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By J. A. Lund, A. M. Lawson

THE structures of quenched eutectoid and hypereu-tectoid Fe-Cu alloys have been examined by X-ray diffraction and by optical and electron microscopy. The relevant portion of the Fe-Cu phase diagram is given in Fig. 1. Several values have been reported for the solubility of copper in a Fe at the eutectoid temperature, including 1.4 wt pct by orton' and 2.13 wt pct by Wreidt and Darken.2 Alloys containing 4.8 and 7.5 wt pct Cu have been prepared from two batches of Ferrovac E iron (0.005C and 0.013C) and electrolytic tough pitch copper (99.90 Cu). Specimens of dimensions 0.8 by 0.8 by 0.1 in. were cut from hot-rolled material, austenitized, and quenched into brine at 25°C. Similar specimens were also cooled in the furnace, after a short soaking treatment at 1100°C, at a rate estimated to be 10°C per min in the temperature range of 900" to 500°C. X-ray diffractometry was performed on quenched and on furnace-cooled bulk specimens using iron radiation. Only a bcc phase could be detected in all samples. Lattice parameters were calculated from measurements on four lines, made up of two resolved high-angle doublets. Comparisons were made against a silicon standard. Results are shown in Table I. Based on X-ray diffraction studies of a series of alloys of lower copper concentrations, orton' estimated that the tattice constant of a Fe at 25°C increases 0.0014A per wt pct Cu in solution. Extrapolating Norton's data, it may be concluded that all copper was retained in solution in the brine-quenched 4.8 pct Cu alloy, and that approximately 5 pct Cu was also held in solution on quenching the 7.5 pct Cu alloy. Typical microstructures of brine-quenched specimens, as observed by optical microscopy, are shown in Figs. 2 and 3. Precipitation of the E phase (copper-rich) occurred along the y grain boundaries on quenching the 7.5 pct Cu alloy, rendering them readily detectable in the microstructure, Fig. 3. The original boundaries in the 4.8 pct Cu specimens were gener- ally not discernible, however. This indicates that the z phase which was seen in the higher-copper alloy was probably of proeutectoid origin. Thin foils for transmission electron microscopy were obtained from bulk specimens by spark machining to 0.006 in. thickness, followed by electrolytic polishing. Typical transmission electron micrographs

Jan 1, 1967

By William Kent

William Kent, Pi.~t~bIJrQh, Pa.: The steel rnanufac.tnret of this country nlust ever he grateful to Dr. Dudley for his painstaking and conscientious endeavor to estaldish the relation between the chemical analysis and the wearing capcity of steel rails. They tnust thank him for the vast array of $acts he presents, and for having given them sixty-four analyses with which to combat his own conclusions and to establish their own, which are entirely opposite to his. In Dr. Duclley" discussion of his former investigation, at the Pittsburgh meeting, he said, "If you do not like my conclusions, draw your own conclusions." I have studied his last paper as thoroughly as the limited time since I received it would adruit, and have drawn some concluvions which I will first state, and then attempt to demonstrate. Briefly stated, my conclusions are: lst, That as far as these 64 analyses reveal anything of service to railmakers and cotsumera, it is that within the following chemical and physical limits, viz., Carbon,..0.20 to 0.60 Pisovphorue ,..0.026 to 0.146 Silicon,.. 0015 to 0.480 BInnganese.......0.262 to 0 880 Phosl~horus un~ts,..20.3 to 6.72 Bending weight,. 2270 lbs. to 4260 Ibs. Drfl~ctinn,.. 13O to 190° or in other words within the limits of rienrly the whole range of the chenlical and bending testa of these 6-2 mils: the wearing capacity bears no relation at all to mrbon, to phosphorus, to silicon, to mnnganese, to phosphorus units, to bending weight or to deflection or if there is any relation between the wearing capacity and thest! six or sr!ven variables, it is so obscured by the action of other cause or variat~les not yet known, that such relation cannot be expressed by any practical formula. 2d. That the difference in wearing capacity of these 64 rails was not due to unrbon, to phosphorus, to silicou, to manganese, or to anj combinntion of these four elements, but that it was due to some other cause or cornbination of causes, of which Dr. Dudley's whole iuvestigtion furnishes 11s no clue whatever. A few of the nlarry possible causes I lnay name : sulphur, copper, oxide of iron inclossl air or other gases, orerblowing, underblowing, oyrhaiting, undcrIreatinp, too hot-finishing, too cold-finishing, cold-straightening, toc great or too litkle rductiun hlu the rail to the ingot, or the portion

