Search Documents

By Sven Fornander

L. F. Reinartz (Armco Steel Corp., Middletown, Ohio) —I would like to know, in the practical application of the Kalling process, what kind of a lining was used, how thick was the lining, and how much metal was treated at one time? S. Fornander (author's reply)—The rotary furnace is lined with a course of fireclay bricks 6 in. thick. This course is backed by 5 in. of insulation. The furnace has a capacity of about 15 tons. Mr. Reinartz—How was the ladle preheated? Mr. Fornander—As pointed out in the paper, the furnace was heated by a gas flame in the beginning of the experiments. During these first tests, however, the desulphurization was inconsistent. We think that this was due to the fact that iron droplets sticking to the furnace walls were oxidized by the gas flame. Now, the furnace is operated without preheating of any kind, and the results are much better. T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—I might add one comment. This furnace was heated with a flame and for a time they had a little difficulty due to some residual metal in the rotating drum that would oxidize in between treatments and they found therefore, that it was very essential to drain the drum completely of metal so that they would not build up any ferrous oxide between treatments and they eliminated some of their erratic heats by maintaining those more reducing conditions. It was interesting to watch this operation. As soon as the drum started to rotate there was considerable flame, at least, at the time I saw it, that came out around the flanges, indicating there was quite a little pressure on the inside of the drum. W. 0. Philbrook (Carnegie Institute of Technology, Pittsburgh)—Is the reaction slag in the Kalling process liquid or solid, and how is it separated from the metal? Mr. Fornander—In the process there is no slag in the usual sense of the word. The lime powder does not melt during the treatment. After the treatment the lime is still in the form of a fine powder. It is separated from the metal by means of a piece of wood of suitable size placed within the furnace before it is emptied. D. C. Hilty (Union Carbide & Carbon Research Laboratories, Niagara Falls, N. Y.)—Dr. Chipman has given us some of his ideas in connection with a specific effect of silicon and silica on sulphur elimination and how silicon might interfere with desulphuriz- ing in the blast furnace. I wonder if he would like to elaborate on the possibility of a similar effect of silicon in the Kalling process? J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—Silicon does not interfere with the Kalling process. Anything that has strong reducing action is good for desulphurization. In these tests where the temperature was low compared to blast furnace temperatures, the silicon that is in the metal is a better reducing agent than the carbon. At high temperatures, carbon is the better. It is not the silicon in the metal that interferes with desulphurization, it is the silica in the slag. Mr. Joseph—I might add that the metal that was tapped from the drum after desulphurization was really at quite a low temperature. It was not measured, but I think it was well under 1300 °C, probably 1200" or a little above that. That was one of the difficulties, and I think there is no question about the fact that the Kalling process—in that it affects desulphurization between powdered lime, solid and liquid iron— is a reaction definitely between the solid lime and the liquid iron. E. Spire (Canadian Liquid Air, Montreal, Canada) — This Kalling process seems very interesting to us and after all it is only a mixing action that is taking place between the iron and the slag. We have attempted to do the same thing in another way. We have placed at the bottom of the ladle a porous plug through which we injected an inert gas. It can be nitrogen or argon. This plug is placed at the bottom of the conventional ladle and gas injected through the plug. That has appeared in our patent. To define this new type of treatment, I use the word gasometallurgy. I do not know if you like it, but it is a way of defining methods of treating metal using gases. What we do is exactly what is done in the exchange process in another way. We have a porous plug at the bottom with a high lime slag on top of the metal. Using this method, we have very good agitation of metal and slag, and with a small flow of gas, we can achieve a very strong agitation. For instance, in the 500 lb ladle, we use only 5 liters of gas a minute. We have an agitation compared to very rapidly boiling water in a pail. Moreover, the agitation can be controlled to create any amount of mixing desired. In a few minutes, with this method, the sulphur dropped from 0.58 to 0.11. These results have been improved since, and we have obtained results like 0.08

