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By Hsun Hu

Three single crystal strips of a 3 pct Si-Fe alloy with approximately (110) [001], (210) [001], and (100) [001] orientations were rolled at room temperature to 30, 50, and 70 pct reductions in thickness. Their deformation and annealing textures were studied. In most cases, the change in texture upon recrystallization and subsequent growth can be described as rotations around the <I10 > axes. A < WO > rotational relationship was also observed. The temperature dependence of recrystallization textures was discussed. WhILE considerable data have been published on the rolling and annealing textures in silicon-iron crystals, very little study has been made on the texture formation at various stages of rolling deformation, and during the process of recrystallization. Dunn&apos; in some of his early works had studied the orientation of recrystallized grains in crystals cut out from lightly rolled (10 to 20 pct reduction) large grained sheets. He found that in most cases a third-order twin relationship exists between the crystal and the recrystallized grains. This orientation relationship actually corresponds to rotations around the <110> axes. The more recent studies of Dunn &apos; and of Dunn and Koh &apos;5 on the rolling and annealing textures in various silicon-iron crystals were concerned mostly with a cold-rolling reduction of 70 pct and annealing at 980OC for recrystallization. Reductions of similar magnitude were also employed by Walter and Hibbard in rolling columnar crystal aggregates of a silicon-iron ingot. A systematic study of the effect of rolling reduction on the deforma- tion and annealing textures is still lacking. Regarding the effect of annealing temperature on the texture formation, Dunn3 has observed a change in therecrys-tallization texture by annealing a 70 pct rolled (1 10) [001] crystal first at a low temperature then atahigh temperature. But the details of texture formation during the annealing treatments were not thoroughly investigated. The present investigation was undertaken to study the texture developments at various stages of rolling deformation and of the recrystallization process, so that a better understanding on the texture formation in silicon-iron crystals may be obtained. EXPERIMENTAL PROCEDURE The three single crystals used in the present investigation were selected from the group of single crystal strips previously prepared7 from a high grade commercial Si-Fe alloy with 3 pct Si. The thickness of these single crystal strips was 0.040 in. The orientations of the three crystals as determined by the X-ray back-reflection Laue technique are shown in Table I. Each of the three crystals was rolled at room temperature along the strip direction to 30, 50, and 70

Jan 1, 1962

By R. Maddin, C. H. Mathewson, W. R. Hibbard

Recent publicationsl.2 establishing the presence of cross-slip in strained metallic single crystals oriented wholly within the area of single slip as predicted from the generalizations of Taylor and Elam3 described these markings as they appeared during the initial stages of the deformation process. At that time, the plane having a common glide direction with the primary slipping plane was reported as the cross-slip plane although the specific direction was not confirmed. Consequently, in continuation of the research, it seemed advisable to investigate the micro-graphic appearance of cross-slip together with the Laue back-reflection X ray analysis and stress-strain data during the later stages of the deformation process. Accordingly, a single crystal of brass (72.75 pct Cu, 0.01 pct Fe, 0.01 pct Pb, 27.23 pct Zn) was polished mechanically and repolished electrolytically after the manner described in the earlier paper.&apos; Three pairs of flat surfaces, parallel to the specimen axis, and (1) perpendicular to the plane containing the pole of the primary glide plane and the specimen axis, (2) perpendicular to the plane containing the pole of the cross-slip plane and the specimen axis, and (3) perpendicular to the plane containing the slip direction and the specimen axis, were polished mechanically and repolished electrolytically, resulting in a final minimum gauge diameter of 0.4864 in. in a gauge length of 3.36 in. The specimen was elongated in tension and load-extension readings were taken following the method described in the initial investigation.&apos; Observed reorientations were obtained from a series of Laue back-reflection photograms at the center and ends of the gauge length and at various positions around the circumference of the specimen. These were interpreted after the manner of A. B. Greninger.4 Cross-slip (Fig 1 and 2) was found with the first appearance of the primary slip clusters and usually joined members of these clusters. In addition, a third set of entirely different markings (Fig 3) could be noted. The displacement of this third set by the primary slip lines was measured as 8300 at. diam (3.04 microns). Since the specimen was carefully observed at high magnifications before any deformation and no markings of any type could be noted, it would appear that this third set was formed during the deformation process prior to the initiation of classical primary slip. Additional extensions produced no unusual change in the appearance of either cross-slip or the third set of markings. The number of lines increased with increasing elongation and appeared, generally, in areas where earlier markings were present. The continuity of the clusters of cross-slip lines in Fig 4, 5 and 6 illustrates that they are neither noticeably displaced by nor do they displace the primary lines at this stage. In Fig 7, cross-slip appears in a long narrow localized band approximately 45 degrees from the stress axis. This somewhat resembles a twin band except for the lack of a sharp boundary. After a shear of 0.257, suffcient additional glide occurred on the cross-slip plane to displace the primary slip lines (Fig 8). Generally, where a large number of cross-slip lines could be observed in an area on one flat surface, few cross-slip lines appeared on the diametrically opposite position on the parallel flat (Fig 9). These, of course, were not matched observations on the same glide ellipses. It was extremely difficult to make such comparisons. The third set of markings (Fig 10) was extensively displaced by glide on the primary slip planes. A plot of the width of primary slip clusters versus their displacement of the third set of lines is shown in Fig 11. The slope and the linearity of the plot suggest that each primary glide plane slips to a constant maximum value of shear before further slip is transferred to another plane. A shear value of 0.28 was determined in this case. Heidenreich5 has presented a similar schematic representation of glide for aluminum. After the specimen had attained an elongation of 51.8 pct, corresponding to a shear of 0.973, cross-slip appeared very prominently in certain areas as shown in Fig 12, yet at diametrically opposite positions very little cross-slip could be noted, Fig 13. Classical conjugate slip was found at this advanced stage in the deformation, Fig 14, which corresponds to the axial location shown at 12 in Fig 15. It should be noted that cross-slip occurs within the conjugate slip clusters and on the same plane as the cross-slip associated with the closely spaced primary lines which constitute a background in less distinct focus. The third set of markings noted at all stages in the deformation of the

