Search Documents

By Y. C. Liu, G. A. Alers

The anisotropy of Young's modules has been measured in a series of Cu-Zn alloys containing from 1 to 28 wt pct Zn and cold-rolled to 97.5 pct reduction in thickness. These modulus data show a transition in texture as a function of zinc content. In alloys containing 3 pct Zn or less, the texture is essentially that of copper. A transition is clearly seen to develop in 5 and 8 pct Zn alloys, and to have been completed in a 12 pct Zn alloy. Increasing the proportion of zinc to 28 pct does not produce any further changes in texture. The ease and clarity with which this texture transition can be seen in the modulus data is in great contrast with the inccertainty in the visual detertiination of the range of texture transition from a series of pole figures. It is also shown that the rolling texture of the high zinc content alloys cannot be a one-COIIIponenl texture, characterized by the (110)(112) ideal orientations, as usually assumed. A second, quite important component must also be present. Furthermore, the present data are inconsistent with matrix orientations on which the "oriented growth" hypothesis of the Formation of recrystallization textures is based. THE rolling textures of binary fcc alloy systems have generally been considered to lie between two terminal textures. One of these terminal textures is the copper type and the other is the 70:30 brass type. Alloys of intermediate solute content exhibit a texture which is said to be a transition between the two terminal textures. On the basis of efforts to correlate rolling and recrystallization textures, two concepts have been advanced in the literature on the nature of these transition textures. One school1 suggests that the addition of alloying elements, e.g., zinc, causes a gradual rotation about one of the (111) poles from the (358)( 523) ideal orientation of the copper-type rolling texture to the terminal {1 10)( 112) ideal orientation used to describe the rolling texture of 70:30 brass. This concept is depicted in Fig. 1 with the angle of rotation corresponding approximately to the zinc content and is designated here as the "rotational concept", since the ideal orientation of the transition textures varies continuously with alloy content. The other concept,' the "mixture concept", suggests that the copper-type rolling texture is a two-component texture. {358) (523) and {110)(112). The addition of alloying elements affects only quantitatively the relative amounts of these two components—a decrease in the amount of material in the {385}(523) orientation and an increase of that in the {110)(112) orientation with increasing solute content. An experimental distinction between these two concepts is essential to a better understanding of both the mechanism of formation of rolling textures and the subsequent formation of recrystailization textures in fcc metals. Because of the lack of resolution inherent in pole figures, it has not been possible to differentiate between the two concepts on the basis of this data. Both concepts, in fact, make use of the same set of pole figures but interpret them in a manner acco-rding to the view held.'" Experimental results obtained from inverse pole figures or selected-area electron diffraction3j4 simply -yield more refined pole figures but do not eliminate the ambiguity of interpretation. Quantitative measurement of an entirely different, orientation-dependent property must thus be considered

Jan 1, 1967

By Walter W. Bradley

FOR a number of years up to the economic setback of the 1929-1931 period, the greatest proportional advances in the mineral industries in California were made among the substances in the nonmetallic groupings, particularly among the so-called industrial minerals and the salines. During the past year or two, although these have not regained the stride that marked their progress in the preceding decade, we can still record, -some new developments. California produces annually between 55 and' 60 different minerals on a commercial scale. Of these, some 40 to 45 comprise the "structural," "industrial," and "salines" materials as grouped in the reports of the State's Division of Mines. Barite-The barite deposits of California were described in Report

