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By A. Taylor

NICKEL-RICH alloys hardened with small additions of titanium and aluminum and centered around that region of face-centered-cubic primary solid solution, 7, where the atomic ratio of nickel chromium is about 3 to 1, form an important series of high temperature materials because of their resistance to oxidation, high temperature strength, and excellent creep characteristics at elevated temperatures.' With suitable heat treatment it is possible to precipitate a phase based on the ordered face-centered-cubic y' phase, Ni,,Al, from the randomly ordered nickel-rich y face-centered-cubic primary solid solution. By adjusting the ratio of aluminum to titanium the precipitation of needles of the hexagonal intermetallic compound n-NiaTi may be effected. In the present investigation, the main interest was focused on the interrelationships among the y, y, and 7 phases. By using alloying elements of high purity and a suitable melting technique the presence of carbides and nitrides could be completely obviated, although it is realized that their presence is probably essential in alloys of commercial importance. As a preliminary to the study of the Ni-Cr-Ti-A1 system, it was necessary to establish the constitutional diagrams of the three contiguous systems, Ni-Cr-Al, Ni-Ti-Al, and Ni-Cr-Ti, which together form the nickel-rich corner of the Ni-Cr-Ti-A1 quaternary tetrahedron. Accounts of this work on the ternary systems have already been published by the author. A preliminary disclosure of the author's investigations on the ternary and quaternary systems has been made by Hignett2 and has since stimulated work in the same field by Nordheim and Grant." Before the detailed account of the quaternary system, a brief description will be given of the three contiguous ternary diagrams on which it is ultimately founded. Ni-Cr-Ti System The 750° and 1000°C temperature isothermals of the Ni-Cr-Ti system as determined by Taylor and Floyd' are shown in Figs. 1 and 2. The single phase fields of greatest interest are occupied by the extensive face-centered-cubic y primary solid solution of chromium and titanium in nickel, and the close-packed-hexagonal Daltonide, n-Ni3Ti, from which tie-lines radiate across the very wide y+n two-phase field. The chromium-rich primary solid solution is represented by a. As may be seen from the diagrams, the extent of the y phase field increases quite appreciably as the temperature is raised from 750" to 1000°C. Isoparametric lines for the y phase are shown in Fig. 1. They are interesting in that they are almost parallel to the y/r+n boundary. Thus the determination of the tie-line directions is entirely dependent on the exact stoichiometry of composition of the 7 phase. Ni-Ti-Al System The 750°C isothermal section of the nickel-rich portion of the system Ni-Ti-A1 as determined by Taylor and Floyd is shown in Fig. 3.' The regions of greatest interest are the extensive y primary solid solution of titanium and aluminum in nickel, the y' Berthollide phase field based on the ordered face-centered-cubic structure of Ni3Al, and the hexagonal Daltonide phase, n-Ni3Ti. As may be seen from Figs. 3 and 4 the area occupied by the y phase is substantially the same at 750°C as at 1000°C, but the area of the 7 phase is considerably greater at the higher temperature. The tie-lines radiate from n-Ni3Ti across the y+v and y' + v two-phase fields and are evenly distributed

Jan 1, 1957

By F. S. Crawford

IRON and copper are mined in the Lake Superior district. The iron mines of the district have the best safety record for that industry in the country as a whole, while the copper mines of the district rank second in two of the four years recorded (Table 1). In Utah copper comes mainly from open-pit mines, which enables that state to lead easily in safety. All of the Michigan production comes from deep underground workings. About 60 per cent of the iron miners in St. Louis County, Minnesota, are employed at open-pit mines; this favorably affects the combined open-pit and underground accident-frequency rate, as this county provides most of the Minnesota-mined iron ore. In Michigan, however, there are few open-pit mines, the bulk of the production coming from underground mines, while all of the Wisconsin production, just across the state line from Michigan, is from underground mines. In spite of the fact that fewer mines in Michigan use the safer open-pit method, the iron-mining industry of that state maintained a consistently low record from 1931 to 1934; however, it was many points behind its nearest competitor, Minnesota, with its much greater production from open-pit mines.

Jan 1, 1939

By George Rice

INSTANTANEOUS outbursts of gas in underground workings are similar in effect to great blasts of explosives, but without heat effects. Fortunately they occur only in a few localities in exceptional coal fields of the world and under exceptional geologic conditions. Such violent outbursts should not be compared with the ordinary outflows of gas into coal mines or with explosions of gas and dust. The phenomenon is essentially one of gas held in circumscribed areas under very high pressure and as a mining face or heading approaches such a place and the mining excavation sufficiently weakens the natural surrounding dam or shell, this is burst by the pressure just as by the discharge of a mass of explosives. The outbursts, so far as known to the writer, have been confined to coal beds and have not occurred in other mineral deposits. Hence, as discussed later, he believes that it is the relation of the gases to the coal material that is a factor in conjunction with others in producing conditions which permit the phenomena to occur when mining is done. The gases in most instantaneous outbursts have been hydrocarbon gases but in two coal fields they have been definitely found to be chiefly or wholly carbon dioxide. One of these localities in which CO2 outbursts have been frequent and have caused loss of life is in the southern part of the Gard basin, near Alais, in southern France. In 1919, the writer visited the Fontaine mine in this field the day following the occurrence of an outburst by which two men were smothered by carbon dioxide and fine dust. After 24 hr. the CO2 had not been entirely removed by the ventilating current. Occasional outbursts of CO2 have also occurred in other small basins in France, causing accidents, as in Puy-de-Dome. However, mines in the Gard basin, north of those in which CO2 outbursts have occurred, have experienced hydrocarbon gas outbursts.