Jan 1, 1950

By F. R. Pyne

The following notes are presented in an endeavor to point out the disadvantages attending the use of chrome brick in reverberatory furnaces in which are conducted the treatment of materials of such a nature that absorption by the brick is of too great value to be wasted, and these values must be recovered, if possible, in order to prevent metal losses that can not be tolerated. Several years ago one of the large Eastern copper refineries decided to utilize basic material in place of siliceous material in the walls of their reverberatory furnaces for the treatment of very foul blister copper, as the latter rapidly corroded the siliceous linings. It was also expected that there would be less slag formation, with a consequent decrease in the cost of treatment and a reduction in the metal losses. Magnesite brick were first used, but while the corrosive action of the foul material was greatly reduced, and the amount of slag formed was very much less, the magnesite proved to be unsatisfactory in certain parts of the furnace, because of its tendency to crack and spall badly when subjected to the alternate heating and cooling that takes place in a reverberatory refining furnace. This made many repairs necessary, and consequent frequent interruption in the operation of the furnace, which, together with the high price of the magnesite brick, ran up the cost of maintenance to an unreasonable amount. It was, therefore, decided to substitute chrome brick for magnesite brick in the parts of the furnace affected. The results, as far as the reverberatory furnace was concerned, were very satisfactory. The corrosion due to the action of the foul blister was small and the amount of slag formed was no greater than when using magnesite, and the tendency to crack and spall shown by the magnesite was eliminated. Gradually the use of chrome brick was extended to all furnaces, those treating blister copper as well as those melting cathodes, and the results were so satisfactory that the siliceous roofs were replaced by roofs of chrome brick except in certain places where experience showed a more satisfactory performance on the part of the silica brick. It was immediately recognized, for both the magnesite and the chrome brick, that the metal absorption was very heavy, but it was felt that the

Jan 1, 1918

By Robert A. Cook

In the increasing struggle to cheapen the cost of our iron and steel products a great deal of attention lias been given to economies in the manufacture of coke; and while but little lias been accomplished in this direction in the United States, the narrow margin between cost and market-price, which has obtained here for the past few years of continuing manufactur ing depression, has brought the coke-maker face to face with the problem, how to save, and benefit by it, the hitherto waste products of distillation. I These may be summed up under three heads, generally rank ing, in value, in the following order: 1. Ammonia salts.. 2. Oil- or tar-products. 3. Gas. There are cases in which the last may assume the position of greatest importance. The greatest obstacle encountered by the American coke maker, on investigating the subject, has been the apparent necessity of discarding his existing plant of bee-hive ovens, and erecting an entirely new and very expensive system of retort ovens, against the product of which Be has probably been prejudiced from his earliest knowledge of the subject. The object of this paper is to bring prominently before our coke-experts a brief history of the development at Sheffield, England, of a most successful system of the utilization of by products in connection with all already existing plant of bee hive ovens. This system has now been in satisfactory operation for about five years, and is applied to a series of blocks of ovens, comprising-about 140- in all At this plant, belonging to the well-known firm of Newton,

Jan 1, 1897

By W. C. Elli, M. E. Fine

YOUNG&apos;S modulus of elasticity in metals ordinarily decreases with rising temperature. The range of the thermoelastic coefficient at room tem- 1/E dE/dT perature (temperature coefficient of modulus, is illustrated1 by the values for tungsten and hard-drawn aluminum, —95 and —1220x10-6 eg C-1. However, a nearly zero thermoelastic coefficient is observed in some ferromagnetic alloys over a limited temperature range. In these alloys, as the temperature is raised, an increase in modulus arising from loss of ferromagnetism compensates the normal decrease. Iron-nickel alloys containing 36 to 52 pct Ni behave in this manner. In the present investiga- tion, the dependence of the modulus and thermo-elastic coefficient on cold working and annealing were studied in iron-nickel alloys in this range of nickel. Although these alloys, when fully annealed, have a coefficient near zero over a very small temperature interval, the temperature range of low coefficient can be extended greatly by straining and then stress-relief annealing. The modulus of face-centered cubic iron-nickel alloys annealed at 1000°C does not vary linearly with composition at room temperature but, as shown by the solid line of fig. 1, from Koster,&apos; is minimum at 40 pct Ni and maximum at 87 pct Ni. The modulus increases with applied magnetic field but retains the minimum near 40 pct Ni. Schematic change of modulus with temperature for three compositions is shown in fig. 2.&apos;. &apos; With increasing temperature, the slope becomes less negative, goes through zero (temperature of minimum modulus for the alloy), becomes positive, and resumes its normal negative value above the Curie

