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By M. Metzger, L. E. Hendrickson

Grain boundary attack in 16 pct HCl was found to be substantially the same at low penetrations in zone-refined aluminum (individual impurities 0.1 at. ppm), superior electrolytically refined aluminum (51 at. ppm), and aluminum with various impurities at much higher levels. It was concluded that impurity atom segregation affecting corrosion would have been detected and that the corrosion susceptibility did not originate in this segregation but in the structure of the boundary. It was pointed out that the significance of most previous studies in this system had been obscured by an unrecognized autocatalytic copper reaction. Although general corrosion rate was also impurity-insensitive , there was shallow pitting attributed to iron seg-regation and a hillocked surface texture associated with copper; these were interpreted as due to cathodic damage affecting- cathode distribution. THE grain boundary corrosion suffered by high-purity aluminum in hydrochloric acid has been the object of some interest (the earlier work is summarized in Ref. 1). The central metallurgical question here is whether the corrosion susceptibility of a boundary originates in its structure or in impurity atom segregation. An attempt to study this question revealed large catalytic effects associated with small quantities of the copper impurity in the aluminum, 220 ppm, or in the corrodent, and these magnified the preferential boundary attack and obscured the intrinsic susceptibility question.' After the catalytic effects had been examined,"' test conditions could be designed to avoid them and methods developed for studying the shallow boundary penetrations prevailing when they were absent.= It then became possible to determine whether intrinsic boundary corrosion in aluminum involves impurity segregation. The older work provided no firm information on grain boundary segregation of specific solutes influencing corrosion although several studies suggested iron segregates.4,5 perryman4 found in 10 pct HC1 that the slowly developing (microns per month) grain boundary grooves were deeper in material of higher iron content (range 10 to 550 ppm, with 5 to 80 pprn Cu) but he did not measure the depths of general corrosion, which were probably several times greater, and his reference surfaces may have varied more than did the groove depths. Metzger and Intrater's results for 20 pct HC~,' which yielded higher time-average rates (mm per month) and deeper penetrations, suggested that boundary segregation of iron (range 4 to 230 ppm, with 22 pprn Cu) decreased the penetration rate. However. in the stronger acid the autocatalytic l.E. HENDRICKSON, Student Member AIME ,and M. METZGER, Member AIME, are Research Assistant and Professor of Physical Metallurgy, respectively, Department of Mining, Metallurgy and Petroleum Engineering, University of Illinois, Urbana, Ill. Manuscript submitted March 11, 1968. IMD effect of the copper impurity is greater1,2 and it is now evident that their corrosion rates had been much magnified by this effect and did not provide a proper basis for the analysis of segregation. In exploratory studies of other solutes (made under the same conditions), 1000 ppm additions of Mg, Mn, or Si or 100 ppm Ca were without effect.1 Montariol6 noted that boundary attack in 22 pct HC1 persisted after zone refining although with fewer deep fissures (ranges 0.06 to 4 ppm Cu, 4 to 23 ppm Fe). Autocatalytic effects may have influenced these results also and those of Perryman.4 The present objective was, as a first step, to see whether quantitative tests designed to exclude autocatalytic influences would indicate the existence of low-level impurity effects on intrinsic boundary corrosion. Comparison of electrolytically refined with zone-refined aluminum of lower copper and iron contents revealed no differences in boundary corrosion, but certain impurity-sensitive differences in general corrosion morphology were noted and investigated further at higher impurity levels. I) EXPERIMENTAL PROCEDURE A) Material. A selection from commercially available material was made with the cooperation of several producers. An electrolytically refined lot (III-A, 1 ppm Cu, 2.4 ppm Fe) studied previously3 provided a starting point. Since material of substantially higher copper content could not be used if the autocatalytic corrosion reaction were to be avoided,2,3 a lot (III-B) of about the same purity was added as a check, two zone-refined lots (I-A and I-B) with copper and iron an order of magnitude lower were selected for comparison, and an intermediate lot (11) was included. Analytical data are given in Table I. For copper in I-B and iron in I-A and I-B, the actual concentration is thought to be near the limit given, i.e., about 0.1 ppm. For titanium, vanadium, and chromium in III-B, the actual amounts are thought to be, like those in III-A, substantially lower than in the zone-refined lots (these elements concentrate in the solid on freezing). Data are given later for some additional lots surveved. B) Specimen Preparation and Procedure. one by 3 cm blanks with a notched stem were cut from 1-mm cold-rolled sheet, annealed 24 hr in air at 650°C, and quenched in an air stream (42°C per sec initial cooling rate, 100 sec to cool to 100°C). The high annealing temperature maximized diffusivities and approach to equilibrium impurity distributions. A water quench, in principle more efficient in preserving the distribution established, was undesirable because the boundaries were almost plane and they tended to shear and migrate during the quench and thus to be separated from any existing impurity atmosphere. Test procedures, previously described,3 involved electropolish-ing, etching 2 min in 10 pct HF at 24.0°C, and expos-

