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By F. Twyman, D. M. Smith

THOSE chemists (they are still greatly in the minority) who use the spectroscope, use it very often, and find it almost indispensable. As a means of detecting minute quantities of the metals it is unrivalled. A metal can be readily distinguished in the presence of any other element, compound, or mixture without the necessity of separation. The qualitative analysis of the metallic constituents of a substance, which the spectroscope gives so easily, is a sure basis for planning a chemical analysis. As the determination of each element proceeds the purity of precipitates may be checked as often as desired. If, possessing these advantages, the spectroscope has been neglected in general chemistry, it is not surprising that it was neglected in metallurgical chemistry; for many of the impurities which are of industrial interest, even when they are present in a metal or alloy in small quantities, are not then always easily detected by the examination of their visible spectrum. The history of the development of the art has been given in Bureau of Standards Scientific Paper No. 444.

Jan 1, 1928

By R. P. Abendroth

This study is concerned with the kinetics of selective oxidation of chromium in a commercial Fe-Cr-Ni alloy. Selective oxidation of chromium in this alloy, by use of a low oxygen-potential atmosphere, leads to the formation of a compact, protective layer of Cr2O3. This layer serves to protect this alloy from gross scaling when it is subsequently exposed to severe oxidizing conditions at high temperature. The interaction of low oxygen-potential atmospheres close to equilibrium with Fe-Cr and Ni-Cr alloys has been studied by others."' These studies werk concerned with the surface-structure variations under slightly oxidizing conditions. NO detailed study was made of the oxide scale formation kinetics, however. The alloy samples were cut from 0.012-in.-thick sheet, with an apparent surface area of 7.1 sq cm. These sheet samples were abraded through 4/0 metallographic paper, and washed in alcohol and acetone. The analysis of the sheet alloy is (in weight percent): 42 pct Ni, 5.5 pct Cr, 0.09 pct C, 0.18 pct Al, 0.36 pct Si, 0.26 pct Mn, balance Fe. The weight gain vs time data were obtained with a 2-g capacity fused-silica spring—cathetometer system. The spring deflection was optically magnified ten times before being read by the cathetometer. A sensitivity of about 0.01 mg was attainable. The spring was enclosed in a water jacket maintained at 60°C to minimize the effect of temperature changes. The sample was suspended from the spring with a fused-silica hangdown and was positioned in the thermal center of a mullite furnace tube. Sample temperature was read with the aid of a thermocouple placed outside the mullite tube and an inside vs outside temperature calibration. Temperature change during the course of a run was ±0.25°C, with a temperature gradient of less than l.O°C over the length of the sample. Total temperature uncertainty was no more than ±3.0°C. Alignment difficulties between the hangdown and radiation shields in the furnace tube required that the sample be positioned in the furnace when cold, and heated with the furnace until the temperature stabilized at the desired point. This required 5 to 6 hr, and was carried out in Matheson ultrahigh-purity hydrogen. Oxidation was started, after evacuation, by introducing a hydrogen-water vapor mixture, obtained by saturating hydrogen with water vapor at 31.00o ± 0.02oC. Oxidation was continued for 90 min. Gas flow was 300 ml per min during heat up and oxidation. Since only several milligrams of oxide are formed on each sample, chemical analysis of the oxide is difficult. A representative analysis is: 80 pct Cr2O3, 5 pct Fe2O3, 3 pct Al2O3, 4 pct MnO, 7 pct SiO2, 1 pct or less NiO. X-ray diffraction analysis of the oxide as formed on the alloy gives rhombohedra1 Cr2O3, and barely distinguishable amounts of a cubic spinel phase, and possibly AlZOs and SO2. The identification of these latter two compounds is by no means certain. The spinel phase could be based on iron or manganese as these elements are present in significant amounts in the oxide. The results of the kinetic studies using 31°C dew-point hydrogen-water vapor mixtures were found to conform to a parabolic rate law. In many cases the parabolic plot consisted of two intersecting straight lines, defining an early and a late rate for a particular run, and in the other cases the parabolic plot consisted of one straight line for the entire run. The slopes of the various straight lines were determined by the method of least squares. Reproducibility of the data was good enough for multiple runs at the same temperature such that the value given for the rate constant is the average for two or more closely similar values, rather than widely varying values of the rate, where more than one determination is indicated in Table I. The exhibition of only one or of two rate constants during a run can happen at the same temperature. Thus, Table I shows that at 11'74°C a single rate constant was obtained from one sample, while other samples oxidized at the same temperature gave an early and a late rate constant. It should be noted that the single rate constant corresponds very closely with the early rate constant. This is also true at 1153°C. The time at which the late rate started to appear was variable, usually occurring 20 to 40 min after oxidation had started.

Jan 1, 1964

By AIME AIME

ENGINEERS in the past have been largely associated with private enterprise and there has been a considerable tendency on the part of some members of our profession to depreciate government service for engineers. We engineers must change our mental attitude about employment in government service, particularly in view of the present most friendly attitude of the U. S. Civil Service Commission toward engineers for major posts in our Government. We must also take a much more active interest in public affairs. It must be realized that the national-defense program, which we are now organizing, will require for its effectiveness large numbers of engineers skilled in a wide range of technical and administrative services. In fact, the success of this undertaking will depend largely upon the extent to which our Government can command expert engineering talent to serve during the emergency. There is an acute shortage of technical and supervisory engineering personnel not only in the industries concerned with national defense but also in the Army, Navy, and other defense agencies of the Government. By an Act of Congress, approved on Oct. 9. 1940. $9,000.- 000 was turned over to the U. S. Office of Education, the regular defense agency of the Government which has co-operated with higher education for

Jan 1, 1941

By S. H. Williston

IT not often that bore hole surveys can be checked by actual. civil engineering methods. A recent Arizona survey was checked by normal surveying methods and the comparison of the results should be of value to both oil and mining men. During the summer of 1948 the Phelps-Dodge Corporation, at its Copper Queen property near Bis-bee, Ariz., drilled a 1245 ft, 8 in. diarn, churn drillhole in a mineralized area and cased part of it, intending to use it to transfer mill tailings for stope fill. The hole, as frequently occurs, was not straight, and, in endeavoring to locate the bottom in the underground workings, they found no evidence of the hole at the underground coordinates directly below the surface location. The noise of the drilling tools was reasonably clear, but the direction of sound was uncertain. Preliminary tests with available equipment were not successful in locating the bottom of the hole. Because of the mineralized character of the area and the fact there was some casing in the hole, any magnetic method of well surveying would give results of doubtful value. Sperry-Sun gyroscopic well-surveying instruments were finally used to locate the bottom of the hole. These instruments consist of a gyroscope to determine azimuth and either a pendulum or bubble inclino-meter. A multiple shot camera photographs both instruments on a single film and superimposes the photograph of a watch. Coordination of depth with time at the surface makes it possible to select the corresponding picture for any depth. After making several runs of the empty instrument housing from the top of the hole to the bottom to make sure there were no obstructions in the hole, three surveys on wire line were completed during the afternoon. The three surveys, in which readings were taken at different points in the hole on each survey, were computed and gave the following locations of the bottom of the hole in relation to the surface collar: survey No. 1—24.92 N, 30.30 W; survey No. 2—24.24 N, 31.11 W; survey No. 3—26.54 N, 27.72 W. Then the data from the three surveys were combined into a single set of calculations which gave a location for the bottom of the hole: combined surveys—24.27 N, 30.16 W. (Fig. 1.) Immediately upon the determination of the coordinates at the bottom of the hole, a drift on the 1300 ft level was started toward the indicated loca- tion some 38 ft northwest of the coordinates of the surface location, The bottom of the hole was located within the drift round in which it was expected, and the transit survey run to the actual location of the hole indicated N 27.18, W 29.71. This shows a discrepancy between the well survey and the transit survey of 0.45 ft in the westerly direction and 2.91 ft in the northerly direction. All surveys, both gyroscopic and transit, fell well within the width of an ordinary drift. While this is satisfactory for almost any and all mining requirements, a theoretical examination was made as to reasons for the discrepancy. A study of the course of the hole indicates that considerable right turn or spiral existed, and in all probability the surveying instrument was pulled out of alignment while traversing the turn by approximately 0.05 ft at the top and another 0.05 ft in the opposite direction at the bottom of the instrument. If such an allowance were to be made, the survey calculations would almost exactly correspond with those determined by transit. This sort of discrepancy would be minimized by the use of stabilizing guides. It is unfortunate that physical laws probably effectively prevent the use of gyroscopic instruments in EX and AX diamond drill holes. The directive power of a gyroscope falls off inversely at some rate between the third power and the sixth power of the diameter. Present instruments can be run in casing 53/4 in. ID or over and might be adapted to somewhat smaller diameters, but the difficulty of reducing these diameters to 11/4 in. or 2 in. is almost insurmountable at the present time. Acknowledgment The author wishes to express his appreciation to the Phelps-Dodge Corporation for permission to publish this article, and to the Operating and Engineering Departments for their cooperation on the survey; also to Donald Hering, of the Sperry-Sun Well Surveying Co., who actually made the survey and calculated the results.

