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By L. R. Weisberg, E. A. Miller

Single-crystalline films of silicon of good quality were vacuum-deposited on sapphire. The improved crystallinity was achieved by the strict exclusion of oxygen from the evaporation system, including the use of a "oxygen-free" silicon source. To minimize possible contamination of the source, the silicon was sublimed from the solid at about 1390° C. using a simple electron bombardment system to heat the silicon. This resulted in deposition rates of about 5 to 7 µ per hr and film thicknesses of 4 to 20 µ. The vacuum during deposition was ordinarily about 5x 10-8 Torr, DESPITE the success achieved in the chemical vapor deposition of silicon on sapphire using Silane,1-4 vacuum deposition has not provided comparable properties. For example, Chu et a1.5 vacuum-deposited silicon on single-crystalline substrates of A12O3, Sic, ThO2, and other compounds, and, although some epi- but the use of ultrahigh vacuum (about 1 to 3 x10-9 Torr) during deposition did not significantly improve the results in the oxygen-free system. The crystalline quality of films deposited on (0001) sapphire was found to be considerably superior to (1102) sapphire surfaces. Using (0001) sapphire, single-crystalline films were deposited at temperatures as low as 780° C and as high as 1075°C, with the best crystalline quality obtained at about 1000°C. At this temperature, hole mobilities over 250 sq cm per v-sec were achieved. taxy was indicated, single-crystalline films were not produced. More recently, Salama, Tucker, and young6 evaporated silicon on single-crystalline sapphire, but only poor crystallinity was observed, and low carrier mobilities were measured. In the present experiments, good-quality single-crystalline films of silicon on sapphire have been achieved by specifically excluding oxygen from the evaporation. This included not only the use of a "clean" vacuum system but, of special importance, the use of an oxygen-free silicon source. This has also been shown to provide a dramatic improvement in silicon homoepi-taxy.7 As a result, silicon-on-sapphire films with hole mobilities over 250 sq cm per v-set were achieved, and single-crystal films were grown as low as 780°C and as

Jan 1, 1969

I;. D. Godshall, Everett, Wash. (communication to the Secretary) : In Mr. Morse's interesting paper several statements occur which seem to require correction and comment. This is the more appropriate, since Mr. Morse has mentioned me by name, and has cited my "Review of the Russell Process,"* so that silence on my part might be taken as indicating an assent which I cannot give. On the first page of his paper Mr. Morse says that the " goingback " of chlorination was " the only difficulty encountered at Aspen," and adds that he has " never seen any explanation " of the cause. The plain inference is that he now fills this complete

Jan 1, 1896

By Samuel Taylor

IF I LIVE another fourteen months and am still con-nected with the coal industry, I shall then have com-pleted a half century with it. Since May, 1874, when .I first entered the bituminous workings as a miner, I think I have held almost every position connected with a mine except possibly that of mule driver, for which I was unfitted by reason of my religious upbringing. We are all agreed, at least I have not heard it contra-dicted, that there is serious over-production in the bituminous industry. This has come about in various ways and is easily explained. During the Fuel Admin-istration, I recall making an estimate of the possible output of the bituminous mines of the country provided they were given a full force of men and a full-car supply; my estimate was a little over a billion tons a year. A few months ago, the late Francis H. Peabody, of Chicago, made a practically identical estimate. If, however, both of these conditions should happen con-currently, there would very soon be no market for the coal, and many of the mines would close down. Even today, if 10 per cent. more cars were furnished, to the bituminous mines, market prices would drop very seriously.

Jan 4, 1923

By N. A. Gokcen, E. S. Tankins, G. R. Belton

Equilibrium in the reaction H2(g) + O[in liquid iron, cobalt, or nickel] = H2O(g) has been investigated over wide temperature and composition ranges. Oxygen has been found to obey Henry's Law in each of the three metals at 1550°C. The standard free-energy changes for the above reaction are given by: (1550° to 1700°C) ?Foco = -45,360(±290) + 16.16(±0.16)T (1490° to 1700°C) ?Fo Ni = -48,170(±220) + 16.12(±0.12)T (1465° to 1700°C) where the standard state for dissolved oxygen is the I wt pet solution. ThE thermodynamic behavior of dilute solutions of oxygen in molten iron has been the subject of many investigations over the last thirty years,'-'4 the majority of the investigators having utilized the reaction:

Jan 1, 1964

By Clifford Wilson

SCREENED pipe is designed with the view of restraining the fine, free-running sands of the production zone from entering oil wells. Its successful use is dependent on a number of factors. The nature and effects of some of these factors can be determined through experiment and observation, but some of the elements that have a distinct bearing on the use of screened pipe can be evaluated only by estimate. The important subsurface conditions which affect the use of screened pipe are: 1. Depth of production zone. 2. Extent of production zone. 3. Reservoir pressure. 4. Character and relative quantity of oil and gas. 5. Character of sediments a. Consolidation of beds. b. Variation in beds. c. Grain-size gradation of sands. d. Free-running characteristics of sand from different levels. Aside from the use. of mechanical equipment and tools, the measures to be taken in the installation of screened pipe involve: 1. Size of liner. 2. Length of liner. 3. Design and mesh of screen. 4. Portion of liner to be screened. 5. Manner of setting liner. 6. Preparation of or washing of the well before or during the setting of the screen. 7. Manner of bringing in the well. 8. Manner of flowing the well. Values applicable to the actual subsurface conditions that exist at any well can only be approximated. The accuracy of the estimate will be measured by the amount and quality of the evidence at hand and the personal factor of ability to interpret the evidence fairly, whether

Jan 1, 1932

By P. G. Shewmon, W. M. Robertson

The derivative of the surface tension with orientation, ??/??, for copper has been measured over the entire unit triangle. This derivative or torque term was determined from the variation of the dihedral angles at the intersection of twin boundaries and free surfaces. High-temperature anneals in graphite with a hydrogen atmosphere gave torque terms of 0.097 at (111), 0.066 at (100), and 0.0257 at (110). A variation from -36oto +23oC in the dew Point of the H2 had no effect on these values, nor did a change from 99.98 to 99.999 pct Pure copper. The removal of graphite from the system decreased ??/?? slightly. Considering the surface near a low-index plane to be smooth except for occasional steps, the free-energy increment per cm of step is calculated, and it is shown that the observed variation of ??/?? is consistent with a random distribution of steps and an interaction energy between steps. Integration of ??/?? gave the relative values of y at (100), (110), and (111) as comPared to ymax: (Y111/Ymax) =0.974, (Y110/Ymax) =0.996, (y100/Ymax) = 0.983. The ratio of the surface tension of coherent twin boundaries to the surface tension of the free surface was found to be (yT/ys) = 0.027 * 0.011. In a crystalline solid the surface tension y (surface free energy per unit area) depends on the orientation of the surface relative to the crystallographic axes of the crystal. Measurements of this variation of y with surface orientation have been reported for metals only within the last few years. Consider the grain boundary groove shown in Fig. 1. Here the three surfaces are all normal to the plane of the paper, and each has a different surface tension, y1, y2, and y3. If the system is at equilibrium, the total surface free energy must remain unchanged for a slight vertical displacement of the intersection (points A, B, and C are kept fixed). As shown by Herring,' the following equation is obtained:

Jan 1, 1962

By R. M. Foley, Hidesaburo Kurushima

About 25 pct of all Japanese pyrite comes from the Yanahara mine on Honchu Island. For the past 40 years lack of an economical recovery process forced the operator, Dowa Mining Co., to sell the pyrite for its contained sulfur only, leaving 7 million tons of high grade iron ore waste. Introduction of the Dorrco FluoSolids roasting system enabled the company to make use of its iron sulfides and also to find a market for the mine's considerable pyrrhotite production. The success of this project is of great importance to Japan's economy since it points the way toward material increase in her natural resources. Prior to use of the present process, no practical method was available for commercial exploitation of known large tonnages of pyrrhotite, while the copper content of the even larger deposits of pyrite made the roasted residue unacceptable for the iron and steel industry. In Europe, large amounts of copper-bearing pyrite cinder are given a chloridizing roast for separation of the copper and iron but this treatment is not economical in Japan where salt is imported from as far away as Egypt.

