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By Richard W. Lodge

In the crucible-method of assaying ores for silver a certain amount of litharge is essential to supply sufficient lead to collect the precious metals. The object of this paper is to point out that the use of a large excess of' litharge in the assay of some ores will give results for silver that are uneven as well as low. So far as I know, however, an excess of litharge does not affect the results obtained in the crucible-assay of ores for gold. The main reasons for using, in the crucible-assay, much more litharge than is required to givc the necessary lead button are: 1, its action as a flux; 2, its action as a desulphur-izer; and 3, its action as an oxidizer, especially on metals like copper and nickel, whereby they are forced into the slag as oxides and thus prevented from passing into the lead button. Hence, by the use of much litharge in the crucible-assay more ore call often be taken than in the scorification-process, and a lead button obtained which call possibly be cupelled at once or after a single scorification. The method is specially advantageous with an ore carrying much copper or similar impurity and poor in silver, when the assayer does not wish to resort to a wet-analysis for the determination of the silver. It is well known that some ores give better results when assayed by the scorification-method, while others give better results by the crucible-method. For several years I have noticed that, when much litharge was used with certain sulphide and arsenical ores, the results were considerably lower than when the scarification-method was used. This fact was more forcibly brought out in connection with certain work carried on this year by Messrs. H. A. Frame and

Jan 1, 1908

E. R. Buckley, Flat River, Mo. (communication to the Secretary*) :—Some statements in the paper of Mr. Keyes relative to the nature and formation of the Ozark lead- and zinc-deposits seen1 to me erroneous and misleading, and I respectfully present the following criticisms, placing Mr. Keyes's original statements in quotations. Referring to the Ozark dome: (p. 192.) "It is a region that has been repeatedly upraised and planed off, until in the middle portion the oldest known rocks only are exposed." Does he mean that the St. Francois mountains, which have always been considered as lying on the eastern flank of the Ozark dome, are the middle of the dome ? Or does he mean that the Cambrian rocks of the generally-accepted middle are the oldest known rocks ? Certainly not the latter, and if the former, his idea of the middle of the dome is not in accord with that of others who are familiar with the region. (p. 203.) "... the ore-deposits are definitely associated with, or localized by, geologic structures of some kind that produce in effect basins in which the underground waters are impounded, or their flow retarded." This statement does not appear to be altogether consistent with the facts, since the ore bodies of the Joplin district, as the rule, occur in those parts of the Mississippian formation which have a tendency to accel erate the flow of ground-water rather than retard it. I migh name the open, brecciated ground near Joplin, Webb City, and Oronogo as especially noteworthy illustrations. The ore-bodies, everywhere, occur in positions where there must have been a free and copious circulation of dilute lead- and zinc-solutions in the presence of reducing constituents. The inequalities in the distribution of the ore-deposits are

Jan 1, 1910

By A. J. Weinig

The Liberty Bell cyanide precipitate is unique in that it is apt to vary widely in composition in the course of very short periods of time, and a method of refining and melting that would prove highly satisfactory at one cleanup would yield7almost a hopeless "mess" at a second. Table I gives a general conception of the wide range in grade and composition of those raw precipitates. It is evident that no one standard flux could be expected to produce a high-grade bullion with such a widely variable precipitate, and that any method of treatment with acid requires most careful consideration. Refining by Acids Naturally, our first efforts to improve our precipitates were directed along the lines of acid treatment. Table II embodies the results of careful sampling and analysis of one cleanup at the time when wet refining reached its maximum development at this mill. We have now discarded all methods of wet refining, successfully replacing them by a more scientific method of flux calculation described herein, but it is believed that a general description of this wet refining is warranted as it throws some interesting side lights on acid refining in general. Table I.—Range of Composition of Raw Precipitates Per Cent. Gold and silver.................................... 25.0 to 75 Zinc.............................................. 18.0to 30 Lead............................................. 0.5 to 52 Copper........................................... 0.5 to 20 Silica............................................ 1.0 to 5 Calcium oxide...................................... 4.0 to 8 Sulphur.......................................... 0.5 to 8 Column A gives the analysis of the raw precipitate; column B, that of the precipitate after heating with steam, with frequent addition of hydrochloric acid until a point was reached where the batch had a strong tend-