Jan 1, 1951

By S. H. Williston

IT not often that bore hole surveys can be checked by actual. civil engineering methods. A recent Arizona survey was checked by normal surveying methods and the comparison of the results should be of value to both oil and mining men. During the summer of 1948 the Phelps-Dodge Corporation, at its Copper Queen property near Bis-bee, Ariz., drilled a 1245 ft, 8 in. diarn, churn drillhole in a mineralized area and cased part of it, intending to use it to transfer mill tailings for stope fill. The hole, as frequently occurs, was not straight, and, in endeavoring to locate the bottom in the underground workings, they found no evidence of the hole at the underground coordinates directly below the surface location. The noise of the drilling tools was reasonably clear, but the direction of sound was uncertain. Preliminary tests with available equipment were not successful in locating the bottom of the hole. Because of the mineralized character of the area and the fact there was some casing in the hole, any magnetic method of well surveying would give results of doubtful value. Sperry-Sun gyroscopic well-surveying instruments were finally used to locate the bottom of the hole. These instruments consist of a gyroscope to determine azimuth and either a pendulum or bubble inclino-meter. A multiple shot camera photographs both instruments on a single film and superimposes the photograph of a watch. Coordination of depth with time at the surface makes it possible to select the corresponding picture for any depth. After making several runs of the empty instrument housing from the top of the hole to the bottom to make sure there were no obstructions in the hole, three surveys on wire line were completed during the afternoon. The three surveys, in which readings were taken at different points in the hole on each survey, were computed and gave the following locations of the bottom of the hole in relation to the surface collar: survey No. 1—24.92 N, 30.30 W; survey No. 2—24.24 N, 31.11 W; survey No. 3—26.54 N, 27.72 W. Then the data from the three surveys were combined into a single set of calculations which gave a location for the bottom of the hole: combined surveys—24.27 N, 30.16 W. (Fig. 1.) Immediately upon the determination of the coordinates at the bottom of the hole, a drift on the 1300 ft level was started toward the indicated loca- tion some 38 ft northwest of the coordinates of the surface location, The bottom of the hole was located within the drift round in which it was expected, and the transit survey run to the actual location of the hole indicated N 27.18, W 29.71. This shows a discrepancy between the well survey and the transit survey of 0.45 ft in the westerly direction and 2.91 ft in the northerly direction. All surveys, both gyroscopic and transit, fell well within the width of an ordinary drift. While this is satisfactory for almost any and all mining requirements, a theoretical examination was made as to reasons for the discrepancy. A study of the course of the hole indicates that considerable right turn or spiral existed, and in all probability the surveying instrument was pulled out of alignment while traversing the turn by approximately 0.05 ft at the top and another 0.05 ft in the opposite direction at the bottom of the instrument. If such an allowance were to be made, the survey calculations would almost exactly correspond with those determined by transit. This sort of discrepancy would be minimized by the use of stabilizing guides. It is unfortunate that physical laws probably effectively prevent the use of gyroscopic instruments in EX and AX diamond drill holes. The directive power of a gyroscope falls off inversely at some rate between the third power and the sixth power of the diameter. Present instruments can be run in casing 53/4 in. ID or over and might be adapted to somewhat smaller diameters, but the difficulty of reducing these diameters to 11/4 in. or 2 in. is almost insurmountable at the present time. Acknowledgment The author wishes to express his appreciation to the Phelps-Dodge Corporation for permission to publish this article, and to the Operating and Engineering Departments for their cooperation on the survey; also to Donald Hering, of the Sperry-Sun Well Surveying Co., who actually made the survey and calculated the results.

Jan 1, 1951

By B. M. Larsen, T. E. Brower

A perspective is presented of the steel plant sulphur distribution and elimination problem from coal to liquid steel ready for teeming, giving distributions of sulphur over a range of coke sulphur content, and some methods of sulphur control, in the blast furnace, external desulphuriza-tion between blast furnace and open hearth, distribution between fuel, slag, and metal, and methods and limitations of control of sulphur in the open hearth furnace. AS a part of the 1951 AIME symposium on sulphur in steelmaking, it was thought that a discussion of the distribution of sulphur throughout the whole series of operations, from coal and ore to finished steel ingots, might have some value in giving a perspective on the whole problem. The following discussion is an attempt to present such an overall picture. The order is that of the actual plant operations, beginning with a very brief consideration of the coking process. Sulphur in Coal and Coke Since by far the largest source of sulphur entering the steelmaking cycle is in the coal used to make coke for the blast furnace, it would seem reasonable to eliminate some of it, either from the coal, or the coke, or during the coking process. This has appeared impracticable up to the present, at least, for two main reasons: the low activity of the organic sulphur in either coal or coke, and because of price limitations involved in treating a low cost material such as coke. A variable portion, usually M or less, of the sulphur is present in coal in the form of pyrites or similar compounds, and a large part of this sulphur may be removed in the coal washery. Most of the sulphur, however, is normally present as "organic" sulphur, intimately associated with the coal structure. Its distribution prevents any separation by mechanical means. Its low activity makes improbable ' any rapid chemical removal, although hydrogen will remove sulphur from both coal and coke. Thus, prolonged recirculation of coke oven gas in the coking process would tend to leave a smaller percentage of the total sulphur in the coke residue. Table I shows a typical distribution of sulphur from coal into products in the coking process. As the sulphur in the coal increases, the sulphur in the coke tends to increase in about the same proportion. Sulphur in the Blast Furnace The best picture of the situation in the blast furnace is provided by a sulphur balance of raw materials entering, and of products leaving, the furnace. The difficulties in accurate weighing and sampling of the variable solid materials entering this process, and the number of hours required for the raw materials to descend through the furnace under variable operating conditions, make it difficult to obtain an accurate balance. However, balances made over periods of weeks or months tend to average out some of these uncertainties. Table I1 presents three typical sulphur balances similar to a number that the writers have calculated. In most of these the slag volume calculated from the sulphur balance is, in some instances more, and in other instances less, than the value corresponding to the best input and output balances of the other slag constituents (lime, silica, alumina, etc.). Probably the greatest source of error in these calculations is the sulphur content of the slag. Despite some possible inaccuracies the balances of Table II show rather definitely the following points: 1—That 87 to 95 pct of the total sulphur input is in the coke and 95 to 97 pct of the total sulphur output is in the slag. Also, that if any sulphur leaves the furnace with the gas it is relatively small, amounting to a possible 1 pct or less. 2—At the lower sulphur coke level of 0.86 pct the total amount of sulphur charged is 15 Ib of sulphur per ton iron increasing to 26 lb per ton at the higher sulphur, intimately associated with the coal struc-rare burdens containing sulphur-rich ores will the total sulphur burden fail to be nearly proportional to the content in the coke used. 3—The 7 to 9 pct of the total sulphur input from the limestone of furnaces B and C is due to the relatively high sulphur content of the stone, 0.226 and 0.265 pct, respectively. In the case of furnace A, the sulphur content of the limestone was only 0.06 pct which resulted in only 3 pct of the total sulphur input coming from this source. It is rather interesting to compare the sulphur balances of a typical ferromanganese furnace with