Jan 1, 1931

By Frank Kneeland

SAFETY FIRST is a popular motto-most mining companies have adopted it. It is probable, however, that in the majority of cases it is only a motto and gets no further than the office stationery or the bulletin board at the mine's entrance. In but few industries is there employed a greater diversity of machinery and mechanical devices than in coal mining. The list ranges all the way from mechanical stokers to wood-working machinery and undercutters. Many of these devices, particularly those employed in wood working, are extremely dangerous. In 1913, 23 per cent. of all fatalities occurring in coal mining in the U. S. were caused by machinery of some sort or other. Although the forms of accidents occurring with mining machinery are legion, they generally arise from one or more of five causes: (a) Falls from ladders, platforms, etc.; (b) coming in contact with moving machines or parts thereof; (c) electric shocks; (d) failure of some machine part; (e) mismanipulation of valves, levers, switches or other hand-operated controlling devices. The steps which may be taken to prevent accidents from the above causes are almost as numerous as the accidents themselves. There is, and can be, no panacea for all mishaps, nor for any one class of accidents. There is no mathematical or other formula that will bring immunity under any set of conditions. Common sense is the only guide. The remedy for the first-named class of accidents is simple and generally effective-namely, make the staging, ladder, platform, or other support, abundantly strong to carry any possible weight that it may be called upon to bear; provide ample railings on platforms or runways, and non-slipping feet on movable ladders.

Jan 1, 1915

By E. V. Daveler

THE milling plant of the Alaska-Gastineau Mining Co. is located at the town of Thane, Alaska, on Gastineau Channel, 4 mi. south of Juneau and directly across the channel from the Ready Bullion mine of the Treadwell mines on Douglas Island. Previous to the organization of the Alaska-Gastineau Mining Co., in 1912, the milling was done at the stamp mill of the Alaska Perseverance Co. located at the mine in Silver Bow Basin. But the contemplated increase in production made it necessary to locate the mill on Gastineau Channel, as not enough water was available at the mine during the winter months, nor was there room for taking care of the large tonnage of tailings that would ultimately be discarded from the mill. CHARACTER OF ORE The gold and silver values occur in quartz lenses associated with pyrrhotite, galena, arsenical pyrites, and zinc blende. These lenses occur in large bodies of slate, schist, and metagabbro, which also carry some valuable metallic contents. With the essential low cost of mining, it was necessary to mine large bodies of low-grade material containing the high-grade streaks. Of the minerals, pyrrhotite, the magnetic sulfide of iron, is predominant, and galena is the next sulfide present in quantity. The gold occurs free and coarse and associated with the iron sulfide in its finer state. The silver occurs with the lead or is alloyed with the gold. A chemical analysis of the ore shows Silver 0.10 oz. Magnesia 0.4 per cent. Silica 59.7 per cent. Sulfur 1.2 per cent. Iron 5.2 per cent. Lead 0.1 per cent. Alumina 21.4 per cent. Zinc 0.2 per cent. Lime 5.0 per cent.

Jan 1, 1920

By A. C. Wallace

THE development of the natural resources of any district of any magnitude, inevitably gives rise to many problems off title, usually due to the greatly enhanced value of the land. The development of the mining industry in the Quapaw Agency has been no exception to this general rule. Our problems, how-ever, have not been many or particularly serious. The Quapaws were allotted and patents issued by the United States Government in 1895. These patents contained a restriction against alienation for a pe-riod of twenty-five years. The effect of the restric-tion was to prevent the Indian from selling, leasing, or in any way encumbering his land. The Govern-ment, in a paternalistic spirit, sought to teach the Indian thrift and industry and to insure him a place of residence. This is evidenced by the first Leasing Act passed by Congress, which permitted only incom-petents and those physically disabled to lease their land for either agricultural or mining purposes. The able-bodied Indian was denied the right to lease. It soon became apparent to the Government, how-ever, that this was a mistaken policy, and in 1897 a General Leasing Act was passed by Congress and it was under this act that the mining industry in the Quapaw Agency was developed. The act, reads as follows: "That the allottees of land within the limits of the Qua- paw Agency, Indian Territory, are hereby authorized to lease their lands, or any part thereof, for a term not ex-ceeding three years, for farming or grazing purposes, or ten years for mining or business purposes. And said al-lottees and their lessees and tenants shall have the right to employ such assistants, laborers, and help from time to time as they may deem necessary: Provided, That when-ever it shall be made to appear to the Secretary of the Interior that, by reason of age or disability, any such allottee cannot improve or manage his allotment properly and with benefit to himself, the same may be leased, in the discretion of the Secretary, upon such terms and conditions as shall be prescribed by him. All acts and parts of acts inconsistent with this are hereby repealed." It was the interpretation of this Act that gave rise to our first serious problems. It will be noted that the Act says that "allottees of land" within the limits of the Quapaw Agency are authorized to lease their land. Thus, the first question was presented by the use of the term "allottee," and the question was as to whether or not Congress intended to limit the Quapaw Indian to the leasing of his own allotment or did Congress mean that the term "allottee" was synonym-ous with "Indian" and intend to give the Indian a right to lease both his allotment and his inherited land and was an Indian without an allotment an "allottee" even though he was a member of the Qua-paw tribe and the owner of the Quapaw land by in-heritance, and not being an allottee, could he lease his inherited Quapaw land under the authority granted in this Act?