Jan 1, 1917

By W. S. Gresley

The traces of fossils herein described were discovered in or upon piles or heaps of iron-ores upon the docks at Erie, Pa. The author has worked among these ore-piles since 1890, when his attention was first directed to what looked like organic remains upon certain specimens collected. All the specimens described and figured herein were found by him, and, as no ironore is used at Erie, and no other iron-ores, save those of the Lake Superior region, find their way to the stock-piles at this place, there can be no question but that the specimens in question are genuine ore transported from that region over the great lakes, and cannot have been brought in from other ironore regions. The author has reason to think that no fossil remains have been reported hitherto as occurring in the iron-ores of the Lake Superior region, and he believes that these specimens, however imperfect, rank among the oldest forms of which man has any knowledge. The illustrations are engraved from photographs of drawings. The specimens themselves have not been photographed, because their condition would have prevented bringing out, by that process of reproduction, all the markings as clearly as is necessary, and would have rendered the specimens otherwise less distinct by reason of the blotchy character of their colors, the presence of cracks, or of marks more or less in contact with those of the organisms. In drawing these remains, therefore, I left out everything upon the specimens of ore that did not seem to belong in any way or contribute to their value as illustrations of the fossils. According to information obtained from the dock superintendent at Erie, Pa., the majority of these specimens came from the Chapin mine, Iron Mountain, Menominee range, Mich. As to the rest of them, I stupidly failed

Jan 1, 1897

Discussion of the paper of ALBERT SAUVEUR, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 93, September, 1914, pp. 2439 to 2449 G. K. BURGESS, Washington, D. C.-This very instructive contribution by Professor Sauveur to our knowledge of that puzzling substance, Hadfield's manganese steel, should not only be read in connection with the paper of Messrs. Hopkinson and Hadfield referred to by Professor Sauveur (Bulletin No. 87, pp. 513 to 530, March, 1914); but one should also have in mind, as throwing much additional light upon the questions raised, two papers recently presented before the Iron and Steel Institute, the one by Sir Robert Hadfield (Journal of the Iron and Steel Institute No. II, 1913) on Heating and Cooling Curves of Manganese Steel, the other by Messrs. Hadfield and Hopkinson (ibid., No. I, 1914) treating of the Magnetic and Mechanical Properties of Manganese Steel. We then have brought together for this substance, the thermal, magnetic, and mechanical properties as well as the resulting microstructure, for the definite heat treatments described, and in particular after long annealing between 500° and 700° C. Sir Robert Hadfield and Professor Hopkinson see in the properties found for manganese steel (of C = 1.25 and Mn = 12.5 per cent.) a demonstration of the untenableness of the allotropic theory of iron, whereas Professor Sauveur reaches the contrary conclusion, that some of the facts observed can be explained only in terms of the existence of beta iron in steel of this composition. There is another possible hypothesis: namely, that these several series of experiments shed no light on the subject of the allotropy of iron, or at least as regards the existence of beta iron. However heretical it may sound, I am inclined to this last belief.

Jan 4, 1915

By William Metcalf

One of the first questions that naturally occurs to one who handles steel is, " Why does steel harden?" To answer this question the chemist and physicist have devoted much thought and experiment, and while they have enriched our store of knowledge of the nature and composition of steel, it cannot be said that they have yet solved the problem involved in its hardening. In this communication I desire to direct attention to a line of investigation yet new, in the hope that it may receive the attention. of those who have the time and ability to pursue it. I refer to magnetism. There are so many parallels between the action of magnetism on iron and steel and their behavior under different processes of manipulation that it would seem. as if there must be some connection between tile forces at work in the different cases, if, indeed, there be not an identify of force in all of these cases. Magnetism, as me know it, may be merely the visible manifestation of forces, which may serve as a guide to lead us to an exact knowledge of the structure, tile strains, and the resistances with which me have to deal in iron and steel. If a magnet be brought close to a pile of iron filings, the little pieces of iron will fly to the maguet and attach themselves to it, with their longer axes lying in the direction of the force. If molten cast iron be poured into an iron mould,—a chill,—the iron upon crystallizing will form needlelike crystals, with their long axes normal to the surfaces of the mould. • If the iron is at the proper temperatare and the quantity small, compared to the mass of the mould, the whole of it, will be chilled, or set, in 'the hard needlelike crystals