Jan 1, 1951

By J. A. B. Forster

W. G. WOOLF*—The paper has a wealth of data that take careful, detailed study. As has been indicated the highlights can be only touched in the paper. The design and the arrangement of the rabble teeth as well as some of the other details of operation show a very careful study and a scientific approach to the problem which in most plants using hearth roasters are matters of trial and error with empirical conclusions and, perhaps too often, just arbitrary supervisory preferences which may be erroneous. Here the problem has been approached from a scientific angle which think well merits careful study. The ability to treat the tonnages they get through these furnaces think is made easier by reason of the high sulphide sulphur in the resulting calcines which the balance of the plant—the leaching and so on—can cope with. As indicated by Mr. Weldon in his dis- cussion earlier this morning, in most zinc plants an attempt is made to have as low a sulphide sulphur content in the roaster calcine as possible. But in the operation of the Risdon plants, they are able to cope with sulphide sulphur content up to 5 pct which is far beyond the amount of sulphide sulphur that can be handled elsewhere. I think the autogenous roasting is made easier because driving out the last percentages of sulphide sulphur brings on the necessity for extraneous heat, and that is further exemplified because even at Risdon the author shows the desirability of using some oil to better the operation, particularly for uniformity of roasting results and to obtain more regularity of furnace operation. A. A. CENTER*—Regarding the hard crusts in the beds of the furnace and autogenous roasting, the paper speaks of the former being due, at least to a considerable extent, to lead sulphide in the crusts. I wonder if the author has considered the hard crusts as being due in large part to zinc sulphate. While I was developing large zinc operations we ran into hard crusts which had to be dug up. I took several lumps which were so hard they showed the marks of the rabble teeth very plainly and kept them in my office for some weeks. A visitor came along one day, and as he was having similar troubles, I told him what we were doing about ours. I started to pick up one of these lumps and to my amazement the thing crumbled in my hands whereas originally it had been so hard it wore the rabbles down very rapidly in the furnace. I sent the sample to the laboratory and found that it analyzed very high in water-soluble zinc and sulphate-sulphur. The crumbling of the lumps was evidently due to the anhydrous zinc sulphate gradually taking on moisture from the air and forming crystalline zinc sulphate seven parts water. The increase in volume would, of course, result in disintegration of the lumps. As to getting a high tonnage in the autogenous roast, that is partly because of finishing at about 5 pct sulphide sulphur. It is a real job to get down to, say, ½ pct sulphide sulphur, which is what is usually desired, and still put through a good tonnage.

Jan 1, 1950

By W. Rostoker, S. Spachner

A N alloy of 50 pct Ni-50 pct Fe is currently manu- factured in tape thickness down to 1/8 mil. In the annealed form, this alloy produces an almost square hysteresis loop. This has generally been related to the fact that by proper rolling and annealing practice a sharp cube, (100) [OOl], texture can be developed. As part of a program directed toward an understanding of the relationships between magnetic properties and structure of tape core materials, analyses were made of preferred orientations in tapes of various thicknesses. Annealed tapes of this alloy in 2, 1, 1/2, ¼, and Y&apos; mil gages were acquired from commercial sources. Pole figures constructed for the 2 and 1 mil tapes showed the expected sharp cube texture. However, the ½, ¼, and ? mil annealed tapes showed no evidence of any preferred orientations. A comparison of two transmission patterns is shown in Fig. 1. The origin of the absence of texture in the tapes of less than 1 mil thickness was explored in some detail. The basic questions were whether the heat treatment for the thinner tapes was wrongly selected, whether the initial cold worked textures were different, or whether the actual thickness of the tape exercised some influence on its annealing characteristics. Quantities of the five gages of tape were acquired in the as-rolled condition just prior to the final anneal. Pole figures of the cold worked textures were constructed for each of the tapes. Eye estimates of in-

Jan 1, 1956

By W. D. Forgeng, P. F. Wieser

MnSi alloys containing from 2 to 24 at. pct Si have been investigated by metallographic and X-ray methods. Contrary to published data, the temperature of the ß-manganese to a-manganese transformation is lowered by the addition of silicon. The existence of two additional intermediate phases E and ( is demonstrated. E, ranging in composition from 12 to 15.5 at. pct Si, forms by a peritectoid reaction between ß manganese and the second new phase, (. The latter phase is homogeneous at silicon contents from 16.2 to 18 at. pct and forms peritectically from the 0 phase and liquid. The eutectic reaction occurs between the ( phase and MnsSi rather than the ß phase and Mn3Si. As a result of this investigation, a modification of the manganese-rich section of the MnSi equilihrium diagram is proposed. The binary diagram of Mn-Si, according to Hansen,&apos; Fig. 1, exhibits in the low-silicon region (below 24 at. pct Si) a peritectic transformation at 900°C of 0 manganese + Mn3Si to a manganese as determined by R. Vogel and H. Bedarff2 as well as a thermal effect at 980°C between 16.2 and 22.6 at. pct Si reported by the same authors. The nature of the latter transformation was unknown. K. Amark, B. Boren, and A. westgren3 reported indications that possibly four more phases existed in the range of 10 to 27 at. pct Si. The present investigation deals with the phase relations in the range of 2.1 to 17.7 at. pct Si. A few spot checks were conducted up to 23.84 at. pct Si. EXPERIMENTAL PROCEDURE Small experimental heats were prepared by induction melting in a vacuum furnace using argon as a protective atmosphere. The crucible was of commercial-quality magnesia. The furnace charge consisted of silicon metal and dehydrogenated electrolytic manganese. The typical analysis for these materials is shown in Table I. The molten alloy was tapped into 2-in.-square, 7-in.-long ingots. After visual inspection, a small quantity of alloy in the middle portion of the ingot was separated for use in this investigation.MnSi alloys containing from 2 to 24 at. pct Si have been investigated by metallographic and X-ray methods. Contrary to published data, the temperature of the ß-manganese to a-manganese transformation is lowered by the addition of silicon. The existence of two additional intermediate phases E and ( is demonstrated. E, ranging in composition from 12 to 15.5 at. pct Si, forms by a peritectoid reaction between ß manganese and the second new phase, (. The latter phase is homogeneous at silicon contents from 16.2 to 18 at. pct and forms peritectically from the 0 phase and liquid. The eutectic reaction occurs between the ( phase and MnsSi rather than the ß phase and Mn3Si. As a result of this investigation, a modification of the manganese-rich section of the MnSi equilihrium diagram is proposed. The binary diagram of Mn-Si, according to Hansen,&apos; Fig. 1, exhibits in the low-silicon region (below 24 at. pct Si) a peritectic transformation at 900°C of 0 manganese + Mn3Si to a manganese as determined by R. Vogel and H. Bedarff2 as well as a thermal effect at 980°C between 16.2 and 22.6 at. pct Si reported by the same authors. The nature of the latter transformation was unknown. K. Amark, B. Boren, and A. westgren3 reported indications that possibly four more phases existed in the range of 10 to 27 at. pct Si. The present investigation deals with the phase relations in the range of 2.1 to 17.7 at. pct Si. A few spot checks were conducted up to 23.84 at. pct Si. EXPERIMENTAL PROCEDURE Small experimental heats were prepared by induction melting in a vacuum furnace using argon as a protective atmosphere. The crucible was of commercial-quality magnesia. The furnace charge consisted of silicon metal and dehydrogenated electrolytic manganese. The typical analysis for these materials is shown in Table I. The molten alloy was tapped into 2-in.-square, 7-in.-long ingots. After visual inspection, a small quantity of alloy in the middle portion of the ingot was separated for use in this investigation.

