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By AIME AIME

PLANS for the Semi-centennial Meeting have almost reached completion, although in any undertaking of such magnitude a few changes are always to be expected at the last moment. As worked out up to the time of going to press, the program of the meeting is shown below. The headquarters will be the Irem Temple, in Wilkes-Barre.

Jan 1, 1921

THE committee in charge of arrangements for the meeting of the Institute in September has com-pleted its program. The headquarters of the meeting will be at the Palace Hotel, San Francisco, and the registration committee will be at the hotel all day on Sunday, Sept. 24, and from 8 a.m. until noon on Monday. On Sunday afternoon, automobiles will be available for sightseeing trips around the city. Monday will be devoted to technical sessions. In the morning, there will be sessions on Mining and on Iron and Steel; in the afternoon, sessions on Mining and Milling. At these sessions, in addition to the papers mentioned in the tentative list printed in August, there will be presented three papers on the geology, mining and milling of the Comstock lode; one on the Aztec mine, Baldy, N. M.; one on the Colombian oil fields; and one on charcoal precipitation of cyanide solutions. The luncheon on that day will be Dutch Treat, for men only, at the Engineers Club. On Monday evening, there will be an informal buffet supper at the home of F. W. Bradley. On Tuesday morning, a party of 50 men will leave for Hetch Hetchy. During the four days of the trip, the party will see the Priest tunnel and earth dam under construction by steam-shovel and hydraulic-fill methods, the Big Creek shaft and tunnel, early intake power plant and tunnels and the Hetch Hetchy dam under construction. For those who remain in San Francisco, Tuesday will be "San Francisco Day." There will be motor trips to the Presidio, Cliff House, Golden Gate Park, and other points of interest, and shopping trips to Chinatown. On Wednesday, "University of California Day," the party will be guided through the university by members of the Mining Association, the affiliated stu-dent society, and will see the Greak Theatre and not-able buildings. Thursday will be "Leland Standford, Jr. University Day." Automobiles will leave the Palace Hotel at 10 a.m., and will return from the university at 4.30 p.m. Friday has been reserved for trips to the Selby Smelter, to Mt. Tamalpais, or to other points of interest. Arrangements will be made to visit the mines or gold dredges in California, if members desire to do so, but such trips must of necessity be considered special trips and arrangements will have to be made to suit the convenience of the individual or party. The Golf Committee will make arrangements for those who wish to play golf.

Jan 9, 1922

By R. T. Hukki

THE accepted basis of comparisons between mills of different diameter is the percentage critical speed. If n = actual mill speed, rpm, nc = calculated critical speed, rpm, np = calculated percentage critical speed, and D == inside diameter of the mill in feet, then n, In the following analysis capacity, T, is expressed in short tons per hour, tph, and power consumption, P, in kilowatts, kw. Accordingly power consumption per unit of capacity, P will be expressed in kilowatt hours per short ton, or kw-hr per ton. In all equations D refers to the inside diameter of the mill in feet and v to the peripheral speed of the mill in feet per minute inside the liners. ' Comparison between separate mills must be based on equivalent grinding conditions, i.e., same feed, same size distribution of feed, same size distribution of product, and same percentage of solids. In addition, comparisons between separate rod mills must be based on the same rods, same type of liners, and same percentage rod load. Comparisons between separate ball mills presuppose the same balls, similar liners, and same relative ball load. The practical np-range through which the equations apply varies, being narrower for fine grinding in ball mills and wider for coarse crushing in rod mills. The Relationship between Capacity and Speed It is the general belief that the capacity, T, of a tumbling mill is directly proportional to the speed of the mill, other things remaining constant.' Mathematically this is represented by the equation T - c¹ n tph [4] where c, is a factor related with the grinding characteristics of the ore, method of reduction, and the units chosen. It is proposed here that the general equation relating mill capacity and speed should be of the form T = c¹ nm tph [5] In other words, the capacity should be proportional to the mill speed raised to power m, the numerical value of the exponent being 1 5 m 5 1.5, depending on the circumstances. Eq. 5 can also be written in the following forms: T = c, (np)m tph, and [6] T=Ca vm tph, [71 where v = peripheral speed of the mill in feet per minute. If the observed capacity of a mill at speed n¹ is = T¹ tph, the capacity T² of the same mill at speed n² should be T² = T¹ (n²/n¹)tph [8] The Relationship between Power Consumption, Mill Diameter, and Speed The only well known theoretical deduction relating power consumption, P, and mill diameter appears to be the formula of duPont introduced by Gow, Guggenheim, Campbell, and Coghill.' According to duPont, the power required to operate a mill is a function of the mass of the balls, of the lever arm of the ball mass, and of the speed of the mill. The ball mass per unit of mill length is proportional to the square of the diameter, the lever arm is directly proportional to the diameter, and the critical mill speed or any percentage thereof is inversely proportional to the square root of the mill diameter. Following this reasoning, the original duPont formula is of the form P = c4D² c D • c6D-0.5 = c7D2.5 [9] If the mill speed in the above equation is expressed in terms of Eq. 3, the duPont formula may be written as follows: P=f1(D2) f2(D) f³(—np) or [10] vD P = c np D2.5 kw [11] Eq. 11 may also be derived from the mechanical principle of force, which is equal to mass x acceleration. Power necessary to operate a mill may be considered to be an homogeneous linear function of the force developed. Ball or rod mass per unit of mill length is a function of D2. The acceleration factor of the ball or rod mass is a function of the peripheral speed of the mill. Thus P = f4(F) = /x(D2) f5(v) Indicating that v = nDn, and n = c9 np /vD, the above equation becomes P = f2 (D2) -fa (D ca np/vD