Jan 1, 1952

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-' cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

Jan 1, 1967

By C. R. Knopp

Gas-oil relative permeability ratio is an important relationship in oil reservoir predictive calculations. A correlation has been developed from 107 gas-flood k/k tests on Venezuelan core samples. The correlating parameter is based on restored-state water saturation tests and' is applicable to both consolidated and poorly consolidated sandstone reservoirs. Data of the correlation show that there are no distinguishah1e differences between the mass-data groupings for the two c1assifications A procedure is recommended for running .sufficient relative. permeability analyses to compute a geometric mean of the sample group. The geometric mean is more representative of the total core, and probably the entire reservoir. For example, while only one in four of the k,,/k,., test curves agreed closely with the resultant correlation of this report, the geometric mean curves of the 16 suites (three samples or more). showed good agreetment ill three cases out of four. INTRODUCTION The gas-oil relative permeability ratio is an important, fundamental relationship in most oil reservoir predictive calculations. Predictive calculations are made to estimate future reservoir production characteristics and ultimate oil recovery. The k1,/k2, relationship is specifically needed to relate the surface gas-oil ratio to the reservoir oil and gas saturation, and to calculate the relative movement of these phases within the reservoir whenever some of the more complex driving mechanisms are present. Laboratory k1/k2, tests are not generally run as a routine analysis. Consequently, k1/k2 data often are not available when needed because the cost of laboratory work could not be justified or the need for such data had not been properly anticipated. When laboratory k1/k2, data are available, they are often very difficult to interpret. For example, wide divergence is sometimes shown in a family of k1,/k1, tests representative of the producing horizon in a single well. With these considerations in mind, a study was made to determine if a relationship might exist between the k1,/k2, curve and some other simple laboratory test criteria. The most probable k1/k2, curve correlation for Venezuela described in this paper is the result of the investigation. The presented correlation defines the most probable gas-flood k,,/k,, curve through the medium of air-water capillary displacement and centrifuge water saturation tests. The laboratory procedures of these tests are. relatively simple, and inexpensive; test data should be. widely available- from routine analysis. DATA AVAILABLE, LABORATORY METHODS The report correlation utilized 107 gas-Hood k1/k2, tests run on sandstone cores of Venezuelan reservoirs. Table 1 is a general tabulation of data pertinent to the tests, while Table 2 summarizes the data. Thetests include 96 from Western Venezuela and 11 from Eastern Venezuela. Eighty-two- of the 107 test samples were sandstones that varied from poorly consolidated to-unconsolidated; 25 were consolidated. The average sample porosity was 26.7 per cent and the average permeability was 1,121 md; these values typify the better sandstone reservoirs of' Venezuela. The Welge gas-flood technique,' based on fundamental Buckley-Leverett frontal displacement theory, was introduced in about 1952 and is widely accepted in the industry. The laboratory procedure is relatively simple, rapid, and can be performed on small core samples. While there have been some minor variations in sample preparation and laboratory procedure in the tests used for the correlation, these tests can be generally summarized as follows. The core sample was first sol vent-extracted and dried. Connate-water saturation was restored by the oil-flushing or evaporation-blow down methods. At the beginning of gas flood the hydrocarbon pore volume was completeiy saturated with the test oil phase. Unsteady-state gas-oil displacement then began with the injection of nitrogen or helium. while the displaced oil and gas phases were incrementally metered at the out-flow face. From the test data, the k,,/k,, curve was calculated by the Welge method.' The individual oil and gas relative permeabilities were also calculated." CORRELATING PROCEDURES In attempting to establish a basis of correlation, we found that broad mid-range sections of 105 of the 107 k,,/k,, test curves could be closely duplicated by a straight line. Only two curves did not show a degree of linearity in this region. Correlation-curve definition parameters were subsequently developed from this observation of consistent mid-range linearity. Possible correlating variables were limited to the physical properties measured on core samples that (1) were widely available as common test data and (2) could be easily and cheaply obtained through future laboratory work. The more obvious possibilities were porosity, permeability and

Jan 1, 1966

By J. Chipman, G. G. Hatch

One of the important functions of the iron blast furnace is the desulphur-ization of pig iron before it enters the steelmaking furnaces. However, the increasing concentrations of sulphur in the metallurgical coke, source of approximately 90 pct of the sulphur present in the blast furnace charge, and demands for higher rates of production within recent years have increased the need for greater desulphurization within the iron blast furnace. Furnace operators are beginning to look for desulphurizing agents other than blast furnace slag to accomplish the desired degree of desulphurization. A considerable amount of work has been done on desulphurization outside the furnace with soda ash, calcium carbide and various synthetic slags. Whether the desulphurization of pig iron is accomplished wholly inside the furnace or partly inside and the remainder outside, will be determined by the economics involved. Regardless of which is the case, it is believed that it is necessary to have a better understanding of the physical chemistry of desulphurization by blast furnace slags. To this end, it is the object of the present investigation to attempt what is believed to be the first equilibrium study of the distribution of sulphur between liquid pig iron and a wide range of blast furnace slag compositions. Review of Literature There is a considerable amount of information in the literature concerning the desulphurizing power of iron blast furnace slags, the solubility of various sulphides in the slags, and the effect on desulphurization of temperature, of elements dissolved in the liquid iron, and of viscosity. However, there is nothing to indicate that the equilibrium distribution of sulphur between liquid iron saturated with carbon and iron blast furnace slags has been studied experimentally. Wentrupl has made probably the most detailed study of the desulphurization of pig iron to date. He considered that there are three distinct aspects involved, namely: 1. Desulphurization within the blast furnace (by lime and manganese). 2. Subsequent desulphurization by manganese. 3. The effect of subsidiary reactions on the desulphurization by manganese. The experimental work carried out by Wentrup was devoted mainly to obtaining a better understanding of how desulphurization by manganese was accomplished in the mixer and the ladle. Particular attention was given to the part played by carbon, silicon, and phosphorus associated with manganese in the iron, and the effect of temperature on desulphurization. The experimental results indicated that desulphurization by manganese is purely a process of crystallization of manganese sulphide. The addition of silicon to iron melts containing 3.5 pct carbon and less than 0.5 pct manganese had no noticeable effect on desulphurization, but with 1-2 pct manganese the silicon additions improved the desulphurization. Additions of phosphorus also resulted in improved desulphurizati011 by manganese, but the effect was not as marked as in the case of silicon. It was also found that desulphurization by manganese was further improved by lowering the temperature. In order to explain desulphurization inside the blast furnace, Wentrup considered the system iron, sulphur, calcium, oxygen, manganese. (silicon). The distribution of sulphur between the metal and slag was represented by the following equation: (SS) _ (S)Fe + (S)Ca + (S)Mn .... [S] = [s] [1] The parentheses and the brackets represent the equilibrium concentrations in weight per cent of the slag and metal constituents, respectively. Since FeS D (FeS) _ (FeS) (S)Fe LfeS - [FeS] [S] [2] (CaO) + S e (FeO) + (S)Ca _ (FeO)(S)Ca. (S)Ca _ (CaO) Kl = (CaO)[S] [S] ~K1(FeO) [3] Mn + S D (S)Mn (S)Mn (S)Mn K' = [MnpT "1ST = *lIMnJ !4) Substitution of Eq 2, 3, and 4 into Eq 1 resulted in if = L- + *> (Sol + K^ (S) [51 Eq 5 was used to calcu1;lte -f^j and [S] at 1480°C for slags containing 30-50 pct lime, 0.1-2.5 pct iron oxide, 0-26 pct silica, 2 pct sulphur and iron analyzing 1.5 pct manganese. The value for LFaB at 1480°C was found to be equal to 4.5, based on the experimental work of Bardenheuer and Geller.2 The results of the calculations are shown in Table 1. Although the slags are hypothetical and do not represent the range of compositions found in ordinary blast furnace practice, the calculations indicate that lime is effective in controlling desulphurization only if the iron oxide and silica contents of the slag are kept low. Schenck3 did not claim K1 to be a true equilibrium constant, but an empirical value which varied with the silica content of the slag.