Jan 10, 1958

A self-appointed, committee consisting of J. Waldo Smith, Chairman, Richard S. Buck, J. J. Carty, J. Parke Channing, E. L. Corthell, Alfred Craven, Thomas Crimmins, Gano Dunn, George Gibbs, Alex. C. Humphreys, F. L. Hutchinson, Charles Warren Hunt, D. S. Jacobus, John W. Lieb, William Barclay Parsons, George H. Pegram, Charles F. Rand, Calvin W. Rice, Robert Ridgway, William L. Saunders, Merritt H. Smith, Bradley Stoughton, and William H. Wiley, organized a course of seven free lectures on military engineering, which were given by Captains Thomas M. Robins, Richard T. Coiner, Edward D. Ardery, Corps of Engineers, United States Army, and which was under direction of Major General Leonard Wood. The United Engineering Society presented, without charge, the use of the auditorium for the purpose of these lectures, but the interest proved to be more than three times as much as had been expected, and it was therefore necessary to divide the courses into three parts, one of which was given in the afternoon in the auditorium of the United Engineering Societies Building, one in the evening in the same place, and another in the evening in the auditorium of, the American Society of Civil Engineers. These lectures occurred on Mondays, from Feb. 14 to Mar. 27, 1916. The subjects and speakers were as follows: Feb. 14, 1916: Organization and Duties of Engineers in War, and what Engineers in Civil Life will be called upon to do in the Defence Of the United States. Captain Thomas M. Robins, Corps of Engineers. Feb. 21, 1916: The Service of Reconnaissance Including Surveying, Mapping and Sketching, Photography and Map Reproduction. Captain Richard T. Coiner.

Jan 5, 1916

By AIME AIME

Russell B. Paul, Chairman of the Special Committee on Divisional Relationships, presented the interim report of his Committee which was published in the September, 1945, issue of MINING AND METALLURGY and a copy of which is incorporated in the official minutes of this meeting. The following specific actions were taken by the Board of Directors in relation to the six recommendations in the Summary of the Report as published: (1) Mr. Haider, Chairman of the Petroleum Division, presented the formal request of his Executive Committee that the headquarters of the new Secretary of the Petroleum Division be established in Dallas, Texas. After lengthy discussion in which the point was made that the success of this program would depend upon effective co-operation between the Chairman of the Division, the Secretary of the Petroleum Division, and the Secretary of the Institute, the request was approved. The new secretary will be selected by the Division and will be employed by the Institute in the capacity of an Assistant Secretary. (2) The following item in the report was approved:

Jan 1, 1945

By C. Y. Garber

INTEREST in the sink-float plant operated by the Bunker Hill and Sullivan Mining and Concentrating Co. at Kellogg, Idaho, has recently been largely confined to the preparation and reconditioning of the galena medium. The ease and simplicity of these operations in a concentrating mill producing a flotation lead concentrate has occasioned enough comment to possibly justify a brief description. The subject is treated from an operator's viewpoint only; no effort is made to discuss it in a theoretical or technical manner. PLANT AT BUNKER HILL The sink-float plant was first operated in December 1941. It was built for the purpose of quickly increasing mill capacity with a minimum of equipment. It is the Huntington-Heberlein sink and float process using galena medium and is operated under license from the Sink and Float Corporation, New York city. Lead-zinc ore from the Bunker Hill mine is crushed to pass a I ¼ in. screen and is then washed and separated on vibrating screens having 4 ½ -mm. round-hole punched plates. The screen undersize, amounting to 33 per cent of the mill feed, is dewatered and sent to the ball-mill feed bins. The screen oversize goes to the sink-float plant, where 50 per cent of the oversize, or 33 per cent of the mill feed, is float, which is washed free of medium and disposed of as a tailing. The remaining 33 per cent is sink, which, after washing, is crushed to pass ½ in. and joins the undersize in the ball-mill feed bins. The normal plant capacity is 1700 tons per 24 hr. About 1.7 per cent of the total lead and 3.3 per cent of the total zinc in the feed is lost with the sink-float tailings (Table I). [ ] More complete descriptions of the H. H. process and Bunker Hill sink-float plant are given in several recent articles, listed at the end of the paper. PREPARATION OF MEDIUM AT BUNKER HILL New medium is made intermittently as needed, usually 12 hr. in each 6 days. A small portion of the current mill flotation concentrate is diverted from the lead cleaner cells to a I-in. vertical sand pump and pumped to a two-cell 36-in. Agitair flotation machine, where NaCn and ZnSO4 are added and the grade of concentrate is improved as shown in Table 2. Tailing from this operation is returned by gravity