Jan 1, 1881

By Murray F. Hawkins

One problem of reservoir engineering is the early estimation of the size of newly discovered reservoirs. Often these reservoirs are the expansion type in which sizeable pressure drops occur incident to the production of small fractions of the oil reserve, above the bubble point, and a material balance equation may be solved to find the reserve. The early form of this equation' considered only the compressibility of the oil. Later Hall2 showed that the compressible nature of the formation rock is a significant factor in production above the bubble point, and he presented a new equation which includes a formation (rock) compressibility term. This note presents a further extension of the material balance equation as applied to volumetric, unsat-urated reservoirs above the bubble point by including a term for the presence and compressible nature of the interstitial water. DERIVATION OF EQUATION During a decline in average reservoir pressure, ?p ?p, — p1 the initial reservoir volume V,, will decrease to some value V, due to the reduction in pore volume as a result of a decline in the hydrostatic pressure within the formation, and v, = V,, [l — cr ?p]......(1) The formation compressibility c, is expressed in terms of change in pore volume per unit pore volume per psi. Simultaneously the connate water within the formation expands from an original volume V,, = S,V,, to a new volume V,, V, = s,v,, [I + c,npl.....(2) The difference [Vp — V,] is the hydrocarbon pore volume at pressure p and may be equated to the volume of the remaining oil, or [N — N,] B, = V,,, [I - C~A;] - S,.Vpi [l + cwnjl.........(3) But the initial oil in place in terms of the initial reservoir volume, connate water, and formation volume factor is Ilividing Equation 3 by Equation 4 eliminates V,, to give,

Jan 1, 1956

By F. F. Aplan

INTRODUCTION The production of coal is a major part of the mining industry. In recent years the production of clean coal has exceeded 600 million tons per year and is reported to have reached 660 million tons in 1977. Some data on the magnitude and utilization for the year 1975 is given in Table I. In that year 648 million tons of soft coal were produced and of this 267 million tons or 41% approximately was produced by mechanical cleaning. Of the 374 million tons of raw coal sent to the preparation plant, 28.6% or 107 million tons was discarded as refuse. In the same year approximately 6 million tons of anthracite were produced and nearly all of this was cleaned. Table I also gives coal utilization statistics for 1975. Excluding the approximately 20% that goes to the coke ovens or to export, the vast bulk of our production is used for steam power generation and a lesser amount for captive production of industrial power and process steam. While much of the nation's coal (e.g. strip mined western, sub-bituminous coal) may be removed from the ground in relatively pure form by modest selective mining techniques, other coal requires preparation in order to remove ash and sulfur constituents and produce an acceptable steam or coking coal. Preparation is often a valuable adjunct to mining in that rather non-selective, low cost, bulk mining techniques may be used underground while the preparation plant is used to reject refuse at low cost above ground. The principal reason for the use of coal preparation is to convert raw coal into an acceptable commercial product by removing the high ash and high sulfur refuse material.

Jan 1, 1979

By F. Julius Fohs

Centrally located with relation to the largest iron- and steel-producing districts of the United States, the fluorspar-deposits of Kentucky possess increasing interest and importance. As typical of the numerous fluorspar-mines of Kentucky and Illinois, I have selected for description the Memphis, because it and others of its immediate group exhibit the conditions characteristic of all. I. The Memphis MiNe. This mine lies 5 miles NW. of Marion, in Crittenden county, Kentucky, a station on the Chicago and Nashville division of .the Illinois Central R. R. For the first mile and a half out of Marion we see only Birdsville or Middle Chester sandstones of Mississippian age. Then we cross a fault of about 850 ft. displacement, and the Ste. Genevieve oolite sets in. Beyond the fault, oolite is the predominant rock, except that the hills to the north have a capping of Cypress or lowest Chester sandstone, 80 ft. below which is an outcrop of from 6 to 10 ft. of Ste. Genevieve (Rosiclare) sandstone. Occasional sink-holes are noticed, and as the mines are approached evidence of faulting is again seen. A line of .crude head-frames and open-cut dumps, extending for more than a quarter of a mile, marks the Klondike vein. The open-cuts are from 15 to 20 ft. deep, and in most of them, from the surface down, was found the reddish gravel which is really fluorspar—some of it white or purple and crystal-clear (if the red clay is washed off), and some carrying iron and silica, and stained by waters from the decaying limestone walls. In one of these cuts, at a depth of 20 ft., white and purplish honey-combed fluorspar was found, in which the larger cavities are due to the leaching of limestone and calcite, and the minute ones to the leaching of zinc-hlende.