Jan 1, 1935

By Elmars Ence, Harold Margolin

The Ti-Fe and Ti-Fe-0 systems were re-examined because of the controversy regarding the existence of Ti2Fe, and to consider all available data points to the existence of Ti,Fe. The Ti-Fe-0 system contains two ternary compounds: E, corresponding to Ti2Fe; and y. SEVERAL authors have investigated the constitution of titanium-rich alloys of the Ti-Fe system. The most extensive study of titanium-rich portions of the Ti-Fe system was by Van Thyne, Kessler, and Hansen,' who investigated this system up to 50 pet Fe and used the highest purity materials available for their alloy preparation (iodide titanium was used for alloys up to 20 pet Fe). According to Van Thyne et al., phase relationships in the region of investigation are governed by phases a,ß, and TiFe. No evidence of an intermetallic compound Ti,Fe was found. although earlier. works by Laves and Wallbaum,' and Duwez and Taylor' reported its existence. Rostoker's study on the occurrence of TilX phases" confirmed the findings of Van Thyne et al. Rostoker proposed that the compound Ti Fe found by Duwez does not exist but is actually a ternary compound, Ti1Fe3O, originated by inadvertent oxygen contamination. The partial isothermal section of the ternary Ti-Fe-0 system as reported by Rostoker' seems to confirm this explanation. In the course of phase diagram work conducted at New York University, however, certain irregularities were observed to be associated with ternary systems of the type Ti-Fe-X. The ternary phase 6, observed in the systems Ti-Fe-Mo' and Ti-Fe-V." was found to be structurally identical to the com-pound Ti2Fe as reported by Duwez and Taylor, and to Rostoker's compound Ti1,Fe2O. Since the amount of oxygen possibly present in the Ti-Fe-Mo and Ti-Fe-V systems could not account for the observed amounts of the compound, it appears that the d phase in these systems is not Ti,Fe,O. On the other hand, considering the amounts of the 6 phase, particularly in the Ti-Fe-Mo system, the location of the phase was uncertain. It was felt that the introduction of the Ti2Fe phase would alleviate some of the inconsistencies of the two systems. Because of the uncertainties relating to the phase Ti2Fe, or Ti1Fe2O, it appeared worthwhile to re-examine the Ti-Fe and Ti-Fe-O systems in the vicinity of these compounds with highly sensitive metallographic techniques and with X-ray methods. Experimental Procedure Alloy Preparation—For the study of the binary system four alloys were prepared, containing 26.9 (30 wt pct), 34.0 (37.5 wt pet), 41.2 (45 wt pet), and 56.3 (60 wt pet) atomic pet Fe, and for the ternary Ti-Fe-O system 18 alloys were prepared in the composition range of 1.6 to 16.9 atomic pet 0 and 24.3 to 55.7 atomic pet Fe. The materials used for the Ti-Fe alloys were iodide titanium (99.98 pet Ti, 0.002 pet 0) and Ferro-vac-E iron (99.95 pet Fe, 0.0052 to 0.0072 pet 0). For the Ti-Fe-O study the materials used were sponge titanium containing less than 0.06 pet 0, Ferrovnc-E iron, and Baker's analyzed TiO2. The nominal weight and atomic percentages of the ternary alloys prepared are shown in Table I. Melting—Charges of 10 to 15 g were melted in a nonconsumable arc furnace in argon atmosphere according to the technique described elsewhere.'" Since there was practically no weight loss through the various stages of melting and oxygen losses have not been observed previously, it appeared justifiable to use nominal composition for interpretation of data. Iodide titanium control buttons, of the same mass as the Ti-Fe charges, and melted under the same conditions, were used to check hardness pickup during melting. A hardness increase of 2 to 3 Vhn was found. Heat Treatment—The specimens were annealed in quartz capsules under argon. To avoid contact between the specimen and capsule material all specimens were wrapped in titanium sheet. The annealing times are given in Table 11. The attain-

Jan 1, 1957

By Maurice Magee

The Ducktown ore deposits have been known, explored, and mined for 120 years. Eight massive sulfide ore bodies occur in highly folded and metamorphosed graywacke, graywacke conglomerate, mica schist, chloritegarnet schist, and staurolite schist of Precambrian age. The ore deposits are tabular bodies that have been extensively folded, generally conform to the enclosing rocks, but show local complex differences. The ore deposits, ranging in size from 250,000 tons to over 20 million tons, are composed principally of the minerals pyrrhotite, pyrite, chalcopyrite, sphalerite, and magnetite. Gangue minerals are quartz, calcite, actinolite, tremolite, hornblende, garnet, and masses of schistose wall- rock. Three fault systems are present that have influenced ore control and ore body configuration. Hydrothermal effects are evident in wall-rock alteration. Evidence of retrograde metamorphism is extensive in the wall and ore associated rock. Preliminary isotopic age dates have indicated four possible metamorphic events during the Paleozoic Era. Ore genesis is considered to be hydrothermal replacement of receptive beds, predominantly highly calcareous zones, quartzitic zones, and brecciated shear zones. Ore deposition is thought to have occurred during the Devonian Period, with later mobilization and recrystallization of the ore and gangue during Middle and Late Paleozoic times.

Jan 1, 1968

By D. M. Davidson, P. F. Kerr

The Permian Cutler Formation in Kane Creek, Utah bears uranium ore in fissure-type vertical veins. This fissure vein formation and its associated host rock bleaching, weak argillic alteration, and base-metal sulfide mineralization along with the development of hydrothermal minerals, a 60 m.y. isotopic Pb/U age, and well-crystallized uraninite's structural control, give evidence of ore deposition in a hydrothermal environment consistent with Laramide mineralization. Mica polymorph studies indicate first, that temperature during the hydrothermal alteration or subsequent ore deposition did not exceed 200°; hence Cutler deposits are classified telethermal; and secondly, that rock alteration and ore deposition are closely related both in time and space, as is seen in argillic alteration sequence. Ore deposition in an alkaline to slightly acid reducing environment is postulated. Ore textures and mineral associations and distributions also indicate that carbonate complexes may have been transported with the deposing ores. Bleached rock formations are not primary strati-graphic phenomena. Bleaching, or changes in ferric iron content, results from a chemical process involving reduction and conversion of hematite to a soluble aqueous ion. Nearby Chinle bedded deposits (Moss Rack sandstone), containing shale lenses, fossil wood, organic debris and minor fractures, overly the Cutler formation. Chinle ores have a single reported isotopic age of approximately 200 m.y. Their chemical environment is assumed similar to that of the Cutler ores, though slightly more acidic. Two genetic, paradoxically divergent interpretations of the bedded deposits are derived from available spectrographic, petrographic, X-ray and chemical analyses. Kane Springs canyon is located southwest of Moab, Utah, south of the Colorado River and northwest of the Lisbon Valley mining district (Fig. 1). Uranium deposits occur along the northeast flank of a Kane Creek salt anticline where two geologic formations bear ore, the Permian Cutler and the Triassic Chinle. The Cutler deposits' fissure vein formation is an unusual occurrence in the Colorado Plateau. The Chinle deposits appear to be of the normal sedimentary type. Associated with the vein deposits are a number of features, including argillic alteration of sedimentary strata. The minerals of these deposits and their associated features have been studied in detail in a two year program entailing both field and laboratory techniques. STRATIGRAPHY A stratigraphic section of the lithologic units in the Kane Creek area is given in Table I.