Jan 1, 1881

By H. Fechtig, R. H. Buck, A. G. Guy

MULTIPHASE diffusion has been studied for many years in two-component systems1,2 and many of the experimental aspects are now fairly well understood.314 Although by no means all of the problems connected with the two-component case have been solved,' attention has recently been directed to the more complex situation involving three components. The pioneer work of Clark and Rhines6 yielded a qualitative picture of the types of behavior that can occur, and Clark7 has suggested conventions for describing the various phenomena. Kirkaldy and co-workers8,9 have made quantitative studies in several ternary systems and have offered explanations of the occurrence of isolated and nonisolated precipitates. At present, however, there is no comprehensive theory for the variety of phenomena observed in ternary, multiphase diffusion. By analogy with several studies that have been made of multiphase diffusion in the binary Cu-Zn system,2'10'11 a similar exploratory study was made of Cu-Zn-Ni alloys lying along the line in the ternary diagram from the point 80 Cu-20 Ni to the zinc corner of the diagram, Fig. 1. A principal question to be answered was whether initially plane interfaces would remain plane during the course of one-dimensional diffusion. The diffusion specimens studied are described in Table I. The five separate alloys from which they were made were melted in evacuated Vycor capsules from 99.9 pct purity copper, zinc, and nickel. Since some of the alloys were too brittle to be swaged, all of the alloys were used in the cast condition. To facilitate later homogenization, the molten alloys were solidified by plunging the capsule in water. Homogenization heat treatment was done at 720°C for 20 hr. The five nominal compositions in weight percent zinc and nickel, respectively, were: 37.5, 12.5; 44.0, 11.2; 50.0, 10.0; 55.0, 9.0; 65.0, 7.0. Ln Table I the alloys are identified only by their zinc content. Sandwich-type diffusion specimens were prepared by pressure welding disk specimens, each about 3 mm high by 10 mm in diameter. Welding was done in a special threaded vise which was heated at 500°C for about an hour in an atmosphere of flowing hydrogen. A measurement of the separation of the phase interfaces was made on a polished flat on the welded specimen, and then the specimen was sealed in an evacuated capsule and given the diffusion treatment shown in Table I. The diffused specimen was sectioned longitudinally

Jan 1, 1965

By C. E. Sims

IN an earlier paper by Sims, Moore, and Williams: data were given to show that hydrogen contents of 0.3 relative volume (0.00033 wt pct), existing at the center of 4-in.-square cast-steel coupons, could be removed by aging at 400°F for 125 hr. At the end of that time, complete restoration of normal ductility for the steel was obtained. Replicate specimens of the same steel were aged at room temperature up to 555 days or .18 1/2 months. At the end of that time, the hydrogen content at the center had fallen to 0.13 relative volume or 0.00015 wt pet, but there was no perceptible change in the ductility. On the basis of experience with accelerated aging of 1-in. and 4-in. coupons and room temperature aging of 1-in. coupons, it was predicted that, some time after two years and when the hydrogen content has been reduced to about 0.10 relative volume, there would be some recovery of ductility. One set of three bars remained, and these were held for 1310 days, or more than three years. Then tensile test bars were cut from the center, and these bars were sampled for hydrogen analysis at the time they were broken. The sample specimens were cylinders % in. in diam x 1 1/4 in. in length. The data showed that in this time the average hydrogen content had fallen to 0.096 relative volume or 0.00011 wt pct, and the ductility had increased sharply. Elongation had risen from 10 to 17.3 pct, while reduction of area increased from about 16 to 27.5 pct. On the basis of these data, fig. 1 was drawn to replace fig. 15 of the earlier paper. Extrapolation of the curves of fig. 1 indicates that it would require a period of about 2200 days or approximately six years at room tem- perature to reduce the hydrogen to the minimum value and to recover full ductility in the center of the coupons. The aging process apparently involves the movement of hydrogen from the interior to the surface of the bar and evaporation at the surface. This flux of gas presumably follows some diffusion mechanism, and an effort was made to use the aging data, obtained at room temperature and at 400°F, to calcu-late coefficients of diffusion, in the hope that they might indicate the nature of the diffusion. The conclusion was reached. however. that the data were inadequate for such a purpose.