Jan 1, 1952

By J. O. Edstrom, G. Bitsianes

Parabolic rate constants were determined for the formation of wiistite by the solid state reaction between magnetite and iron. The reaction was diffusion controlled and inert marker studies indicated that the mass transport through the wiistite layer was accomplished by means of iron migration. Relationships between rate constants and self-diffusivities are discussed. The transport capacity for iron through dense wustite layers was found to be sufficient to carry on reduction, even in gaseous reduction processes. REDUCTION of iron oxides has been the subject of many investigations. Most of the work, however, has been done on rather crude material and there have been difficulties in correlating the data on a quantitative basis. The reverse process of the oxidation of iron has been studied more thoroughly and usually by starting from the pure metal. As a result, the mechanisms of oxidation are now fairly well known.It has generally been found that the oxidation of metals follows the so-called parabolic 1aw;Q hat is, when the oxides are formed as dense layers, their thicknesses are proportional to the square root of the reaction time. This parabolic law follows directly from Fick's first law of diffusion The flux, J, is defined as the quantity of diffusing substance passing per unit time through unit area of a plane at right angles to the direction of diffusion. This flux is proportional to the concentration gradient of the diffusing substance, and the factor D, known as the diffusion coefficient, is introduced as the proportionality factor with dimensions of (length)'/time. If the flux is measured as the increase of thickness of the oxide layer (Ax) per unit time (t) and the assumption is made that the concentrations of the reactants at the phase boundaries of the layer are independent of time, Eq. 1 reduces to Integration of this expression yields the parabolic function ax = k . t. [31 The product of the diffusion coefficient and the concentration difference across the oxide layer is included in the constant k. When iron is exposed to a highly oxidizing atmosphere, the oxide phases are formed normally in a topochemical fashion, i.e., the interfaces between the phases maintain parallel positions to the original surface of the specimen. Above 570°C, the phases are orientated usually in the order of iron, wiistite, magnetite, and hematite, a condition in conformance with the requirements of the Fe-0 system. Below 570°C, the wiistite phase is unstable and has not been found as a normal constituent in the oxidation products of iron. There is a strong probability that continuous layers of the solid oxides are formed as the specific volumes of the phases increase in direct order from iron to hematite.' , ' Regarding mass transport through dense solid oxide layers, Wagner' has postulated that diffusion in oxides generally may be interpreted as migration processes of ions and electrons. There must be normally a concentration gradient across the growing oxide layer for diffusion to occur. This condition requires that there be deviations from the ideal stoi-chiometric composition of the oxide and accordingly deviations from the strict order of an ideal lattice. Such "lattice defects" include interstitial ions, cation and anion vacancies, quasi-free electrons, and electron holes and are decisive for all migration processes.' Cations, anions, and electrons all may have some mobility in the oxides but the movement of one of the particles generally far exceeds that of the others. Previous work', 1,2,7 has shown that during the oxidation of iron the migration through the wiistite layer, and probably also the magnetite layer, is confined to the movement of iron ions. Migration through hematite, however, has been found to take place by oxide ion movement. These behaviors are in direct agreement with the type of vacancies present in the respective oxides. Reduction of Iron Oxides The gaseous reduction of iron oxides, like the oxidation of iron, takes place in a topochemical fashion at distinct interfaces between the appearing phases."-'" Porosities might be expected in these reaction products, since their specific volumes are less than that of the starting material. Frank and van Der Merwe" have shown, however, that it is theoretically possible for nonporous layers to form if the degree of misfit in specific volume is less than about 15 pct. These aspects on porosity formation

Jan 1, 1956

By Rudolph G. Wuerker

MUCH descriptive matter has appeared on the subject of suspension roof supports, or roof bolting, as it is more commonly called. The widespread introduction of roof bolting into coal mines and metal mines is truly phenomenal. Mine operators were quick to recognize the advantages of supporting wide openings without hindrance to machine maneuverability and ventilation. Although suspension roof support has long been installed at St. Joseph Lead Co. mines in southeast Missouri,'" its application to coal mining presented new problems, such as proper anchorage and bearing for the bolts, bolt diameter, and spacing of bolts. After continuous testing and experimenting at the mines, standard roof-bolting materials were determined.'!' The study reported in this paper is not concerned with such details as bolt diameter, which may be considered already solved in practice. In the tests discussed here, small models patterned on actual bolts were found to function in the same way and as satisfactorily as their prototypes. The aim of these tests was rather to investigate the influence of roof-bolting systems on the stress distribution around mine openings and to study the fracture patterns obtained in actual testing. Little was found about this in the literature, as testing of suspension roof methods and quantitative measurements are only now coming to the fore. Several suggestions and actual measurements have been made to evaluate critically the functioning of roof bolting systems, single roof bolts, and parts thereof. Outstanding among them is Bucky's outline of structural model tests.'" Since none of the suggested testing equipment was available, however, for the experiments discussed below, a different approach was chosen. The response of a mine roof under stress has often been compared to that of a beam. The slow coming down and bending through of beam or plate-like banks of shale, sandstone, or top coal is a familiar occurrence, extensively cited in the literature." It was felt that testing of roof-bolt systems installed in a concrete beam which was loaded in bending would be a fair approximation of the behavior of a mine roof underground. Another school of thought considers the roof behavior over an underground opening in connection with the stress distribution all around a circular or rectangular opening. This is more accurate, and leads to the concept of a dome-shaped zone of material destroyed under tensile stress. This is likewise a common sight in unsupported roadways where the continuous fall of roof results in what has been called the natural outline of roof fracture. This theory could not be tested and is treated separately in Appendix B. It is important to note that according to both assumptions the immediate roof fails in tension; the use of a beam in these tests, therefore, should give information valid for either of the two theories. With the testing equipment at hand it was possible to load concrete beams 6xlx0.5 ft under two-point loading, giving an equal bending moment over the center part in which the model bolts were installed. A comparison was made of the ultimate loads needed to break plain beams and beams in which roof bolts were installed. Arrangements were made with: 1—plain beams; 2—bolts with plate washers, some with holes drilled at 90" angles and others with holes drilled at 45" angles; 3—bolts with channel irons underneath; 4—bolts in holes filled afterward with cement; and 5—bolts anchored in a stronger stratum. The foregoing arrangement is made in order of increasing strength, as assumed from the theory of reinforced concrete. Likewise, laminated beams with wooden model bolts and with combinations of the foregoing set-ups were tested. All in all, 21 experiments were made out of the much greater number of combinations possible. There were, too, some trial tests. Enough observations from this limited number were made to interpret the behavior of mine roof, supported by various types of suspension bolts, at fracture. In present-day concepts, which have been proved by mathematical derivations and stress analyses, any opening driven underground will change the distribution and magnitude of the stresses existing around it. It does not matter whether the stresses become visible, as in rocks whose strength is less than the forces acting upon them, or whether they are invisible, as in the gangways lacking evidence of rock pressure. In this latter case the rocks can withstand changes in stress-distribution. To consider the mine roof as a beam, there are, with transversal loading, tensile stresses in the lower fiber and compressive stresses in the upper layers above the neutral axis of the beam. Beams of brittle material such as rock and concrete fail exactly as shown in Fig. 1. Nearly all model beams showed the same fracture pattern as that of a tension crack. The influence of support, by roof bolting or conventional