Jan 1, 1967

Discussion of the paper of F. C. NEWTON, presented at the New York meeting, Feb-ruary, 1915, and printed in Bulletin No. 9S, February, 1915, pp. 473 to 477. H. 0. HOFMAN, Boston, Mass.-The results of these large-scale experiments, which were carried on at Perth Amboy, show that there are many differences between theoretical conceptions and their applications to work on a large scale. The author has given reasons why the results of bringing a desilverizing kettle to the high melting point of the zinc-silver alloy, Zn3Ag2, melting at 665° C., are not satisfactory. In all probability the alloy is dissolved in the lead; it may also be decomposed by the lead; the practical result is that this high temperature does not work. It remains now for the laboratory man to carry on systematic experiments

Jan 5, 1915

By S. E. Bretherton

This title introduces the subject I wish to describe to my fellow members, very few of whom, I 'hope, have ever had as much trouble with the smelting of ore containing much zinc, either in the lead blast furnace or the matting furnace, as circumstances have forced upon me: First, for several years in Leadville, Colo., after the sulphide ores containing zinc had been developed with greater depth and were sold to the intereats with which I was connected for smelt-ing in the blast furnace for the recovery of the lead, silver, and gold; then, in New Mexico and Arizona, where the principal source of ore supply for our custom smelter was from miners who sent most of their product in the form of concentrates, which we briquetted and smelted in the blast furnace, producing a matte containing copper, silver, and gold, for which we were paid; together with some zinc and lead, which was penalized if in excess of a maximum base set by the refinery to which we sold our copper matte; last, but not least, my experience in Shasta county, Gal., where for the sake of recovering $13 per ton value in copper, silver, and gold, I have smelted ore containing as high as 40 per cent. zinc (the last 18,951 tons smelted averaged 15 3/10 per cent. zinc) which we not only lost, but which it cost us money to lose. After such an experience, and knowing that, instead of being worth only $13 per ton, such 15 per cent. zinc ore should be worth about $30, including zinc at the present market value, the question of recovering the zinc in a profitable manner from such ore became very interesting to me. During several years' time I sent samples, of from 5 to 1,200 lb. each, to be tested by the different best-known zinc-recovery plants, and experimented with several processes proposed by others for the treatment of such ore, with but little encouragement, until I

Jan 1, 1914

By Alfred V. de Forest

WE are now assembled in this hall for the eighteenth lecture in honor of the memory of our greatest American metallurgist, Henry Marion Howe. Many of his most intimate contemporaries, led, as was fitting, by Professor Sauveur, have described his vital accomplishments in three fields: as a leader in technical industrial development; in theoretical research; and finally as a teacher and source of inspiration for nearly two generations of students. In 1914 Professor Howe had retired from active teaching, but maintained his laboratory at Columbia University under the care of Arthur G. Levy, with whom he published many of the papers that later were incorporated into his last book, "The Metallography of Steel and Cast Iron." My position at the time was that of personal assistant to Professor Campbell-no pay, no duties, but the great privilege of preparing specimens, taking pictures and attending to some of the current consulting work. Whenever possible, I visited Howe's laboratory to chat with Levy and gather ideas about the wonderful field of metallography-in which I was a rank amateur, rescued by the quiet enthusiasm of Donald Smith of Princeton from an instructorship in civil engineering. Levy let me act as a fly on the wall during the Professor's occasional visits. Busy as he was, Professor Howe took the time and trouble to encourage my interest, as he had done for hundreds of others. He told me how he went about gathering his own information speculating as to causes, considering experiments, and verifying his conclusions. I ventured to mention some tests I had run on the irregular stretching of wires of different metals. He read the small volume I had prepared of ill-assorted facts and fancies and remarked: "Nobody cares for your theories or the history of your tests. Describe what you found as briefly as possible and perhaps I can help you to publish." Curiously enough, among my discards were some autographically recorded load-versus-electrical-resistance measurements. Taken with inadequate knowledge and equipment, these curves did not reproduce consistently, but if the relationship between strain and resistance had then been explored, the latest type of strain gauge might have been in useful service for the past 25 years. Professor Howe was a gifted teacher, perhaps because he was primarily an ardent and assiduous student. His own eagerness to learn and his willingness to revise and extend his opinions constantly encouraged those of his environment to be diligent and painstaking in the pursuit of knowledge. In honoring his memory, I also wish to bring to mind the kindly, humorous and quiet Levy, and join his name again, as it was for too brief a space in the past, with that of many-sided Henry Marion Howe. FACTORS OF IMPACT STRENGTH The subject chosen for the Howe Memorial Lecture by Dr. Gillett last year