Jan 1, 1955

By T. P. Chen, F. W. Bowdish

Studies made with a captive bubble apparatus on the sulfidization and collection by amyl xanthate of true chrysocolla specimens have defined the ranges of pH value and sulfide concentration which permit contact between the bubble and the mineral surface. Titanium compounds were the most effective of the materials found to activate the sulfidization of chrysocolla. With titanium activation, the contact angles and the ranges of pH value and sulfide wncentration giving bubble contact were all increased. Chrysocolla ores were concentrated by flotation. Chrysocolla ores occur at many localities in grade and quantity sufficient to make mining and millin feasible, but no satisfactory method of concentratio has been found. Although chrysocolla may be leached with acid, only those ores without acid-consuming gangue may be leached economically. Because of its potential importance, a study of the conditions nece sary for flotation of chrysocolla has been carried ou The literature contains a few references to flotation of chrysocolla. Two methods were developed by the U. S. Bureau of Mines.1,2 The first consisted of a fatty acid soap and a high xanthate as collectors of chrysocolla from a synthetic ore, while the second involved the use of hydrogen sulfide and xanthate. Ludt and DeWitt3 demonstrated the difference in adsorptive powers of chrysocolla and quartz for bas triphenyl methane dyes and suggested the use of butyl, hexyl or octyl-substituted malachite green as collector. Jackel4 emphasized the effects of combin tions of reagents such as Aerofloat 31, pine oil, and Reagents 404 and 425 with sodium sulfide and zinc hydrosulfite as conditioning agents. Although he reported recoveries of 89% from a synthetic ore and 98% from a natural ore containing azurite, malachite, chalcopyrite and chrysocolla, careful application of Jackel's method to chrysocolla from Tyrone, N.M., failed to give a high recovery. MATERIALS AND TECHNIQUE Samples from Inspiration, Ariz., and Tyrone and Magdalena, N. M., were used for experimentation and verified as true chrysocolla by leaching tests, specific gravity tests and X-ray diffraction. Chrysocolla does not dissolve at pH 4, although malachite and azurite do. Chrysocolla is about half as dense as the copper carbonates. X-ray diffraction analyses by the powder camera method confirmed the samples as true chrysocolla. A captive bubble apparatus, which cast an enlarged image of the air bubble and the mineral surface upon a screen, was used to check on the character of the surfaces. The specimens were prepared by grinding a flat surface on a glass plate using fine abrasive; then they were washed and kept in distilled water until they were to be treated with reagents. Before each reagent treatment, the specimen was carefully checked for cleanliness in the captive bubble apparatus. It was assumed that the surface was clean if, after fine grinding and washing of the specimen, the bubble would not stick. Specimens were handled with glass forceps, and precautions were taken to avoid contamination of the mineral surfaces. Contact angle measurements were carefully made several times on each treated specimen to obtain reliable average values. EFFECT OF pH VALUE AND SODIUM SULFIDE CONCENTRATION In each experiment, a specimen with a freshly ground surface was immersed for 10 min in a solution of sodium sulfide, washed and immersed for 15 min in a solution containing 30 mg per 1 of potassium amyl xanthate. The specimen was then washed again in distilled water and tested for contact angle in the captive bubble apparatus while submerged in distilled water. In this series of experiments, the pH of the sulfidizing solution was varied from 3 to 7, and the concentration of sodium sulfide, containing 60% Na2S, was varied from 50 to 650 mg per 1. Many combinations of pH value and sulfide concentration resulted in no contact between the bubble and the surface, but over a limited range of conditions, contact angles varying from 24ºto 52ºwere obtained. The data in Fig. 1 show sulfidization conditions that lead to bubble contact and those that do not. The region of contact is surprisingly small, which may indicate why flotation of chrysocolla involving sulfidization has proven so difficult in practice. Several features of the system are illustrated in Fig. 1. In the region between pH values of 4 and 6 with sodium sulfide concentrations below about 350