Jan 1, 1910

By Morris Cohen, William P. Kimball

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expressioll for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: , = Zlxl{xl - P) + ZsXsiP - xs) [I] Zl(xl -P)+ Zs{P - xs) where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, xl and xs are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The d equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid-to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling. the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

Discussion of the paper of C. A. HEBERLEIN, presented at the New York meeting. February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 497 to 504. H. D. PALLISTER, State College, Pa. (communication to the Secretary).-Mr. Heberlein gives some valuable information concerning a branch of mining and metallurgy which has been neglected during the last few years. His results with fine grinding and Deister tables suggest the possibility of the mining and concentration of a number of low-grade cinnabar deposits. Can Mr. Heberlein give us some idea as to the loss of quicksilver during this concentration? The advances in the metallurgy of quicksilver have been few and far between in recent years. Most miners prefer to go on in the old way with the Scott furnace and the large brick condensers. The large brick condensers are expensive to build and to keep in repair, and on account of the thick walls are extremely slow in cooling the gases; and further, the joints between the bricks offer passages for the quicksilver vapors unless great care is used in building the condensers.. The escape of vapor at the top of the furnace is another source of loss and I see the people at the Oceanic mine have overcome this in a very ingenious way. I recently returned from the Terlingua quicksilver district of Texas, where the only operating company, the Chisos Mining Co., is operating a 20-ton furnace of the Scott type. They had considerable difficulty with getting a good extraction, clue to too high heating in the furnace with its .resulting diffIculties. Recently they have been running with ashpit and fire doors closed and have been able to keep the heat lower, thus getting much better results and practically verifying the results obtained at the Oceanic mine.

Jan 5, 1915

By William P. Kimball, Morris Cohen

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expressioll for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: , = Zlxl{xl - P) + ZsXsiP - xs) [I] Zl(xl -P)+ Zs{P - xs) where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, xl and xs are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The d equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid-to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling. the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

NOW continuing with the preparation of the moulds I say that it is necessary to give the greatest attention to the differences of the clays as well as to the differences of those things that you wish to mould; and to know that every concavity in the mould produces a convexity and every convexity a hollow following the shape of the original pattern that you have. The pattern should be a body of a harder mated than the thing [78] you wish to mould with and of a substance that is not swollen or disintegrated by moisture. Its archetype may be of marble, bronze, lead, or any other metal, or also of wood, wax, tallow, gypsum, sulphur, or other plaster compositions-in short, of whatever you may have or whatever succeeds best for you, depending on whether the works are large or small and easy or &cult to mould. If you wish to cast them in bronze, you must mould them with loam, covering them with it and then drying it. There are some things in which it is enough to form only one part, such as half- or bas-reliefs. These are easy if they have no undercuts. Some other patterns that are easily handled are formed in two halves, or in three or four pieces, if they are of a hard material. There are also moulds for large statues, which, if one desires to make them of bronze, are first made of wax according to the ordinary procedure. I have in mind to describe every one of these processes in their own place. There are like- wise some moulds that are difficult to make, like scenes on a plane to which figures in full relief are attached, or twisted ornaments or other detached things that cannot be withdrawn from the mould without break-