Jan 1, 1969

By Arthur West

It is the purpose of this paper to describe briefly some recent large power stations for blast furnaces, where the blast is exclusively supplied by gas engines using furnace gas. The stations are given in the chronological order in which they were designed, in order to indicate the various improvements suggested by experience. Fig. 1 shows the blowing-engine station of the Bethlehem Steel Co. at Bethlehem. Although the picture shows only five blowing engines, the house now contains 11 engines. In the diagrammatic plan the arrow shows the position and direction of camera. This station handles five modern blast furnaces of 450 to 500 ions capacity each. In this, as in all the other stations described in this paper, each furnace is blown by two single tandem gas engines. Ten engines are thus required for five furnaces, leaving one single tandem spare engine. This spare capacity has been shown by several years' experience at Bethlehem to be adequate to insure continuous operation. The engines in the Bethlehem station are right hand and left hand, arranged in pairs. The outboard bearings of each pair are close together so that there is not room for passageway between them. On the right of the picture are shown the inclined drums communicating with the cold-blast lines outside of building, so that any engine may be operated on any furnace. The illustration shows four cold-blast gate valves with pipes passing through wall, but since the photograph was taken the drums have been extended to take care of a fifth valve for a fifth furnace. At the extreme back of the picture can be seen the tubs of three twin vertical-horizontal Southwark steam blowing engines, which, although of modern design and as good as new, are not operated because of the greatly reduced blowing cost shown by the gas blowing engines. The next station built is shown in Fig. 2. This is the plant of the Minnesota Steel Co. at Duluth, Minn., and is at present constructed for five engines, to handle two furnaces, with one spare engine. The engines are of practically the same size as those at Bethlehem. Instead of being arranged in right-hand and left-hand pairs, as at Bethlehem, all the engines are of the same hand; this arrangement has some ad-

Jan 1, 1915

By R. D. Begley, A. W. Khair

Introduction The technique being investigated here uses a physical mine model which consists of a plexiglass room-and-pillar model 11.4 x 11.4 cm (4.5 x 4.5 in.). It is placed at the bottom of a larger plexiglass box 25.4 x 30.5cm (10 x 12 in.). The box is then filled with a model material representing geologic overburden. Sand has been selected because of its deformability under gravitational forces. The mine model is capable of creating a cavity and induces movement on the surface of the model material. This surface disturbance can be measured using a photographic technique called holographic interferometry. This paper discusses results of an investigation of the possibility of generating subsidence criteria using physical mine models and laser holographic interferometry. Problem Statement Subsidence appears to be widespread in two states - Pennsylvania and Illinois - although serious subsidence is found in localized areas of numerous other states (HRB Singer Inc., 1977). The US Bureau of Mines estimates that more than 1618 km2 (400,000 acres) of urban areas are threatened by subsidence. Pennsylvania and West Virginia contain 57% of these threatened areas, with the remainder being spread out over 16 states (Johnson and Miller, 1979). Events of subsidence have been reported in urban areas, including Pennsylvania (Gray et al., 1977) and Illinois (Mahar and Marino, 1981). One location has observed three episodes of subsidence beginning in 1950 (Bruhn et al., 1981). These subsidence events all occurred over abandoned room-and-pillar mines. Some mines have been abandoned more than 50 years (Bauer and Hunt,1981) . Available research does not offer much on the problem related to time dependent subsidence, especially those associated with the failure of remnant coal pillars. The physical modeling technique developed at West Virginia University is capable of measuring both instantaneous and time delayed subsidence. Laser Holographic Interferometry Laser holographic interferometry, or holometry, uses the interference properties of laser light to measure small movements of objects. The object requires only optical access and no surface instrumentation. This technique is closely related to photoelasticity. Both techniques rely on the uniqueness of the light reflected off or through an object in any given state of stress. The entire measurement process is done remotely without any surface instrumentation and without using a camera. The interferogram is constructed and visual observation will yield fringes on all areas that yielded or moved. The displacement represented by one fringe was determined by Wilson et al. (1977) and is given by the relationship: [d ='1(1) 2 cos 8 where d = displacement of one fringe 6 = incident angle of laser light A = wavelength of light (632.8 x 10-9 meters for Helium-Neon lasers)] In summary, holometry is capable of detecting very small movements of objects under study. It is a very sensitive process that requires laser light and vibration free experiments. Experimental Program Lab Facilities The primary components of the facilities were the laser and the optical table. The light source was 50 milli-watt, Helium-Neon laser. The optical table was a granite slab weighing nearly one ton. All experiments were performed on the optical table. It consists of a large table sitting on air cells similar to car innertubes. Six air cells were placed on top of two layers of wood and Styrofoam. Figure 1 is a schematic diagram of the vibration free table. Even with these precautions, the experiments still had to be performed at night to reduce potential traffic related vibrations. Room-and-pillar mine models consisting of three different pillar sizes were constructed out of plexiglass. The models were designed to represent three different extraction ratios. Figure 2 shows the models. The extraction ratios were determined by the tributary loading concept (Peng, 1978). These models were the primary component of a seam extraction simulator. A schematic of this simulation device is shown in Fig. 3.