Jan 1, 1950

By F. M. Morris

A large reserve of thick coal in southwest Virginia was developed by Clinch-field Coal Co. in 1957-1958 to produce a nominal rate of 1500 tph raw coal. Operation features coal cleaning in transit. Refuse removed averages 35 pct. Evolution of plant from initial conception to completion is discussed, selection of means applied is explained, and performance to date us design expectation is described. The long-range plan calls for ultimate handling capacity of 40,000 tpd raw coal with anticipated clean coal capacity of 26,000 tpd on a three-shift basis. From a materials handling viewpoint, the Moss No. 3 operation is principally of interest as an ensemble. Generally speaking, it uses time-tested equipment and ideas but some of these are employed on a scale that may be new in the industry. At present about 20,000 tpd of raw coal are being handled. This is expected to increase to 40,000 tpd as soon as business conditions justify it. The purpose of this paper is to discuss the evolution of the plant as to materials handling practices, to describe briefly the equipment and methods used, and to comment on performance in certain areas. The subject divides itself naturally into four phases: 1) operations at the mines, 2) transportation from mines to plant, 3) raw coal handling into the plant, and 4) transportation of refuse away from the plant. OPERATIONS AT THE MINES The coal reserves for Moss 3 are in southwest Virginia where Dickenson, Russell, and Buchanan Counties come together. This area contains about 15 square miles and over 100,000,000 tons of coal. Here the No. 4 (Tiller) and No. 5 (Jawbone) seams of the Norton Formation lie so closely together that for practical purposes, they constitute one seam of coal. This seam, which is called the Thick Tiller, varies from 10 to 18 ft in thickness and underlies Sandy Ridge, a mountain cresting between 2400 and 3300 ft above sea-level. At 18-ft seam height (which is considered to be the maximum practical mining height) the parting between seams will be about 3 1/2 ft thick and each bench of coal will be about 7 ft thick. Depending on the amount of impurities in the seams Drover. total reject in this height coal may approximate 50 pet by wt. It will average about 35 pet for the property as a whole. The first move in developing this resource was made in 1953 when contour maps of several square miles around Duty, Va., including all the known outcrop, were made by photogrammetry. At this time, it was felt the prospective operation would be served by the Clinchfield Railroad and a photogrammetric route survey was made by this railroad from Haysi to Duty. Study of the resulting maps indicated only one site—adversely owned—which might accommodate the size washing plant to be erected. Water resources of a dependable nature seemed nonexistent. In 1954 bulk washability tests were made on the Tiller Bench at the Moss No. 1 preparation plant. The tests indicated this portion of the seam, mined separately, would wash to 4 pet ash with good recovery. Also in 1954, development of Moss No. 2, south of Sandy Ridge, was begun. This mine is in the Tiller Seam where it is about 100 ft below the Jawbone Seam. The reasons for developing a mine in the normal Tiller Seam before tackling the Thick Tiller seemed compelling: Railroad service could be established quickly, communications were better (though not good!), more was known of the seam (it had been mined in the years 1911 to 19241, and there was no essential property to be acquired. After some legal skirmishing, the Norfolk & Western Railroad was granted the right to serve the new mine. Three decades earlier the old mine had been served by the Clinchfield Railroad. The event which triggered active development of Moss 3 was the Appalachian Power Co.'s decision in 1956 to build a 450,000-kva power plant on Clinch River at Carbo. This solved the problem of marketing the steam coal which inevitably must be a product of a mine in the Thick Tiller. Management promptly decided to build the preparation plant at Carbo where an excellent site was owned; where railroad service existed; where telephone service could be obtained; and where roads, bridges, and water supply were tolerable.

Jan 1, 1961

By F. R. Hensel

Up to the present time few attempts have been made to produce hard nonmagnetic materials by heat treatment of austenitic steels. The usual result has been to cause them to pass into the martensitic stage, thus destroying to a great extent the typical austenitic properties, since this involves a transition of a portion of the iron from a face-centered to a body-centered type of atomic arrangement. High-strength nonmagnetic materials such as might be provided by properly hardening austenite are required in the electrical industry for different machine parts. In Europe nonmagnetic retainer rings for restraining the end-turns of the rotor windings in turbo-alternators have been developed as a special application of high-strength austenite. In testing1 a 28,000-kva. three-phase Siemens turbo generator running at 3000 r.p.m. at full load current, the losses in the short-circuit test were 450 kw. for the magnetic ring and 286 kw. for the nonmagnetic, and the difference should be attributable to the magnetic ring. The differences in temperatures during the same test are given in Table 1 and these show the advantage of a nonmagnetic over a magnetic retainer ring.