Jan 1, 1941

By F. D. Wright, H. D. Fara

The solution to the plastic and elastic stresses around a circular shaft in a hydrostatic stress field that has appeared in two editions of a widely used book on rock mechanics1 is in error. Although this is a relatively minor matter, the correct solution was not found by a literature survey, so it appears worthwhile to present it. For a homogeneous, isotropic, rigid plastic-elastic body in plane strain which obeys Tresca's yield criterion the following equations must be satisfied:'," In the plastic zone,

Jan 1, 1963

By Jerome F. Kuzmick

Condusions. From the work on aluminum powder, the following general con clusions can bc drawn: I. The physical properties of aluminum compacts, such as density. strength and ductility, increase with increasing pressure, up to the practicable pressure limits. 2. Good properties ill aluminum con pacts can be secured only by the use of high pressures, because it is neccssary to rupture the refractory oxide film on aluminum powder. 3. Considerable softening of the specimens occurs upon sintering. regardlers of the pressure used. General Conclusions 1. For relatively short-time sintering. molding pressure is a very important factor in the final physical properties of the sintered specimens. 2. The effect of pressure. is difierent for each metal, so that few general rules can be drawn that would apply to all metals. 3. In many cases, fur a particular metal powder and sintering temperature there is a critical pressure at which the best physical properties can be obtained. 4. The principles of cold work and in nealing and their effect on grain structure applied to massive metal also holds true for sintered metals. 5. Particle size, at least for electrolytic iron powder, does not have a. great effect on ultimate grain six. DISCUSSION [E. E, Schumacher presiding V.. V. Crane. *—I was particularly impressed with Dr. Kuzmick's work on tin IF not the illustration, particularly the Second one. a very good illustraition of hot preessing. in that

Jan 1, 1945

By Simon D. Strauss

Production and consumption of nonferrous metals in the United States during 1950 were at peak levels for the postwar period, as is shown in Tables I, II, and III. The trend of production was upward through most of the year. At the year end, with the possible exception of the Tri-State zinc-lead district, the large mining operations in the country were running at capacity. The absence of serious labor interruptions during the year was an important contributing factor in the increased out-put of metals, since in each of the previous postwar years there had been a number of major strikes which affected production adversely.

Jan 2, 1951

By Richard A. Hawkins

O the American coal man, Australian coal mining most appear to have little, if any, influence on American coal-mining practice and to bear little relation to it. Actually, the relationship has been close, for Australian operators have carefully studied American practice by reading American technical publications, by consulting American engineers, and by visits to Ameriean operations. They have leaned heavily on America for their supply of mechanization equipment and many American mining-machinery manufacturers are active in that country, supplying its needs and furnishing technical assistance. Australia's influence on American coal mining has been obscure and probably negligible. However, it seems reasonable to assume that this influence will increase. The wartime development of air transportation will inevitably bring these two countries into much more intimate contact than existed in recent years. American servicemen. many of them former miners and coal-mining technicians, have visited Australian operation, while stationed in that country, have talked with operators and men over there, and undoubt-

Jan 1, 1945

By A. W. McReynolds

E. OROWAN*—I observed the phenomenon of jerky yielding many years ago with zinc25 and cadmium single crystals. A significant point was that the jerks occurred not only when the stress was raised but also (sometimes, after a pause of many minutes during which no trace of creep was observable) at constant stress. The phenomenon may be closely linked with the inertia of the testing machine and of the specimen, although the inertia alone cannot account for it. If, during the test, the resistance of the material to plastic deformation suddenly diminishes while the applied force remains constant, a sudden deformation follows until the yield stress has risen, by strain hardening, to the level of the applied stress (= the value of the previous "upper yield point."). When this is reached, the rate of deformation has attained a maximum value because, up to this moment, the applied force was higher than the plastic resistance of the specimen, and the difference was used for accelerating the moving parts of machine and specimen. The kinetic energy accumulated is now transformed into plastic work by further deformation; that is. the deformation overshoots the point at which the plastic resistance equals the applied static force. When the kinetic energy has been used up, therefore, we are left with a specimen the yield stress of which is higher than the applied stress, and no further deformation can occur (apart from a little creep) until either the applied stress has been raised to the new yield stress level, or the yield stress has fallen by thermal recovery to the level of the applied stress. While this occurs, a new upper yield point can develop, for example, by precipitation.26