Jan 1, 1942

By F. L. Grammer

The analyses given in Table I. were made several years ago at my request at a plant using Lake ores. They are of two furnaces, one making basic, the other Bessemer pig— they gave 6 casts each in 24 hr., also two flushes of cinder between each cast. They are offered simply for the sake of reference as, so far as I know, it is unusual to find so frequent full analyses made and none are on record. The variations in manganese-content in the first and second flushes on the basic furnace are interesting, if no more than a freak—the first flush being invariably higher in manganese. The iron-content of the two slags from an average of 12 flushes shows: Basic. Bessemer. Per Cent. Per Cent. Total iron...................................... 2.85 1.70 Combined iron................................ 0.72 0.52 Free iron....................................... 2.13 1.18 The greater iron-loss in the basic slag, while known, has never heretofore been so clearly set forth. This may modify the arrangement for handling slag; heretofore usually determined by proximity of the dumping-heap. If a nearby heap is used on contiguous territory, in the past, tilting molten-slag pots were used. If the Pittsburg flood-records for 30 years are a fair criterion the government regulations were inadequate, and molten slag was dumped in such a manner as to throttle the Monongahela at the time of the spring thaws. At Pittsburg the slag, where it is carried to a distance, is frequently granulated in pits and then removed in cars to which it is conveyed by clam-shell buckets. This practice is also quite customary where the slag is intended for the manufacture of slag cement. The production of 500 tons of cast-iron daily means about 300 tons of- slag and at 2.113 per cent. equals 6.4 tons

Jan 1, 1914

By William Metcalf

ONE of the first questions that naturally occurs to one who handles steel is," Why does steel harden ?" To answer this question the chemist and physicist have devoted much thought and experiment, and while they have enriched our store of knowledge of the nature and composition of steel, it cannot be said that they have yet solved the problem involved in its hardening. In this communication I desire to direct attention to a line of investigation yet new, in the hope that it may receive the attention of those who have the time and ability to pursue it. I refer to magnetism. There are so many parallels between the action of magnetism on iron and steel and their behavior under different processes of manipulation that it would seem as if there must be some connection between the forces at work in the different cases, if, indeed, there be not an identity of force in all of these cases. Magnetism, as we know it, may be merely the visible manifestation of forces, which may serve as a guide to lead us to an exact knowledge of the structure, the strains, and the resistances with which we have to deal in iron and steel. If a magnet be brought close to a pile of iron filings, the little pieces of iron will fly to the magnet and attach themselves to it, with their longer axes lying in the direction of the force. If molten cast iron be poured into an iron mould,-a chill,-the iron upon crystallizing will form needlelike crystals, with their long axes normal to the surfaces of the mould. If the iron is at the proper temperature and the quantity small, compared to the mass of the mould, the whole of it will be chilled, or set, in' the hard needlelike crystals

Jan 1, 1881

By James Douglas

I had the good fortune to visit the Stockholm Exposition just before its close in October last, and to get a glimpse of the methods used in Sweden in making the wonderful steel and iron for which its furnaces are so famous. My time and opportunities for observation were limited, but some points which I noted may be worth bringing to the notice of the Institute. The Exposition itself was confined to the natural and artificial products of Scanclinavia, and therefore iron and steel held a very prominent place in it. There was a complete collection of the rocks and ores of the Peninsula made by the Geological Survey; and every iron-mine of note exhibited a glass model of its workings, as well as classified specimens, accompaniecl by thorough analyses of the ores. Another feature of interest was the display of models of the old mining-machinery, in the invention and introduction of which Sweden led the way, and of the old and new surveying-instruments and compasses devised for the exploration of the Swedish iron-ore bodies, all of which are more or less magnetic. The magnetometric collection and exhibit of methods of operation made by Prof. Nordestrijm were supremely instructive. The larger metallurgical works, such as those of the Kopparberg and Sandvik companies, exhibited their wares in separate pavilions, in which crude and manufactured objects were arranged most eflectively and tastefully; while the smaller companies erected in the Industrial Arts Building trophies, every one of which was an object of beauty. One was struck on all sides by the fine asthetic feeling exhibited in the ingenious installation of materials and objects not easily lending themselves to artistic treatment. Hammers, picks and drill-steel were grouped into mural designs which it was a delight to look at.