Jan 1, 1954

By R. L. Sandefur

Professor Kim's excellent review article1 on ultimate pit planning contains a statement of the apparently widely held but incorrect belief that "kriging provides information on the confidence limits around the estimate which no other extension technique is capable of supplying." If a geostatistical approach is valid, there are several good reasons for using kriging but uniquely provided confidence limits is not among them. If kriging is possible, then confidence limits can be calculated for any other linear estimate. Kriging is the procedure which finds the weighing coefficients which minimize the estimation variance [ ] is the variance of blocks like the one being estimated. wi is the covariance of the estimated block and the i-th sample. oij is the covariance of the i-th sample and the j-th sample. Ai is the weighing coefficient for the i-th sample. N is the number of samples. The formula for estimation variance can also be used to calculate confidence limits on blocks estimated by any linear combination of sample grades including: 1) Polygons a. Hole nearest block centroid is assigned weight 1. All other holes are assigned weight 0. b. Polygonal area weighing. The samples are assigned weights directly proportional to their polygonal areas of influence within the block. The weights sum to 1. 2) Inverse distance weighing. The samples are assigned weights directly proportional to the reciprocal of their distance to some power from the block centriod. The weights sum to 1. Often only holes nearer than a certain distance and/or the nearest hole in each octant is considered. If there is an antisotropy to the ore body, an elliptical transformation often gives more accurate results. The most popular inverse distance weighing function is inverse squared distances (IDS). 3) Simple average. All samples within a certain distance are assigned the same weights which sum to 1. As an example of the applicability of the above formula to any linear estimate an internal verification on copper grade of 665 blast holes on the 1040 bench at Utah's Island Copper mine is presented. Internal verification is simple and applicable to non-linear estimates as well. Any sample (drill hole, bulk, trench, or chip) is dropped out, the value of the dropped sample estimated and compared with the actual value. If this is done for all samples, a measure of confidence limits is obtained. Internal verification is used in Cominco's MEPS system4 and in the BLUEPACK system.5 Comparison of block values against estimates697 is not dissimilar to internal verification. Results of the internal verification are presented below:

Jan 1, 1980

By F. H. Wilson, M. L. Kronberg

The low temperature recrystalliza-tion of very heavily rolled copper produces a fine grained structure with a high degree of preferred orientation. Additional heating to within a few hundred degrees of the melting point may induce an abrupt and pronounced increase in the grain size, with the resulting crystals having new orientations. This behavior at high temperatures is commonly termed "secondary recrystallization." Several investigations have dealt with the phenomenon arid have served to bare many features of the beha~ior.1-4 In general,observations have been made on the sizes and shapes of the grains, and data have been presented showing the existence of an induction period in isothermal experiments. Although it has been well established that the orientation before the change is statistically (100) 10011, the so-called "cubically aligned" texture, there is no such agreement on the orientation after the change. For example, Dahl and Pawlek1 describe it as being equivalent to an approximately 30" rotation about the [l00] axis of the ideal cubic texture which is parallel to the rolling direction, the resulting orientation being near (210)[001]; and Cook and Richards2 find an orientation of approximately (110)[L12]. Since the completion of most of the work to be reported in this paper, Rowles and Boas3 have published their ver] illuminating paper on "secondary recrystallization," in which they present convincing evidence for a third orientation and show that their esperiments give no evidence for either of the other two orientations. The orientation is described as equivalent to an approximately 30° rotation about a [ 111] pole of the ideal cubic orientation. The existence of a variety of reported orientations is not unique for copper, for a similar state of affairs exists for other systems that have been studied— aluminum, nickel, nickel-iron alloys, and others. It seems therefore that the existence of this variety does not necessarily constitute a contradiction, but rather indicates that different experimental conditions yield different results. The fundamental nature of the phenomenon has not been elucidated. However, it has been generally recognized that the large grains could be the end product of growth of a few select grains already existing in the sample in minor amounts—too small to allow detection—or that entirely new ones could be formed by a process of nu-cleation and growth. Existing experimental evidence does not distinguish between these two most apparent possibilities. Nevertheless, the former has been more generally favored largely because our current understanding of the state of an annealed metal has not made it seem reasonable to expect a nucleation event to occur at temperatures above those required for the primary recrystallization. Observations on the Preparation and Heating of Twin-bearing Cubically Aligned Copper The starting material used throughout. the investigation was a bar of OFHC copper, forged and annealed at 950°C. Visual inspection showed the grain size to be around 0.5 mm, and did not disclose any preferred orientation. A chemical analysis showed the following composition: Cu + Ag— 99.99 Pct S — 0.005 pct 0 — <0.005 pct For the preparation of cubically aligned copper, ¾ in. thick slabs were cut from the bar, heavily pickled in concentrated HNO3 and cold rolled to sheets about 0.012 in. thick. The reduction in thickness was approximately 98.5 pct. Standardized annealing techniques were followed. Samples to be heated were lightly dusted with alumina in order to prevent sticking and then sandwiched between 1/16 in. copper plates. The resulting sandwich was heavily wrapped with copper sheet, and then annealed in air. The protection was such that only very thin films of oxide were formed. That the associated light oxidation of the samples had no specific effect on the recrystallization behavior was shown by the similar results that could be obtained on annealing in highly purified and dried hydrogen. Two methods were used in bringing samples to temperature: (1) by placing the package directly in the furnace at temperature and (2) by placing the package in the furnace at room temperature, and then slowly increasing the temperature. The corresponding heating rates are illustrated in Fig 1, and will be referred to as "rapid" and "slow," respectively. Unless specified otherwise, all anneals will be of the former type. Metallographic examination was made on samples prepared by electrolytic polishing and etching as described in the Metals Handhook.* STRUCTURES FOUND BEFORE "SECONDARY RECRYSTALLIZATION" OCCURS Annealing the rolled material for 1 hr at 400°C produced a heavily twinned, cubically aligned structure, the grain size being of the order of 0.03