Jan 1, 1931

By W. E. Rudolph, R. E. Baylor

DUE to its location in the Atacama Desert, one of the most barren of the earth's surfaces, Chuquicamata's water supply presents unusual problems. Yearly rain-fall averages less than one tenth of an inch at the plant. However, there are summer showers above 12,000 ft in the Cordillera to the east, the resulting run-off flowing through old river valleys buried beneath more recent volcanic formations, to be impounded within sediment-filled basins. This water emerges at springs where the outlets of these basins are blocked by lava flows, and here are formed the small streams which feed the only important river of the region, the Rio Loa. Chuquicamata's water is obtained from these springs and rivulets. [ ] The map above indicates four pipe lines from which potable and industrial water are supplied. Potable water, amounting to 4500 metric tons per day, is conveyed in the Toconce pipe line from springs 59 miles due east of Chuquicamata. This water is used not only for drinking, but also for boilers and other needs requiring high quality. For industrial water at the oxide plant, there are two 12-in. pipe lines from the Rio San Pedro, carrying a total of 17,000 metric tons per day of slightly brackish water. This water is at present used mainly for leaching and for hygienic purposes. Water Source Found For the present and future needs of the sulphide plant, it was calculated that at least 32,000 metric tons per day of make-up water would be required. For this purpose, a pipe line of 44 miles length was constructed to bring in the entire flow of the Arroyo Salado, one of the eastern tributaries of the Loa. The salt content of this water is so high (over 5000 parts per million of solubles, mostly chlorides) that it is highly detrimental to farming, and the Chilean Government had been studying projects to separate these waters from others of the Loa system in order to improve agricultural conditions in the fertile valley of Calama. So it happened that the Government was willing to award rights to the Arroyo Salado waters under agreement whereby the Mining Company removes waters from the Rio Loa system above Calama for all time. The outlet of these waters, after serving their purpose at the new concentrator and leaving the plant in tailing, is the Salar de Talabre, an old salt lake which presents fully ten square miles of surface to serve as an evaporating pan, the outlets having now been blocked by dams. Here the dry climate of Chuquicamata is a favourable factor, evaporation averaging slightly above 1/4 in. per day. The Toconce and San Pedro pipe lines have been functioning from 26 to 34 years, and through the use of special cleaning tools which were developed at the plant, as well as deaeration of the more active Toconce water, these pipes are now maintained at capacities which do not diminish as years go on. Constructing the Dam The Arroyo Salado pipe line design and construction involved certain special and interesting features, and inasmuch as this line and its intake works are solely for the needs of the new sulphide plant, more detailed description is given. The waters are impounded at a gravity dam constructed of concrete to a height of 100 ft above the river bed, keyed into the precipitous Dacite walls of the narrow canyon (barely 6-ft wide at the bottom, only 25-ft width at 50 ft above). A small secondary dam was built 100 ft down stream from the main dam, providing a pool of 15-ft depth to protect the main structure from flood flows over the spill-way during the rainy season. A system of four 36-in. syphons was designed for discharging these flood waters from the lower depths of the lake, in order to avoid eventual sedimentation behind the dam. The lake has a length of 3300 ft, and its water level is controlled by an adjustable spillway permitting draw-down of eighty inches, amounting to 41,000 metric tons of available capacity. This regulation is necessary because of wide fluctuations in stream flow between day and night due to freezing of feeders. During the construction of the dam the entire river flow was handled within a 36-in. pipe line some 2000 ft in length. As the excavations proceeded

Jan 1, 1952

By C. S. Barrett, A. Smigelskas

There have been no publications of the deformation and recrystallization orientations of the metal beryllium, yet pronounced textures would certainly be anticipated since it is close-packed hexagonal in structure. Having an axial ratio approximately that of magnesium, beryllium probably deforms by nearly the same slip and twinning mechanisms that operate in magnesium, and the textures are likely to be similar or but slightly different from the magnesium textures. In the tests reported below this is found to be the case; the textures are found to differ from those of magnesium only in the details of the scatter from the average orientation. This report covers not only samples rolled at room temperature, but some rolled at elevated temperatures. Since magnesium has been suspected by some investigators of altering its crystallo-graphic deformation mechanism at elevated temperatures, it was considered possible that beryllium might do so and alter its textures accordingly. No pronounced alterations were found, however. Unfortunately, the theory of deformation textures is not in a state of development that permits one to deduce the deformation mechanism from a knowledge of the textures, which means that the similarity of textures at different rolling temperatures, reported here, cannot be taken as definite evidence that the deformation mechanism is actually the same at all temperatures. The general similarity of the deformation textures of magnesium and beryllium also extend to the recrystallization textures of the two metals, judging by the pole figures for recrystallized sheet presented in this report. Samples were prepared in the form of composite sheets made up of small pieces stacked in a pile. Each piece was trimmed with scissors so that an edge was parallel to the rolling direction, dipped in paraffin, and assembled into the pack by aligning it under the cross hair of a microscope. As the desired orientation was obtained on each piece it was secured in place by touching with a hot wire to melt the paraffin. A stack of ten or fifteen pieces was built up in this way, then trimmed to the shape of a T; the portion to be X rayed was then etched to the shape of a wire about 0.045 in. diam with 6N HCl. This method of shaping the sample is a modification of that used by Bakarian on magnesium.' The absorption of the rays in the sample was so slight that it caused no difficulty in interpreting the films. Exposures were made with a 0.030 in. diam pinhole, using molybdenum radiation (40 kv, 25 ma, Type A film at 5 cm, 2 to 3 hr exposures). With the recrystallized specimens it was found necessary to oscillate the specimen so as to reduce the spottiness of the lines. A range of oscillation of 5" was SUB- cient to produce reasonably satisfactory patterns, though the quality was somewhat inferior to that of the deformation texture patterns, and only two degrees of intensity were read from the arcs on the films. Typical photo-grams for each of the deformation textures and the recrystallization texture are assembled in Fig 1. The pole figures were plotted in the usual way with the intensity of the various portions of the diffraction rings estimated by eye. Seven to nine films were made of each sample and each was carefully read in plotting the pole figures. Typical series included exposures with the beam normal to the rolling direction and at 11, 26, 41, 56 and 71" to the cross direction, plus two exposures with the beam normal to the cross direction, and at 11 and 79" respectively to the rolling direction. The rolling was in each case considered sufficient to develop the final texture: the reduction by cold rolling was 84 pct (from 0.0045 to 0.0007 in. thickness), following prior hot rolling in longitudinal and transverse directions and recrystallization; the reduction by hot rolling at 800°C was 90 pct (0.010 to 0.001 in.), following similar prior treatment; the reduction by rolling at 350°C was 88 pct (from 0.005 to 0.0006 in.) after similar prior treatment. The recrystallization texture was determined on a sample rolled at 350" to a reduction of 88 pct (0.0165 to 0.002 in.) after similar prior treatment, then mounted between steel strips to keep it flat and annealed at 700" in an atmosphere of argon. Discussion of Results The results of the X ray determinations are assembled in the pole figures of Fig 2, 3, 4 and 5 for rolling at