Jan 1, 1899

By R. S. Archer

THE name molybdena was employed by Pliny to denote various substances resembling lead. Later this name was applied to galena-the naturally occurring sulfide of lead-or substances of similar appearance. By the middle of the eighteenth century, it was applied to graphite and to the mineral sulfide of molybdenum (MoS2) now called molybdenite. This confusion is quite understand- able inasmuch as these substances look and feel very much alike. In 1778, the Swedish chemist Scheele published a treatise in which he pointed out essential differences between graphite and molybdenite. On treatment with nitric acid, molybdenite, unlike graphite, produced a peculiar white earth with acidic properties which he called molybdic acid. Since the same mineral gave off sulfurous fumes on heating, he concluded that it was a sulfide of molybdenum. In 1790, there appeared an account of the isolation by P. J. Hjelm of the new element molybdenum, as a metallic powder, by heating the oxide with carbon. It was not until Bertelius conducted the necessary experiments, about 1818 to 1825, that the foundation of the chemistry of molybdenum was laid. The only recorded use of molybdenum during the first century after its isolation was as a chemical reagent, primarily for the determination of phosphorus. It was not until the last decade of the nineteenth century that the use of molybdenum in steel appears to have been investigated. A

Jan 1, 1953

Spencer Gulf takes off from the Great Australian Bight cutting a 200 mile deep wedge of water into the South Australia coastline. A pale winter sun shines yellowly on the choppy surface of this body of water which is progressively more salty as it approaches Port Augusta at the head of the Gulf. Once Port Augusta thrived as a grain port and the speedy clipper ships began or ended their legendary races there. On the eastern shores of Spencer Gulf, farm land spreads away from the water's edge. The western side of the gulf meets marginal grazing land of acacia tree and salt bush. Part way down the gulf, there are two industrial towns facing each other from opposite shores; Port Pirie on the east and Whyalla on the west. These towns are like half brothers, the common parent being the founders of Broken Hill Pty. Ltd., (BHP) who began lead smelting at Port Pirie and discovered iron ore near Whyalla needed for the lead smelting process. The iron deposits later became the inspiration for BHP's iron and steel business.

Jan 10, 1964

By G. Pomey

Heat-resisting chromium steels and alloys treated at 825° or 9.50°C (1527° or 1742°F) in a carburizing atmosphere exhibit an extensive carbide precipitation. This carbide precipitation may be succeeded by the FeCr a phase or by a carbide with a higher carbon content. Point analyses carried out with an electron mi-croanalyzer make it possible to study the depletion of chromium in the matrix after precipitation has occurred and to determine the chemical composition of carbides. In particular the content in the carbides of Fe, Ni, and W, elements which substitute Cr, can be accurately determined. HEAT-resisting chromium steels and alloys employed in the construction of gas carburizing and carbonitriding furnaces are subjected to a succession of oxidizing atmospheres during heating and cooling and to carburizing atmosphere during isothermal stage. Such a sequence of thermal cycling causes embrittlement and corrosion in the furnace materials. A quantitative study of the structural changes induced in the furnace materials has not received much attention in the past. However, utilization of the electron probe microanalyzer and other modern techniques has permitted a point analysis of the various phases formed and to follow their relative evolution. This paper gives results as regards the nature and composition of the carbide precipitation and the distribution of chromium in the matrix during only the carburizing periods. The structural changes subsequently produced during oxidizing periods will be presented eventually. METHODS AND MATERIALS Metallographic, X-ray diffraction and Castaing electron-probe microanalysis1 techniques have been employed to study carbide precipitation and evolution and the changes in the composition of the matrix in heat-resisting steels and alloys.