Jan 1, 1950

By G. P. de Forest, G. O. Hiers

The object of the experiments reported in this paper is to determine the eutectic composition of copper and tin and to determine the location of the part of the liquidus line immediately above the eutectic composition in copper. Three methods were used in the investigation: (1) the method of dissolving copper in a bath of molten tin at constant temperature, with the idea that when the bath was saturated with copper its copper content, by analysis, together with the temperature at which the saturation took place would locate a point on the liquidus line; (2) the method of the differential cooling curves, and (3) the method of microscopic examination. This paper is principally concerned with the results of the last two methods mentioned. The results of the first method, that of dissolving copper in molten tin, did not agree with the results of Miller,&apos; by the same method, nor with the results of other investigators by other methods, nor yet with the results of the cooling-curve experiments and microscopic examination reported here. Solution of Copper in Molten Tin To determine the amount of copper that would be dissolved by molten tin at a given constant temperature the apparatus shown in Fig. 1 was used. It consists of a cast-iron pot a, 6 in. deep and 8 in. dia., well cleaned inside and dressed with graphite. This pot, which holds 15 lb. of tin, g, rests on a hot plate b with resistance winding c. The thermocouple d leads to a Wilson-Maeulen temperature regulator for maintaining the temperahre at the heating coils at a fixed temperature to within ±5°C. There is a shallow bath of solder e on the top of the hot plate to improve the thermal contact between the plate and the pot. An insulating jacket f of asbestos prevents the irregular radiation of heat from the apparatus. The copper stirrer h slowly rotates in, and is dissolved by the bath of molten tin g. This bath is protected from excessive oxidation by a layer of charcoal j. The stirrer h is fixed to the lower end of the iron tube k, which is so mounted that it can be driven by a motor with reducing gear. The temperature of the bath is indicated

Jan 1, 1930

By Franklyn W. Oatman

In order that the conditions which obtain in an oil well may be readily understood, a brief description of a typical California well and a number of the phenomena accompanying same will be given. That the necessity for the exclusion of water be realized, the effects of water intrusion, a description of methods of prevention, .and a discussion of causes of failure will be presented, followed by a summary and recommendations. Fig. 1 shows a section of a typical well which illustrates the relation of oil sands to overlying strata. It indicates a deep water sand separated from the oil sand by shale, and the proper place for the final shutting off of water. In this well a comparatively thick stratum of compact shale protected the oil from overlying water so that the operation of landing the water string was a simple matter. In some wells the protecting stratum may be only from 3 to 5 ft. thick and very careful operation is necessary in order to land the water string of casing properly and not puncture through to the oil sand. The cases just cited are common, but occasionally, after excluding overlying water, productive oil sands are drilled through in the expectation of finding more productive underlying sand, and a water-bearing stratum is tapped. In this case the problem is the reverse of the normal; water must be prevented from ascending rather than descending. A discussion of well-drilling methods is not within the scope of this paper, except such operations as pertain to shutting off of water. A brief outline of the several conditions which may accompany drilling follows. Some or all may be present in any particular case. The direct relation of these to prevention of intrusion will be discussed in detail further on. In drilling, the hole becomes more or less irregular in shape, and rough, and as the casing follows the bit into the well it does not fit snugly against the walls. As a result, water may descend between the casing and walls of the well. If a circulation pump is not used during drilling, the hole is simply punched through and the pulverized material removed from the well by means of a bailer. If circulation is maintained there is a continual flow of water down inside the casing and up around the outside between the pipe and the walls of hole. This keeps an open space around the pipe.