Jan 1, 1950

By C.P. Clingerman

The recent iastallation of a combination dust catcher, gas washer and precipitator at Carrie blast furnaces of the Homestead Steel Works has given very satisfactory results. The following description of the gas-cleaning installation is based on actual operating experience. When Carrie blast furnace No. 3 was rebuilt the decision was made to fine-clean all the gas produced by the furnace, because the management wanted fine-cleaned gas for fuel in the stoves and boilers. In order to keep the installation cost as low as possible, the gas-cleaning system was streamlined. All by-pass lines and goggle valves for bypass lines were eliminated from the system. A radical departure from the use of 8-in. tubes in the Cottrell-type precipitators was made by using 12-in. diameter tubes in a single compartment, the single compartment being divided into two units by a single partition wall in the top header. The Furnace Proper A few of the characteristic points and dimensions of the furnace proper are: Hearth diameter.............. 26 ft. o in. Bosh diameter............... 29 ft. 1 3/4 in. Stock-line diameter........... 20 ft. o in. Large-bell diameter........... 14 ft. 8 in. Small-bell diameter........... 6 ft. 6 in. Height of furnace from center of iron notch to bottom of large bell, closed............ 94 ft. 4 in. Height of furnace from center of iron notch to main platform ...................... 105 ft. o in. The furnace top is equipped with a MC-Kee revolving distributor, the operation of which is electrically interlocked with the skips, bell hoists, and coke-weighing and charging apparatus through a Freyn automatic charging control. The gas leaves the furnace first through four offtakes, 5 ft. 9 in. in diameter, then through uptakes that, are approximately 85 ft. high, which feed into a single down-comer that is 9 ft. in diameter. Dust Catcher The primary dust catcher installed (Fig. I) may be described as a single-cone type. The inlet pipe at the top of the dust catchei is 9 ft. in diameter; it is flared to a conical shape as it extends down inside the dust-catcher shell, which is 35 ft. in diameter, 37 ft. high on the straight side, and has a conical top and bottom. The slope of the bottom is so0 with the horizontal. The cone-shaped pipe inside the dust-catcher shell is 42 ft. high and is 19 ft. 7 in. in diameter at its bottom lip where it releases the gas inside the dust catcher. The ratio of the area of the inside cone at its bottom lip to the

Jan 1, 1943

By C. P. Clingerman

The recent iastallation of a combination dust catcher, gas washer and precipitator at Carrie blast furnaces of the Homestead Steel Works has given very satisfactory results. The following description of the gas-cleaning installation is based on actual operating experience. When Carrie blast furnace No. 3 was rebuilt the decision was made to fine-clean all the gas produced by the furnace, because the management wanted fine-cleaned gas for fuel in the stoves and boilers. In order to keep the installation cost as low as possible, the gas-cleaning system was streamlined. All by-pass lines and goggle valves for bypass lines were eliminated from the system. A radical departure from the use of 8-in. tubes in the Cottrell-type precipitators was made by using 12-in. diameter tubes in a single compartment, the single compartment being divided into two units by a single partition wall in the top header. The Furnace Proper A few of the characteristic points and dimensions of the furnace proper are: Hearth diameter.............. 26 ft. o in. Bosh diameter............... 29 ft. 1 3/4 in. Stock-line diameter........... 20 ft. o in. Large-bell diameter........... 14 ft. 8 in. Small-bell diameter........... 6 ft. 6 in. Height of furnace from center of iron notch to bottom of large bell, closed............ 94 ft. 4 in. Height of furnace from center of iron notch to main platform ...................... 105 ft. o in. The furnace top is equipped with a MC-Kee revolving distributor, the operation of which is electrically interlocked with the skips, bell hoists, and coke-weighing and charging apparatus through a Freyn automatic charging control. The gas leaves the furnace first through four offtakes, 5 ft. 9 in. in diameter, then through uptakes that, are approximately 85 ft. high, which feed into a single down-comer that is 9 ft. in diameter. Dust Catcher The primary dust catcher installed (Fig. I) may be described as a single-cone type. The inlet pipe at the top of the dust catchei is 9 ft. in diameter; it is flared to a conical shape as it extends down inside the dust-catcher shell, which is 35 ft. in diameter, 37 ft. high on the straight side, and has a conical top and bottom. The slope of the bottom is so0 with the horizontal. The cone-shaped pipe inside the dust-catcher shell is 42 ft. high and is 19 ft. 7 in. in diameter at its bottom lip where it releases the gas inside the dust catcher. The ratio of the area of the inside cone at its bottom lip to the