Jan 5, 1928

By C. M. Weld

In the course of my professional work in China during the fall of 1907, I had an opportunity to visit the iron-ore mines at Ta-yeh in Hu-pei province (long. 114O 50t E., lat. 30' 20t N.). It occurs to me that a rescript and discussion of my notes taken at that time should be of interest, particularly as supplementing the exceedingly interesting recent paper of Thomas T. Read on The Mineral Production and Resources of China.' Ta-yeh is situated near the right bank of the Yangtze river. The mines are at an average distance of about 16 miles from the river-port Shi-hui-yao, which in turn is some 70 miles SE. of Hankom. The ores are shipped to the works of the Han-Yeh-P'ing Iron & Coal Co. at Hanyang, as also very largely to the Japanese government iron- and steel-works at Wakamatsu, Japan. Smaller qnantities have been exported to the Pacific coast of the United States. These ore-deposits have been briefly noticed in a number of publications, but, so far as I know, Mr. Read's description, in his chapter or1 the iron-ores of the Chinese Empire,2 contains the first attempt to define their geological character. In his more recent paper Mr. Read follows very closely the text of his earlier description. To quote briefly from the recent paper, he says : " The iron-ores at Ta-yeh .... lie along the contact between a marble and an intrusive body of a dark-gray syenitic rock." He refers to a figure which exhibits in plan, but not in section, the relative positions of the syenite, ore-bodies, and limestone. The contact is seen to trend approximately E-W., with the syenite on the north and the limestone on the south. " The syenite lies to the north of the marble, and a few miles farther north the marble again appears, iron-ore again being present along the contact." No litho-

Jan 1, 1913

This is a most interesting paper and some data in it are corroborated by work I did at Watertown Arsenal some time ago with iron powder. I would like to ask Dr. Wulff to say just a little more about the compressive and tensile stresses on the surface of compacts. JOHN WULFF (author's reply).-Our work has not yet been completed; although enough data have been obtained with cylindrical compacts of iron to permit some conclusions. Briefly, in a compact 3/4 in. high and 1/2 in. in diameter pressed at 48 tons per sq. in., the residual stresses on the surface measured by X-ray diffraction techniques are as follows: The radial stresses on top center and bottom of compacts are practically zero; the longitudinal residual stresses on the side walls are near the top quarter of the compact about seven tenths that of the yield point of mild steel in tension; at the center surface of the compact they are in compression and in magnitude about 0.3 that of mild steel in tension; near the bottom, they are practically zero. F. V. LENEL.?- I was particularly interested in the work that Messrs. Wulff and Seelig reported on the influence of lubrication on the density of parts. In connection with the work of the American Society for Testing Materials on determining the green density of a compact, we ran into considerable difficulty in getting reproducible results of green density determinations. It was much easier to get a reproducible green density when the lubricant was mixed with the powder than when the lubricant was applied to the die walls; particularly when the die was not perfect-i.e., if it was somewhat rough or out of round. In this case, it was almost impossible to get reproducible green densities when the die walls were lubricated, while it was not too difficult to get reproducible

Jan 1, 1946

By Arthur H. Leigh

Anode mud, the residual material collected from the bottom of the electrolytic cells during the refining of copper is leached, roasted, fire-refined and cast into Dore1 metal anodes. Dore1 metal is a gold-silver-copper alloy containing 80 percent silver. The metal is processed electrolytically using the Moebius system to refine silver and separate gold, platinum and palladium. The Moebius cell cathodes receive a deposit of silver crystals which are melted and cast into 1000 ounce silver bars with 999 Fine minimum purity. Gold mud is collected in fabric bags and cast into gold anodes for further refining in the Wohlwill cells. Wohlwill cells are unique in that gold, the noble metal, can be put into solution electrolytically without the use of aqua regia. Gold is collected on high purity gold foil cathodes and cast into 400 ounce bull ion with 999.7 Fine minimum purity. Platinum and palladium remain in the electrolyte progressively increasing in concentration and are finally separated and purified by precipitation.