Jan 1, 1964

By Alan D. Smith

Mine roof fall characteristics of 250 falls in 5 different room-and-pillar coal mines, located in Pike, Martin, and Floyd counties, were investigated to determine the relationship of selected parameters associated with roof failure and the assumed condition of the mine roof before failure. The selected parameters used in the study included: presence of cracks and water before the occurrence of fall, sloughing of coal ribs, floor heave condition, type of roof support (resin or mechanical anchor bolts), distance to coal face, and time of occurrence of fall after initial coal extraction. In addition, research hypotheses, utilizing multiple linear regression techniques, were generated to test the relationship among the selected parameters and mine roof condition. The results indicated that the vast majority of falls portrayed some presence of water before the actual fall, occurred in less than 30 weeks after initial coal excavation, located usually greater than 30 meters from nearest coal face, gave evidence of cracks in mine roof before occurrence of fall, generally portrayed a good roof condition before the fall, showed presence of sloughing of coal ribs, and gave no occurrence of floor heave before occurrence of fall. In terms of the characteristics of the original support systems in the mine roof falls studied, most roofs were either supported by mechanical-anchor bolts or resin or full-column bolts; very rarely did the roof appear to fail if supported by posts or cribs. A detail inspection of the hypothesis and model comparison results gave supporting evidence that the condition of the roof is not dependent on the usual indicators of potential failure, such as presence of cracks and moisture. In fact, in most cases of mine roof failure, the immediate roof condition was rated as good or better, which gives little or no indication of pending failure and collapse. Hence, a combination of factors that are not easily accessible to measurement, are the dominant factors in the determination of roof fall-potential areas.

Jan 1, 1984

By F. D. Rosi

The plastic properties of extended silver and copper crystals of varying purity were studied as a function of crystal orientation in the early stages of flow. Variations in the gross shape of the shear stress-shear diagram and in the properties of critical Variationsshear stress and shear-hardening coefficient were correlated with changes in slip-band developments. The phenomenon of work hardening is discussed in terms of the existing dislocation theory. IT appears certain from the early studies on the deformation characteristics in metal crystals1-3 that plastic flow takes place in a preferred crystallo-graphic slip system which is determined by the geometry of the crystal (law of maximum shear stress), and that the value of shear stress for this system is independent of crystal orientation (law of critical shear stress). Experimentally, it has been demonstrated further that the law of critical shear stress can be extended to include extensive plastic flow.&apos; Thus, the shear-hardening coefficient, which is defined as the slope of the shear stress-shear curve, also is considered to be independent of orientation. It is noteworthy that deviations from this empirical shear-hardening law have been reported in cubic crystals whose initial orientation favors slip on more than two systems.&apos; Moreover, this law appears to have been derived from stress-strain data relating to relatively high values of shear strain (0.5 to 4), where widespread slip and complex distortions can be expected, regardless of crystal orientation. Since existing data indicate that the strain inhomogeneity in a crystal is manifested particularly in the early stages of flow, it would appear that a more exacting test as to the fundamental nature of the shear-hardening law would be to investigate systematically the shape of the stress-strain curve as a function of crystal orientation in the earlier stages of deformation. With regard to the general form of the shear stress-shear curve for cubic crystals, early studies show a parabolic hardening law, where the shear 1 stress is proportional to the square root of the shear-strain. Since this law was predicted theoretically by Taylor" in his original dislocation model for hard- ening, it has been accepted widely as a fundamental flow characteristic of cubic metals. However, it was recently pointed out by Masing6 hat the parabolic law is not the elementary form of hardening in cubic crystals, but instead is a consequence of complexities in the flow process (e. g., deformation bands and unpredicted secondary slip). Thus, in the very early stages of deformation (< 2 pct extension) where the occurrence of such complexities is unlikely, a different strain-hardening behavior might be anticipated. This view is supported by the recent work of Rosi and Mathewson7 on high purity aluminum where a linear law was obtained for extensions up to 2 pct. A linear hardening over a wider range of deformation also was reported by Rohm and Kochendorfer8 ho deformed aluminum crystals under conditions approximating pure shear. Even more pertinent is the recent evidence of Masing and Raffelsieper9 on high purity aluminum crystals. It was found that for crystals having initial orientations near a <l00> or <1ll> axis, a high hardening was obtained, whereas crystals with a <110> orientation exhibited a low and linear hardening curve followed by a region of more rapid hardening. Since much still remains obscure concerning the details of strain hardening as well as slip-band formation in face-centered-cubic crystals in the early stages of deformation, the present study was undertaken to evaluate the effect of crystal orientation on these two important manifestations of glide. It is important to note here that at the time of this study, Lucke and Lange11 presented information on the orientation-dependence of the shape of the strain-hardening curve in aluminum of various purities. Their work, which essentially represents an extension of that of Masing and Raffelsieper, in many respects is parallel to that of the present study. Experimental Procedure Production of Single Crystals: Single crystals of silver and copper of varying purity were used in