Jan 1, 1946

By B. F. Tillson, C. M. Haight

I. General Remarks..........................723 1. Location............................723 2. Characteristics of the Orebody..................725 (a) Mineralogical (b) Shape, Strike, Dip, Size, Etc. (1) Ore (2) Country Rock 3. Historical Sketch........................725 11. Mining Method..........................726 1. Outline of Methods Now in Operation............... 726 (a) Stopes (b) Fill . (c) Pillars (d) Slices (e) Transportation (f) Miscellaneous 111. Mining Operations........................727 1. Shaft..............................727 (a) Sinking (b) Dimensions and Equipment, Sketches (1) Size, Inclination. Direction, Etc. (2) Timbering (3) Stations (4) Track (5) Hoisting Equipment (a) Skips (b) Engines and Ropes (c) Idlers (d) Man Cars (6) Loading Pockets (a) Operating Figures (7) Headframe

Jan 1, 1918

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

By N. A. Gokcen, J. Chipman

A revised treatment of the authors' published data eliminates the complex relation previously proposed between concentration of silicon and activity coefficient of oxygen in liquid iron. Revised values of the thermodynamic properties of the liquid solution are presented. IN a recent experimental study of the reaction SiO2 (s) = Si+ 2O; Kf, = [% Si] [% O]² [1] the authors' found a substantially constant equilibrium product in liquid iron at 1600°C of 2.8x10-5 They also reported extensive data on the reactions: SiO2 (s) + 2H2 (8) = Si- + 2H2O (g); K'2= [% Si] (H2O/H2 [2] and H, (g) + 0 = H2O (g); K'3 =( H2 O [31 (H2) [%O] From the results on reaction 3 and earlier data of Dastur² on this same reaction in the absence of silicon, they determined the activity coefficient of oxygen, f0, on the basis of the definition K3 = (H2O)/ (H2)f0 [% 0] where K, is the equilibrium constant and f0, is taken as unity in the pure Fe-0 system. Similarly values of fsi were deduced from results on reaction 2. In a more recent study" of analogous reactions in the system Fe-A1-0, it was found impossible to reconcile the results on reaction 3 with Dastur's data; accordingly the latter were ignored and the equilibrium results were extrapolated to find a value of K, at zero concentration of aluminum. This procedure failed to locate the cause of the discrepancy but it did yield reasonable values of activity coefficients. It also avoided introduction of the complex empirical relation between the oxygen activity coefficient and the concentration of the added element. The same type of discrepancy exists for system Fe-Si-0.' In the earlier paper an attempt was made to fit both sets of data by a single curved line (Fig. 6 of ref. l), the form of which is contrary to the theoretical requirement of a finite slope at infinite dilution. In the light of experience on the Fe-A1-0 system the discrepancy must be recognized as one which can be resolved only by more refined measurements. Accordingly Figs. 6 and 10 are retracted. It is pointed out also that until the discrepancy is resolved Figs. 7, 8, and 11 are subject to some uncertainty. Qualitatively the following conclusions still appear valid: 1—The activity coefficient of oxygen is reduced by addition of silicon. 2—In dilute solutions the activity coefficient of silicon increases with its concentration. 3—With respect to equilibrium in reaction 1, the above effects are approximately compensating. The discussion of K'1 in the previous paper requires no revision. It was pointed out that the constancy of the product [% Si] [% 0]² ndicated a compensating effect of the activity coefficients of silicon and oxygen. Therefore, as a very good approximation, K1 = K'1 and the following average values are suggested both for K, and K', at the temperatures 1550°, 1600°, and 1650", respectively, 1.0x10-", 2.8~10-" and 5.5 ~lo-'. Revision of the thermodynamic treatment is necessitated by the recent appearance of new data, based on a combination of combustion and solution calorimetry,' which yields for the heat of formation of low-cristobalite from the elements, the value —209,330 ±250 cal per mol at 25°C. This is about 4000 cal larger than the value previously accepted. The new value for cristobalite is used, together with Kelley's tables of high-temperature heat contents" and entropies and with Korber and Oelsen's' heat of fusion of silicon to obtain the following equation for the standard free energy of cristobalite in the temperature range 1700" to 2000°K: Si (1) + 02 (g) = Si02 (crist.); ?F° = -217,700 + 47.OT [4] The free energy of solution of 0, in liquid iron is:8 O2 (g) = 20 (in Fe); AF° = -55,860 - 1.14T [5] and these two equations are combined to give: Si (1) + 20 = SiO, (crist.); AF° = -161,840 + 48.14T [6] ?F°1873 = -71,700 cal. From the experimental value of K, = 2.8x10-5, Si + 20 = SiO2 (crist.); ?F°1873 = -39,000 cal. [7] The combination of Eqs. 6 and 7 yields the free energy change when liquid silicon dissolves in iron to form the dilute solution of unit activity (1 pct). Si (1) = Si; ?F°1873 = -32,700 cal. [8] The heat effect in this process according to Korber and Oelsen' is an evolution of 28,500 cal per gram