Jan 1, 1973

By George S. Rice

Instantaneous outbursts of gas in underground workings are similar in effect to great blasts of explosives, but without heat effects. Fortunately they occur only in a few localities in exceptional coal fields of the world and under exceptional geologic conditions. Such violent outbursts should not be compared with the ordinary outflows of gas into coal mines or with explosions of gas and dust. The phenomenon is essentially one of gas held in circumscribed areas under very high pressure and as a mining face or heading approaches such a place and the mining excavation sufficiently weakens the natural surrounding dam or shell, this is burst by the pressure just as by the discharge of a mass of explosives. The outbursts, so far as known to the writer, have been confined to coal beds and have not occurred in other mineral deposits. Hence, as discussed later, he believes that it is the relation of the gases to the coal material that is a factor in conjunction with others in producing conditions which permit the phenomena to occur when mining is done. The gases in most instantaneous outbursts have been hydrocarbon gases but in two coal fields they have been definitely found to be chiefly or wholly carbon dioxide. One of these localities in which CO2 outbursts have been frequent and have caused loss of life is in the southern part of the Gard basin, near Alais, in southern France. In 1919, the writer visited the Fontaine mine in this field the day following the occurrence of an outburst by which two men were smothered by carbon dioxide and fine dust. After 24 hr. the CO2 had not been entirely removed by the ventilating current. Occasional outbursts of CO2 have also occurred in other small basins in France, causing accidents, as in Puy-de-Dome. However, mines in the Gard basin, north of those in which CO2 outbursts have occurred, have experienced hydrocarbon gas outbursts. In the Lower Silesian coal field, Germany, there is a group of mines which have been subject to many instantaneous CO2 outbursts, some causing serious accidents, but the greatest disaster occurred recently

Jan 1, 1931

By Howard N. Eavenson

FROM the Pittsburgh coal bed in the four states of Pennsylvania, Ohio, Maryland and West Virginia has been produced an output that, at mine prices, represents a greater value than any other single mineral deposit in the world has yielded.12 While this distinction may in a few years pass to the gold reef of the Witwatersrand, it is possible that eventually, owing to the tremendous reserves still remaining, the ultimate yield of the Pittsburgh bed will be greater than that of any other known single deposit. Considering its importance, not a great deal has been written of its early history and development as a whole; most of the accounts have been of limited localities, or, at the most, of the area within a single state. In "Coal through the Ages" the writer mentioned some references to its early history, but this study will deal not only with its history but with the character of the bed, where and why it was first developed, and its effect upon the states in which it is found. It has not been the intention to write a detailed history of the development of the seam in each locality, as neither time nor inclination were available for doing such work, but only to show the influences that tended to hasten or retard such development. In general the historical matter ends about 1830, when geological surveys began to be made. Some of the maps show data available only since that time, and the sections about coal preparation and coking have been extended to the present time to show the changing conditions. It is believed that the early history includes all published records, and many more sources than those shown in the bibliography were consulted. It is quite likely that some references to coal in this area may be found in the unpublished papers of some of our early soldiers and colonizers, which exist in several libraries, and it is hoped that some future

Jan 1, 1938

By W. A. Tiller, W. C. Johnston

A high-temperature electromagnetic stirrer is described in which heating and stirring are accomplished by independently controlled power sources. The appavatus is suitable lor use at temperatures up to 1700°C in a variety of ambient atmospheres. Some typical examples of the homogenizatimz capabilities of the system are given. THERE are few processes in solidification that are not markedly affected by motion in the melt during freezing. In many instances, the mechanisms are diffusion-controlled, and the transport in the melt may be greatly accelerated by deliberately stirring the melt. In zone-refining, stirring1 assists the removal of rejected impurities from the interface, so the process proceeds at a faster rate. The transition from a planar to a cellular interface is caused by constitutional undercooling in the melt ahead of the interface: and stirring delays its onset. Stirring is valuable for homogenization of melts: and chemical reaction with sluggish kinetics may be accelerated. Finally, it has been observed that grain refinement is related to motion in the melt. Fine grain castings are usually produced by the addition of catalysts to the -melt,' catalysts which are thought to act simply as hetereogeneous nucleation centers. Even here motion is important. Richards and Rostoker 5 applied ultrasonic vibration to a solidifying A1-Cu alloy which had been innoculated with a catalyst and found that the grain diameter fell linearly with the amplitude, the peak acceleration and the power input to the melt from the transducer. Finally, mechanical and electrical stirring alone have been used to generate a fine-grained structure.6,7 Johnston ef a1.' have carried out a series of systematic investigations of grain refinement by electromagnetic stirring in a number of low melting point alloys. They found, for example, that the number of grains per unit volume in Pb-Sn alloys could be increased several orders of magnitude by stirring an undercooled melt at the moment of recalescence. In general, a relation AT .H = constant prevailed for a given grain size, where AT was the undercooling of the melt and H the field strength. In more recent work, deliberate homogeneous nucleation of slightly undercooled melts established that the mechanism of refinement must be one involving crystal fragmentation and subsequent multiplication, rather than a "shower" of nuclei effect.9 It is the purpose of this note to describe a stirring device suitable for use up to 1700°C. At low temperatures mechanical stirring and direct-current methods are feasible, but at high temperatures the problem of a protective atmosphere and of electrode corrosion rules out such procedures. The most convenient method for high temperatures is to use externally generated ac fields for both stirring and heating. With rf induction heating alone, considerable stirring and agitation can be achieved, but in general the penetration of field into the melt is small, and the stirring cannot be controlled independently of the heating. In the present experiments, separate power sources of different frequencies for heating and for stirring were used. A susceptor design was chosen so that the 450 kc rf heating field was completely absorbed in the susceptor. The stirring frequency, 400 cps, hereafter called the af field, was chosen so that a high penetration of the melt proper was achieved. EXPERIMENTAL APPARATUS The apparatus, Fig. 1, consists of a quartz tube and end plates, surrounded by an rf induction coil and six equally spaced af stirring coils, four of which are shown in full and a fifth in section. Each af stirring coil is a transformer of which the secondary is a single-turn water-cooled copper loop and the primary is composed of two 10 amp-117 v Variac cores as shown. These cores are cooled by forced air, as each of the six pairs will carry maximum currents of 15 amp for short periods. Each set of Variac windings are connected in series, but opposite sets are connected in parallel with a three-phase 400 cps 400-v source. By properly phasing the coils in this way, a rotating field is produced. Capacitors C1, C2, and C3 in Fig. 2 are used to match this inductive load to the generator. Fig. 3 shows a cutaway view of the quartz tube. The sample (1 in. diam by 1 in. high) is placed in a tapered alumina crucible. An axial W-26 pct Re thermocouple, enclosed by a protection tube, is provided. The cruci-