Jan 1, 1986

By S. T. Wlodek

The scale md subscale reaction products were identified and their rates of formation were studied in air over the range 1600" to 2000°F (871 " to 1149°C) for periods of up to 400 hr and for hoth the solution-annealed and aged conditions. The effect of prior sltrface preparation on suhscale oxidation was also studied The general oxidation behavior of both Ni-Cr-Mo-Al-Ti type alloys was similar. A surface film of a, Al2O3, forms immediately on exposure Subsequent oxidation continued at a linear rate (QL = 55 * 5 kcal per mole) as colonies of Cr2O3 nucleated at the A12O3/gas interface Further oxidation proceeded at a paraholic rate zvhiclz could he fitted to two successive rate constants. During paraholic oxidation, and depending on temperature, the scale consisted of Cr2O3, NiCr2O4 , and TiO2 with traces of NiO. In the case of Rene 41, the activation energy of both paraholic processes was 66 * 3 kcal per mole suggesting that diffusion of cations tlzrozrgh Cr2O3 was the rate -determining process. An unusual decrease in the oxidation of Udimet 700 at 1900°F where a spinel of Ni(A1,Crh0, zuas the predominant reaction product prevented the accurate assignment of activation energies for this composition. In both alloys internal oxidation of Al2O3 commenced shortly after parabolic scaling was observed. Prolonged exposure prod7tced intemal oxidation of TiN, and in Udimet 700 a complex Mo-Ni nitride was also found. At 1900oF, the subscale reactions in Udimet 700 undergo an inversion which parallels the decrease in surface oxidation; internal oxidation ceases hut is replaced by the formation of "spherodized" 3.' colonies. Surface-preparation techniqtles which introduce appreciable working, such as coarse surface grinding or grit blasting. increase the amount of alloy depletion and internal oxidation in Reni 41. The reverse is true of Udimet 700 for which electropolished or mechanically polished specimens show much more subscale oxidation than strongly worked stirfaces. The strongest commercial nickel-base alloys presently available are generic to the Ni-Cr-Mo-A1-Ti base which exploits the precipitation of Ni3(A1,Ti) as the main strengthening mechanism, while relying on solid-solution strengthening by molybdenum and chromium reinforced by the pre- cipitation of carbides to attain maximum properties. This study characterizes the oxidation behavior of Rene 41, the strongest alloy of the Ni-Cr-A1-Ti type commercially available in sheet form, and Udimet 700, whose higher aluminum and titanium content allows it to exhibit one of the more attractive combinations of high-temperature properties available in a wrought product. The scaling processes of complex, type nickel-base alloys have received relatively little attention. Malamand and vidal as well as Poulignier et al.2'3 have determined the composition gradients across the metal/oxide interface produced by high-temperature oxidation and considered the effect of surface perature, Limited weight-gain data has also been published by Fere 5 for alloys of this type and Radavich6 has identified the reaction products on Udimet 500 and Inco 702 after oxidation at 1832°F. Reference can, of course, be made to the excellent reviews of Kubaschewski and Hopkins7 or Ignatov and Shamgunova8 for a summary of the data available on the oxidation of binary and ternary alloy systems which are related to the more complex alloys considered here. EXPERIMENTAL The analyses of the different commercial heats studied are given in Table I. Using the experimental procedures previously established,9 continuous weight-gain data were obtained on both heats of Rene 41 sheet (A and B) and 150-mil-thick slices of cast Udimet 700. Subscale oxidation reactions were followed by static exposure of cylindrical specimens obtained from swaged Rene 41 (Heat C) and Udimet 700 (Heats E and F). In brief, continuous weight-gain tests were performed on specimens with a surface area of 10 to 12 sq cm. These were abraded through 600 grit Sic paper, electropolished to 2p rms in an electrolyte of 10 pct H2So4 in ethanol, and lightly etched in 10 pct HCl in ethanol before final washing and rinsing in ethanol. All continuous weight-gain data were obtained in dried (-70°F dew point) flowing (1 liter per min) air to an accuracy of +0.1 mg. Subscale oxidation processes were followed by the metallographic examination of 0.5-in-diam by 1.0-in.-long specimens. After an initial center-less grinding, various additional surface treatments were employed to determine the effect of surface preparation on subscale oxidation processes. Before exposure in zirconia crucibles, all samples were lightly etched in 10 pct HCl-ethanol, washed in ethanol, and dried. The depth of internal oxidation was measured to ±0.00025 in. on unetched specimens mounted so as to provide a taper mag-