Jan 1, 1951

By George Beavers

FLASH roasting of iron concentrate is in the experimental stage at Copperhill. The problem is peculiar in that the iron concentrate is predominantly pyrrhotite; the ratio of that mineral to pyrite being 5 to 1. Results so far indicate that the heat, generated in roasting a material containing 52.0 per cent iron and 38.0 per cent sulfur, requires special handling and for this reason the installation costs per ton of roaster feed may be too great to compete with hearth roasting. Interesting features of flash roasting at Copperhill are: 1. The sulfur dioxide content of the roaster exit gas can be varied between wide limits. Eight per cent sulfur dioxide gas, with 1.30 per cent sulfur in the calcine, has been common practice and gas up to 13.0 per cent sulfur dioxide has been possible. 2. Temperatures of the exit gases are very high. When roasting 60 tons or more of iron concentrate per 24 hr. in a modified Wedge roaster, the temperature in the roaster rises to 2000° F. and the calcine is lowered to 0.20 per cent sulfur. If the entire roaster system could be constructed to withstand such temperatures, ideal roasting conditions would obtain as regards sulfur elimination and tonnage roasted.

Jan 1, 1934

By Peter L. Raffo, Walter R. Witzke

RHENIUM has a melting point of 5750°F, the second highest value among the metals.1 Its refractory nature should thus make it a useful material at high temperatures. The only available data on the high-temperature properties of bulk rhenium are from the work of Flagella and Tarr.2 These authors have shown that, over a wide range of temperatures and stresses, no appreciable linearity exists in a log-log plot of the minimum creep rate or rupture life vs stress. The purpose of the present letter is to describe some exploratory experiments designed to study the creep rate-stress-temperature relation and other facets of the creep of rhenium. The tests were carried out in vacuum in the temperature range 2200" to 4000°F (0.43 to 0.72 Tm,) at stresses ranging from 4 to 20 ksi. The powder metallurgy rhenium was purchased as 0.04-in.-thick sheet. The sheet is nominally 99.97 pct pure with the major impurities being iron (70 ppm) and molybdenum (25 ppm). The sheet was machined into specimens having a 1-in. gage length and a 0.25-in. gage width. The specimens were preannealed in hydrogen at 3000°F for 1 hr. This treatment produced

Jan 1, 1970

By Albert Sauveur

Iron, like other metals, solidifies through the formation of dendritic crystals; iron alloys forming solid solutions, like other solid solutions, solidify likewise through the formation of dendritic crystals. The alloying elements or impurities as well as the inclusions segregate generally in the interstices, or "fillings," between the axes and branches of the dendrites; that is, in the portions last to solidify. This results in dendritic segregation or heterogeneity, which is generally persistent and makes possible the revelation of the dendritic crystallization of the metal through the selective action of a suitable etching reagent.' For this purpose, a cuprie solution, such as Le Chatelier's, is generally used, copper being deposited on the pure, or relatively pure, ferrite present in the axes while the fillings remain free, or relatively free, from copper deposition. The dendritic structure, formed on solidification in a steel containing 0.50 per cent. carbon, 0.37 per cent. manganese, 0.12 per cent. silicon, 0.07 per cent. sulfur, and 0.035 per cent. phosphorus is shown, after treatment with Le Chatelier reagent, in Fig. 1 under a magnification of 8 diameters. Commercial steel always contains inclusions of manganese sulfide, which are located in the fillings of the dendrites. Comstock has shown that boiling sodium picrate imparts a dark coloration to these inclusions. We find that this reagent likewise reveals dendritic segregations in commercial steel, as shown in Fig. 2, under a magnification of 8 diameters. which represents the same spot as that shown in Fig. 1. The fillings have been darkened while the axes remain white, the action being, therefore, the reverse of that of cupric reagents. On closer examination, under higher magnification (Fig. 3) it is found that the picrate blackens the small particles of manganese sulfide, that these are frequently surrounded by a rim of white, or relatively white, ferrite, and that both the ferrite