Jan 1, 1968

By W. O. Philbrook, L. D. Kirkbride

IN the normal operation of the iron blast furnace, reduction of the iron oxides is accomplished almost entirely above the tuyeres.' Blast furnace slags usually contain less than 0.5 pct FeO, although higher values may occur with abnormal operation. There is reason to conjecture, however, that incompletely reduced ore may sometimes reach the hearth and enter the slag as a result of heavy slips or, perhaps, even from cores of excessively large lumps of a charge material of poor reducibility. The possibility of reoxidation of iron droplets falling in front of the tuyeres has been considered by several writers. It would be of interest, to know how rapidly iron oxides reaching the slag for any of these reasons could be reduced by reaction with coke or with the high carbon liquid iron in the hearth. In comparison with the hundreds of papers that have appeared on various aspects of the reduction of solid iron oxides by gases and in the presence of several forms of carbon, little work has been published on the reductioin of liquid oxides or slags. Dancey measured rates of reaction of the pure liquid oxides, both FeO and Fe,O,, with molten iron containing about 4.3 pct C. The oxide was dropped into the cup formed in the upper surface of the iron by rotating the crucible and melt. Under these conditions, reduction of either FeO or Fe,O., was completed in less than 10 sec. The present study was concerned with the reduction of FeO from blast furnace-type slags containing less than 5 pct FeO and melted over carbon-saturated iron in stationary graphite crucibles. The results were considerably different from those found by Dancey, as will be discussed later. Although this work is of interest in relation to hearth reactions in the blast furnace, interpretations must be made with caution because the experimental conditions do not duplicate those within a furnace and may not even lead to the same reaction mechanism. The authors were motivated in undertaking this work by an additional interest—the part played by FeO reduction in the mechanism of de-sulphurization of iron by slags under similar experimental conditions. Derge, Philbrook, and Goldman eveloped detailed experimental evidence to support a three-step mechanism for desulphurization like that originally proposed by Holbrook and Joseph' (These reactions are written in molecular form for convenience, but this is not intended to imply the existence of molecules of FeS in the bulk metal phase nor to deny the likelihood of ionic reactions in the slag.) Earlier work by Chang and Goldman" had shown that the overall reaction follows first-order kinetics with respect to sulphur and that the rate of reaction is proportional to the slag-metal interface area, which observations have been confirmed by subsequent work. Later studiese,' have established the influence of al.loying elements on the first and last steps of the reaction. This paper reports a study of step 3 alone, uncomplicated by the simultaneous process of sulphur transfer. Apparatus and Procedure The experiments were made in a conventional high frequency induction furnace powered by a 35 kva Hg spark gap converter. The graphite crucibles used for most of the runs were 14 cm (5.5 in.) deep and 4.8 cm (1.9 in.) ID with 0.75 cm (0.3 in.) wall. An insulating cover with a small opening for withdrawing samples was used to minimize heat loss and infiltration of air into the furnace. The crucible was charged with 300 g of carbon-saturated iron and either 65 or 100 g of prefused slag analyzing 38.0 pct SiO,, 15.4 pct A10 and 47.1 pct CaO. To obtain the cleanest possible interface at the start of the reaction, the metal and slag were brought to temperature together to prevent the rejection of kish graphite that would have been caused by the chilling effect of a large addition of cold slag to carbon-saturated iron. After temperature control had been established, the desired amount of iron oxide was added in the form of a prefused slag of composition 73.6 pct FeO, 7.7 pct AWX and 19.0 pct SiOl. This slag addition was observed to be molten in somewhat less than 1 min, and a very vigorous reaction proceeded for 1 to 2 min after its introduction. Zero time was taken as 2 min after the ferrous silicate slag addition. Slag samples weighing about 0.5 g each were taken periodically by a copper chill sampler." The weight of the initial slag was large relative to the weight of samples removed, so that the slag weight never varied by more than 5 pct during any run. Temperature was measured by a calibrated W/Mo thermocouple immersed in the metal, with a graphite tip cemented over the fused silica protection tube to prevent attack by slag and metal. After some difficulties with uncertain temperatures during the first two runs, the practice adopted to position the thermocouple for reproducible results was to lower the protection tube to touch the bottom of the crucible and then raise it 0.5 cm. The apparent temperature gradient between the bottom of the crucible and the top of the slag was found to be 15°C (27°F). but much of this spread was probably the result of inadequate immersion of the protection tube to off-set conduction losses along the graphite tip when the thermocouple was inserted only into the slag. The temperature of the bath was controlled within 25°C (9°F) during a run.