Jan 1, 1964

By Elmer W. Pehrson

Minerals have played a prominent role in the affairs of man and nations since time immemorial but with the advent of the industrial revolution, expanding use of the products of the mineral kingdom became synonymous with the material progress of mankind. Individuals and business groups have recognized this fact so have been aggressive in searching for and utilizing mineral resources, with notable success. Indeed, their achievements are primarily responsible for the present Machine Age. On the other hand, until recently the body politic has failed to grasp fully the essentiality of minerals although, at times, access to mineral supplies has been an important factor in the political maneuvers of nations. This chapter is concerned primarily with the broader political and economic relationships of mineral resources to the world economy, and with the internal and external actions of nations in the field of minerals. Many factors that condition the mineral economy of regions and the world as a whole, influence the internal and external affairs of individual nations. The more important of these are: 1. The nature of man's dependence on minerals. 2. The problems resulting from the unique characteristics of mineral occurrence. 3. Geopolitical concepts. 4. Minerals and world power. Actions of individual nations affecting their mineral economy seek two basic objectives : 1. Attainment and maintenance of prosperity. 2. Military security. Other objectives may be cited but on careful analysis they become integral parts or extreme phases of the two points noted above. For example, the twentieth century aggressions of the USSR, Germany, Italy, and Japan might be considered as direct bids for world power but they also can be interpreted as exaggerated or mistaken efforts toward military security and peacetime prosperity. Similarly, trade barriers, nationalization of industries, foreign exchange manipulations, taxation, monopolistic prac-

Jan 1, 1959

By Zay Jeffries

Tungsten has the highest melting point of all the known metals, namely 3350 C.; it is one of the hardest of the metals; it has the highest equiaxing or recrystallization temperature after strain hardening, of any pure metal known. It is particularly distinguished because, when composed of small equiaxed grains, it is extremely brittle and fragile at room temperature, and when possessing a fibrous structure it may be ductile and pliable at room temperature. The common ductile metals act in exactly the opposite manner in this respect. The present paper will include a brief note regarding the manufacture of wrought and ductile tungsten. The metallography of wrought and ductile tungsten in the various stages of manufacture will be considered more or less in detail. The general relationships between the properties of tungsten and other metals will also be considered. A discussion will be given explaining why fibrous tungsten is ductile at room temperature, even though past experience with other metals would indicate that it should be brittle. Finally, a brief note regarding some new fundamental metallographic propositions relating to all metals will be given. Manufacture of Wrought and Ductile Tungsten Up to about 10 years ago, it had not been possible to work tungsten mechanically. About the year 1908, Dr. William D. Coolidge, of the General Electrie Go., produced ductile tungsten from what was then supposed to be an inherently brittle metal and which, in fact, was inherently brittle in its normal state, that is, when composed of equiaxed grains. Since that time many products, chief among which are the filaments for electric incandescent lamps, have been made from wrought and ductile tungsten. Tungsten is produced chiefly from the minerals wolframite and scheelite.1-8 The ores may be reduced in many ways. For example, the ore may be fused with alkali carbonates and the fusion dissolved in water; sodium tungstate is formed, which is soluble in water. This

Jan 1, 1919

By J. Ruben Velasco, Roland B. Mulchay

CANANEA has long been recognized as a remarkable field for geologic study. The copper deposits and rocks of the district have been described by many geologists and engineers, but only the most general correlations have been made between Can-anea sedimentary rocks and other known sedimentary sections in the southwestern United States and northern Mexico. The present paper describes the Cananea sediments in greater detail than has been done before and attempts to fit the Cananea sedimentary section more closely into the geologic time table. The lack of well-preserved fossils has made it difficult to date the sediments accurately in geologic time, but it is possible to make tentative correlations between the Cananea sediments and the southeastern Arizona sections, based largely upon lithology and general position in the geologic column. It appears that sedimentation at Cananea and Bisbee may have been closely similar during Paleozoic time. Even such generalized correlations, however, may be subject to considerable modification in the future. The present study has led to the recognition of other problems of age and mineralization relationships in the Cananea district. Cananea is located in the north-central part of the state of Sonora, Mexico, at an elevation of 5270 ft. It is about 135 miles northeast of Hermosillo, the state capital, and 25 miles south of the international boundary. By road Cananea is 40 miles from the twin towns of Naco, Ariz., and Naco, Sonora, and about 50 miles from Bisbee, Ariz. It is served by the Nogales-Naco branch of the railroad, F.C. Pacifico, and is connected with Chihuahua and Mexico City by the Aeronaves airline. The headwaters of three rivers flowing to the Gulf of California are located in the Cananea Mountains: the San Pedro River, flowing to the north; the Sonora River, flowing south and west; and the Mag-dalena River, flowing west. Elenita Mountain, the highest point in the district, has an elevation of 8140 ft. The Cananea Mountains extend in a series of north-south to northwest-southeast spurs and ridges and are surrounded by gently sloping gravel plains. The mineralized area, lying across the southern and central parts of the range, is about 6 miles long and at most 2 miles wide. Elevations at the mines vary from 5300 ft at Cananea-Duluth mine at the southeast end of the district to between 6000 and 7000 ft at the west end of the mineralized area at Puertecitos-Elenita mines. Principal production has been from the intensely mineralized and altered area of Capote Basin in the central part of the district and the immediately surrounding area to the southeast. The district has produced over 2 billion lb of copper, substantial molybdenum, and minor amounts of lead, zinc, silver, and gold. Total production through 1949 is estimated at more than $300 million. In 1900 large-scale development was started at Cananea by W. C. Greene. Until World War II only high-grade ores were exploited; low-grade ores were extracted after the installation of a large concentrator in the early 1940's, and subsequent operations have been based upon mining and processing ores containing less than 1.0 pct copper from open-pit and underground workings. Mining and concentration of such low-grade ores, however, are made possible only by continued high copper prices, and active exploration for high-grade orebodies has been continued throughout the important mineralized areas. General Geology Study of the involved rock pattern at Cananea has indicated a complex geologic history for the district. Widespread alteration and mineralization have masked many of the salient features and have led to widely varying geologic interpretations over the years. Further work will probably disclose new information which will modify current beliefs. At Cananea a conformable series of sediments of probable Paleozoic age was deposited on an unknown basement. Following Paleozoic time there was an extended period of erosion common to many districts in the southwestern U. S., and there is no present evidence of marine sedimentation at Cananea after the Paleozoic. The eroded surface was eventually covered with a great thickness of extrusive volcanic rocks. The entire series of sediments and volcanic rocks was later intruded by a variety of deep-seated igneous rocks. These included the Cananea granite, the Cuitaca granodiorite, the El Torre syenite, the Tinaja diorite, the Campana diabase and gabbro and the Colorada rhyolite quartz porphyry. Faulting of early age, probably prior to the deposition of the volcanic rocks, may have been responsible for the present position of some of the intrusive rock masses. In the Capote mine on the third and fourth levels the northwest-striking Rick-etts fault zone, with apparent offset of about 800 ft, has been sealed by a dike-like mass of Cananea granite which gradually increases in size with depth. In lower levels of the mine the granite forms a large southeast-plunging mass generally following the course of the Ricketts zone. The granite is not known southeast of the Capote-Oversight mine areas and the Ricketts fault does not appear in the vol-canic~ southeast of Capote Basin, but several plugs of Colorada quartz porphyry cut the volcanics along the assumed general southeast trend of the Ricketts zone. These porphyritic intrusives may be the up-