Jan 1, 1961

By Harold M. Feder, Robert V. Schablaske, Irving Johnson, Ewald Veleckis

The stoichiometry, structure, and stability of the internzediate phases formed between zinc and some of the rare earth (RE) metals were systematically exarnined by means of a recording effusion balance and X-ray diffraction analyses. In the La-, Ce-, PY-, Nd-, and Y-Zu systems, at or below about 600 C, the following sequences of phases (REZnx) were found: La, x = 1, 2, 4.0, 5.25, 7.3, 17/2, 11, and 13.0;' Ce, x = 1, 2, 3, 11/3, 4.3, 5.25, 7.0, 17/2,* and 11; Pr,x = 1,2, 3, 11/3 ,* 4.3, 5.3(?), 7.0, 17/2,* and 11; Nd,x = 1,2, 3,* 11/3,* 4.3, 6.5, 8.5,* and 11; Y,x = 1,2,3, 11/3, 4.5, 5.0, 17/2,* and 12.* The structure types of all these phases were classified. In addition, lattice parameters were obtained for the first time for the pluses denoted by asterisks. In the absence of de tectable valency or electronegativity effects the systesnatic trends in the results have been ascribed to the effects of' the lanthanide contraction. For example, the maximum number of zinc atoms in the coordination polyhedron surrounding the RE atom decreases from twenty-four to twenty-two to twenty as the size of the RE atom decreases. THE structures and compositions of a great many intermetallic phases (e.g., the Laves phases) are known to be based primarily, but not exclusively, on the space-filling efficiency of various modes of packing together atoms of different sizes. The valencies and electronegativities of the constituent atoms are, however, also influential. In extreme cases hypothetical intermetallic phases which fulfill the efficient spacefilling requirements may not be present in the constitutional diagram because of thermodynamic instability brought about by the operation of valency or electronegativity factors. Hence, for a detailed study of the influence of atomic size on alloy structure and composition, it would be desirable to minimize variations of valency and electronegativity. The intermetallic phases formed by the rave earths (RE) with some common partner offer an excellent opportunity for isolating the effects of size from those of valency and electronegativity. The rare earths exhibit a large, but smooth, decrease in size (the lanthanide contraction) in the series from lanthanum to lutetium when inter comparison is made for a common valence state, e.g., isolated atoms or trivalent ions. The elements yttrium and scandium are frequently included as pseudo rare earths; their sizes place them in the vicinity of dysprosium and lutetium, respectively. The electronegativities of RE elements vary by less than 10 pet. The trivalent state is the most common; however, the well-known tendency of cerium, praseodymium, and terbium to achieve higher valencies, and of samarium, europium, and ytterbium to seek lower valencies, requires that caution be exercised in the assumption of equal valencies. In the present study the existence, constitution, and structure of each of the numerous intermediate phases formed by zinc with lanthanum, cerium, praseodymium, neodymium, or yttrium were examined systematically and in detail. The investigation was conducted by a recording effusion balance technique and by X-ray diffraction analysis. The results enrich our knowledge of the phase diagrams of these systems. In addition, they present some clear-cut evidences of the operation of the size factor alone. EXPERIMENTAL PROCEDURE Apparatus. The mode of operation of the recording effusion balance and its application to phase studies have been discussed in detail elsewhere.' In this work, an effusion cell containing a finely divided alloy was suspended within an evacuated tube from the beam of an analytical balance. The tube was immersed in a massive molten salt bath whose temperature was controlled to within 0.5o C during each experiment. The loss in weight of the alloy owing to effusion of zinc* was continuously recorded. Two effusion cells, 1/2 in. diam by 1 in. high, were machined from tantalum rods. Two orifices were drilled laterally into the walls of each cell. The orifice areas were determined by calibration with pure zinc: cell A had a total orifice area of 6.5 x 10-41 sq cm, and cell B an orifice area of 9.8 x 10-3 sq cm. By appropriate choices of orifice area and temperature the wide range of volatilities from pure zinc to pure rare earth metal could be investigated. X-ray diffraction powder photographs were made at room temperature with a 114.6-mm Debye-Scherrer camera with both filtered CuKa radiation and filtered CrKa radiation. Lattice parameters were refined by a computer-programmed least-squares analytical treatment which incorporated appropriate extrapolation techniques.2 Frequent use was also made of a special computer program3 designed to generate a powder pattern from an assumed structure in order to verify structural assignments. Materials. Lanthanum, neodymium, and yttrium were purchased from the Lunex Co., cerium from the Cerium Metals Corp., and praseodymium from the St.

Jan 1, 1968