Jan 1, 1924

By D. C. Porterfield

-4s a result of world economic conditions brought about by the European war and the consequent loss of European markets for Venezuelan crude, production in Venezuela decreased from 205,433,000 bbl. in 1939 to 186,134,000 bbl. in 1940, or 9.4 per cent. This decline interrupted a steady annual increase in production from the country, which had been continuous since 1932. The Maracaibo Lake Basin in western Venezuela accounted for 135,738,000 bbl. during 1940, or 73 per cent of the total, as against eastern Venezuela's production of 50,396,000 bbl., or 27 per cent of the total for the country. Corresponding figures for 1939 were 167,688,000 bbl., or 82 per cent of the total from the Lake Basin, and 37,744,000 bbl., or 18 per cent from the east. These comparisons indicate the increasing importance of the newer developments in eastern Venezuela, but it is unlikely that production from the east will ever exceed that from the west. In all, 429 new wells were completed in Venezuela during 1940 as compared to 438 in 1939. Of the 1940 completions, 411 were in proved areas and 18 were wildcats; 389 (95 per cent) of the exploitation wells drilled were producers, I was a gas well and 21 were dry holes, while 6 (33 per cent) of the wildcats drilled were producers and 12 (67 per cent) were dry; 263 of the exploitation wells and 4 of the wildcats were in the Maracaibo Lake Basin and 148 exploitation wells and 14 wildcats were in the east, mostly in the State of Anzoategui. Exploration of the light-oil areas in the Tia Juana and Lagunillas fields was con- tinued during the year with favorable results. Along the lake shore, drilling was confined principally to fill-in wells in the La Kosa, Tia Juana, Laguni!las and Bachaquero fields, although some important semi-exploratory drilling was done in the Pueblo Viejo area between Lagunillas and Bachaquero fields. The only other developments of particular interest in the west were the successful completion of a step-out well lying to the south of the former southern limit of Mene Grande field, which adds considerable proved acreage to that field; and the failure of two wildcats that were drilled near the Colombian border to determine whether the productive sands of the Petrolea field in the Barco Concession, Colombia, extend into Venezuelan territory. In the east no new fields were discovered during the year, although five wildcats were completed as producers. Three of these, Guario No. I, Jusepin-56 and LM-I (Leona), discovered important extensions to previously proved areas and the remaining two, Cantos-I and SPN-I (Socororo), were subsequently proved to have tapped productive sands of small extent and operations in these areas have been suspended. The greatest activity in the east was concentrated in the Oficina field, where 105 new wells were completed during the year and production was increased from 22,540 bbl. per day during January 1940 to 57,627 bbl. per day during December 1940. Important development work was also done in the Jusepin. San Joaquin and El Koble fields.

Jan 1, 1941

By D. C. Porterfield

-4s a result of world economic conditions brought about by the European war and the consequent loss of European markets for Venezuelan crude, production in Venezuela decreased from 205,433,000 bbl. in 1939 to 186,134,000 bbl. in 1940, or 9.4 per cent. This decline interrupted a steady annual increase in production from the country, which had been continuous since 1932. The Maracaibo Lake Basin in western Venezuela accounted for 135,738,000 bbl. during 1940, or 73 per cent of the total, as against eastern Venezuela's production of 50,396,000 bbl., or 27 per cent of the total for the country. Corresponding figures for 1939 were 167,688,000 bbl., or 82 per cent of the total from the Lake Basin, and 37,744,000 bbl., or 18 per cent from the east. These comparisons indicate the increasing importance of the newer developments in eastern Venezuela, but it is unlikely that production from the east will ever exceed that from the west. In all, 429 new wells were completed in Venezuela during 1940 as compared to 438 in 1939. Of the 1940 completions, 411 were in proved areas and 18 were wildcats; 389 (95 per cent) of the exploitation wells drilled were producers, I was a gas well and 21 were dry holes, while 6 (33 per cent) of the wildcats drilled were producers and 12 (67 per cent) were dry; 263 of the exploitation wells and 4 of the wildcats were in the Maracaibo Lake Basin and 148 exploitation wells and 14 wildcats were in the east, mostly in the State of Anzoategui. Exploration of the light-oil areas in the Tia Juana and Lagunillas fields was con- tinued during the year with favorable results. Along the lake shore, drilling was confined principally to fill-in wells in the La Kosa, Tia Juana, Laguni!las and Bachaquero fields, although some important semi-exploratory drilling was done in the Pueblo Viejo area between Lagunillas and Bachaquero fields. The only other developments of particular interest in the west were the successful completion of a step-out well lying to the south of the former southern limit of Mene Grande field, which adds considerable proved acreage to that field; and the failure of two wildcats that were drilled near the Colombian border to determine whether the productive sands of the Petrolea field in the Barco Concession, Colombia, extend into Venezuelan territory. In the east no new fields were discovered during the year, although five wildcats were completed as producers. Three of these, Guario No. I, Jusepin-56 and LM-I (Leona), discovered important extensions to previously proved areas and the remaining two, Cantos-I and SPN-I (Socororo), were subsequently proved to have tapped productive sands of small extent and operations in these areas have been suspended. The greatest activity in the east was concentrated in the Oficina field, where 105 new wells were completed during the year and production was increased from 22,540 bbl. per day during January 1940 to 57,627 bbl. per day during December 1940. Important development work was also done in the Jusepin. San Joaquin and El Koble fields.