Jan 1, 1963

By David J. Mack, Chin Bea Kim

The decomposition of the Ni-Zn eutectoid at 56 wt pct Zn was studied by isothermal transformation. Its progress was followed by metallographic, hardness, and X-ray diffraction methods. Three transformation products were found: lamellar pearlite at high temperatures; an intermediate temperature structure; and martensite at the lower temperaCures. No transition structu,ves were found. THE decomposition of the Ni-Zn eutectoid at 56 wt pct Zn was stuadied as part of a long-range program of study on the eutectoid transformation in alloy systems which do not have one or more components which exhibit allotropy. Available information on the Ni-Zn eutectoid transformation is limited to that presented in connection with the determination of the phase dilagram. No systematic studies of the eutectoid were found in the literature, alkhough the microstructures of the Ni-Zn eutectoid were reported by Tamuru.3 X-ray diffraction data exist for the ß, ß1, y , and y1 phases.' EXPERIMENTAL PROCEDURE The eutectoid alloy was prepared from "A" nickel shot and Bunker Hill super-purity zinc (99.998 pct).

Jan 1, 1962

By Shrikant Lele

INTRINSIC and extrinsic stacking faults may be formed in fcc structures by similar processes with bounding S-and D-Shockley partial dislocations respectively.' The only difference between these two dislocations is that the side on which the fault lies is reversed. The number of nearest and next nearest neighbors of atoms is identical for the two faults, but that of next next nearest neighbors is different. Thus, the energies associated with intrinsic and extrinsic faults may be expected to be different but of the same order of magnitude. An extrinsic fault can be constructed from two intrinsic faults on adjacent close-packed planes. This suggests that the extrinsic fault energy is higher than the intrinsic fault energy. It is, therefore, surprising that extrinsic faults have not been detected in X-ray studies2 of deformed alloys of low stacking fault energy. These have, however, been observed in cerium3 by X-ray diffractometry and in Au-4.8 at. pct Sn4 and Cu-16.6 at. pct A15 alloys by transmission electron microscopy.