Jan 1, 1957

By Karl S. Kurtenacker

In attempting to find a rapid and economical means for solving many of the subsurface problems that confront the highway engineer, the author for the past two years has utilized a Megger Ground Tester on resistivity surveys in conjunction with highway construction. Electrical surveys in connection with highway work are largely shallow depth surveys, thus differing from most other types of resistivity work. Consequently, the readings are affected by a great many qualifying factors such as the density and moisture content of the media under observation and the amount of weathering and leaching. In most cases the surface layer is decidedly heterogeneous in character, and, because of the great number of side hill cuts, the second layer, which in most cases is rock overlain by some sort of surface soil, silt, or debris, seldom lies in a horizontal position. Shallow strata, lacking homogeneity and not lying in a horizontal position, do not lend themselves readily to accurate theoretical interpretations, therefore the author has used empirical rules to a large extent in interpreting depth soundings. The following empirical rules of interpretation are surprisingly adequate for highway work, since much of the work is in the nature of reconnaissance surveying and the results are construed to be approximations. The writer is careful not to risk interpretation on some special feature of the curve, since such features are usually due to random errors or lack of homogeneity among the subsurface strata. Effect of Surface Medium A resistivity depth sounding taken to a depth of 200 or 300 ft. is not much affected by superficial conditions, but these conditions have a great effect in depth soundings to 25 or 30 ft. In shallow soundings the character of the surface medium has a very marked effect on the entire resistivity graph. Fig. 1 illustrates a very striking example. Graphs A and B are depth soundings taken in approximately the same place. The surface stratum is a clay loam but at the place where graph B was taken

Jan 1, 1934

By D. M. Kehn

A method has been devloped for chromatographic analysis Of the vapor and liquid phases Of a a system containing methane to components having 20 or more carbon atoms. The method uses a windowed equilibrium cell in which volumetric phase behavior of the system can be observed accurately and from which small samples of gas or liquid can be withdrawn for analysis. Analyses are made using two chromatographs, one for the lighter and one for the heavier components in a sample. Combination of the two analyses yields a detailed analysis of the gas or liquid sample. The complexity of the condensate heavy ends is evident from the chromatograms of these fractions, and the predominance of the paraffin hydrocarborn serves as a useful marker in interpreting the chromatograms. The K-values obtained in this analytical method are presented for a high-pressure condensate system and predict closely the observed volumetric behavior of the system. INTRODUCTION Quantitative analysis of hydrocarbons from natural gas reservoirs is necessary for several reasons—to calculate the amount of sales gas produced, to calculate the amount of natural gasoline produced, to plan a liquid recovery system, or to calculate the potential economic value of a reservoir produced under one or more of several different conditions. Analysis of natural gas fluids produced to the surface consists of identifying and computing the mol fraction of each component of the mixture. Although methane is the predominant component, varying amounts of ethane, propane, butane, pentanes and heavier components are also present. Materials containing up to 30 carbon atoms occur in amounts which decrease with increasing molecular weight. However, the quantities of components in the 20 to 30 carbon atom range are usually so small that their importance is negligible, and they are undetect-able in natural gas by ordinary analytical methods. All the components up to those having 20 carbon atoms may sigsficantly affect phase behavior, however. Commonly, only the methane-through-pentane fraction is analyzed quantitatively for each component, while components heavier than Pentane are lumped and repored as "hexane- plus". Expensive, tedious techniques are required for analysis of this fraction. Consequently the detailed analyses needed for prediction of reservoir behavior are usually undertaken only when major gas fields are being developed. The need for complete analyses of condensate systems is apparent when it is recalled that most gas fields are produced by pressure depletion. As the pressure declines, some of the heavier hydrocarbons are lost as liquids which are in the reservoir. In many instances the amount of liquid in equilibrium with the gas phase at high pressure constitutes only 1 or 2 mol per cent of the total system. Flash calculations generally must predict the actual amount of liquid with an accuracy of a few per cent in order to be useful. This retrograde condensation has been understood for years, but accurate correlation methods to permit quantitative prediction of phase behavior in the retrograde region are not presently available. The increasing importance of natural gas has made accurate prediction of phase behavior and composition of produced natural gas streams an economic necessity. The work reported here was undertaken to provide a rapid, economical method for obtaining the vapor-liquid equilibrium information needed to predict accurately the composition of the fluids produced from a gas reservoir throughout its life. TO develop this method, a pressure cell equipped with windows was designed and built for observing the volumes of liquid and gas present at reservoir pressures and temperatures. Use was made of established chromatographic methods for rapid and detailed analysis of both phases. This paper describes the equipment and techniques developed for obtaining vapor-liquid equilibrium data, presents the results of analyses of a condensate system, and indicates the usefulness of these data in predicting hydrocarbon phase behavior. DESCRIPTION OF EQUIPMENT USED The equipment used in obtaining the required information on phase behavior and the complete analysis of hydrocarbon mixtures through C, will be described first, followed by a discussion of the operation of the equipment. It will be helpful, however, to consider first a brief outline of the technique used. A sample of separator gas and liquid is charged to the windowed cell (see Figs. 1 and 2) where volumetric equilibrium phase behavior at reservoir pressures and temperatures can be determined. Then samples of the coexisting phases are withdrawn. The methane-through-pentane fraction is analyzed with a chromatograph equipped with a hot-wire detector, and the pentane-plus fraction is analyzed with a second chromatograph equipped