Jan 1, 1941

By Charles O. Burgess

The improvement in the quality of cast iron by means of alloy additions has been a metallurgical accomplishment of recent years. Work in this field has shown that chromium is one of the most effective of such additions but, in general, the influence of chromium has been studied only in connection with other alloying additions, with irons other than foundry irons, or with relatively high percentages of chromium. The present study was initiated for the purpose of determining the influence of small additions of chromium (0.25 to 1.00 per cent) on the quality and resultant properties of cast irons of various foundry grades. The effect of small chromium additions on cast iron was investigated with particular reference to casting characteristics, hardness vs. section, strength, machinability, heat resistance and structure. Material Tested Three separate types of cast iron were investigated as to the effect of small chromium additions. The first series of these irons was prepared from remelted foundry cast iron at the Union Carbide and Carbon Research Laboratories, and the other two series consisted of cupola melts made under usual operating conditions. The first series was made by melting 30-lb. charges of foundry scrap iron containing 2.86 per cent carbon, 2.72 silicon, 0.50 manganese, 0.062 sulfur and 0.794 phosphorus in a carbon resistance furnace. The chromium was added as high-carbon ferrochrome just before pouring. The irons were cast at approximately 1250" C. (2282" F.). The analysis and physical properties of these irons are given in Table 1, test 1. The second set of cast irons was made in a cupola in accordance with normal practice, the charge containing approximately 42 per cent steel scrap and the chromium additions being made to the ladle. Analysis and tests of these heats are shown in Table 1, test 2. A small amount of copper was present in heat C of this series. Further data on the effect of chromium on strength were obtained from a third series of 13 cupola heats containing from 0.06 to 0.50 per cent chromium and made without steel additions. The heats were all

Jan 1, 1933

By R. S. Archer

In the microscopic examination of aircraft-engine parts made of heat-treated alloy steels, the writer has been forcibly impressed by the failure of the usual etching processes to disclose any but gross defects in heat treatment. It seemed particularly desirable to bring out the grain size of the steel, which is indicated in the ordinary etching processes chiefly by the change in orientation of structure from grain to grain. After various attempts, a fairly successful method has been found, which is here presented in the hope that it may be of use to those who have occasion to examine these steels in the hcat-treated condition. The specimens worked with have been mostly chrome-nickel steels heat treated (that is, hardened and tempered) to a Brinell hardness of around 300. A few experiments with other specimens will be referred to later. Briefly, the method employed consists in etching the steel about 10 min. in a fresh solution of picric acid in ethyl alcohol, and then rubbing off the smudge of carbonaceous matter on moist broadcloth. Different samples of almost identical analysis, heat treatment, and physical properties (including resistance to impact) respond quite differently to this treatment. In some, the grain boundaries are developed quite readily, while in others, especially in those whose grain is unusually fine or in which the final hardening heat has not quite obliterated the previous crystallization, the results are more obscure. The exact time of etching to secure the best results also differs for various samples, and the greatest success is usually attained by a process of "tinkering." Such a process is illustrated in a series of micrographs, the first six of which were taken at a magnification of 300 diameters. The properties of the steel are as follows: Carbon, per cent............... 0.42 Brinell hardness.............. 293 Nickel, per cent................ 1.35 Yield point, pounds per square Chromium, per cent............. 0.90 inch........................ 131,000 Copper, per cent................ 0.025 Maximum strength, pounds per Manganese, per cent............ 0.74 square inch................. 144,500 Phosphorus, per cent............ 0.024 Elongation in 1 in., per cent... 28 Sulfur, per cent................ 0.036 Lod impact, foot-pounds...... 51 Reduction of area, per cent...... 57.3

Jan 1, 1920

By W. W. Gorr, R. Smith, E. H. Wyche

THE combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W? and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. DEVELOPMENT OF THE NEW STEEL For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield 18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators 'then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, o.58; Ni, 7.28; Cr, 17.6o; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1946