Jan 1, 1943

By J. A. Morgan

IN the art of roasting sulfides it is well known that the lower the temperature and the higher the pressure of SO, the larger will be the amount of sulfate present in the product. However, the mechanism of sulfate formation is not generally understood. The following experiment" demonstrates in a direct way that, in the roasting of Cu2S, the sulfate forms from the reaction of Cu2O, formed by the oxidation of Cu2s, with gaseous SO, (or SO3) and 0,. Thus, the sulfate does not form at the sulfide surface. The reaction at the sulfide surface is the same whether or not sulfate is formed. Using an indirect method, Ong, Fassell, and Wadsworth' infer that sulfate forms after oxidation, during the roasting of sphalerite, agreeing with the observations of this paper. The method presented here of demonstrating that sulfate forms after formation of Cu2O is to roast a sample of Cu2S and then to locate and identify the phases formed.' A solid cube of cuprous sulfide, made by melting Fisher reagent grade Cu2S powder and measuring about 1.5 cm on edge, was placed on a Nichrome wire grid suspended over the top of an Alundum combustion boat. The assembly was placed in a tube furnace at 600°C and oxygen gas, flowing at 0.60 liters per min, was passed around the specimen for 24 hr. The furnace tube diameter was 1.5 in. The partially roasted sample was removed from the furnace and impregnated with resin No. BR 0014, obtained from the Palmer Products Co., and the impregnated sample was then mounted in Lucite. A cross section was obtained by grinding and the surface was prepared by the following steps: 1) grinding—60 grit, 3M disk, dry; 2) preliminary polishing —60 through 600 grit, 3M disk, dry; 3) polishing— 8 µ diamond putty, silk cloth; and 4) final polishing —1evigated magnesia in isopropyl alcohol, Selvyt cloth. The color micrograph of the polished surface is shown in Fig. 1. The layers present in the micrograph are given along the side. The comwositions of the various layers were established by Debye-Scherrer patterns. From this evidence the following sequence of reactions which occur in the roasting of Cu2S is inferred: 1) The oxidation of Cu2S occurs with oxygen which has been transported through the oxide-sulfate layer by either gaseous or solid state diffu- sion. The products of this reaction at the Cu2S surface are Cu2O and SO,. 2) The SO, diffuses out through the pores in the Cu2O and finally reaches a position in the Cu2O where the oxygen pressure and the SO, pressure have values such that the thermodynamic conditions for the formation of CuSO4 are fulfilled. Then, the mixture of SO2, SO3, and oxygen reacts with the Cu2O to form CuSO1. 3) The CuSO, decomposes by the evolution of SO,, or SO, and O2, to form the basic sulfate. This is reasonable, since the SO, gradient will decrease toward the oxygen gas phase from the CuSO4 layer. 4) For this same reason the basic sulfate will decompose to form CuO. The above sequence of events is based on the assumption that diffusion through the oxide and sulfate layers, rather than the reaction at the sulfide-oxide interface, is rate-determining. This assumption is supported by the observation that these oxide and sulfate layers combined are almost nonperme-able to the flow of gases through them. Acknowledgments This research was supported by the U. S. Air Force, through the Office of Scientific Research of the Air Research and Development Command. The authors wish to acknowledge the helpful suggestions of Ralph Wells of the Applied Research and Developmeit Laboratory, U. S. Steel Corp. References E. A. Peretti: A New Method for Studying the Mechanism of Roasting Reactions. Discussions Faraday Soc. (1948) 4, p. 174. - J. N. Ong, Jr., M. E. Wadsworth, and W. M. Fassell. Jr.: Kinetic Study of the Oxidation of Sphalerite. Trans. AIME (1956) '206, pp. 257-263; Journal OF Metals (February 1956).

Jan 1, 1957

By W. B. Braden

This paper presents a suitable method for predicting gas-free oil viscosities at temperatures up to 500F knowing only the API gravity of the oil at 60F and the viscosity of the oil measured at any relatively low temperature. The API pravity and the one viscosity value are used as parameters to determine the slope of a straight line on the ASTM slanaord viscosity-temperature chart. Then, knowing the slope of the line and one point on the line, the vrscosities at higher temperatures can be determined. The line slope correlations were developed at I00 and 210F since viscosity data are frequently measured at these temperatures. A procedure is given for predicting line slopes from measurements at other tetnperatures. A nomogram is furnished for solving the relationship. The correlation has been evaluated at temperatures up to 5OOF for oils varyzng in gravity from 10 to 33 " API. The correiution is applicable only to Newtonian fluids. Comparison at 500F of true viscosities and those predicted from values at 100F shows an average deviation of 3.0 per cent (maximum deviation of 6.0 per cent). Predictions from the values at 21 0F for the same oils how an average deviation of 1.5 per cent (maximum deviation of 3.4 per cent). INTRODUCTION Correlations have been developed by Beal' and by Chew and Connally' for predicting viscosities of gas-saturated oils at reservoir conditions. Each of these correlations requires a knowledge of the solution gas-oil ratio and the viscosity of the gas-free oil at the reservoir temperature. For temperatures below 350F, measurements of the gas-free oil viscosities can be made easily using commercially available equipment. In thermal recovery processes, however, reservoir temperatures well in excess of 350F are encountered. Viscosity measurements at such conditions are more difficult and time consuming and require modification of existing equipment or the construction of new equipment. Measurements are further complicated by the difficulty of handling highly viscous oils associated with thermal recovery processes. Therefore, it is desirable to have a correlation which allows accurate prediction of viscosities at high temperatures. A commonly used technique for predicting viscosities at high temperatures is to measure the viscosities at two lower temperatures, plot the values on ASTM standard viscosity-temperature charts and extrapolate to the temperatures desired. If either of the values is slightly in error, the extrapolated value can be significantly in error. To justify an extrapolation, three points are actually necessary. This procedure can consume much time, particularly with heavy oils. Considering the cost of viscosity measurements, it would be desirable to eliminate the need for direct measurements by having correlations which would allow viscosity predictions from other physical or chemical properties. Beal1 investigated the possibility of correlating viscosity with oil gravity at temperatures from 100 to 220F. While showing that a general relationship exists, he also found significant deviations. It is possible that correlations will be developed based on oil composition as more information becomes available. While not eliminating the need for viscosity rneasurements, the method presented herein requires that only one viscosity measurement be made. The API gravity must also be known. The theory is based on the fact that the viscosity of paraffins (high gravity) changes less with temperature than does the viscosity of naph-thenes or aromatics (low gravity). The gravity. therefore, is used as a parameter to determine the slope of a straight line on the ASTM standard viscosity-temperature charts. The correlation is applicable only to Newtonian oils, and deviations due to thermal decomposition and nonhomo-geneity cannot be predicted. Oils containing additives have not been evaluated. PROCEDURE Fifteen oils were used in developing the correlation; eight were crudes and seven were processed oils. Oil gravities varied from 9.9" API (naphthene base) to 32.7' API (paraffin base). The temperature range studied was 81 to 516F. Each oil used had a minimum of three viscosity measurements and each plotted essentially as a straight line on the ASTM charts. In all, 91 viscosity measurements were used in the correlation. Saybolt, rolling ball and capillary tube viscometers were used for the measurements. Viscosity data for Samples 1, 2, 4, 7, 10, 11 and 14 were obtained in Texaco, Inc. laboratories. The data for Samples 3, 5, 6, 8, 9, 12 and 15 were from Fortsch and Wilson,3 and data for Sample 13 were from Dean and Lane.' All data points used in the correlation are plotted in Fig. 1. It is seen that some of the viscosity values deviated slightly from the straight-line plots at the higher temperatures. Properties of the oils after exposure to the