Jan 1, 1968

By C. M. Tucker, K. R. Van Horn, W. P. Sykes

Recent investigations of the molybdenum-carbon alloys have been reported by Becker and Ebertl,‡ Westgren and Phragmén2, T. Takei3, and H. Tutiya4. Takei3 studied the Mo-C system by employing metal-lographic and X-ray methods, and the other publications described the determination of the crystal structure of the molybdenum carbides. In exploring this system by a technique previously applied to the tungsten-carbon series5, the results of Takei were confirmed with two definite exceptions; i.e., first the composition of the eutectic, and second the nature of the carbon-rich intermediate phase. Consequently, a more thorough examination of the molybdenum-carbon constitution was initiated in an effort to correlate the data supplied by the microstructures, diffraction patterns and chemical analyses. Metallographic Investigation A briquette of molybdenum powder when heated in a carburizing atmosphere at 1500" to 1600" C. for several hours develops the carbon-rich layer shown in Fig. 1. The carburization was accomplished by placing the briquette in a carbon tube, which was heated in the hydrogen atmosphere of an alundum muffle wound with tungsten resistor. While the macrostructure indicates two distinct shells, and suggests the possibility of two carbon-rich phases, no evidence of this condition could be detected by the microscope, which revealed but one high-carbon constituent. This carbide forms next to the molybdenum as a relatively dense, light-colored zone (Fig. 2) which passes abruptly into an outer layer of spongy texture. As will be noted later, only one intermediate phase was observed in the X-ray photograms prepared of different locations in the carburized zone. The metallographic structure at the inner border of the shell, reproduced in Fig. 3, shows a marked porosity accom-

Jan 1, 1935

By C. M. Tucker, K. R. Van Horn, W. P. Sykes

Recent investigations of the molybdenum-carbon alloys have been reported by Becker and Ebertl,‡ Westgren and Phragmén2, T. Takei3, and H. Tutiya4. Takei3 studied the Mo-C system by employing metal-lographic and X-ray methods, and the other publications described the determination of the crystal structure of the molybdenum carbides. In exploring this system by a technique previously applied to the tungsten-carbon series5, the results of Takei were confirmed with two definite exceptions; i.e., first the composition of the eutectic, and second the nature of the carbon-rich intermediate phase. Consequently, a more thorough examination of the molybdenum-carbon constitution was initiated in an effort to correlate the data supplied by the microstructures, diffraction patterns and chemical analyses. Metallographic Investigation A briquette of molybdenum powder when heated in a carburizing atmosphere at 1500" to 1600" C. for several hours develops the carbon-rich layer shown in Fig. 1. The carburization was accomplished by placing the briquette in a carbon tube, which was heated in the hydrogen atmosphere of an alundum muffle wound with tungsten resistor. While the macrostructure indicates two distinct shells, and suggests the possibility of two carbon-rich phases, no evidence of this condition could be detected by the microscope, which revealed but one high-carbon constituent. This carbide forms next to the molybdenum as a relatively dense, light-colored zone (Fig. 2) which passes abruptly into an outer layer of spongy texture. As will be noted later, only one intermediate phase was observed in the X-ray photograms prepared of different locations in the carburized zone. The metallographic structure at the inner border of the shell, reproduced in Fig. 3, shows a marked porosity accom-

Jan 1, 1935

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.'-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968

By K. D. Jacob, H. L. Marshall, D. S. Reynolds

All types of commercial phosphate rock produced throughout the world contain fluorine in quantities ranging from approximately 0.4 to 1.3 per cent in the Curacao and Christmas Island phosphates to 3.1 to 4.2 per cent in the phosphates of the United States and North Africa1. For a given type of rock, the fluorine content is usually roughly proportional to the phosphorus content. Significance of Fluorine in Phosphate Rock On the basis of chemical and X-ray diffraction studies, Hendricks and co-workers2 concluded that fluorapatite, Cal10F2(PO4)6, is the essential phosphatic constituent of the commercial types of domestic phosphate rock. On the other hand, Bredig and co-workers3 have recently advanced the opinion, also based on X-ray diffraction studies, that the mineral phosphates usually contain carbon dioxide in the apatite lattice, and that the phosphate rocks of the United States are really fluorcarbonate apatites. However, the domestic types of phosphate rock do not seem to differ greatly from coarsely crystalline fluorapatite in their behavior toward chemical reagents in general, and for the purpose of this paper it will suffice to consider fluorapatite as being the essential phosphatic constituent of these types of rock. The available data1 indicate that the different commercial types of domestic phosphate rock usually contain about 12 to 52 per cent more fluorine than theoretically is required to form fluorapatite with all the phosphorus. Calcium fluoride (fluorite) has been definitely identified in only a very few of the samples that have been examined1,2. Bredig and co-workers4 state that fluorapatite can take into its crystal lattice excess calcium fluoride to the extent of approximately 70 per cent of that theoretically required by the formula Ca10F²(PO4)6 without causing more