By J. R. Campbell

It is the purpose of this paper to review somewhat in detail the literature on the subject that is extant, which ought to provoke considerable beneficial discussion. The value of 1 per cent. ash in blast-furnace practice was brought to the attention of the writer when he was connected with the U. S. Steel Corpn. Various groups of blast furnaces in the Pittsburgh district compiled a statement in which the average saving was about 6 c. per ton on pig iron for every 1 per cent. of ash reduction. Later, the same groups of furnaces, when materials had reached a higher price, compiled a statement in which there was a 30-cent saving on pig iron for every 4 per cent. ash reduction in the Pittsburgh district, which was equivalent to 7½ c. for every 1 per cent. ash reduction. In the Chicago district, on long freight hauls of coal and coke from the Pocahontas district, the set-up was 30 c. per ton of pig iron for every 2 per cent. ash reduction, or 15 c. for every 1 per cent. Some years ago, Ralph H. Sweetser, of the American Rolling Mill Co., presented a paper which provoked considerable comment.' To get the matter again before this body a résumé of his computations is given below: Comparison of Pig Iron Costs Ash in Coal. Ash in CoKe, Fixed Carbon in Coke peR Ton OB PIG Iron peN Day, Per Cent. PeR CeNt. Coke. Per Cent. PIG IRon. Lb. Tons 6.00 8.70 89.80 1800 365.0 7.00 10.15 88.35 1860 353.2 Coke with 8.70 Per Cent. Ash Ore mixture, 4144 It). = 1.85 tons @ $5.50.............................. $10.17 Coke, 1800 lb. = 0.90 ton @ $6.50..................................... 5.85 Limestone, 1000 lb. = 0.50 ton @ $1.50................................. 0.75 Labor, $365 per day on 365 tons....................................... 1.00 Supplies and service, $250 per day...................................... 0.68 Overhead, $200 per day............................................... 0.55 Reserve for relining and depreciation................................... 1.00 Total............................................................. $20.00

Jan 1, 1931

By Elliott J. Roberts

In spite of the fact that the percentage of true colloids in an ore grind is very small,' these pulps exhibit many of the properties of true colloidal suspensions. A quartz particle, appreciably finer than 10 microns in diameter, has a settling rate so low that at a dilution of 5:l or over, the capacity of a settling tank to settle such particles would be uneconomical if the individual particle rate prevailed. However, by grouping the finer particles into aggregates or flocs, the settling rate can be increased to an economical value. The colloidal chemistry of pulp thickening is thus chiefly concerned with particles having diameters of between 1 and 10 microns, although particles as coarse as 40 microns in diameter are more or less involved. These particles must be associated in such a manner that they settle at an economical rate and give a clear, supernatant liquid or overflow. The treatment of the subject may be divided into three phases, cach phase having a more or less different colloidal aspect. The first phase is the problem of getting the pulp or suspension into the proper condition of flocculence; the second is the behavior of the flocculent pulp in its initial and intermediate stages of settling; the third is the behavior of the flocs in the find period of settling or thickening stage. Let us look first into the methods and mechanism of obtaining the flocs and then consider their behavior and properties. Flocculation Colloids are merely ordinary substances reduced to a very small particle size, the upper limit being placed by definition at 1 micron (0.001 mm.) diameter by the soil chemists and at from 0.2 to 0.1 micron by various other colloid chemists. The lower limit is reached only when the particles approach molecular dimensions. The term L'colloid" should not necessarily imply lack of crystallinity. Particles as small as 0.01 to 0.02 micron give perfect X-ray patterns, while with 0.005 micron particles the bands on the powder photograph are merely broaderled and diffused.2

Jan 1, 1935

By W. Klement

By quenching liquid alloys, single-phase solid solutions are obtained in the ranges 0 to 42.0 at. pct Co-Au and 0 to 15 and 75 to about 100 at. pet Co-Cu. Metastable solid solutions are also found in multiphase 42.0 to 49.0 and 69. 0 to about 100 at. pet Co-Au alloys. fie inability to achieve complete solid solubiliiies in Au-co and cu-co alloys is rationalized by a conszderation of the rate processes during cooling and solidification. Trends in lattice distortion and shifts in the compositions of the melting-point minima and critical points are discussed for the binary alloys of copper, silver, and gold with some of the transition metals of the first long period. By rapidly cooling alloys from the melt, a continuous series of metastable solid solutions can often be obtained for components of similar crystal structure which normally form eutectic systems.' The eutectic system Au-Co, Fig. 1, and the peritectic system Cu-Co, Fig. 2, were investigated in order to determine the extent of the metastable solid solutions attainable with the present technique.* EXPERIMENTAL PROCEDURES Most of the alloys were prepared by melting weighed quantities of the elements (purity greater than 99.9 pct) under hydrogen in alumina crucibles by means of induction heating. After reweighing, the alloys were cast under argon into 1 mm diam wires. However, it was not possible to prepare some of the Cu-Co alloys with the requisite homogeneity (over about 1 mm3) in this way. For these alloys, reduced powders (purity greater than 99.9 pct) were mixed for 12 to 48 hr, pressed into compacts that were sintered at 1000º to 1050°C for 6 to 48 hr under hydrogen, and then furnace-cooled. Alloy charges of a few mm3, cut from the cast wires or chipped from the sintered compacts, were heated to 1550º to 1600°C in 30 sec in an alumina insert held within a graphite support and then ejected by a pulse of helium onto a lightly polished copper strip on the inner periphery of a rotating wheel. The