Jan 1, 1955

By H. R. Peiffer, R. Geckle

The silver phase of silver and finely divided alumina composites is shown to grow as single crystabs upon solidification from the melt. These crystals grow without the aid of an externally applied thermal gradient or a mold. The single-crystal growth is more readily disrupted as the alumina content varies from the optimum concentration of 20 wt pct. Pretreatment such as variation of fabrication pressure, and presintering of the specimens appear to play a lesser role in this phenomenon. In actual practice the growth of single crystals of metals from the melt is a tedious, painstaking process.&apos; Care must be taken to insure the proper thermal gradients and rate of growth in a vibration-free environment. Excellent single crystals can be grown when these variables are controlled. When a second insoluble and finely divided phase is present in the melt the growth of single crystals is difficult, if not impossible, even under the most favorable conditions outlined above. During the past few years, a composite of silver and alumina has demonstrated an ability to resist flow even though the major phase, silver, is mo1ten. 2 A more surprising feature of this material is the ease with which single crystals of silver grow upon cooling the composite from temperatures above the melting point of silver to temperatures near room temperature. Observations have been made that demonstrate that single crystals of silver will grow even when conditions most unfavorable for growth of pure silver crystals exist. The crystals grown in this manner are imperfect in that a great deal of subgrain structure exists. It is the purpose of this manuscript to qualitatively describe this process and to attempt to isolate the influencing factors of this behavior. MATERIAL PREPARATION The composite material is prepared by powder-metallurgical techniques. Two items of great importance are the introduction of oxygen into the system and the obvious need for a thorough mixing of the metallic and refractory oxide phases. The oxygen is necessary in order that the silver wets the alumina. Without oxygen the phases separate and the material shows no unusual properties. In order to supply the needed oxygen the silver is added in the form of silver oxide which is readily decomposed to oxygen and silver upon heating. The silver oxide is readily obtained in a finely divided form that allows a uniform mixture of the alumina and silver oxide to be prepared. The correct ratio of alumina to silver oxide is mixed in the presence of alcohol in an ordinary food blender. The mixture has the consistency of a thin slurry and after mixing for approximately 20 min is dried and pressed into billets at various pressures. As is shown in Fig. 1, there is no limit to the shape of the specimens obtainable as single crystals. These billets are heated in air in a predeter-

Jan 1, 1964

By James K. Gluck, William E. Galloway, Gary E. Smith, John P. Morton, Christopher D. Henry