Jan 1, 1938

By D. S. Reynolds, K. D. Jacob, H. L. Marshall

All types of commercial phosphate rock produced throughout the world contain fluorine in quantities ranging from approximately 0.4 to 1.3 per cent in the Curacao and Christmas Island phosphates to 3.1 to 4.2 per cent in the phosphates of the United States and North Africa1. For a given type of rock, the fluorine content is usually roughly proportional to the phosphorus content. Significance of Fluorine in Phosphate Rock On the basis of chemical and X-ray diffraction studies, Hendricks and co-workers2 concluded that fluorapatite, Cal10F2(PO4)6, is the essential phosphatic constituent of the commercial types of domestic phosphate rock. On the other hand, Bredig and co-workers3 have recently advanced the opinion, also based on X-ray diffraction studies, that the mineral phosphates usually contain carbon dioxide in the apatite lattice, and that the phosphate rocks of the United States are really fluorcarbonate apatites. However, the domestic types of phosphate rock do not seem to differ greatly from coarsely crystalline fluorapatite in their behavior toward chemical reagents in general, and for the purpose of this paper it will suffice to consider fluorapatite as being the essential phosphatic constituent of these types of rock. The available data1 indicate that the different commercial types of domestic phosphate rock usually contain about 12 to 52 per cent more fluorine than theoretically is required to form fluorapatite with all the phosphorus. Calcium fluoride (fluorite) has been definitely identified in only a very few of the samples that have been examined1,2. Bredig and co-workers4 state that fluorapatite can take into its crystal lattice excess calcium fluoride to the extent of approximately 70 per cent of that theoretically required by the formula Ca10F²(PO4)6 without causing more

Jan 1, 1938

By AUDLEY H. STOW

I. INTRODUCTION. THE general drift of the discussion as to the relative merits of pressure- and exhaust-fans has resulted, if we may judge from the prevailing practice, largely in favor of the latter. The subject has been hitherto treated, however, with special reference to highly gaseous mines, the effect of the form of ventilation upon dust-explosions having been too little considered. Even in mines containing practically no gas, dust-explosions may occur; and if, as I believe, pressure-fans are to be preferred for their effect upon dust, it may be worth while to reopen the debate, and to challenge the advisability of exhaust-ventilation under certain conditions. There are several forms of colliery-ventilation, which may be described as follows: Plain or simple pressure-ventilation, in which the fan acts as a pressure-fan, and the movement of coal is unobstructed at the surface by doors or equivalent devices in drifts or shafts, the traveling and haulage thus being in the return-current. Plain exhaust-ventilation, in which the fan acts as an exhaust-fan, the movement of coal being likewise unobstructed at the surface, and the traveling and haulage being in the intake. Obstructed pressure-ventilation, in which the movement of coal is obstructed at the surface, in order that the traveling and haulage may be in the intake. Obstructed exhaust-ventilation, in which the movement of coal is obstructed at the surface, in order that the traveling and haulage may be in the return. The apparent advantages in running a fan "pressure" during working-hours, and " exhaust" between shifts, seem to justify the recognition of this combination as a standard form of ven-

Feb 1, 1909

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970

Jan 1, 1893

By A. E. Gorum, J. Washburn, E. R. Parker

Experimental evidence was obtained in support of the idea that cleavage fracture can be initiated by dislocation pile-up. The high ductility of MgO crystals when tested in bending comPared to their relative brittleness in tension was explained on the basis that large pile-ups are more likely in a tension specimen. CLEAVAGE fractures have been a problem of major concern for many years. A number of large steel structures have failed in a brittle manner, usually suddenly and without warning; often the failures occurred for no obvious reason and at nominal stress levels well within the generally accepted range. A great deal of data have been collected about factors that contribute to failures,1 but the physics of the fracture process has never been revealed. cottrel12 has recently developed a theory of brittle fracture in ductile materials which was based upon the concept that dislocations moving on two intersecting planes can unite to form a crack nucleus. This theory accounts for the known effect of grain size and for the effect of testing temperature. There has, as yet, been no experimental evidence published that would substantiate this or the earlier theories based on stress concentrations due to piled-up dislocations. The study reported herein was conducted to obtain information that would either substantiate or disprove the