Jan 1, 1963

By Rodney P. Smith

THE solubility of columbium nitride in ? iron has been determined for the temperature range 1191o to 1336°C from the nitrogen content and metallogra-phic examination of a series of Fe-Nb alloys.* (0.0 to 0.92 pct Nb) equilibrated with a purified gas mixture of 1 pct hydrogen in nitrogen. The method is the same as that used by Darken, Smith, and Filer' to determine the solubility of aluminum nitride in y iron. The variation in the furnace temperature during an equilibration period was about ± 2.0°C. Each sample was approximately 1/2 in. wide, 2 in. long, and 1/16 in. thick. A time series at 1200°C using samples of highest columbium content indicated that one day was sufficient for equilibrium; however, to be on the safe side all samples were left in the furnace for either two or three days. Afterequilibration, the samples were brought to room temperature by quenching in water. The experimental results are shown in Fig. 1. To be in accord with the values reported by Wriedt and Gonzalez2 and the temperature coefficient of our results at higher temperatures, the nitrogen content of iron at 1191oC is assumed to be slightly lower than our experimental value. Our data for the single-phase regions are not sufficiently accurate to establish an interaction coefficient for nitrogen in these alloys. However, the change in nitrogen content with change in alloy content for a number of systems (Fe-N-A1;3,1 Fe-N-Ni;372 Fe-N-Si.3949 Fe-N-V;3,5 Fe-N-Cr;3,6 Fe-N-Mo3,7) has practically the same value for the liquid alloy at a temperature near 1600°C as for the solid alloy at temperatures near 1200oC when the alloy content is below a few percent. On this basis the lines through the single-phase regions have been drawn with a slope corresponding to an increase in nitrogen of 0.0013 pct per 0.1 pct Nb.3 The straight lines through the two-phase regions were drawn with a slope corresponding to a one-to-one atom ratio of nitrogen to columbium in the nitride. The X-ray

Jan 1, 1962

By A. Gatti, R. L. Fullman

A very fine dispersion of aluminum oxide is produced by internal oxidation of solid-solution alloy of 0.14 pet A1 in Ag. The particle size of the aluminum oxide is approximntely 50 to 100A in radius. The yield strength of the alloy is increased markedly by internal oxidation. A further increase in strength is produced by cold working the internally oxidized alloy. Recrystallization is retarded by the finely dispessed aluminum oxide particles, so that the strength increase resulting from cold work is retained on annealing at temperatures 14 to about 700°C. MANY workers'-3 in the past have studied various aspects of the internal oxidation of aluminum-silver alloys. This paper is an extension of these studies with emphasis placed on the effect of time and temperature of annealing on the strength of these alloys after oxidation and subsequent cold working. Two general conditions are necessary to internally oxidize an alloy. First, oxygen must diffuse through the base material more rapidly than does the addition; otherwise oxidation will take place as a surface layer. Secondly, the affinity of oxygen for the addition must be greater than for the base material. After internal oxidation of certain alloys takes place, a marked increase in hardness accompanied by higher yield stress and improved creep properties is noted, presumably as a result of the highly dispersed oxide within the base material. Meijering and Druyvesteyn1 also noted that the internally oxidized portion of a partly oxidized alloy failed to recrys-tallize under annealing conditions that led to coinplete recrystallization of the unoxidized part. EXPERIMENTAL-METHODS AND PROCEDURES Few alloys can be made to contain a second phase that is extremely stable at high temperatures. Silver plus aluminum in solid solution was chosen for these internal oxidation studies because of the high rate of oxygen diffusion through silver and the very stable nature of aluminum oxide. Two alloys were vacuum cast. The nominal compositions were: Alloy A—1 pct Al, balance Ag; Alloy B—0.1 pct Al, balance Ag. Chemical analysis, which does not distinguish between aluminum and aluminum oxide, showed the conlposition to be: Alloy A—1.6 pct Al, and Alloy B—0.14 pct Al. The ingots were machined for surface cleaning, swaged and drawn to 0.020-in. diam wire. A sample 20 ft long of the 0.020-in. dianl wire of each composition was annealed 24 hr at 800°C in pure dry hydrogen. Each wire was then cut into two equal pieces. Photomicrographs of the 0.14 pct A1 alloy are shown in Fig. 1, the annealed 0.020-in. wire at the left and the oxidized wire to the right. The oxidation treatment for the first set of data was 1000 hr at 800°C in air. After this treatment the 1 pct A1 proved to be brittle. It is assumed that high alunlinum oxide concentration at the grain boundaries was responsible. The 0.14 pct Al wire remained ductile and all further data were derived using this alloy. One-half of this wire, about 5 ft, plus 5 ft of as-homogenized wire, was then drawn cold to 0.005 in. diam. All tensile tests were conducted with an Instron Engineering Corp. tensile-testing machine, Model TT-B. Unless otherwise indicated, the tests were made at room temperature with a strain rate of 0.1 per min. All metallographic samples were etched with an aqueous solution of 2 pct each of CrO3 and H2SO4 . EXPERIMENTAL RESULTS AND DISCUSSION PARTICLE SIZE DETERMINATION A study was made of the particle size of the aluminum oxide produced in the samples of Ag + 0.14 pct Al, oxidized 1000 hr at 800°C. A cross section of the as-oxidized wire was mounted in bakelite, polished, and etched with an aqueous solution of 2 pct each of CrO3 and H2SO4. The specimen was then thoroughly cleaned by stripping successive coatings made by applying 10 pct nitrocellulose in amyl acetate. The final replica of the cross section was made by applying 2 pct nitrocellulose in amyl acetate. The replica was stripped, transferred to a copper screen, shadow cast with chromium at 10 deg and photographs taken using a Phillips Metallix electron microscope at an accelerating potential of 100 kv. A photograph of an etched sample of the as-oxidized material is shown in Fig. 2. We believe the pits in the photograph are places were A12O3 inclusions were sitting in the matrix. By inspection, it appears that the volume fraction ob-