Jan 1, 1950

By T. Watanabe, S. Karashima, H. Oikawa

Creep tests of a! iron and its solid-solution Fe-Mo, Fe-Co, and Fe-Si alloys with bcc structure were conducted under constant stresses in ferromagnetic and paramagnetic temperature regions above 0.5T,(T, is the absolute melting temperature). It was found their high-temperature creep behavior changed in the vicinity of the magnetic transformation temperature, that is Curie temperature, TC. In the ferromagnetic region below the steady-state creep rates were lower than those expected from the extrapolation of the data in the paramagnetic region, the amount of decrease being affected by solute addition. Also, activation energies for steady-state creep were different in the two temperature regions. The observed changes were concluded to be due to the effect of ferromagnetism on diffusion. It is well-known that plastic deformation of metals and alloys in the temperature region where mobility of atoms becomes high enough is controlled by atomic diffusion." Many experimental results394 on fcc and hcp materials have been reported to confirm this view. In bcc metals and alloys, not much basic investigation of creep deformation has been performed. In particular, experimental work on iron5-&apos; and its alloys, covering a quite wide temperature range is extremely scarce. On the other hand, the effect of ferromagnetism on diffusion has recently been demonstrated in a iron and its alloys;&apos; it has been made clear that diffusion rates in ferromagnetic temperatur~e region are significantly lower than those expected from diffusion measurement in the paramagnetic region. Therefore, it is concluded that the magnetic effect influences the high-temperature creep behavior in a! iron and in its alloys. The present authors have conducted creep experiments on a iron and its solid-solution alloys over a very wide temperature range, and have demonstrated the magnetic effect. A part of the result has already been reported elsewhere.26 In this paper, the experimental results will be described in detail. While the manuscript was in preparation, a similar magnetic effect on creep deformation of a iron was reported by Ishida . Though their experiments covered an extremely wide temperature range, the creep stresses varied from several thousand psi to several ten thousand psi with decreasing temperature. Consequently, it may be said that there remain some questions concerning their results. I) EXPERIMENTAL PROCEDURE The materials used in the experiments were pure iron and its alloys; they were prepared by vacuum melting (10"" mm Hg) electrolytic iron (99.9 pct), molybdenum powder (99.9 pct), ultrapure silicon, and cobalt pellet (99.5 pct) in alumina crucibles. The ingots were hot-forged to plates 10 mm thick and 50 mm wide, and then were hot-rolled at about 700°C into sheets 1 mm thick. Creep specimens, 5 mm in width and 15 mm in gage length, were machined from the sheets. They were annealed at temperatures which were well above their respective recrystallization temperatures. The chemical compositions of the metal and alloys are shown in Table I together with their heat treatments. High-temperature creep tests by the use of a lever-type creep testing machine were carried out in argon atmosphere under constant tensile stress. In order to keep &eep stress constant within about *0.5 pct, stress change due to specimen elongation was compensated by tensile force of a stainless-steel bellows which was inserted between the loading lever and lower specimen grip with the assumptions of a linear relationship between change in cross section and strain and uniform strain along the section. Beyond the limit of compensation by the bellows, small amounts of load were removed after appropriate strains. The testing temperatures were maintained to within i2"C of the reported values. Creep deformation was auto-graphically recorded at the upper (moving) specimen grip using a linear differential transformer which was held by a stainless-steel rod mechanically connected to the lower specimen grip. It was also directly measured with a dial-gage reading to -& mm. 11) EXPERIMENTAL RESULTS AND DISCUSSION 1) Creep Curves of a Iron and Its Alloys. Creep curves of a! iron, Fe-Si, Fe-Co, and Fe-Mo (<2 at. pct Mo) alloys usually consisted of three stages, that is transient (primary), steady-state (secondary), and accelerating (tertiary) stages. An example is illustrated in Fig. 1 for a! iron. However, in Fe-Mo alloys with more than 2 at. pct Mo, an inverse transient creepZ8 was observed as indicated in Fig. 2. The inverse behavior, which varied with the amount of molybdenum, may be due to the substructure* in the annealed specimen as was sug-

Jan 1, 1969

By G. A. Swanquist, E. M. Morales

INTRODUCTION The idea of water management and control at the Church Rock Mill operations began to take shape in February 1979. At that time, we were already investigating the feasibility of decreasing the fresh water requirements so that the solids would become the limiting factor in tailings impoundment utilization. The area for solution evaporation could be kept at a fraction of the normal requirements under the standard process of full water usage. The Church Rock Mill is an acid leach circuit followed by solids/liquid separation with thickeners in counter current decantation, and solvent extraction. Following the normal design of acid leach circuits, reuse of tailings solution was not incorporated in the original mill process design. INITIAL WATER CONTROL INVESTIGATIONS The investigations to decrease the fresh water requirements centered around modifying the grinding circuit from the present semi-autogenous grinding (SAG) mill in closed circuit with hydrocyclones, to open circuit grinding with a rod mill. The open circuit grinding with the SAG mill and rod mill in series had the potential of decreasing the water requirements for grinding and leach dilution by approximately 50% or 1.4 m3/min (300 gpm). The grinding pulp density would be maintained at 70 to 72% solids, and the leach dilution to 50% solids would be accomplished with acid tailings liquor recycle. In such a grinding circuit arrangement, the SAG mill would provide the primary or coarse grind, and the rod mill would be used for the fine grind. By the SAG mill and rod mill series grinding method of water control and other secondary water controls in various places downstream from the grinding circuit, the required necessary evaporation area was estimated at 120 acres of liquid surface. A second method of water control at grinding was investigated. A two-stage cyclone classification circuit appeared to have a good potential of achieving the same water reduction at a much lower capital and operating cost. However, in retrospect, this would not have been a viable method since a high slime recycle load would have been established hindering classification. The use of reagents to neutralize the acid tailings solution was not considered seriously at that time, since it would have materially increased operating costs, although it would have also allowed more tailings solution recycle and consequently, less fresh water usage. However, with the tailings solution deposition area available at that time, it was not then necessary to incur the high cost of neutralization. The control expected by the series grinding of semiautogenous and rod mills would have been sufficient to maintain a water consumption/evaporation equilibrium well in line with the available land area. IMPLEMENTATION OF NEUTRALIZATION OPERATIONS During the summer of 1979, the UNC Church Rock Mill experienced a tailings dam breach which resulted in a prolonged mill shutdown. Upon resumption of operations at the end of October 1979, tailings deposition was restricted to a small portion of the tailings impoundment area. Figure 1 shows the general tailings area and the limits of the present deposition area in the central part including the borrow pits. These borrow pits had been excavated to provide materials for tailings dam construction. Immediately after resumption of operations, it became evident that it would be necessary to control the quantity of liquid to be evaporated because of the small confined area available for tailings solution deposition and to maximize the deposition time in the tailings area. The water control required had to be exercised on a large scale, and to be in operation as quickly as possible. An obvious solution was to reuse the tailings liquor in mill process. Immediate steps were taken to install the necessary equipment for tailings neutralization on an interim basis. Anhydrous ammonia was selected as the primary neutralization reagent since it was the quickest system that could be placed in operation. Previous laboratory tests indicated fair results with ammonia neutralization. Such a system required a minimum of installed equipment and handling. INITIAL NEUTRALIZATION OPERATIONS Actual neutralization operations began on November 26, 1979. The raffinate solution which normally would have been discarded was pumped to a 3.7 m (12ft) diam by 4.3 m (14ft) tank for reagent contact, see Figure 2. At this tank, anhydrous ammonia was added directly from the tanker trailers and controlled at pH 7.0 nominally. Agitation was provided by air sparging. The neutralized product formed a highly viscous slurry in the grinding circuit which resulted in pumping and cyclone classification problems.