Jan 1, 1960

By C. R. St. John, R. W. Lindsay, Charles R. Austin

MANY of the factors influencing the creep behavior of ferrous alloys have been investigated and reported upon in the literature, including such variables as grain size, steelmaking practice, nature and stability of the microstructure, and the effect of alloying elements in steels. However, with respect to the latter, the microstructures involved are usually heterogeneous and as a result the effect of the addition is related to its effects on the various phases present in the microstructure. In the instances where this structure consists of ferrite and carbide, the behavior of the alloy addition will be related to its action in strengthening ferrite and in opposing temperature softening of ferrite as well as coalescence of carbide. The present paper is the third in a series comprising a comprehensive review of investigations on the properties of iron binary alloys. 1.2 Its purpose is to describe the results of isolating one microstructural phase, namely ferrite, and studying its creep characteristics in both the unalloyed and alloyed conditions. This should aid in establishing to a large degree the importance of ferrite in the creep behavior of steels consisting of the previously mentioned ferrite-carbide aggregate. REVIEW OF PREVIOUS WORK In view of the fact that the present investigation deals only with the effects of silicon, manganese, chromium, molybdenum, nickel, and cobalt, and to a certain extent with the effects of carbon, the review of previous literature will be confined to these elements. Practically no references were encountered dealing with the influence of these elements on the creep characteristics of the isolated phase. However, various contributions have dealt with the creep behavior of low-carbon steels alloyed with the elements under consideration. A particularly concise review in this respect is given by Bullens (Battelle)3 and much of this material has been drawn upon. The definite improvement in creep resistance and high-temperature strength conferred by molybdenum is well known. Published suggestions by the A.S.M.E.4 permit of an increase of some 2000 to 5000 lb. per sq. in. in permissible design loads over a temperature range from 650° to 1000°F. as a consequence of additions of 0.40 to o.60 per cent of this element in carbon steels of the order of o.25 to o.35 per cent carbon content. Babcock and Wilcox Tube Co.5 has published data showing the pronounced increase in stress necessary to cause one per cent creep per 10,000 hr. when additions of 0.5 or 1 per cent molybdenum are made to a plain carbon steel. These data apply to temperatures over a range from 800° to 1000°F.

Jan 1, 1945

By J. E. Burke, C. W. Mason

IN attempting to study precipitation from a tetragonal lattice using solid solutions of bismuth in tin, it was found that although a Widnmanstatten pattern is observed 1 only a qualitative analysis of the orientation relationships is possible, because of the unusual structural changes that accompany the precipitation process MICROSCOPICAL STUDIES Alloys were made from Chempur tin (Standard samples 42b and 42c, National Bureau of Standards), and bismuth (Kahlbaum C P ) by melting neighed quantities together under palm oil, stirring well, and casting in a heated graphite mold The polishing and etching techniques employed largely govern the visibility of the structural changes The preliminary surfacing operations were similar to those recommended by Villela and Bergekoff,5 through BehrManning 3/o abrasive papers, lubricated by a solution of paraffin in kerosene A rough metallographic polish was next given, using a thin cotton cloth charged with relevigated alumina (maximum particle size of about 4µ) and soap solution, repeated etching and polishing served to remove disturbed metal For high-power examination better preparation was necessary It was found that on such soft metals the threads of the fabric, rather than the abrasive, cause most of the scratching Cotton outing flannel, which had been brushed so that the nap lay down, was fairly satisfactory, but a Heavy grade of silk velvet (not the noncrushable kind) was found to be better, especially after some use A better procedure was as follows The metal lap was warmed slightly, and a 4-in circle of woolen broadcloth was cemented to its center by a thin film of melted paraffin The broadcloth was then moistened with water, and a 30 to 40 per cent solution of sodium hydroxide heated to about 50°C was poured over it, allowed to stand for 1 to 2 min and then washed off It was neither necessary nor desirable to remove all the sodium hydroxide from the cloth, since its etching action aided in the removal of the flowed layer from the sample The cloth was then charged with a paste of the relevigated alumina in water Since this lap did not remove deep scratches, it was necessary previously to polish the specimen on some material such as the silk velvet The sodium hydroxide softens and partly gelatinizes the woolen lap covering, permitting a scratch-free polish, but its action continues, and the cloth deteriorates after about 24 hr This is not serious, because a new lap can be prepared in about 5 min, and only small pieces of cloth are used Etching with a strongly acid solution of ferric chloride was found satisfactory for removing the flowed layer For the final etching, the most satisfactory reagent was that of Taffs,7 the formula for which is FeC13 6H20, 2 grams, HC1, 5 c c , H2O, 30 c c , C2H5OH (95 per cent), 60 c c This etchant reveals differences in com-