INTRODUCTION Surface mining and in situ leaching of uranium have the potential to alter ground-water quality around mines and leach sites. Of particular concern is the fate of uranium and its associated trace elements: molybdenum, arsenic, and selenium. We wish to under- stand the natural processes that control trace element concentrations in ground water and how these processes will influence dispersion of the elements from a mineralized zone, both naturally and during and after mining or restoration. For example, it is commonly recognized that the trace elements are soluble in oxidizing ground water but are insoluble, and can be precipitated, in reducing ground water. Thus oxidizing, metal-bearing water leaving a deposit could re- enter reduced ground, causing the water to be re- reduced and the trace elements to be, reprecipitated. In a sense, this is recreating the original mineralization process. To accomplish the above goals, we have (1) examined the theoretical controls of concentrations based on the available geochemical and thermodynamic data, (2) determined the major ion composition and oxidation-reduction status of Oakville waters because of the influence of these factors on trace element solubility, and (3) determined trace element concentrations and distribution in Oakville ground water. The last approach is used to evaluate how well actual behavior follows predicted behavior. This report focuses on two elements, uranium and molybdenum, because they exemplify the results obtained. The report also is restricted to a regional study of Oakville ground water. Results of more de- tailed study in and around major uranium districts in the Oakville and much of the raw data that support the conclusions in this report are presented in Galloway, Henry and Smith (1980). This report is part of that larger study, which concerned the depositional systems, hydrology, and geochemistry of the Oakville. The U.S. Environmental Protection Agency funded the study, under grant numbers R-805357-01 and R-805357-02. Theoretical controls were determined by reviewing the available literature on aqueous chemistry and behavior of uranium and molybdenum. To aid in under- standing water chemistry, Oakville water analyses were run through a modified version of the computer model WATEQF (Plumer, Jones, and Truesdell, 1976). WATEQF calculates speciation of dissolved ions and determines saturation with respect to a variety of minerals. In the discussion below, ion activity products (IAP) are compared with the equilibrium constant (KT) for various reactions and mineral products. Values of log IAP/KT near zero indicate that the water is in equilibrium with a mineral. Values less than -1 indicate considerable undersaturation and values greater than +1 indicate oversaturation. Galloway, Henry, and Smith (1980) give a more complete discussion of the application of this approach to Oakville water chemistry. Eh-pH diagrams have been constructed or adapted from the literature to predict what form -- dissolved ion or stable mineral species -- uranium and molybdenum assume under various conditions. Construction of the diagrams has followed procedures described by Garrels and Christ (1965). This approach is particularly appropriate because the solubility of the elements is Eh-dependent, and Eh varies greatly within the Oakville aquifer. A number of assumptions or approximations are inherent in the use of Eh-pH diagrams and chemical models such as WATEQF and in the interpretation of water chemistry in general. Both Eh-pH diagrams and chemical modeling rely entirely upon available thermo- dynamic data, including free energies of formation and dissociation constants for various reactions. These values are known to varying degrees of accuracy. Most major ions and minerals are relatively well control- led; however, data for trace metals are much poorer. Thermodynamic data are not available for some minerals, and for other minerals, two or more divergent values exist. By necessity, we have relied on the judgment of others to evaluate thermodynamic data. Calculations by WATEQF and constructions of Eh-pH diagrams are based on an assumption of equi1ibrium. Equilibrium may not be comnon in low-temperature aqueous environments; at best, ground-water composi tion may be in a state of dynamic equilibrium, continuously changing due to changes in environmental conditions. Eh-pH diagrams show what phases are stable at equilibrium under given conditions; they do not prove that the phases actually exist. Many minerals persist or form metastably under conditions outside their equilibrium stability field. The kinetics of reactions, which cannot be evaluated here, are important in determining what phases occur. Kinetics may be less of a problem for ground water that travels and evolves slowly through a semihomogeneous matrix than for many other natural systems. Eh-pH diagrams show equilibrium fields only of phases included. They do not indicate anything about stability relative to phases not included in the diagram. WATEQF, obviously, cannot calculate the degree of saturation of a mineral not included in the program or for which the appropriate ions were not analyzed. Thus, a mineral that was not considered may be the most stable phase under a given set of conditions and may control the solubility of a trace element. Also, this study is limited exclusively to in- organic compounds. Organic material is known to be an

Jan 1, 1980

By Chingyuan Y. Li, C. Y. Hsieh

Realizing that aluminum will have a great role to play in the coming industrialization of China, Chinese geologists have long been looking about for some aluminum deposits. The possible sources appear to be alunite, the alumina-rich shales, and the bauxite deposits. The locations of deposits are shown in Fig. I. Alunite Our attention was first directed to the alunite deposits along the southeastern coast of China. Table I summarizes the reserves now believed to exist in that region. Other alunite deposits have been found in Kiangpei, Szechuan province; Charming. Liuyang and Hsanshan, Hunnan province Tsingchow and Chowyuan, Shantung province. No reserve figures are available. High-alumina Shale Shale high enough in aluminum to serve as a source of that metal has been found in northeastern China(Tab1e 2). In Manchuria, the Manchuria Light Metals Co., at Antung and Fushun, operating under Japanese control, has been the only active producer of aluminum. It is not known, however, whether the company uses local raw materials or imports ore from elsewhere.* Shantung Bauxite Bauxite was first recognized in China at Paoshan, Shantung province. Although the reserve is reported to be large (estimated at 271 million tons), the high content of insoluble residue (SiO2) and mineral composition (diaspore) are dis-

Jan 1, 1948

By Chingyuan Y. Li, C. Y. Hsieh

Realizing that aluminum will have a great role to play in the coming industrialization of China, Chinese geologists have long been looking about for some aluminum deposits. The possible sources appear to be alunite, the alumina-rich shales, and the bauxite deposits. The locations of deposits are shown in Fig. I. Alunite Our attention was first directed to the alunite deposits along the southeastern coast of China. Table I summarizes the reserves now believed to exist in that region. Other alunite deposits have been found in Kiangpei, Szechuan province; Charming. Liuyang and Hsanshan, Hunnan province Tsingchow and Chowyuan, Shantung province. No reserve figures are available. High-alumina Shale Shale high enough in aluminum to serve as a source of that metal has been found in northeastern China(Tab1e 2). In Manchuria, the Manchuria Light Metals Co., at Antung and Fushun, operating under Japanese control, has been the only active producer of aluminum. It is not known, however, whether the company uses local raw materials or imports ore from elsewhere.* Shantung Bauxite Bauxite was first recognized in China at Paoshan, Shantung province. Although the reserve is reported to be large (estimated at 271 million tons), the high content of insoluble residue (SiO2) and mineral composition (diaspore) are dis-

Jan 1, 1948

By D. M. S. Bhatia, Richard D. Hagni

Five sulfide minerals from the Magmont mine, southeast Missouri were sampled for 31 trace elements in over 300 samples by laser microprobe spectrographic analysis of polished sections. The concentration of several trace elements shows a pattern of progressive variation with depth (space) and variation with different paragenetic stages (time) of each mineral. Factor analysis of the geochemical data shows sympathetic correlation both in space and in time of Bi, Cd, Ge, and Sn in galena and sphalerite, and Ni and Co in sphalerite and marcasite.