Jan 1, 1955

By Herbert Clark Hoover, Lou Henry Hoover

QUESTIONS of assaying were explained in the last Book, and I have now come to a greater task, that is, to the description of how we extract the metals. First of all I will explain the method of preparing the ore1 ; for since Nature usually creates metals in an impure state, mixed with earth, stones, and solidified juices, it is necessary to separate most of these impurities from the ores as far as can be, before they are smelted, and therefore I will now describe the methods by which the ores are sorted, broken with hammers, burnt, crushed with stamps, ground into powder, sifted, washed, roasted, and calcineda.

Jan 1, 1950

By B. J. Nelson, F. N. Rhinos

Studies upon the rates of oxidation of copper alloys containing small quantities of the alloying elementsl,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a' continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidiza-ble alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal sub-scale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants- Similarly, large volumes of Precipitated oxides tend to deposit in various patterns that may be expected to

Jan 1, 1944

By F. N. Rhinos, B. J. Nelson

Studies upon the rates of oxidation of copper alloys containing small quantities of the alloying elementsl,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a' continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidiza-ble alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal sub-scale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants- Similarly, large volumes of Precipitated oxides tend to deposit in various patterns that may be expected to

Jan 1, 1944

By T. B. Nolan, R. N. Hunt

In terms of present metal prices, analysis of extant records of the Eureka district indicate past production of the magnitude of $200,000,000 in recovered silver, lead, and gold. Production to date has been thoroughly oxidized ore from massive replacements, fissures, manta, and pipe-like bodies-in large part from the massive Eldorado (middle Cambrian) and Hamburg (middle to late Cambrian) dolomite horizons. In the productive area of about 6 square miles carbonate rocks comprise 80 per cent of the section, which includes early Cambrian to late Ordovician horizons. Four-fifths or more of the district's production came from a block of Eldorado dolomite in Ruby Hill that was moved in over younger horizons on strands of a regional thrust fault. The lower 500 to 600 feet of the block was much fractured and brecciated and became host to the ores. The Ruby Hill fault, a late normal fault, limits the Ruby Hill block of dolomite on the north for its entire length of nearly a mile and terminates the downward extent and exploitation of its ores. It introduced an hiatus of some 40 years in the district's development. Drilling of the past 20-odd years, followed by underground work, has now exposed the down-faulted extension of the Ruby Hill block of Eldorado dolomite and its contained ores, dropped 1800 feet in a dip shift to depths beneath the surface of 2000 to 3000 feet. The ores at depth are the sulfide counterpart of those mined in early years on the footwall side of the fault. The ores of the district may be attributed to the same source as the intrusive quartz diorite outcropping in a limited way south of Ruby Hill but found at depth elsewhere in drill holes. The long north-south axis of the district, its anticlinal structure, its major faults, and the distribution of the intrusives and, in their relation to the surface, the ores themselves, all suggest that erosion has not cut deep enough to expose the extent of intrusives and the ores consequent upon them.

Jan 1, 1968

By Edwin S. Johanson, Ronald H. Wolk, Clarence A. Johnson, Harold H. Stotler, Katherine C. Hellwig

The H-Coal process, an ebullated bed reactor system for converting coal to liquid fuel, is described. Results from long-duration continuous flow bench-scale operations with Wyoming Wyodak, Arizona Black Mesa, and Utah Kaiparowits Plateau coals are presented. Economic data on the conversion of these coals to liquid products are given. The potentials of the H-Coal process in regard to coal from western producers is stressed.