Jan 1, 1941

By Allan T. Gwathmey, J. Bruce Wagner, Kenneth R. Lawless

Between 250°and 550°C in oxygen pressures of 10 to 760 mm Hg, the relative oxide thicknesses formed per unit time on the (100), (111), (110), and (320), decreased in this order. The predominant oxide orientation was (001)Fe3O4 and [110] Fe304 A small amount of a-Fe2O3 which exhibited a fiber pattern was observed in all oxides except those formed at 250°c in low oxygen pressures. IN order to understand the properties and behavior of thin films, particularly their role in oxidation reactions, there is needed more experimental information on their structure, composition, and kinetics of formation on clean surfaces of known geometry. The present study was undertaken to obtain such information for thin oxide films formed on single crystals of a body centered cubic metal, iron. Crystals in the form of spheres were used in order to expose all possible crystal planes to the reactant gases simultaneously. Using this procedure the relative rates of oxidation of all planes could be estimated, and those exhibiting, maximum or minimum oxidation rates could be selected for a more intensive study of composition and expitaxy. Since the three types of information were obtained from the same experiment using a single crystal substrate, any differences between rate, composition, and expitaxy on the several planes may be attributed to the influence of the substrate structure. EXPERIMENTAL The starting material for this study was Armco iron rods, 6 in. long and 3/8 or 1/2 in. in diam. The analysis was reported to be 99.8 pct Fe, with major impurities listed as carbon 0.018 pct, manganese 0.027 pct, phosphorous 0.005 pct, sulfur 0.029 pct, silicon 0.005 pct, and copper 0.11 pct. These rods were cleaned with ether and heated in an atmosphere of moist hydrogen at 950°C for three days. The purpose of this treatment was to decarburize the iron and to provide a consistent, uniform grain size for the growth of single crystals. Crystals in the form of rods, up to 1/2 in. in diam and 2 in. long, were prepared by a method similar to that reported by Leidheiser and Buck.2 Spherical crystals, 3/8 and 1/2 in. in diam and having a handle about 1/4 in. in diam by 112 in. long, were machined from the single-crystal rods. After machining, each crystal was etched in aqueous nitric acid to remove the cold-worked metal at the surface. Before each experiment, the crystal was polished mechanically with metallographic papers through number 4/0, and electropolished in a perchloric acid-acetic anhydride mixture by the method of Jacquet and Rocquet.3 The crystal was washed in running distilled water for at least 5 min. The excess water was blotted with a soft paper tissue, and the crystal was placed in an all-glass reaction vessel (See Fig. 1). The crystal was heated at 550°C in hydrogen for at least 8 hr prior to the oxidation in order to reduce any surface oxides and to help relieve any stresses in the metal. For the structure and composition studies, flat faces were cut parallel to (loo), (111), and (110) planes on the iron crystal spheres. The orientation of these faces was checked by a back-reflection X-ray diffraction technique. The faces were within 2 deg of the desired orientation. The flat faces were treated as described above except that prior to electropolishing they were given an additional polish on metallographic felt saturated with twenty-minute levigated alumina. After the crystal was heated in hydrogen for at least 8 hr, the temperature was adjusted to the desired value, and the hydrogen was evacuated. Commercial oxygen which had been purified by successively passing through tubes containing magnesium perchlorate, Ascarite and magnesium perchlorate was admitted to the desired pressure as measured by a mercury manometer. A resistance-wound furnace surrounded the oxidation chamber, and a temperature controller maintained the temperature within ±3°C. The furnace was provided with a small window for observing the crystal. The changes in thickness of the oxide films were followed by observing the interference colors. The oxidation was allowed to proceed until the desired oxide thickness was attained on a given crystal plane. The experiment was terminated by evacuating the oxidation