Jan 1, 1982

By D. J. Mack, R. E. Reiswig

Six examples of the peritectoid transformation were selected from the literature and studied by the method of isothermal transformation. The kinetics and mechanisms of five of the examples are presented as TTT diagrams and photomicrographs. The exist-enc- of a peritectoid in the sixth case is doubtful. ALTHOUGH the peritectoid transformation per se has been known for many years, no precise published data exist concerning the kinetics or mechanisms involved in transformations of this type, except for the brief treatment by Rhines, et al. 1,10 Bearing in mind the fact that investigations of recent years are uncovering more and more peritectoids and suspected peritectoids, a thorough study of the well-established peritectoids appeared to be in order. It was for this reason that a study of the kinetics and morphological mechanisms of six binary peritectoids was undertaken. The six peritectoids selected from the literature for study were those reported at 7.02 wt pct Al-Ag, 26.0 wt pct Sb-Cu, 30.5 wt pct Sb-Cu, 32.3 wt pct Sn-Cu, 8.35 wt pct Si-Cu, and 21.2 wt pct Al-Cu. These selections were based on availability and purity of components, ease of preparation and heat-treatment, and estimated reliability of the available equilibrium diagrams in the regions of interest. EXPERIMENTAL PROCEDURE The alloys used in this investigation were induction melted in electrode-grade graphite and chill-cast in cast-iron split molds. In all cases, the alloys were so brittle that they could easily be broken into samples weighing 1 or 2 g. Chemical analyses showed that the alloys used were close to the respective peritectoid compositions reported in the literature and that the impurity levels were low in all cases. Metallographic examination showed uniform distributions of phases in all samples, indicating uniformity of composition in the samples studied. Isothermal transformation studies were carried out in fused-salt media, using the familiar inter-rupted-quench method. Uniformity of temperature in the salt baths was maintained by continuous stirring with a stainless-steel agitator. On the basis of actual observations of the temperature fluctuations, the estimated temperature control was + 10C for the Ag-Al and Cu-Sb alloys and ±30C for the Cu-Sn, Cu-Si, and Cu-Al alloys. The accuracy of all temperature measurements was estimated to be ±1°C. It was found necessary to mount metallographic specimens of the Ag-Al alloy in cold-curing methyl methacrylate, since the temperatures encountered in mounting in bakelite or lucite caused an appreciable degree of transformation to the ß phase. For the other alloys, wood-flour-filled bakelite mounts were used to avoid extraneous X-ray diffraction lines during the later examination of the metallographic specimens on a Norelco Geiger-counter d if f r ac tomete r. In the X-ray diffraction procedure, agreement between the published diffraction patterns and those obtained in this study was good. This was particularly important for phase identification, since the literature contained little in the way of micrograph description in some cases. Etching of the silver-aluminum alloy for metallographic examination was done by swabbing with either of the following reagents: 1) 10 g CrO3, 1 g (NH4), SO2, 0.5 g NH4NO3, 100 ml H2O, or 2) 10 ml NH4OH, 1 ml 20 pct KOH, 4 ml 3 pct H2O2, 5 ml H2O. The other alloys were etched with the usual bichromate etchant: 2 g K2Cr2O7, 1.5 g NaC1, 8 ml conc. H2SO4, 100 ml H20 (swabbed vigorously). EXPERIMENTAL RESULTS A) The Ag-Al peritectoid at 7.02 wt pct Al— The phase equilibrium involved in this peritectoid is shown in Fig. I.2 The phase boundaries in the vicinity of the peritectoid were most comprehensively established by Hume-Rothery, et al,3 who placed the equilibrium temperature at 448 °C and the equilibrium compositions of the a ß&apos; and y phases at 6.11, 7.02, and 7.24 wt pct Al, respective The alloy used in this study analyzed4 6.95 wt pct A making it slightly hypoperitectoid according to the accepted equilibrium diagram. The rate of the transformation a+ y — ß&apos; varies rapidly with degree of undercooling below the equilibrium temperature, passing through a maximum in the vicinity of 350°C. Thus the TTT dia-

Jan 1, 1960

By D. S. Tomalin, D. F. Stein

The effect of reducing oxygen to low concentrations on the fracture of high-purity iron single crystals has been examined at 78° and 20°K. It is found that iron single crystals grown by the strain-anneal method usually contain a few occluded grain boundaries which may become embittled in the presence of oxygen, thereby nucleating cleavage fractures. High purity with respect to interstitial elements was found to inhibit twinning and evidence is presented for an orientation dependence of the resolved yield stress. Deformation occurred by slip rather than twinning at both temperatures of testing with elongations of as much as 9 pct at 20°K. THE fracture properties of iron single crystals have been observedl-3 to be a function of temperature, orientation, and purity. Allen, Hopkins, and McLennan1 demonstrated that at 78°K iron single crystals became increasingly brittle as the tensile axis approached the (001) pole of the stereographic unit triangle. Iron crystals with the tension axis near a (001) pole were completely brittle and orientations near the (011)-(111) boundary were very ductile, achieving a 100 pct reduction in area prior to fracture. Later work of Biggs and pratt2 and of Edmondson3 demonstrated that by reducing the carbon content of the single crystals the transition between brittle and ductile failure at 78°K could be shifted to orientations nearer the (001) pole. Ed-mondson went further and pointed out that any mechanism which tended to increase the yield strength of the iron (i.e., carbon addition, pre-strain) also increased the tendency for brittle behavior at 78°K. Thus by a reduction of carbon content Biggs and Pratt were able to obtain ductile behavior to within 20 deg of the (001) pole, and Ed-mondson was able to obtain ductile behavior to within 26 deg of the (001) pole. Edmondson&apos;s material had a total interstitial content (carbon, oxygen, and nitrogen) of approximately 60 ppm and, although Biggs and Pratt reported no analysis, indications were that their iron contained comparable impurities. Stein, Low, and seybolt4 purified iron single crystals to a total carbon, oxygen, and nitrogen content of approximately 20 ppm. They observed a lowering of the yield stress with this increased purity, and thus one might have expected an observation of increased ductility. Although they tested specimens of orientations which the previous workers had indicated should be ductile, the crystals failed at a 78°K in a brittle manner with little elongation. Stein noted,&apos; however, that about 90 pet of the failures could be traced in origin to occluded grains. Allen et al.1 and Edmondson3 do not report examination of their cleavage surfaces, but Biggs and pratt2 reported that microscopic examination of the cleavage surfaces of many of their specimens revealed the presence of small occluded grains. Honda and cohen6 and Keh7 have also observed the initiation of fracture at occluded grains in iron single crystals. Therefore, the additional complication of occluded grains must be considered in studying the properties of iron single crystals and the origin of fractures determined if the ductility exhibited by the crystals is to be considered meaningful. Various investigators8-12 have studied the effects of impurities on grain boundaries in high-purity polycrystalline iron. Rees and Hopkins10 showed that the addition of oxygen to low-carbon (0.002 pet) iron weakened the grain boundaries, causing a shift from transcrystalline to intercrystalline fracture and a progressive decrease on the brittle-fracture stress with increasing oxygen content. In addition, it has been shown by Low and Feustel11 that the addition of carbon to polycrystalline iron containing oxygen eliminated grain boundary brittleness. Thus, oxygen can embrittle grain boundaries in high-purity polycrystalline iron, but the addition of an appropriate amount of carbon can eliminate the oxygen-induced brittleness. The oxygen content (19 ppm) of the iron "single crystals" employed by Stein el al. was large enough to suspect impurity effects at the occluded grain boundaries. Allen et al.1 Biggs and pratt,2 and Edmondson3 may have masked any occluded grain problem in their specimens considering the relatively high carbon levels they employed. stein13 demonstrated that the addition of as little as 0.9 ppm C to previously purified (less than 5 x 10-3 ppm C) "single crystals" would increase the elongation from a few percent to more than 20 pet at 78°K and the fracture was not associated with grade boundary initiation.