Jan 1, 1974

By C. H. Green

. RECENTLY two papers on the structure of eutectics were read before the British Institute of Metals, one by F. L. Brady1 and the other by A. Portevin.2 In the preparation of photomicrographs of laboratory specimens as illustrations for student work, and in connection with various researches; the writer has been working along the same line for some, time and, therefore, was much interested in the results given, especially those of Portevin. He has correlated the information on the subject and has outlined a broad scientific basis for future work along this line. It is largely with the idea-of adding something by way of illustration to the work already done that this paper is written. The eutectic is generally understood to mean the alloy having the lowest melting point of any alloy of the system, and in which the melt becomes supersaturated with reference to the two or more phases which, separate out simultaneously (or alternately). From the surface pattern, the eutectic means; a structure with no primary crystals. It is not always easy to get the exact eutectic composition in making any alloy; in fact, a slight range in composition may be expected and some of the coarser particles may be richer in either of the composing metals. Even when chemical analysis shows the right composition, differences in density of the pure metals may cause segregation, or. supercooling resulting from different crystallizing properties may give a surface pattern the appearance of being on one side of the eutectic point. However, the alloys on either side of the eutectic composition, showing primary crystals of one of the phases and the effect of the pro-eutectic form on the surface pattern of the eutectic make a very interesting study, which is slightly touched upon in this paper. The phases, or microconstituents, of a eutectic may be pure metals (Pb-Sb, Tl-Au), solid solutions (Cd-Zn), a pure metal and a solid solution; (Ag-Sn), or a pure metal or solid solution with an intermetallic compound (Sb-Mg, Sb-Cu, As-Cu, Bi-Te, etc.).

Jan 2, 1925

By William H. Bassett, C. J. Snyder

Cable sheaths made from common lead have been used to protect underground cables since the beginning of the power-cable industry. Only within the last few years, however, has a systematic study of the production methods and of the causes of failures in cable sheathing been undertaken. Recent increases in the use and demands for service made upon power cables have emphasized the importance of high-quality cable sheaths. It was customary for the users to attribute the cause for their sheath failures to the lack of purity of the lead, but this contention has not been borne out by field and laboratory inspection of the sheaths. During the past two years the writers have had an opportunity to examine various types of sheaths that were removed from power cables after failure. These samples were obtained from various parts of the country and represent, it is supposed, the production of the principal cable manufacturers. Aside from corrosion, the common field difficulties can be classified either as mechanical or structural, as outlined below, and when structural irregularities are found they can all be attributed to manufacturing causes and in no way reflect the purity of the lead. Clasxification of Cable Sheath Failures Other Than Corrosive Mechanical Irregularities A. Splits caused by excessive internal pressure B. Injuries such as nail holes, cuts, tsars, etc. C. Intercrystalline cracks caused by vibration Structural Irregularities A. Splits C. Voids in wall of sheath a. Caused by imperfect welds a. Blisters 13. Holes through sheath b. Laminations a. Caused by yellow oxide inclu- D. Questionable structures sions in sheath wall a. Prominent flow lines b. Blowouts by entrapped gases b. Large areas filled with suboxide during manufacture c. Scattered yellow oxide or dirt C. Caused by inclusions of dirt and

Jan 1, 1933

By R. W. Armstrong, D. H. Feisel

Self-diffusion in pure crystalline solids has been described through extension of the Cohen and Tum-hull volume -fluctuation model originally proposed for diffusion in simple liquids. It is shown, for a number of crystalline solids, that the self-diffusion coefficient, D, obeys the relationship where a is the lattice spacing, v the Debye frequency, Z' the lattice-volume fluctuation per atom required for a diffusion jump, and (?V/Vo) the relative increase in the lattice volume resulting from thermal expansion between O°K and the temperature under consideration. The calculated value of Z' is dependent upon the difiusion mechanism and the lattice geometry. ThE need for an increased understanding of mass-transport processes in crystalline solids has resulted in much research to determine rates of self-diffusion.' For several metals (e.g., copper, silver, and iron), the experimental values of the self-diffusion coefficient, D, have been determined over a large interval of temperature and the accuracy of D has been investigated through repeated experiments. Also, a number of empirical and theoretical diffusion studies have established a rational basis for understanding the D values for the different elements.2"6 The empirical diffusion analysis by Sherby and simnad6 supplied the main stimulus for the present study. Sherby and Simnad, reviewing the self-diffusion data for a substantial number of pure crystalline solids, suggested that sufficient data were available to establish with some certainty the apparent intrinsic material properties which influence D. Without explicit regard for any mechanism of diffusion, these investigators obtained an empirical relationship for D which correlated the self- diffusion coefficient for each element with the melting temperature, crystal structure, and valence of the particular element. Their analysis is only unsatisfactory in that the effect on D of crystal structure is not very clear and the valence to be assigned to an element is not always straightforward. The present study is an attempt, from a very different viewpoint from that of Sherby and Simnad, to establish a basis for understanding the self-diffusion coefficients for crystalline solids. This analysis was undertaken for the purpose of developing a general expression for D which would explicitly depend on the mechanism of diffusion. The main result of the study is that diffusion in crystalline solids may be described in terms of a volume-fluctuation model which was originally proposed by Cohen and Turnbull7 to describe diffusion in simple liquids. The model appears to be useful for predicting self-diffusion coefficients in crystals. The following sections describe the volume-fluctuation model for diffusion, the application of this model to crystals, and the resultant agreement with experimental data. 1) THE VOLUME-FLUCTUATION MODEL FOR DIFFUSION Cohen and Turnbull7'8 developed their model for liquid self-diffusivity for the purpose of describing certain properties of liquids, glasses, and the liquid-glass transition. A hard-sphere model for the liquid structure is used. In this model, the size of a spherical molecule or atom is fixed for all temperatures by the interatomic spacing at the absolute zero of temperature. At any temperature above O°K, the atom is viewed as being contained within a larger spherical cage defined by the interatomic spacing of the atoms at that temperature. A random distribution of varying cage sizes is assumed to exist in the liquid. An individual diffusion jump occurs when the free volume of an atom (the volume of the cage containing the atom minus the volume of the atom) is large enough for the atom to jump out of its cage. With this physical picture of diffusion in liquids, Cohen and Turnbull derive the following equation for self-diffusivity: D=Doe-yv*/vf [1] where Do is the product of three factors which are the diffusion-path geometry, the diffusion-jump distance, and the velocity of the diffusing atom, v*