Jan 1, 1962

By Kim Beattie

IN spite of the fact that in 1944 Canada experienced a decline in production of all her leading base metals-nickel, zinc, lead, and copper; despite uncured headaches in the coal-mining industry; and cheerfully ignoring a still further drop in gold, the most valuable product of her mines, which had the lowest output of any year since 1931, the Canadian miner retains the traditional optimism of miners everywhere as he looks forward to the postwar period. Some factors should keep the Canadian mining industry from being too optimistic of the coming era of peace, but the fraternity generally holds that its confident attitude towards the future is based on sound reasons. The decline in production in the Canadian mining industry last year can be almost wholly attributed to the serious shortage of labor and the difficulty in obtaining transport and supplies in remote areas. Some falling off occurred in the demand for certain strategic metals, but the diversion of gold miners, especially, without replacements being obtainable, to direct war work or allied pursuits, was certainly the principal cause of the reduced output in 1944. But that is a situation which will right itself at the close of the conflict.

Jan 1, 1945

By R. F. Hehemann, Darrell W. Smith

The kinetics of alloying- in W-5 rot pct Re powder compacts were investigated at temperature about the upper limit for the formation of the x phase, such that a single intermediate phase was involved in the process. The rates and directions of motion of the a-o and o-b interface were assessed as functions of tinze at the sintering teri7peraticve by quantitative izetallog-ralhic techtziques. The iiotion 01 these interjuces could be specified approxitnate1.y by u Parabolic )-ate law and deviations from this ,rate law were attribuled to a complex interaction between surface dif&apos;fusion and volume diffusion during the initial stages of sintering. WHEN binary or more complex alloys are produced by sintering compacted blends of elemental powders, a complication is encountered which does not arise in the sintering of pure metals. In addition to concern for grain size and densification, the rate of inter diffusion of the component elements must be considered. The general problem of alloying during sintering has been treated by numerous investigators.&apos;-7 These investigations have been concerned only with systems that form continuous series of solid solutions and a concentric-sphere diffusion model4 provides a useful description of homogenization in these stems.&apos; Some controversy remains, however, over the contribution of surface and grain boundary diffusion to the homogenization process. Heckel% ePorts that homogenization can be described by volume diffusion at all temperatures, whereas other invetiators&apos;&apos; recognize the importance of surface and grain boundary diffusion, particularly at lower temperatures. Analysis of the homogenization process in partially miscible systems is complicated by the motion of the interfaces separating the individual phases. A simple analytical solution does not exist for such finite systems with spherical symmetry. It was the purpose of this work to examine the kinetics of the formation and dissolution of an intermediate phase in a binary system through an assessment of the motion of the interfaces separating this phase from the terminal solid solutions. PROCEDURE The W-Re system is an example of a partially miscible binary system and was selected for study because of its current importance in refractory-metal technology. The equilibrium phase diagram, Fig. 1, shows that the o phase will be formed by interdiffu-sion between tungsten and rhenium. At temperatures between approximately 2125" and 282O°C, the o phase will appear as the only intermediate phase in the diffusion system. In this work, a mixture of elemental powders containing 5 pct Re was employed. In such a mixture, the rhenium particles will be distributed randomly in a tungsten matrix. During sintering, a o-phase layer will form at the W-Re interface. The development and subsequent disappearance of the o phase are controlled by the relative rates and directions of motion of the 0-0 and a-p interfaces. The motion of these interfaces can be inferred from quantitative metallographic measurements of the average radii of the o shells surrounding rhenium particles. Elemental tungsten and rhenium powders of commercial purity were employed in these investigations. The rhenium powder was spheroidized from +200 mesh agglomerates by plasma-arc spraying and was then classified to yield a powder composed of essentially

Jan 1, 1967