Jan 1, 1965

By C. K. Gupta, P. K. Jena

Niobium (columbium) metal in the form of a button has been produced by calciothermic reduction of niobium pentoxide using sulfur as the heat booster. In these experiments with 50 g of niobium pentoxide per batch, the influence of percentage of calcium in excess of the stoichiometric, the percentage of sulfur by weight of the niobium oxide, and the outer-wall temperature of the bomb on the quality and yield of the metal has been studied. The maximum yield on this scale was 78 pct using 50 pct excess Ca and 20 pct of S and at a bomb-wall temperature of 600°C. In experiments conducted on 500 g of niobium pentoxide, reduction with 40 pct excess Ca and 20 pct of S, and at a bomb-wall temperature of 500°C, the.yield of the metal improved to 82 to 84 pct. Some of the reduced-metal samples have been electron-beam melted and the button melts thus obtained have been observed to be extremely ductile and capable of cold reduction to 98 pct without intermediate annealing. NIOBIUM, because of its high melting point (2468oC), its ductility, its resistance to corrosion especially in liquid metals, its high-temperature mechanical properties, and its relatively low capture cross section (1.1 barns) for thermal neutrons, has potentialities as a structural material in the field of nuclear engineering. Niobium and its alloys are also gaining importance in high-temperature technology as components in aircrafts, jet engines, and missiles, electronics, chemical engineering, and surgery. In 1904 Weiss and Aichel 1 produced niobium by reduction of its pentoxide by misch-metal. Since then a large number of investigations have been carried out for the extraction of niobium from its compounds. The various routes through which the metal niobium has been extracted from its compounds can broadely be classified into the following groups: a) reduction of its halides, oxides, and fluo-salts with metals like calcium, magnesium, sodium, and aluminum;2-10 b) reduction of its halides with hydrogen and oxides with carbon or carbides;11-18 c) electrolytic winning from its halides and fluo salts;19-25 and d) thermal decomposition and disproportion ion of its halides26-30 Among the processes in commercial use at present are sodium reduction or fused-salt electrolysis of potassium niobium fluoride, carbide or carbon reduction of the oxide, and hydrogen or metallothermic reduction of the chlorides. In 1907 Von Bolton2 prepared niobium by reducing niobium pentoxide with aluminum. Dennis and Adam-sona attempted reducing the oxide with magnesium powder in argon atmosphere and the resulting metal contained as much as 5 pct O. Mondolfo8 claimed a method for the reduction of the oxides with aluminum. In the case of both magnesium and aluminum reduction, it has been stated31 that by-product oxides such as MgO or A12O3 would involve a major separation problem. Further, in the case of alumino-thermic reduction, the solubility of aluminum in niobium and intermetallic formation have to be reckoned with. In 1922 Bridge3 produced niobium by calcium reduction of niobium pentoxide. Dennis and pdamson&apos; obtained the metal by a similar method with an oxygen content of 0.2 pct. In most of the cases of metallothermic reduction of niobium oxides mentioned above, the metal niobium is obtained in the form of powder. In an attempt to produce massive niobium metal, lock&apos; used iodine as the thermal booster in the bomb reduction of niobium pentoxide by calcium. Massive niobium metal was obtained with a maximum yield of 75 pct containing 0.1 pct 0. Joly32 carried out experiments on calcium reduction of niobium pentoxide on a 2-kg scale using sulfur as the heat booster in a sealed bomb filled with argon. In his experiments, the reaction was initiated by passing a current through niobium spiral wire embedded in the charge. In a typical run consisting of 2000 g of niobium pentoxide, 3100 g of calcium, and 800 g of sulfur (S/Nb2O5 = 3.3), he obtained massive metal in the form of a very uneven mass with a yield of -57 pct. With lower amounts of sulfur and calcium, powder niobium mixed with small metal globules was obtained and the yield was also poor. From these experiments he concluded that this method is not a suitable one for industrial development considering the quality and yield of metal obtainable and the possible hazards with higher ratios of sulfur to niobium pentoxide in the -~charere. In the present work, a detailed investigation on the calciothermic reduction of niobium pentoxide in a stainless-steel bomb in presence of sulfur as the heat booster was undertaken on a laboratory scale.

Jan 1, 1964

By Roland J. Lapee

A history of the progress made in copper refining in Montana is presented. The casting furnaces and the newly rebuilt electrolytic refinery are descmbed and operating details are given. Experiences with various addition agents, effects of rernoval of chlorine from the electrolyte, and effects of separan on electrolyte and on copper deposit are discussed. Observatzons are made on the effect of various impurities in anode copper and behavior of thezr salts in electrolyte and in slime, on treatment of slime for removal of copper, and on electrolyte puriification problems. The improved method for production of starting sheets is described. Attention is given to new materials for construction and to improvement in matrials handling ad quality control. COPPER refining at Great Falls, Montana, dates back to 1892. The original plant produced 65,000 lb. of cathodes per day at a current density of 16 amp per sq ft. In this plant anodes and cathodes were handled to and from the cells by means of hand-operated chain blocks and were moved about the plant by hand trucks. Cathodes were melted in coal-fired, reverbera-tory furnaces, were charged by hand, and refined copper was dipped by hand and cast in iron molds. In 1916, a new, modern plant with capacity to refine 18 million Ib. copper per month was built. Two refining furnaces were built, and each was provided with a twenty-mold Clark casting wheel. In 1922, the furnaces were converted to the use of pulverized coal: in 1923, to the use of oil; and in 1928, to the use of natural gas. In 1926, the plant was enlarged 50 pct. The use of pulverized coal for refining copper at Great Falls was discussed1 in a paper presented at the Salt Lake City meeting of the Institute in September 1925. Also, a comparison of the use of various fuels in copper refining furnaces was discussed 2 in a paper presented at the New York meeting of the Institute in February 1932. Prior to 1943 the cellroom was operated with twenty-five 720-lb. anodes and 26 cathodes per cell. Four cathodes, each weighing about 165 lb., were produced from an anode. In 1943 the weight of the anode was reduced to 460 lb., and two cathodes, each weighing about 190 lb., were produced from an anode. In 1949, a Billet Casting Wheel for the production of 3 in. diam phosphor deoxidized billets was built. A paper, presented at the New York Meeting of the Institute in February 1956, describes3 this plant and operation. In the electrolytic refinery, production is controlled by variation of the current density. In 1956, germanium rectifiers on a separate electrical circuit were provided for the starting sheet section so that current density could be maintained at any desired figure. Also in 1956, a program of modernization and enlargement of the Electrolytic Copper Refinery was started. This program, when completed, will raise the capacity of the Great Falls Electrolytic Copper Refinery approximately 33 pct, to 33 million lb. of cathodes per month. Furnace capacity for melting cathodes and anode scrap is ample to take care of the increased production from the electrolytic refinery. This fortunate condition came about primarily as the result of the three following changes: 1) The furnaces were lengthened 10 ft in 1922 when the fireboxes were found unnecessary for burning powdered coal. 2) Furnace life, and hence furnace capacity, was increased by the successful efforts of the Copper Refinery staff to develop a method for sanding furnace side walls and roof. 3) The natural gas being used has a very low sulfur content. As a result, it is possible to reduce time spent rabbling and poling and thus greatly increase tons per furnace charge. TANKHOUSE AND TANKS The Great Falls Electrolytic Refinery is 535 ft long by 252 ft wide. The cells are arranged in four crane bays in which are operated seven 10 ton Whiting Cranes. The old cells are in groups of ten, with circulation of electrolyte through five cells in cascade and with aisles between the groups of ten cells. The new cells are nested in groups of sixteen with no aisles, are all on one level, and have individual circulation to each cell. Present plans call for 1792 commercial cells and 128 stripper cells. To reduce confusion during the construction period, and to use the cranes, cars, and other equipment already on hand, the cells in the rebuilt section were designed to have approximately the same inside dimensions as the cells in the old part of the

Jan 1, 1962

By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates&apos; have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959