Jan 1, 1981

By C. H. Herty

The results of a study of the open-hearth process from the physicochemical viewpoint are given. This study includes experimentation in small laboratory furnaces and in standard 100-ton furnaces. The behavior of manganese, carbon and phosphorus are quantitatively explained. The action of "residual" manganese is discussed with reference to its relation to iron oxide dissolved in the metal. The solubility of CO in steel and its relation to dissolved FeO and carbon is given. The equation for phosphorus elimination has been tested out on a 200-ton furnace and the results are given in the text. The effect of temperature and slag composition on the elimination of metalloids in the basic open-hearth process has been qualitatively understood since the early days of steel making. The quantitative effect has, however, only recently been brought to attention. The effect of slag composition has received more attention than that of temperature, primarily because the range of finishing temperatures in the basic open-hearth process is small compared to the large variations found in the composition of the slag at different periods during the process, and to the variations occurring with the use of raw materials of different degrees of impurity. The effect of slag composition on the elimination of metalloids has been studied by Styril from the thermochemical standpoint. This method is open to serious errors, in that thermochemical data at 2900&apos; F. are very inaccurate and in many cases completely lacking. Feild2 has calculated equilibrium constants from the rate at which the metalloids are eliminated. The effect of slag viscosity on rate of elimination will affect the constants calculated by this method. Whitely,a Colcough4 and others have used slag compositions as the basis for calculation of constants by which the extent of elimination may be calculated.

Jan 1, 1926

By J. L. Taylor, P. Duwez

PARTIAL phase diagrams of titanium with iron, cobalt, and nickel have been established by previous investigators.1-3 These diagrams seem to be reliable, at least for concentrations of titanium ranging from 0 to about 50 at. pct. More recently, Long and his collaborators have presented a tentative titanium-nickel diagram covering the titanium-rich side.&apos; These various studies indicate that in each system three intermediate phases exist and correspond to the compositions Tia, TiX, and TiX2 (or TiX3). The purpose of this paper is to review the available information on the crystal structure of these phases and to give the results of additional X-ray diffraction studies. Previous Work A summary of the work of Wallbaum and his collaborators"-&apos; is presented in table I. The first intermediate phase on the titanium-rich side of the three systems, with iron, cobalt, and nickel, is of the Ti2X type and has a face-centered cubic structure. Although it is stated that the unit cell contains 96 atoms: no lattice parameters are given. The second phase is centered around the compositions TiX for the three systems. The crystal structure of this phase is mentioned in a short note" as being body-centered cubic (CsCl type), but no parameters are given. The analogy between the three systems, which is perfect as far as the two phases of the type Ti2X and TiX are concerned, disappears at the titanium-poor end of the diagrams. In the system titanium- iron, TiFe2 has an hexagonal (MgZn2 type) struc-ture with the parameters given in table I. The existence of TiFe3 has also been reported8 (table I) but was questioned by other investigators2 and is also refuted by the present study. In the system titanium-cobalt, a phase corre-sponding to the composition TiCo2 has been investi-gated by Wallbaum and Witte6 who claim that the structure is cubic (MgCu2 type) for alloys slightly deficient in cobalt and hexagonal (MgNi2 type) for alloys slightly deficient in titanium. The parameters of the two phases are given in table I. In the system titanium-nickel, the nickel-rich phase corresponds to the composition TiNi3 and has been described as hexagonal7 with the parameters given in table I. The present investigation was initiated for the purpose of filling in the gaps in the knowledge con-cerning the structure of the various phases sum-marized in table I. Since the titanium used by Wallbaum and his collaborators was only 95 pct pure,&apos; it was found desirable to redetermine the lattice parameters of the alloys prepared with a

Jan 1, 1951

By Robert B. Sosman

The chance that a Howe Memorial Lecturer will be able to refer back to a personal contact with the distinguished metallurgist for whom this lectureship is named grows steadily I I did not have the pleasure of his personal acquaintance, but I did receive from him in 1916, quite unexpectedly, a letter commenting On a paper that I had recently published27 On "Types of Prismatic Structure in Igneous Rocks." The paper was written for geologists and petrologists, but it had an application, naturally, to the crystallization of iron and steel in a mold. The letter impressed me at the time, and still does, with the breadth of of Howe&apos;s interests and his perseverance in keeping up with the progress of any branch of knowledge that had metallurgical connotations. Scope of the Lecture During several years preceding the date mentioned I had worked in collaboration with Arthur L. Day and E. T. Allen8 at the Geophysical Laboratory, Carnegie Institution of Washington, on the temperature scale as defined by the nitrogen thermometer at high temperatures. Later (1928-1947) I had the opportunity of helping to apply this experience to the pyro-metric problems of the steel industry. Because of the range of its temperatures, the multiplicity of the methods used, and the variety of its purposes, pyrometry in the open-hearth process has always offered a fertile field for both research and development. I am therefore devoting an hour to the subject of temperatures in the basic open-hearth furnace, the furnace that makes most of our steel in the united States. I would direct your attention particularly to the choice of the first two words in the title of the Lecture. One sometimes hears or reads of the ((temperature of such-and-such a furnace," as if it were a single, measurable, characteristic quantity. I need hardly emphasize to any one who has ever operated a furnace or a kiln that " temperature of the furnace " is a meaningless phrase. Even if we confine our attention to the space enclosed by the roof, walls, and hearth of an open-hearth furnace, it is doubtful whether any such space has ever been so uniform in temperature that the phrase would have a meaning. In any furnace, there are many different temperatures, capable of being measured at many different places, and actually being measured for several different purposes. These pyrometric purposes, methods, and results, if given in detail, would expand this lecture into a book on the basic open-hearth process. I must therefore confine myself to a statement of the range of temperatures as they have been observed in various parts of the furnace, indicating in a general way why they are measured, and mentioning the methods that are available without attempting to describe these