Jan 1, 1964

By Albert Sauveur

THE senior author of this paper has expressed the belief that when gamma iron transforms into alpha iron on reaching the A3 point, each gamma grain does not change bodily into one or more alpha grains but that the alpha phase forms first at the boundaries and along the crystallographic planes of the austenite grains.1 To quote: On cooling through the point A, at about 900° C., iron passes from the gamma condition to a. new allotropic form generally designated as alpha. This transforma¬tion, however, is not instantaneous. There are good reasons for believing that it begins at the grain boundaries and along the octahedral planes of the crystals and that it progresses until each grain of gamma iron is changed into a grain of alpha iron, the resulting structure being similar to that of gamma iron. Were it possible to retain at room temperature pure iron but partially transformed, it seems probable that a Widmanstättian structure, or rather, as later explained, a martensitic structure would be observed (Fig. 1), consisting of alpha iron at the boundaries and at the octahedral planes, and of a groundmass of gamma iron. In order to confirm, if possible, the accuracy of that view, a number of experiments were conducted. Polished samples of electrolytic iron were heated in a vacuum, maintained in the gamma range for several hours and quenched in different media. It was hoped by such means to produce and retain on the polished surfaces a pattern which would reveal the mechanism of the allotropic transformation. The samples were placed in evacuated quartz tubes, heated to 1000° C. and held 2 hr. at that temperature. The tubes were then immersed in the quenching bath. Iced brine and liquid air were used first. The polyhedral austenitic structure existing at the time of immersion was very clearly revealed (Fig. 2). This is generally ascribed to iron volatilizing at the grain boundaries.

Jan 1, 1929

The Library of the above-named Societies is open from 9 A.M. to 10 P.M., except on holidays. It contains about 70,000 volumes and 90,000 pamphlets, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated from sources of information. To these the Library, through its Library Service Bureau, can render valuable service through correspondence; letters requesting information will receive especial attention. The Library is prepared to furnish references and photographic copies of articles on mining and metallurgical subjects; to determine the existence of mining maps, and to furnish general information on the geology and mineral resources of all countries. All communications should be made as definite as possible so that the information received may be what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape.