Jan 1, 1965

By W. Chubb

By measuring the hardness of metals at temperatures just above and just below their allotropic change point, it has been established that crystal structure has a real effect upon the strength of metals. The DPH of cobalt, iron, titanium, uranium, and zirconium have been measured at temperatures up to 1000°C. It was found that the body-centered-cubic crystal structure is always the softer structure when it is involved in an allotropic transformation. The close-packed and more complex structures are inherently harder, and may be expected, therefore, to be better base materials for high strength alloys. IT has been observed that for metals with nearly the same melting point (i.e., tin and lead, magnesium and aluminum) the metal with the more complex crystal structure has a higher tensile strength and hardness. It might be asked whether this effect is really caused by the difference in crystal structure; and, if so, just what is the contribution of crystal structure to the strength of these metals. A qualitative answer to these questions can be obtained by measuring the change in hardness produced by the change in structure in metals exhibiting allotropic forms. The evidence for changes in mechanical properties during allotropic transformations is rather meager. In 1909, Rosenhain and Humfrey' observed that "ß" iron showed much less deformation at the transformation temperature than a iron. By means of a torsion test, Lee found that iron bars were "critically plastic" at the a-7 transformation temperature. Sauerwald and Knehans have shown that the dynamic hardness of iron increases between 900" and 1000°C. In 1930, Albert Sauveur' presented data on the hardness, tensile strength, and torsional strength of pui-e iron up to 1000°C. He concluded, "At 900°C, the a iron transforms into y iron, and this is accompanied by increased strength and stiffness and decreased ductility." The same year, Schischokin" obtained data on the hardness of thallium at temperatures above and below its transformation temperature. His data are replotted on semilogarithmic coordinates as Fig. 1. The fact that his data fall on straight lines in this type of plot is believed to attest to the purity of his metal and the accuracy of his results. In 1941, Nadai and Manjoine" obtained tensile data on pure iron with an indicated increase in strength at about 900°C. These experiments make it quite evident that changes in mechanical properties occur when a metal transforms from one crystal structure to another; but, except for Schischokin's data on thallium, none of the measurements seem accurate enough to determine the relative magnitude of the mechanical property change. Materials The metals that have been examined for changes in hardness during transformation include l—as- deposited commercial electrolytic cobalt about 99.7 pct pure, 2—Armco ingot iron, 3—are-melted iodide titanium of a purity in excess of 99.8 pct, 4—uranium of a purity in excess of 99.5 pct, 5—are-melted iodide zirconium of a purity in excess of 99.8 pct, 6—annealed, 0.08 pct C, rimmed steel, and 7—commercially pure RC55 titanium. While the purity of the first five of these materials leaves something to be desired, it will be noted that the observed hardness discontinuities occurred at the accepted transformation temperatures. (These temperatures are indicated by vertical arrows in Figs. 1 and 3 through 7.) The last two materials are commercial alloys introduced to show the effect of minor alloying elements upon the hot hardness curve. Apparatus Hardnesses at elevated temperatures were determined by means of a vacuum hot hardness machine. A diagram showing the basic features of this machine appears as Fig. 2. This machine is essentially a deadweight hardness .machine in a furnace within a vacuum chamber. The sapphire-tipped indentor

Jan 1, 1956

By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956

By L. Dr. Edeleanu

CRUDE petroleum is a mixture of various groups of hydrocarbons and some bodies containing oxygen or sulphur. These constituents possess properties differing considerably one from another and the proportion in which they are contained in the crude oils is also very different. Owing to this complicated composition the practical use of crude petroleum is much restricted. For example it is sometimes used as a liquid fuel. But its employment in this way is uneconomical because various valuable qualities of the individual constituents are not made use of. The rational utilization of petroleum can only be accomplished if the various groups of hydrocarbons are separated. The mixture of hydro-carbons present in the crude oil must be split up in such a way that the hydrocarbons are divided into various groups having certain predominant characteristics and uses. To accomplish such a separation is the aim of the technical refining of petroleum. ORDINARY REFINING BY DISTILLATION AND CHEMICAL TREATMENT Hitherto this has been accomplished by two processes, namely, fractional distillation and chemical treatment of the distillates obtained. Distillation Process The process of distillation consists in the separation of the constituents of petroleum into various fractions, the boiling points of which lie within certain defined limits. The fractions so separated possess certain special qualities in common, which enable them to be applied for specific purposes in practice. For example, we have the fractions known as benzene, illuminating oils, heavy oils, lubricating oils, etc.

