Mass Transport—If the reaction is to proceed at the gas-metal surface, as described above, dissolved carbon and oxygen in the liquid iron must come to the surface and gaseous carbon monoxide must move away from the surface. Details of the mass-transport mechanisms depend on the kind of system under consideration. For a stirred metal bath in contact with a CO gas phase, the transport of C and 0 to the surface can be described by 1 Do Mols CO evolved per sec = — 1/16— Do/do Agm (CO-Co*) = 1/12 Do/do Agm *(Co-Co*) [3] In this equation, Do and D, are the diffusion constants for oxygen and carbon in liquid iron, 6, and 6,. are the boundary-layer thicknesses, A,,,, is the

Jan 1, 1959

By Gilbert H. Cady

Those coal mining and preparation engineers and operators who read this article will probably be most concerned with those parts which deal with the applied aspects of coal petrology in the fields of mining and technology. Actually the two categories overlap to such a degree that they are essentially one. The article appears to suggest that there are two points of veiw in the field of applied coal petrology. From one viewpoint the interest is in the attributes of the various macerals (Fig. 4)-vitrinite, exinite, and inertinite-in terms of utilization (when the coal is burned, coked, gasified, hydrogenated, etc.). From the other point of view, assuming that the macerals do possess individuality in behavior, interest attaches to the possibility that coal of a particular type (maceral composition) can be prepared by discriminating methods of preparation and blending. Most of the 29 items listed for mining and technology can be assigned to one or the other of these two categories.

Jan 5, 1958