Jan 1, 1954

By R. F. Lynch, J. D. Wood

The Al-1.0 pct Mg alloy 565 7 was studied using optical microscopy and electron microprobe X-ray analysis. Constituent particles were found to exist inter-dendritically in the as-cast material in a region of precipitate free a -aluminum. Five phases besides a fine precipitate and a-Al were identified in the cast structure: Fel3, Fe2Al7, Mg2Al3, CUMgAl2, and Cu2FeAl7. Thermal treatments conducted for 100 hr at 1180°, 1130°, 1080°, 1030°, 980°, and 880° F revealed a general dissolution and spheroidization of the in-terdendritic constituent network observed in the cast structure. The principal constituents present in the thermally treated structures were FeAl3 and Fe2Al7 with the relative amount of Fe2A17 to FeAl3 increasing with a decrease in the treatment temperature. The phases Present in the wrought structure were identical to those observed after the thermal treatments, with the constituent particles strung out in the direction of rolling. ALLOY 5657 is a nonheat-treatable commercial purity Al-1.0 pct Mg alloy utilized extensively because of its bright finishing characteristics. This investigation was conducted to determine the constituents present in 5657 alloy, and to study the effect of extended thermal treatments on morphology. Numerous studies have been carried out to establish the equilibrium diagrams for various aluminum systems,1-3 with phase identification based on X-ray analysis, morphology, and the etching response of relatively large particles. Phragmen4 conducted a study of the phases in aluminum eutectic systems and compiled a "corrected" table of etching responses, drawing on his work plus that of Schrader,5 Keller and Wilcox,6 and Mondolfo.7 A review of the original work of Keller and Wilcox, and Mondolfo, which was concerned with the constituents found in commercial alloys, reveals that in numerous cases their etching responses differ from those reported by Phragmen and from each other. These inconsistencies may occur because a specific constituent will react to a given etch in a varying manner depending upon its size, the elements dissolved in the phase, the other constituents surrounding a phase, and the solute content of the matrix. Work with a commercial orientation was conducted on alloys 2024 and 3003 by Sperry8,9 and on alloy 3003 by Barker,10 where the relationship between the phase diagram and the nonequilibrium structure of an alloy was examined. Backerud11 investigated the A1-Fe binary system and found that at high cooling rates the equilibrium eutectic reaction forming a-A1 and FeA13 is replaced by another lower temperature eutectic reaction forming a-A1 and metastable FeAl6, a constituent first identified by Hollingsworth et al.12 Most of the above mentioned studies were conducted on materials having a significantly greater alloy content than 5657 alloy, where the relatively small size and sparse distribution of second phase particles hinders the process of identifying constituents. EXPERIMENTAL PROCEDURE Material with a composition as given in Table I was examined in the as-direct chill cast, hot rolled and cold rolled conditions, and after thermal treatment of the cast structure. Thermal treatments were terminated by a water quench. Microscopic examination was conducted under various lighting conditions following the application of standard etchants as specified in Table 11. A semi-quantitative electron microprobe X-ray analysis was conducted for Al, Mg, Fe, Cu, Si, Zn, and Ti. RESULTS AND DISCUSSION Microstructure of the As-Cast Material. Particles of second phase material were found to exist inter-dendritically, principally in regions of precipitate free a-Al, as illustrated in Fig. 1. Adjacent to the ingot edge was a region of inverse segregation, resulting in an increased amount of second phase material containing large sized particles which aided in phase identification. Phase Identification. Cast Structure. Five phases besides a-Al and a fine precipitate were identified using optical microscopy and electron microprobe X-ray analysis, as presented in Tables II and III, respectively. FeA13 and Fe2A17 are often found with Fe2A17 forming a sheath around the core of FeAl3, resulting from an incomplete peritectoid reaction. These phases have a nearly identical appearance under white light, although they are easily differentiated under crossed polarizers, as characteristically illustrated in Figs. 2(a) and 2(b), respectively. Microprobe analysis con-