Jan 1, 1967

By J. W. Evans

ONE of the most important and frequent calculations that the extractive metallurgist is called upon to make is that of the standard free energy change of a reaction (?F°). For many reactions of metallurgical interest, the lengthy arithmetical calculations have been eliminated by the use of free energy-temperature diagrams which have been constructed by Ellingham,1 Richardson and Jeffes,2 Kellogg,3 and Osborn4 (e.g., for oxides, sulphides, halides) from critical surveys of existing data. The speed and simplicity of making calculations with these graphs make them of great practical value and, this should be stressed, in the majority of cases no greater accuracy is obtained by the individual calculations from specific heat data, entropies, and heats of reaction. With the increasing industrial application of vacuum methods to the winning of metals, notably at present magnesium and the alkaline earth metals, it is necessary to calculate low metal vapor pressures above reaction mixtures. The existing free energy diagrams usually give values where the solid and liquid metals are at unit activity. To obtain the free energy change associated with the reaction Metal (solid or liquid) = Metal (gas) it is customary to calculate this from either vapor pressure equations or from the appropriate free energy functions. This paper presents graphically the free energies of vaporization of a number of metals of economic importance which can be used in conjunction with other free energy diagrams. Certain metals have been excluded on the following grounds: titanium, tungsten, molybdenum, and platinum have very high heats of vaporization and boiling points and the uncertainty of these values arising from difficulties of high temperature measurements makes free energy values of doubtful accuracy; the data for cobalt, vanadium, and zirconium are uncertain; finally, arsenic, antimony, and bismuth could not be conveniently included. because of the presence of mixtures of polyatomic and mona-tomic vapors in the temperature range considered. Free Energy Diagram In Fig. 1, the standard free energies of vaporization per mol (?F°T) have been plotted for the temperature range 0" to 2000°C for the reaction M (solid or liquid) = M (gas) The data have been obtained from the free energy functions — (F-H298)/T for the solid, liquid, and gaseous elements and the heats of vaporization at 298°K, i.e., ?H298 (vapor). The values of these functions have been taken without change from the recent critical survey by Brewer;' the bulk of this data is from Kelley7 with adjustments in the light of more recent work. Values of the function — (F-H298) /T at T = 298°, 500°, 1000°, 1500°, and 2000°K were employed. Where possible, a further independent value was obtained by using the boiling point, i.e., where ?F°T = 0. All calculations are based on the assumption that the metal vapors are monatomic and that the boiling points refer to those temperatures at which the partial pressure of the monatomic vapor above the metal is 760 mm. For the alkali metals, e.g., sodium, potassium, and lithium, diatomic gas molecules are present as minor species; details of these are discussed by Brewer." On the basis of the above values and allowing for the change in slope at the melting point, straight line graphs were constructed and extrapolated to 2000°C. The deviation from a straight line did not exceed ±500 cal, which in all cases appears less than the probable error in the ?F°T values.