Jan 1, 1915

By G. W. Crane

When ore was discovered on the Tintic Standard property in the spring of 1916, new developments were immediately started both north and south of that property, on the supposition that in East Tintic the ore would be found to occur in northerly trending channels, similar to those so characteristic of the older camp. But 9 years of developments have failed to establish the existence of such a channel. This is due undoubtedly to important differences in the geology of the two camps, that were not recognized, and is indicative of the danger in the general tendency toward interpreting the geology of East Tintic too strictly in terms of that of the older camp. It should not be forgotten that while the two sections have had practically the same geological history, the net results of a long series of geologic processes have developed in them conditions that differ so widely and in so many particulars that the necessity of regarding them as essentially different districts seems apparent. In an effort to emphasize this fact, this paper is devoted chiefly to a comparison of the geological conditions as found in the two camps and is addressed more particularly to those familiar with the geology of the Tintic district. Following a short description of the several ore discoveries and of the Tintic Standard mine is a brief discussion of the evidence of ore channels in East Tintic. For my information regarding the Tintic Standard mine, I am indebted to the courtesy and generous assistance of Messrs. Wade and Snow of the Tintic Standard Mining Co. East Tintic District The Term East Tintic district is here used to represent that eastern part of the Tintic mining district lying between the productive portion of the old camp of Tintic on the west, the foot hills of Goshen Slope, on the east, the Denver and Rio Grande Railroad on the north, and Silver Pass on the south, all in Utah County. As represented by the geological map, Fig. 1, it includes an area about 4 miles wide, east and west, and 5 miles long, north and south, within which the Tintic Standard mine is about centrally located. The map is a compilation of data supplied, for the most part, by the Chief Consolidated Mining Co. and represents the

Jan 1, 1927

By Walter Stern

THE self-potential or spontaneous polarization method is one of the oldest in the field of electrical exploration. When applied in prospecting for ore bodies, it is one of the most rapid and inexpensive means of locating indications of ore bodies at shallow depth. Usually, the procedure is to survey the equipotential lines of the electrical field that is generated by the electrochemical activity of the ore near the ground-water level, and to localize the so-called negative centers or points of greatest negative anomaly. Another field procedure involves the measurement of potential differences along potential profiles, generally laid out at right angles to the assumed strike. Again, in such survey, the basis for establishing the presence of ore is the location of negative potential anomalies. The earlier writers on the subject, notably Schlumberger1 and R. G. Wells,2 did much to clarify the fundamental electrochemical phenomena involved. Interpretation of the field data, however, remained largely qualitative. In 1925, A. Petrovsky3 analyzed the relation between the shape of the potential anomaly curve and size and depth of an ore body by assuming the subsurface body to be a polarized sphere.4 Along similar lines of approach, Edge and Laby5 considered the ore body a dipping sheet with limited extent in the direction of strike, while Poldini6 based the theory on the assumption of a dipping bar. The following study endeavors to enlarge [ ] FIG. I.-ORE BODY CONSIDERED AS DIPOLE upon these earlier investigations and attempts, on the basis of the potential distribution of a polarized bar, to indicate certain characteristics of the anomaly curve that make possible the determination of depth, size and dip of a subsurface body. THE SPONTANEOUS POLARIZATION FIELD SET UP BY AN ORE BODY If a sulphide ore body is subjected to oxidation varying in degree in its upper and lower parts according to the difference in the concentration of oxygen within the surrounding medium, an electrical potential field is set up. The form and distribution of this field will be investigated herein with special reference to its components on the earth&apos;s surface. Under the simplifying assumption that the ore body may be considered as a dipole with the point sources QI and Q2 situated at its upper and lower ends (Fig. I), the potential of the spontaneous polarization at point P is given by the following equation:

Jan 1, 1944

By M. G. Benz

The superconducting performmce of diffusion-processed Nb3Sn is influenced by its micro structure. High isotropic transverse current density may be achieved in this material by a process which forms a precipitate of ZrO, within the Nb3Sn. FOR an ideal type-I1 superconductor, little or no transport current can be carried in the mixed state; i.e., little or no transport current can be carried above the lower critical field H,,, where the field penetrates abruptly in the form of current vortices or fluxoids, even though full transition to the normal state does not occur until the upper critical field H,,.&apos; Fortunately, nonideal type-I1 superconductors can be readily obtained and these carry large transport currents up to the upper critical field H. Both theoretical and experimental investigations have attributed this current-carrying capability for nonideal type-I1 superconductors to pinning of the fluxoid lattice by heterogeneities in the microstructure of the superconducting material. These heterogeneities may take the form of dislocations or dislocation clusters,2"5 grain boundaries: structural imperfections introduced by phase transformations; radiation damage,8"10 or precipitates.11"15 Nb3Sn formed by diffusion processing is a type-I1 superconductor. Heterogeneities are needed for high superconducting critical currents above H,,. This paper will cover: a) what the microstructure of diffusion-processed NbSn looks like; b) what changes in the microstructure take place when the system is doped with precipitates, and c) how these changes in microstructure influence the superconducting critical currents. EXPERIMENTAL Preparation of Samples. Diffusion processing was used to form the Nb3Sn. The procedure used was as follows: a) coat the surface of a niobium tape with tin; b) heat-treat this tape at a temperature above 930°C to form a layer of Nb3Sn at the Sn-Nb interface. Such a layer of NbsSn is shown in Fig. 1 The thickness of the NbsSn layer formed was controlled by the time and temperature of the heat treatment. The same general procedure was used for preparation of both undoped samples and samples doped with a precipitate. An additional step was included in the preparation of the doped samples which consisted of internal oxidation of zirconium to form ZrOn. The details of the doping process will be reported in a later paper. Sample Testing. The Nb3Sn tape samples were soldered to a copper or brass shunt. Current and voltage leads were then attached to the sample in the usual four-probe resistance measurement configuration. The sample was cooled to 42°K. In some cases it was cooled in the presence of a high magnetic field and in other cases with the field turned off. The results were the same for both cases. The samples were oriented in a configuration with field transverse to current but could be rotated such that the angle between the field vector and the wide side of the tape sample could be changed. Measurements up to 100 kG were done in a superconducting solenoid and measurements above 100 kG in a water-cooled copper magnet at the MIT National Magnet Laboratory. Once the test field was reached, the current in the sample was increased until voltage was detected across the sample. The critical current was taken as the current at which voltage was first detected in excess of background noise. In most cases this was 1 to 2 x 10~6 v for a— in.-wide sample carrying several hundred amperes with a in. separation between voltage leads and with a 10 "-ohm shunt resistance. RESULTS AND DISCUSSION Microstructure. Examination of the microstructure of the undoped Nb3Sn shows rather large-diameter (1 to 2 columnar grains growing outward from the niobium surface toward the tin surface. As the layer is made thicker by longer diffusion times, these grains grow longer. Few new grains are started. Transmission electron microscopy shows little or no second-phase material within the bulk of the Nb3Sn layer. The microstructure of a diffusion-processed NbsSn layer changes quite drastically when the system is doped so as to form a precipitate within the NbsSn layer. Instead of large-diameter columnar grains of NbaSn forming, smaller-diameter (0.5 to 1 ) equiaxed grains of Nb3Sn decorated with the precipitate form. Fig. 2 shows a transmission electron micrograph of a Nb3Sn layer doped with zirconium oxide. This layer has been etched so that one may look between the grains