Jan 1, 1970

By G. K. Manning, E. R. Stein, E. E. Underwood

Columbium, carbon. and nickel additions were made to iron-base alloys with 20 pct CY. The effects on microstructure, precipitation-hardening characteristics, and High-temperature properties were investigated by means of metallographic, hot-hardness, and magnetic measurements. An austenitic alloy consistilzg of Fe-20Cr-14Ni-0.8C-2.5Cb had higher hot-lzaciness at 1700°F than the other alloys investigated. Its favorable standing is attributed to an enhanced interaction of Cb and Cr4C particles dispersed within a stable austenitic matrix. FOR the past 20 years, cobalt- and nickel-base alloys have been used for the more stringent high-temperature applications because of their excellent creep resistance. Although their performance is quite satisfactory, other base materials must be considered for large tonnage, low-cost applications such as for the automotive gas turbine. Iron-base alloys are also used extensively, but at somewhat lower temperatures, primarily because of the instability of particles or because precipitation occurs at relatively low temperatures. Since unusual stability has been reported for Fe-Cb and Cb-C compounds.1-3 it was hoped that effective amounts of these compounds could be taken into solution at temperatures just below the melting range, then precipitated upon reheating. Actually, strengthening was found to occur by both precipitation hardening in some alloys and by phase transformations in others. Among the alloys investigated, that with the best high-temperature properties owes its strengthening to a combination of carbide particle interaction and a relatively stable austenitic matrix. EXPERIMENTAL PROCEDURES Small preliminary melts of about 100 g were made in a vertical Glotube furnace, using alundum crucibles and an argon atmosphere. Alloys weighing 35 lb were melted in a basic-lined induction furnace, also under argon. The compositions of the alloys are given in Table I. The nickel-free alloys were usually ferritic, while those containing nickel were generally austenitic. Depending upon the particular heat treatments, or the combination of alloying elements, two-phase alloys of ferrite and austenite could be obtained. In the following text, however, the nickel-free or nickel-bearing alloys are referred to simply as either ferritic or austenitic alloys respectively. The small ingots were swaged at 2000°F, in steps, to rods of approximately 3/16-in. diam. The large ingots were forged at 2100°F to 1-in. sq bars. No difficulties were encountered in swaging or forging any of the alloys to as much as 90 pct reduction in area. For heat treating at temperatures above 2000°F, specimens were sealed in quartz tubes under a partial pressure of helium. No special precautions were found to be necessary at lower temperatures. Intermetallic compounds in the preliminary alloys were identified by means of X-ray diffraction measurements. Correlation of these results with micro-structural characteristics (such as color, shape, size, and location) of the compounds aided in their identification. Magnetic susceptibilities were also obtained at room temperature with a Magne Gage instrument after the various heat treatments. To

Jan 1, 1962

Sykes, W. P.-Effect of Temperature, Deformation, Grain Size, and Rate of Loading on Mechanical Properties of Metals. Discussed by Zay Jeffries, W. H. Bassett, F. E. Carter 3 Evans, Geo. Watkin.-Alaskan Coal Fields. Discussed by P. N. Moore, H. H. Stoek, G. S. Rice, H. Emerson 4 Eavenson, Howard N.-Run-off and Mine Drainage. Discussed by J. R. Campbell, Andrew B. Crichton, J. B. Warriner, R. V. Norris, H. G. Moulton, H. B. Wright 7 Andrews, Allen, and Garcia, John A.-Skip Hoisting for Coal Mines. Discussed by R. V. Norris, Geo. S. Rice, H. N. Eavenson, E. A. Holbrook, Robert Obert, Andrews Allen, T. M. Chance 12 Rice, Geo. S.-Coal-pillar Drawing Methods in Europe. Discussed by Carl Scholz, D. Harrington; H. 1. Smith 16 Knapp, Arthur.-Modified Oil .well Depletion Curves. Discussed by Roswell H. Johnson 21 Alvey, Glenn H., and Alden W. Foster.-Barrel-day Values. Discussed by Roswell H. Johnson 22 Matteson, W. G.-Secondary Intrusive Origin of Gulf Coastal Plain Salt Domes. Discussed by Eugene Coste, E. W. Shaw, Joseph E. Pogue, F. G. Clapp, E. DeGoIyer, W. G. Matteson, H. W. Hixon, R. Van A. Mills 23 Reger, David B,-Carbon Ratio of Coals in West Virginia Oil Fields. Discussed by J. T. Singewald, Jr 33