Jan 7, 1917

By Ray W. Carpenter, Ralph Hultgren, Raymond L. Orr

Heats of formation of Au-Zn alloys of compositions Au3Zn and AuZn were rneasured at several temperatures by liquid tin solution calorimetry. The data for Au3Zn show that much smaller heat and entropy effects are associated with the a2- a1 transformation than for the a1 - a transformation. This result is consistent with reported X-ray diffraction studies which indicate that the a1 and (a2 phases have ordered structures which only slightly differ, whereas the a phase is disordered. The heat of formation of AuZn(ß') does not change significantly between 322o and 8000 K, confirming that the ß' alloy remains highly ordered to high temperatures. Not many measurements have been made of the energies of order-disorder transformations in alloy phases. In many cases these energies may be conveniently determined by measuring heats of formation as a function of temperature. Many alloy phases approximately obey Kopp's law of additivity of heat capacities; as a consequence their heats of formation do not change with temperature. In ordered alloys, however, a decrease in degree of order with increasing temperature will contribute an endothermic component to the heat of formation. Thus, for ordered phases where other anomalous contributions to heat capacity in the alloy or its pure components are absent, a measured change in the heat of formation may be attributed to the energy of disordering. A portion of the Au-Zn phase diagram1" is shown in Fig. 1. The composition AuZn(ß') has a well-ordered superlattice structure of the CsCl type at room temperature. The alloy is considered to remain ordered to its melting point,1 although, from X-ray diffraction data and electromotive force measurements of zinc activities, Terpilowski3 concluded that considerable disordering began at -673°K. The Au3Zn composition is a disordered fee solid solution (a) at high temperatures. Between 693o and 543oK, the ailoy orders to form the a1 phase, having a structure based on the L12(AuCu3) type, but with a regular distribution of ordering faults in the c direction, making it tetragonal. Below 543oK, the alloy orders further by means of slight atomic shifts, without diffusion, yielding a complex long-period orthorhom-bic superlattice structure, a2.4-7 Heats of formation of Au3Zn(a2) and AuZn(ß') were measured at 363°K by Biltz et al.8 by aqueous solution calorimetry. Heat capacities of several alloys between 14.9 and 38.4 at. pet Zn in the range from 373" to 723°K were measured by Iwasaki ef al.6 Stoichiometric Au3Zn, however, was not included in the alloys measured, the nearest composition being 26.1 at, pet Zn. Also, the heating rate used for the measurements, 2 deg per min, may not have permitted equilibrium to be reached in the neighborhood of the transformations. Heat contents of solid and liquid AuZn were measured between 488o and 1138°K by Kubaschewski.9 It was decided to determine the ordering energies of Au3Zn and to check on the possible disordering of AuZn by measuring the heats of formation of these alloys at several temperatures. The present paper reports measurements by liquid tin solution calorimetry of the heats of formation of the three phases of Au3Zn at temperatures within their regions of stability, and of AuZn at a low (322°K) and a high (800°K) temperature. EXPERIMENTAL Alloy Preparation and X-Ray Examination. Ten-gram ingots of Au3Zn and AuZn were prepared by melting weighed amounts of gold (99.95 pct Au) and zinc (99.99 pet Zn) together in sealed evacuated Vycor tubes at 1060°K, followed by rapid quenching. The resulting ingots were homogenized at 900°K for 10 days. The Au3Zn alloy lost no weight in preparation, the loss from the AuZn alloy was enough to introduce an uncertainty of only 0.1 at. pet in its composition. Filings for X-ray examination were taken from various parts of each ingot and strain-annealed at 723°K for 20 min in vacuo. The Au3Zn filings were quenched rapidly to retain the disordered phase. Diffraction patterns were determined with an X-ray dif-fractometer using copper Ka radiation.

Jan 1, 1968

By Paul M. Tyler

MUCH has been said in print, and much more that was unprintable, about burdensome controls, taxation, and multiplying restrictive, regulatory, or taxing activities of the Federal Government, but not so much has been said about ways and means whereby the Government can and does render economic assistance. Economics has been defined as the study of men earning a living, and economic assistance to industry as well as to individuals properly should take the form of helping enterprisers to help themselves rather than charity. Proposals to have the Government play Santa Claus must be examined carefully if -only to avoid undue favoritism to politically important persons and downright venality by potentially crooked public officials. Thomas Jefferson is credited with the remark that the best government is the one which governs least. Paternalism is abhorrent to most Americans.

Jan 1, 1947

By William Campbell

FiRst I must express my deep appreciation for the honor of being privileged to give the Howe Memorial Lecture this year and at the same time my feeling of inadequacy to do justice to the subject. The first Howe lecturer was most fittingly, Professor Sauveur, his contemporary and friend, and the subject was beta iron. Last year the second Howe lecture was delivered by Dr. Mathews, one of his most distinguished pupils, who spoke on austenite. This year, the Howe Professor of Metallurgy was chosen to deliver the third annual lecture, and the subject ought to be martensite. No one but Professor Sauveur could have brought to life what was considered by many to have been dead and buried, and he so persuasively and convincingly proved to us by his experiments the existence of something that the followers of that new cult "X-Ray and Crystal Structure " would have us believe is simply alpha iron. And Dr. Mathews from his wide practical experience was so easily able to convince us that austenite was not only the most wonderful of the iron-carbon series, but that it was the wonder alloy of the future. If I were to follow in the footsteps of my distinguished predecessors, I would talk to you about martensite. But when I had planned this lecture, I found that I was writing about Professor Howe and his work and his influence on the science of metals of today, and that martensite had become the secondary theme. And when finally I was obliged to choose a title, I remembered that it was in 1901 I came from Roberts-Austen with a letter of introduction to his very dear friend, Henry Marion Howe, at the Columbia School of Mines, to continue my work at the next bench to Dr. Mathews. Since then a quarter of a century has gone by, and during that time all branches of science seem to have been remade, so great has been our advancement in knowledge and discovery. And now that Metallography has finally established its place as an important branch of science, with its own textbooks and literature, I would like to review what seem to me to be the most important advances we have made in the last 25 years. To do this, I would start with Howe's "Iron, Steel and Other Alloys," and end with Jeffries and Archer's " Science of Metals." In the preface of the former, Professor Howe wrote: My warmest thanks are due to the friends who have aided me with their counsel and knowledge. In particular, let me thank most sincerely Prof. Margaret E. Maltby

Jan 1, 1926