Jan 1, 1969

By J. S. Bowles

THE martensite transformation in lithium, dis- covered by Barrett,&apos; has been studied extensively by X-ray techniques by Barrett and Trautz,² and Barrett and Clifton.V he present paper reports the results of an investigation into the metallographic characteristics of lithium martensite. Such an investigation has not been carried out before. The spontaneous transformation in lithium consists of a change from a body-centered cubic to a close-packed hexagonal structure with the hexagonal layers in imperfect stacking sequence." As far as is known at present, this transformation can be regarded as being crystallographically equivalent to the body-centered cubic to close-packed hexagonal transformation that occurs in zirconium,5 although stacking errors have not been reported in zirconium. From a study of the orientation relationships in zirconium, Burgers5 as proposed that the martensite transformation, b.c.c. to c.p.h., occurs by a heterogeneous shear on the system (112) [111]. The crystal-lographic principle underlying this proposal is that the configuration of atoms in the (112) plane of a b.c.c. structure is exactly the same as that in the (1010) plane of a close-packed hexagonal structure based on the same atomic radius. The pattern in 2v2 both these planes is a rectangle d X 2v2d where v3 d is the atomic diameter. Thus a close-packed hexagonal structure can be built up from a body-centered cubic structure by displacing the (112) planes relative to each other.* This mechanism leads to orientations that can be described by the relations: (110)b.c.e. // (0001)c,p.h.; [111]b.c.c. // [1120]c.p.h Observations confirm these relations. In zirconium, Burgers&apos; measurements indicated an angle of 0" to 2" between the close-packed directions, while Barrett&apos;s measurements on lithium indicated an angle of 3". According to the Burgers&apos; mechanism, the martensite habit plane for this transformation would be expected to be the (112)b.c.c. plane, for this plane would not be distorted by the transformation. One of the purposes of this investigation was to find out whether the observed lithium habit plane agrees with this prediction of the Burgers&apos; mechanism. Experimental Procedure Materials: The lithium was from the same purified ingot used by Barrett and Trautz.² The Bridgman technique was used to produce single crystals. To maintain a temperature gradient in the melt, during the production of these crystals, it was necessary to use a steel mould with a wall thickness of only 0.015 in. Metallographic Techniques: Lithium specimens could be given an excellent metallographic polish by swabbing them gently with cold methyl or ethyl alcohol.? The best results were obtained with methyl alcohol saturated with the reaction product, lithium alcoholate. With higher alcohols the reaction became progressively slower and the attack became an etch pit attack rather than a polish attack. Butyl and amyl alcohols were used for macroetching. After polishing, it was necessary to remove all traces of alcohol from the specimens; otherwise, on subsequent quenching in liquid nitrogen, the alcohol froze to a glassy film. The alcohol was removed with dry benzene. The benzene in turn had to be removed before quenching, but since it does not react with lithium it could be allowed to evaporate. The specimens could then be quickly quenched before they began to tarnish. This operation could be carried out in air on all but excessively humid days when it was advisable to use an atmosphere of dry nitrogen or argon. For examinations at room temperature, the specimens could be transferred directly from the benzene bath into a bath of mineral oil. In mineral oil the specimens oxidized slowly by the diffusion of oxygen through the oil but the structure remained visible for about an hour. Lithium Martensite: Specimens prepared in the manner described above transformed spontaneously to martensite with an audible click when quenched into liquid nitrogen; i.e., M, was above the boiling point of nitrogen (77°K). The disparity between this result and the M, temperature of 71°K, found by Barrett and Trautz, is probably to be attributed to the large grain size and freedom from mechanical deformation of the specimens used in the present work. The relief effects produced by the transformation did not disappear when specimens were quenched from liquid nitrogen into mineral oil at room temperature. This permitted the microstructures to be studied at room temperature where, of course, the martensitic phase was no longer present. Typical micrographs of lithium "martensite" made at room temperature are reproduced in figs. 1, 2, and 3. As anticipated by Barrett and Trautz, the microstruc-