Jan 5, 1921

By G. R. Love, C. C. Koch

The changes in superconducting properties with aging time have been studied ,for the pecipitation reaction in a Tc-30 at. pct V alloy. Superconducting critical temperature, upper critical field, and relative critical current density were determined by ac susceptibility techniques. Aging produces changes in critical temperature of both matrix and precipitate which can be rationalized by compositional effects. maximum flux pinning (critical current density) occurs at a time during aging when subgrain boundaries are completely decorated with precipitates and the subgrain centers remain precipitate -free. The particular effectiveness as barriers to flux motion of planar defects which enclose regions of low deject density is discussed. THE precipitation of a second phase can dramatically modify the superconducting properties of type I1 super-conductors. According to Livingston and Schadler1 one might expect changes in the primary, secondary, and tertiary superconducting properties of the material. Changes in matrix chemistry caused by precipitation can alter the fundamental superconducting parameters; critical temperature, Tc, and thermody-namic critical field, Hc. The concimitant changes in electron mean free path (reflected in normal state resistivity) can affect the critical fields Hc 1, IIc2, Hc3. Finally, the presence of precipitate particles may hinder the motion of flux lines and may considerably improve the current-carrying capacity in high-field superconductors. The influence of precipitation on superconducting properties has been studied in a number of systems.2 Magnetization measurements have been used to study the influence of precipitates on flux pinning in lead-base alloys by Livingston3 and Evetts et al4 In these alloys precipitates induced magnetic hysteresis and flux trapping. The amount of hysteresis increased with the volume fraction of precipitate and decreased with coarsening of the precipitate. Jn an Al-Zn alloy5 and an A1-Ag alloy6 the initial precipitate size was presumably smaller than a coherence length and coarsening increased magnetic hysteresis5 and critical current density.6 The influence of precipitation on superconducting properties has also been studied in several of the commercially interesting Ti-Nb7-10 and zr-Nb11 alloys. The maximum in critical current density for these alloys was confined to a narrow range of either isothermal aging time" or isochronal aging temperature7 during the precipitation reaction. Thus, experimental evidence and theoretical considerations suggest there is an optimum precipitate size, spacing, and density, and a critical composition with respect to the matrix for flux pinning. What these "optimum" values might be and the relative importance of each is still not clear, although a few generalizations can be made. It is generally accepted1' that particle sizes smaller than the coherence length or larger than the inter-flux line spacing are poor pinning centers. In high Hc2 materials, precipitate sizes for maximum values of critical current density lie in the range of 50 to 2000Å,9,7 and there are indications that increasing dissimilarity between precipitate and matrix produces increasing pinning force.13 Because of several interesting features of the aging reaction in a Tc-30 pct V alloy, we have chosen to study the influence of precipitation on the superconducting properties of this alloy. The physical metallurgy14 and a survey of the superconducting properties" of the Tc-V alloy system have been reported. The Tc-V phase diagram is presented in Fig. 1. At 1500°C the Tc-30 pct V alloy is in the single phase 6 field. Samples quenched from the 6-phase field have a CsCl structure X-ray diffraction pattern at room temperature and it has been proposed that the 6 structure is closely related to the bcc lattice.14 When held isothermally below the eutectoid temperature, 115O°C, the 6 phase decomposes into the CsCl and hcp phases.

Jan 1, 1970

By William H. Shockley

THERE was an, extensive mining and industrial exploitation of Russia, about 20 years ago, by Belgian, French and British capitalists; but the results were discouraging. It is said that the Belgian and French public together lost approximately $400,000,000, chiefly in the coal and iron industry of southern Russia. This loss is largely accounted for by the fact that most of the companies were formed, as usual in " boom " times, to sell stock; and that thorough investigations were not made. In 1906, renewed interest was taken in Russian mines, especially in those of gold and copper, and a considerable literature is growing on this subject; but as yet I have seen no account of one of the large Russian mining estates. The following notes on such property, where the conditions are so different from those in the mining regions of the United States, should be of interest This inadequate and probably somewhat inaccurate account is made up, partly from my own notes made on the ground, in the summers of 1904 and 1905, and partly from a volume on the geology and resources of the estate issued several years ago, containing surface-and mine-maps, and from a pamphlet published in 1904, giving a general account of the condition and prospects of the property. This pamphlet includes a report made by Arthur L. Pearse, a member of this Institute, in 1899. Both these books are in Russian, and were prepared by the Bogoslovsk Mining Co., which owns and operates the property. Articles in many other languages have appeared dealing with various matters connected with the estate; but I know of no other general account of it. In numerous books and articles on the Urals and Siberia, however, localities are described in which somewhat similar conditions prevail. Recent papers by