Jan 9, 1914

By M. C. Chang, J. Dasher

The Crucible mine in Pennsylvania, operating on Pittsburgh seam coal, is rated at 5000 tpd. The washing plant, built in 1943, is rated at about 400 tph, using hydroseparator boxes to wash the coarse coal (4 x 5/16 in.) and hydrotator units for the fine coal (5/16 x 0). It is generally acknowledged that gravity concentration equipment cannot be used efficiently to bene-ficiate coal finer than about 65 mesh. Before the present flotation circuit was installed, Crucible recovered its fine coal slurry, predominantly —24 mesh material, by passing it through a battery of five 14-in. and one hundred and ten 3-in. Hey1 & Patterson cyclones in parallel with a 75-ft Dorr thickener. About two thirds went to the cyclones and one third to the thickener. Underflows from cyclones and thickener were filtered, respectively, in one 12-disk Eimco and two 4-disk Oliver filters fitted with stainless steel cloth. The resulting cakes were added to the coarse metallurgical coal. The filtrates, overflow from the 3-in. cyclones, and thickener overflow were recycled to the coarse coal plant. The three major problems encountered in this system became acute when the mine switched from track-mounted machinery to the more economical off-track equipment. The quality and uniformity of product declined, too much slime accumulated in the circuit, and waste pond disposal became highly impracticable. Lowering of Quality and Uniformity: Since the filter cake was not beneficiated in any way, addition of this material, which contained about 18 pct ash. would certainly lower the quality of metallurgical coal. Difficulties of handling the high-ash, high-moisture cake were compounded by the lack of adequate blending facilities at the mine, making it impossible to maintain uniform feed for the coke ovens. For a two-month test period, to verify the source of trouble, all filter cake was excluded from the metallurgical coal. The excluded filter cake was stocked in the yard. Slime Buildup: The moisture retained in the coarse coal products and the filter cake provided daily the only means of slime bleed from the circuit. As this bleed was not enough to offset the incoming fines in the raw coal feed, there was excessive buildup of slimes. To operate at all, it was necessary to purge the system each weekend by pumping all the solids from the thickener to a waste pond. The slimes built up during the week progressively increased the apparent viscosity and density of the circulating plant water, so that hydroseparators and hydrotator units had to be constantly adjusted. Uniformity, yield, and quality of the metallurgical coal suffered in consequence, and the filter cake ash and moisture contents increased from Monday to Friday. Limited Waste Disposal: Location of the plant does not permit unlimited waste pond area. Maintenance of a waste pond for the purpose of emptying the thickener during weekends became a costly burden that could not be tolerated. HOW THE PROBLEMS WERE SOLVED The flowsheet (Fig. 1) chosen to overcome these difficulties is considered the one most economical to install and operate. In a preliminary change made before the flotation circuit was installed, the cyclones and thickener were first operated in series, the overflow from the 3-in. cyclones, after flocculation, being discharged into the thickener and the thick-

Jan 1, 1960

By T. M. Geffen, R. E. Gladfelter

Lipson1 has recently presented a technical note wherein theoretical considerations were used to demonstrate. that the adsorption us saturation relation for a linear absorption method is not necessarily a single valued function of saturation.1 It was concluded that the absorption us saturation relationship is subject to the same hysteretic effect as is the flow behavior between the drainage and imbibition systems. It is the purpose of this note to show, by experimental results, that for the manner in which fluids are distributed in porous materials during fluid flow, the relative X-ray absorption us saturation relationship is single-valued regardless of the saturation history. The design of the apparatus used to measure relative X-ray absorption of cores undergoing fluid flow tests is similar to that described by Morgan, McDowell and Doty. A few modifications have been incorporated in the design to increase sensitivity and simplicity of measurement. The sensitivity is such that for usual types of cores a recording pen movement of approximately 12 linear in. is occasioned between the recording of the core dry and when it is completely full of an absorbing liquid, a solution of approximately five per cent by volume of iodo-benzene in a close-cut hydrocarbon fraction, or a solution of 50,000 ppm sodium iodide in water. Two types of experiments were conducted, one in which the liquid was inside the core, and the other with the liquid outside the core. Tests with the liquid inside the core were run to cover the saturation range encountered in both the drainage (gas drive) and imbibition (liquid flood) flow systems. It is pointed out that the same core was used, but the tests were conducted at different times with the recording mechanism balanced at a different position. Therefore, the absolute values of relative X-ray intensity at any saturation are not the same in each test. In the second type of test the same core was used, but this time its pore space cmtained only gas, and various thicknesses of oil contained in plastic cells were placed in front of the dry core. As before. the relative X-ray ah- sorption was measured and compared to the quantity of oil in front of the core. The arrangement of the fluids with respect to the path of X-rays in these two types of tests represent fluid distributions of a wider difference than can be expected between that established in a core just due to imbibition and drainage saturation flow histories. Thus any deviation from a straight line relationship of the log of the relative X-ray intensity us saturation calibration should be readily apparent. Results of the laboratory tests are given in Fig. 1. A schematic diagram showing the position of the fluids with respect to the path of the X-ray beam is given for the two cases investigated. In the case where the oil existed outside the core (Case B), the log of the X-ray intensity (log, I/I,) is related directly to the cell thickness (amount of oil in X-ray beam path). This correlation is in full agreement with X-ray theory. In the case where the oil or water existed inside the core (Case A) which covers both drainage and imbibition types of flow processes, again the relationship between absorption and saturation (amount of oil in X-ray beam path

Jan 1, 1952