Jan 1, 1949

By Robert B. Sosman

The chance that a Howe Memorial Lecturer will be able to refer back to a personal contact with the distinguished metallurgist for whom this lectureship is named grows steadily I I did not have the pleasure of his personal acquaintance, but I did receive from him in 1916, quite unexpectedly, a letter commenting On a paper that I had recently published27 On "Types of Prismatic Structure in Igneous Rocks." The paper was written for geologists and petrologists, but it had an application, naturally, to the crystallization of iron and steel in a mold. The letter impressed me at the time, and still does, with the breadth of of Howe&apos;s interests and his perseverance in keeping up with the progress of any branch of knowledge that had metallurgical connotations. Scope of the Lecture During several years preceding the date mentioned I had worked in collaboration with Arthur L. Day and E. T. Allen8 at the Geophysical Laboratory, Carnegie Institution of Washington, on the temperature scale as defined by the nitrogen thermometer at high temperatures. Later (1928-1947) I had the opportunity of helping to apply this experience to the pyro-metric problems of the steel industry. Because of the range of its temperatures, the multiplicity of the methods used, and the variety of its purposes, pyrometry in the open-hearth process has always offered a fertile field for both research and development. I am therefore devoting an hour to the subject of temperatures in the basic open-hearth furnace, the furnace that makes most of our steel in the united States. I would direct your attention particularly to the choice of the first two words in the title of the Lecture. One sometimes hears or reads of the ((temperature of such-and-such a furnace," as if it were a single, measurable, characteristic quantity. I need hardly emphasize to any one who has ever operated a furnace or a kiln that " temperature of the furnace " is a meaningless phrase. Even if we confine our attention to the space enclosed by the roof, walls, and hearth of an open-hearth furnace, it is doubtful whether any such space has ever been so uniform in temperature that the phrase would have a meaning. In any furnace, there are many different temperatures, capable of being measured at many different places, and actually being measured for several different purposes. These pyrometric purposes, methods, and results, if given in detail, would expand this lecture into a book on the basic open-hearth process. I must therefore confine myself to a statement of the range of temperatures as they have been observed in various parts of the furnace, indicating in a general way why they are measured, and mentioning the methods that are available without attempting to describe these

Jan 1, 1949

By M. H. Caron

BASIC U. S. Patent 1,487,145 on ammonia leaching of nickel ores was issued to the author on March 18, 1924. Equivalent patents in other countries were obtained later. The Dutch Syndicate Brikcarbo became interested in the process in 1935; and a couple of years later the late Dr. H. Foster Bain sent samples of Surigao laterite iron ore to Delft and witnessed tests made there on this material for the Philippines Commonwealth. As a result, the author was asked in April 1940 by Dr. Bain to go to the Philippines to erect and take charge of a pilot plant for the process. The World War prevented carrying out this proposal. The Dorr Co. also became interested in the process at about the same period. The investigations by the Freeport Sulphur Co. on the process as applied to the Cuban nickeliferous laterites, which resulted in the Nicaro enterprise, and the results of this operation have been well described elsewhere.1,²,³,4,5 This Nicaro plant was, in operation for almost two years, and during this period produced about 10 pct of the world nickel production from laterites containing 1.35 pct nickel. This plant and its operation were war measures and, in view of this, activities were suspended in April 1947. The results obtained fully demonstrated the technical feasibility of the process and its economical aspects on a commercial scale. In this respect, it should be understood that it is probable that improvements may be made by further development, and that there are possibilities for advantageous application of the process to garnierite and similar ores with higher values in nickel than the laterite iron ores at Nicaro. While the articles cited above have given a certain amount of information, no general article containing all the important process data has been pub- lished. Since the process is of more than local interest, a fuller knowledge of the fundamental and practical factors of the method may be welcome to those interested in this new field of metals technology. The author, accordingly, takes pleasure in submitting this article to the AIME as it represents in a condensed form the results of many years of research. The brief outlines of the fundamental and other factors and the explanation of observed phenomena are presented with as little discussion of details as possible, consistent with clarity. It is a special satisfaction to the author to make some contribution of his own in return for the benefits of the many valuable publications issued by the Institute during his thirty years of membership. Ores Adapted for Ammonia Leaching: All nickel and cobalt ores which originate from weathering of peridotites or similar basic rocks having sufficient values are suitable for treatment by the ammonia leaching process after a preliminary reduction under proper conditions. The formation of these deposits was probably as follows: In the course of time the basic rocks were attacked by atmospheric agencies; MgO and SiO2 were gradually leached out, and secondary nickel minerals formed, such as garnierite, a hydrated silicate of nickel and magnesia. These secondary products are, however, not stable. They decompose in a further stage of weathering and ultimately only a relatively small residue of insoluble oxides remains, known as laterite iron ore with a small nickel content and very little cobalt. Under these mantles of laterite, richer nickel values may be found, usually indicated by the occurrence of garnierite. The more the ore is disintegrated by nature, the higher the iron content and the better the nickel extractions that may be expected therefrom. Table I shows extractions that may be expected from different types of ores, assuming treatment of -200 mesh products and that all precautions have been taken for obtaining maximum extractions. As for the distribution of the various nickel minerals and compounds that may be present, great variations may occur from locality to locality as well as vertically in a deposit. From such "run of

Jan 1, 1951