Mar 1, 1908

By Albert Sauveur

This paper explains the possibility of using advantageously a boiling solution of sodium picrate to reveal dendritic segregation in steel. The mechanism of the action of the reagent is described. The failure of manganese alone to produce persistent dendritic segregation is also considered. 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.1 For this purpose, a cupric 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

Jan 2, 1924

By W. H. Class

The embrittling effects of oxygen, ozone, nitrogen, air, and surface residues, on NaCl has been investigated. The embrittlement by ozone and oxygen was found to be associated with the formation of a NaClO3 surface compound. In these cases the initial crack that was responsible for fracture (in a bend test) always nucleated at the corners between the tension and side faces. The behavior of air was very erratic and on certain days did not produce enzbrittlement. During these periods, crystals that had become embrittled by the ozone treatment completely recovered their ductility after a short exposure to the ambient atmosphere, It was established many years ago1 that considerable ductility could be obtained in NaCl single-crystal specimens if the crystal surfaces were dissolved in water either during or immediately prior to the test. The original interpretation of this effect by Joffe attributed the enhanced ductility to the removal of surface microcracks by dissolution. Later investigations2'3 have suggested that the exclusion of air from the specimen surface is the criterion for extensive plastic flow prior to fracture. The air em-brittlement in this later work was attributed to the diffusion of gaseous atoms into the surface layers of the crystal, thereby impeding the movement of dislocations. This model satisfactorily accounts for the reembrittlement observed after further air exposure subsequent to the water dissolution treatment. However, the situation has recently become more complex by the observations in several laboratories4-t that under certain conditions air exposure does not impair the ductility of NaC1. It has also been recognized5 that improper drying operations after water dissolution can leave surface precipitates that lead to embrittlement. Cleavage defects on as-cleaved crystals can often be another source of embrittlement. In the present work the effect of the gaseous atmospheres nitrogen, argon, air, oxygen, and ozone, on the ductility of rock salt was studied extensively. The embrittlement resulting from oxygen and ozone exposures was found to be associated with the formation of a NaC1O3 surface film. It is suggested that certain atmospheres, one of which often can be ambient air, which inhibit the formation or favor the decomposition of this compound, can promote ductility. Thus one aspect of the Joffe effect is certainly related to the removal of surface compounds or complexes by water dissolution. The effect of surface precipitates that remain after drying operations and of cleavage defects were also studied. In neither of the latter cases was the embrittlement as severe as that found with a NaClO3 surface layer. PROCEDURE AND SPECIMEN PREPARATION The nature of the embrittlement produced by the agents mentioned above was studied by means of microscopy, mechanical testing, and X-ray diffraction. Specimens were cleaved from large crystals of optical quality sodium chloride obtained from the Harshaw Chemical Co., and, except for those tested in the as-cleaved condition, were given a 15- to 20-sec immersion in distilled water followed by a rinse in absolute methyl alcohol. The specimens were then blotted on a soft, absorbent paper, and dried by a few seconds exposure to a stream of warm, dry air. Such a procedure was found to give a control surface which was microscopically free of residues. (A few crystals were intentionally painted with a concentrated NaCl solution in order to investigate the effect of surface residues). All specimens were of 0.140 sq in. cross-section. Crystals prepared in the above manner were immediately placed in a gas train where they could be exposed to the desired gases for preselected periods of time. For the oxygen and nitrogen exposures, pure reagent-grade gases were employed. The ozone was provided in the form of an ozone-oxygen mixture (approximately 10 pct ozone) prepared by passing commercial grade oxygen over a strong ultraviolet light source. All gases were dried prior to their introduction into the train. Since argon was found to be completely inert in its behavior (i.e., residue-free specimens that were exposed to argon were not embrittled), it was periodically utilized to check the control specimen surfaces as well as the condition of the gas train used for aging the specimens. After exposure to the gaseous media in question, the crystals to be used for the measurement of the strain to fracture were transferred from the gas train to a protective oil bath (without further exposure to the atmosphere) where the tests were conducted in three-point bending. The apparatus was so adjusted that the load could be applied at a constant, continuous rate. Other Snecimens from the gas train were deformed

Jan 1, 1962