Jan 1, 1952

By R. W. Bartlett

Hydrometallurgical processes for copper flotation concentrates avoid the SO2 emission problems associated with smelting, but they require oxidation of copper to obtain solubilization during leaching. The resulting copper ions must be reduced to metal, which normally requires large amounts of energy or energy equivalent reagents such as hydrogen or iron. The conventional reduction method is electrowinning which is labor intensive and involves 35 to 40% of both the entire operating and capital cost of the better hydrometallurgical processes. There is considerable incentive to reduce the cost and energy required for producing copper ions from solution. Furthermore, it is thermodynamically possible to do this using sulfur contained in the concentrate itself. In fact, the thermodynamic potential of oxidizing sulfur from S+4 to the S+6 state is greater than required to reduce cupric ion to metallic copper.1 Realization of this potential in a practical process would significantly reduce the cost of hydrometallurgical processing of sulfide concentrates because sulfur would become a cost-free reducing agent. An apparently practical method is to use SO: and HSO3 ions, obtained by ammonia scrubbing of SO2 from a concentrate roaster gas, to reduce leached copper to metal in an autoclave. This reduction step is the Jumau 1907 A series of steps, including sulfite reduction, constituting a crude flowsheet was suggested by Parker in 1976.3 The present paper describes a detailed complete. sulfite process flowsheet based on materials and energy balances, discusses the chemistry, and discusses further work that is required to develop this process. Process materials, utilities costs, and energy requirements are projected to be unusually low because of the utilization of sulfur from the concentrate. Process Description The sulfite reduction process requires a copper concentrate containing approximately as much sulfur on a weight basis as copper. For those few concentrates that are deficient in sulfur, additional sulfur can generally be obtained by allowing more pyrite to float in the concentration process. The process steps, shown in [Fig. 1], are (1) a fluid bed roast of the concentrate, (2) a leach of the roaster calcine using recycled barren liquor from the reduction autoclave, (3) scrubbing of the SO2 gas with ammonium sulfite liquor to produce ammonium bisulfite, (4) reduction and precipitation of copper in an autoclave by combining part of the SO2 scrubber effluent (SO5

Jan 1, 1980

By Max Roesler

W. L. CUMINGS,* Bethlehem, Pa. (communication to the Secretary+). -In this discussion of Mr. Roesler&apos;s paper, I shall follow Kemp in using the term "granite" to refer to the acid rock called syenite by Kimball. Diorite, as I understand it, is the dark basic rock invariably closely associated with the orebodies. The types of rock of intermediate composition, mainly intrusives, are not under discussion. It is difficult for me to conceive that this granite is the ore-bearing agent, for the following reasons: 1. No isolated orebodies in the granite are known. It would seem that if this rock is the mineralizer, some small bodies, or at least patches and small masses of ore so situated would exist. 2. In 1909 the writer conducted explorations on the Pequena and Grande claims about 1 mile north of West Mine No. 5. This work was done after a very careful magnetic survey had shown a large and uniform area of attraction. As exploration progressed, it became evident that in this case the magnetic attraction was due to disseminated magnetite. Much ore of 40 per cent. Fe was found, but very little commercial ore was shown up. This ore was entirely in the diorite and no granite outcrops are near. The occurrence could easily have been described as "ore formation but very little ore." I cannot conceive how a remote granite intrusion could impregnate a diorite mountain with 40 per cent. of Fe, and prefer to believe that this 40 per cent. of iron was in its real home, rather than in a sort of dioritic "boarding house" after having been evicted by granitic parents. 3. The Ocaña mine, which has produced nearly 500,000 tons, shows no evidence that the granite is the mineralizer. This is admitted by Mr. Roesler on p. 1827. 4. I believe it will not be disputed that all the iron-ore deposits extending along the south coast for 60 or 70 miles are of a similar origin. Evidence available at other points might properly be referred to in discussing the article under review. At the La Plata mines, about 60 miles west of Santiago, the writer has also made explorations. No granite is in evidence. At one point in the bed of a creek is a small body of magnetite about 10 ft. long, entirely surrounded by a hard fresh diorite. To me