Jan 1, 1960

By C. C. Clark, J. S. Iwanski

The purpose of this investigation was to study mi-crostructural changes that take place in a commercial nickel-chromium-iron alloy, such as Incoloy "901," over long periods of time at temperatures up to 13 50°F and to correlate such changes with creep-rupture properties. of the alloy. In the course of the investigation, some microstructural changes were observed which correspond to microstructural alterations found in previous studies of Inconel "X." Microstructural phases have been identified in both alloys with the aid of electron and X-ray diffraction and an electron probe microanalyzer. The materials used in this investigation were from commercial heats of the following chemical composition: Pct Cr Pct Ni Pct Mo Pct Fe Pct Cb Incoloy "901" 12.51 43.67 5.72 Bal. -Inconel "X" 14.61 73.44 - 6.61 1.02 Pct A1 Pct Ti Pct Mn Pct Si Pct C Incoloy "901" 0.10 2.46 0.46 0.24 0.05 Inconel "X" 0.70 2.43 0.51 0.36 0.04 Long-term creep-rupture tests were conducted on Incoloy "901" at temperatures of 1000°, 1200°1 and 1350°F. A summary of these results is shown in Table I along with the results of a long-term creep-rupture test conducted on Inconel "X" at 1500°F. The heat treatments given the specimens are also shown in Table I. When the creep-rupture results on Incoloy "901" are compared with shorter-tertn data, there is no evidence of any undue deterioration of the creep-rupture strength with time, nor is the elongation decreased more than would be expected from the influence of time alone. INCOLOY "901" PHASE IDENTIFICATION Microscopic examination of the Incoloy "901" specimens reveals a dark etching grain boundary constituent in the specimen which was under test for about 11,500 hr at 1000°F. This grain boundary constituent was seen to increase in size as the test temperature was increased to 1200" and 1350°F, Figs. 1, 2, and 3. Simultaneously, an acicular structure of definite crystallographic orientation appears within the grains of the 1350°F specimen, Fig. 3. Under examination with the electron microscope, a fine precipitate is observed in the 1200 °F specimen. Fig. 4. It becomes considerably larger in the 2850-hr 1350°F specimen, Fig. 5. In a few areas the precipitated particles have been replaced by, or transformed to, small needles or platelets. After 7380 hr at 1350°F, Figs. 3 and 6, the needles are much larger and have replaced nearly all of the fine precipitate. X-ray diffraction studies detected the presence of hexagonal Laves phase and hexagonal n phase (Ni,Ti) in the 1350°F specimens, Table 11. Only the Laves phase was detected by X-ray diffraction in the 1200°F specimen and none was detected in the 1000°F specimen. In this latter specimen, however, the small quantity of precipitate in the grain boundaries (presumed to be Laves phase) precludes its detection by X-ray diffraction. Composition of the hexagonal Laves phase is not yet known, although its diffraction

Jan 1, 1960

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By A. E. Lee

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

Jan 1, 1954