Jan 1, 1954

By A. Moskowitz, L. S. Redmerski

The corrosion resistance of stainless steels can be strongly affected by surface treatments. Changes in corrosion resistance can relate to surface composition, integrity and stability of the passive film, and to surface profile (roughness). Operations producing oxidation at the surface, such as annealing, heat treating, and welding, can result in a chromium-rich scale and a chromium-depleted metal surface. In order to restore full corrosion resistance, chemical or mechanical clean-up techniques must remove not only the oxide, but also a very thin layer of metal. Laboratory and field test studies show that these factors are particularly significant in less highly alloyed steels. Annealing stainless in a reducing atmosphere (bright annealing) avoids chromium depletion, but as-bright-annealed material does not display optimum corrosion resistance in certain environments. Electro passiva-tion can be applied to improve pitting resistance without significantly changing bright surface appearance. Potentiometric studies show that electropassivated material also displays significantly greater resistance to breakdown of passivity in acid solutions. The application of special surface finishes for appearance purposes can affect corrosion resistance. Roughness is a key factor. Samples of related appearance but with different surface profiles can show significant differences in corrosion resistance. Thus nonreflec-tive stainless with a relatively smooth surface produced by a special rolling process is much superior to material chemically etched to a similar low reflectivity. THE corrosion resistance of a stainless steel is affected by other factors in addition to its bulk composition and metallurgical structure. These other factors include those relating to the specific chemical and physical condition of the steel's surface. This paper will consider certain aspects of surface condition in relation to corrosion resistance. In particular, studies will be described on the effects of oxidation encountered in heat treating or welding operations, of passivation after bright annealing, and of different surface finishes. EFFECTS DUE TO OXIDATION When stainless steels are exposed to high temperature in an oxidizing environment, as in annealing or welding, the oxides formed are relatively rich in chromium. As a consequence of oxidation, the metallic layer directly beneath the scale may be low in chromium to some very thin but finite depth.1"8 Such a change in chromium content could lower the corrosion resistance at the surface, whether or not the oxide layer is removed. Studies were performed relating to the effect of oxidation and chromium depletion produced during annealing and welding on the corrosion resistance of stainless steels. The nominal compositions of steels used in this study and others are given in Table I. A) Annealing Studies on 17 pet Cr Steels. 1) Effects of Pickling Treatments. Studies were performed to investigate the corrosion resistance of air annealed type 430 stainless as a function of the amount of electrolytic pickling after annealing. The material used in this study had been air annealed and electrolytically pickled in the mill. All scale had been removed, and yet the material showed unusually poor corrosion resistance. Laboratory electrolytic pickling studies were performed to determine whether additional metal removal from the surface would improve corrosion resistance. Electrolytic pickling was performed in a sulfuric acid bath using various conditions of bath acidity, temperature, time, and current density. The samples were then rated for corrosion resistance in a ferric chloride spot test. For this spot test, a solution was prepared by dissolving 10 g of FeCl3 . 6H2O, 5 g of NaCl, and 2.5 ml of concentrated HC1 in 200 ml of water. An area on a specimen was cleaned and a drop of test solution was placed on the prepared area. After 5 min, the drop was rinsed off and the area wiped dry. The spot was then rated between 1 and 5 by visual comparison with standard spots. The numerical rating of the standard spots can be described as follows: 1—No clouding of surface; 2—very slight clouding of surface; 3—slight clouding of surface; 4—moderate clouding of surface; 5—strong clouding of surface. A rating of 1 or 2 was considered to have passed the test, a rating of 4 or 5 represented failure, and a rating of 3 was considered borderline. The severity of etching in this test has been related to the actual chromium content at the surface.4 Etching (clouding) occurs on type 430 stainless (rating of 4 to 5) when the surface chromium content is 14 pct or less. The effects of current density and retention time when electrolytically repickling this material in 6 pct sulfuric acid are shown in Fig. 1. Increasing the cur-rent density or retention time improved corrosion resistance as measured by the spot test. Similarly, increasing acid concentration of the bath or bath tem-perature was found to improve corrosion resistance. The conditions making for improved spot ratings resulted in increased metal removal, regardless of specific pickling conditions used, Fig. 2.

Jan 1, 1970

By K. E. Gray, M. S. Seth

In Part I of this work,1 equations of elasticity were formulated for transversely isotropic, axisymmetric, homogeneous, porous media exhibiting pore fluid pressure. Equations of elasticity and the thermal analogy method were used to determine transient horizontal, tangential, and vertical stresses and radial displacement in a semi-infinite cylindrical region when either a constant rate of pressure or a constant rate of flow is maintained at the wellbore. In this paper, the approach presented earlier is extended to finite reservoirs for the cases of (1) steady-state flow, (2) constant pressures at the well bore and outer boundary and (3) constant pressure at the wellbore and no flow at the outer boundary. Results of this work show that radial and tangential stress gradients are high near the wellbore but diminish rapidt; away from the well; the vertical stress gradient behaves in the same way but is less severe. Radial stresses are compressive or neutral, whereas tangential and vertical stresses may be tensile, neutral or com-pressive, depending upon the boundary conditions, the physical Properties of the system and the radial distance involved (vertical stresses are always compressive in an unbounded system1. For constant boundary pressures, both radial and tangential stresses increase with time whereas they both decrease for a closed outer boundary and constant pressure at the wellbore. The vertical stress decreases with time for both systems. For steady-state systems, radial displacement may be positive or negative, depending upon the dimensions of the system, the pressure differential and the porosity. Radial displacement may be positive or negative for a closed outer boundary but is positive for constant pressures at both boundaries. INTRODUCTION The importance, utility and complexity of a realistic appraisal of the stress state at and local to a wellbore were indicated in Part I. In this paper the analytical approach presented earlier is extended to finite, cylindrical reservoir geometry for the cases of (1) steady-state flow, (2) constant pressures at wellbore and outer boundary and (3) constant pressure at the wellbore and no flow at the outer boundary. Other than the outer boundary of the reservoir being finite, the physical system and assumptions pertinent thereto are the same as before. The reader may wish to review the mathematical development through Eq. 49 of Part I before proceeding here. SOLUTION FOR GENERAL BOUNDARY CONDITIONS THERMAL STRESSES AND DISPLACEMENTS Since normal stresses do not exist at the free boundaries of a system subjected to thermal stresses, the boundary conditions are

Jan 1, 1969