Jan 3, 1917

By L. A. Shipman

The combustion of coal in fuel beds has been practiced as an art for many years; during the last 2 7 years a scientific approach to this subject has contributed a small amount of fundamental data. The subject is a very controversial one. Opinions regarding the performance of the same coal used in the same equipment in different plants may vary from "the best coal ever used in the plant" to "the worst coal ever tired." These opinions can all be true, owing to the various conditions under which the coal was used. Because of these differences, an attempt will be made in this paper to discuss coal facts and coal characteristics as related to the use phenomena observed during the art of firing coal in fuel beds for many years. The work of Kreisinger1 and his associates in the 1,&apos;. S. Bureau of Mines, reported in 1916, was the first scientific attempt I know of to obtain factual data explaining the mechanism of combustion of fuel beds. They gave a chart showing an ignited fuel bed. The air passing up through the fuel bed first combined with the fuel by a reaction resulting in the complete combustion of carbon to CO2, which combined with the carbon in higher levels of the fuel bed to form CO with the absorption of heat. The fundamental facts produced in those experiments proved of much value and checked with practical experiences with hand-fired fuel beds. Hand firing was the prevailing method of stoking coal at that time. The order in which these reactions occur, as shown by Kreisinger and his associates, has been amply confirmed by repetition of this work with different fuels both her? and abroad. These experiments also showed that under their conditions the rate of burning was proportional to the air flow. These data were of practical value to a fireman and were accepted as generally true in all fuel beds. In later years many observations by myself in fuel beds of underfeed stokers and other thick fuel beds such as gas producers, where channeling. increase of particle size, or both, occur. indicated that, instead of the horizontal layers we had thought were present, perhaps the layers were vertical or irregular. Later investigations in fuel beds made by Mayers2 and Barnes3 indicated that the burning takes place in some instances along the surfaces of vertical or irregular channels or cracks in the fuel bed and that under these conditions a reaction occurs that differs from that in the old horizontal-layered handfired fuel beds. Examining the data in Kreisinger&apos;sl experiments, and the information in different charts with different fuels, different retort positions and air admissions of Barnes3 and the gas analysis arid isotherms of Mayers,2 one can check experience observation and come to a conclusion that as particle size of the fuel increases with other conditions the same, the maximum CO2 and temperature

Jan 1, 1947

By L. A. Shipman

The combustion of coal in fuel beds has been practiced as an art for many years; during the last 2 7 years a scientific approach to this subject has contributed a small amount of fundamental data. The subject is a very controversial one. Opinions regarding the performance of the same coal used in the same equipment in different plants may vary from "the best coal ever used in the plant" to "the worst coal ever tired." These opinions can all be true, owing to the various conditions under which the coal was used. Because of these differences, an attempt will be made in this paper to discuss coal facts and coal characteristics as related to the use phenomena observed during the art of firing coal in fuel beds for many years. The work of Kreisinger1 and his associates in the 1,&apos;. S. Bureau of Mines, reported in 1916, was the first scientific attempt I know of to obtain factual data explaining the mechanism of combustion of fuel beds. They gave a chart showing an ignited fuel bed. The air passing up through the fuel bed first combined with the fuel by a reaction resulting in the complete combustion of carbon to CO2, which combined with the carbon in higher levels of the fuel bed to form CO with the absorption of heat. The fundamental facts produced in those experiments proved of much value and checked with practical experiences with hand-fired fuel beds. Hand firing was the prevailing method of stoking coal at that time. The order in which these reactions occur, as shown by Kreisinger and his associates, has been amply confirmed by repetition of this work with different fuels both her? and abroad. These experiments also showed that under their conditions the rate of burning was proportional to the air flow. These data were of practical value to a fireman and were accepted as generally true in all fuel beds. In later years many observations by myself in fuel beds of underfeed stokers and other thick fuel beds such as gas producers, where channeling. increase of particle size, or both, occur. indicated that, instead of the horizontal layers we had thought were present, perhaps the layers were vertical or irregular. Later investigations in fuel beds made by Mayers2 and Barnes3 indicated that the burning takes place in some instances along the surfaces of vertical or irregular channels or cracks in the fuel bed and that under these conditions a reaction occurs that differs from that in the old horizontal-layered handfired fuel beds. Examining the data in Kreisinger&apos;sl experiments, and the information in different charts with different fuels, different retort positions and air admissions of Barnes3 and the gas analysis arid isotherms of Mayers,2 one can check experience observation and come to a conclusion that as particle size of the fuel increases with other conditions the same, the maximum CO2 and temperature

Jan 1, 1947

By N. A. D. Parlee, N. M. El Tayeb

Fe-V alloys with small percentages of vanadium show no deviations from Sieverts&apos; Law up to P~, = 1 atm in the 1600º to 1750ºC region. At somewhat under 8 pct V and up to at least 20pct V, at 1604" and 1661 °C, nitrogen absorption follows Sieverts&apos; Law at low Pn2 values, but deviates from this law beyond critical values of pn2, due to formation of a nitrzde phase of approximately VN composition. The behavior below these solubility limits can be described at all temperatures by the equations: RAO and parlee1 suggested that the nitrogen absorption curve for liquid iron alloys takes the general form shown in Fig. 1 when an alloy nitride precipitate is formed. They showed that the precipitation of 6 titanium nitride from liquid Fe-Ti alloys follows this general scheme and dealt with the general theory involved. Recently, Evans and Pehlke2 reported their research on the precipitation of aluminum nitride from liquid Fe-A1 alloys. Fountain and Chipman&apos;s recent paper3 on the precipitation of boron nitride from solid solution contains a fine example of the analogous behavior which they have been studying in the solid state. Researches on the absorption of nitrogen by liquid Fe-V alloys have been described by various authors.1,4-7 Most of this work has been confined to fairly low vanadium concentrations and rather high temperatures because of difficulties variously described as, formation of surface scums, bridging, and so forth. This behavior and the rough thermo- dynamic calculations made by chipman,8 over eleven years ago, indicated that excessively high vanadium concentrations should not be required for vanadium nitride precipitation. It seemed desirable to look for and study this precipitation in order to fill out the thermodynamically interesting nitrogen absorption data on these alloys. EXPERIMENTAL METHOD The general method used was essentially the same as employed by Rao and parlee,1 in which a Sieverts type of apparatus was used and the precipitation of the nitride detected by the "break-point" in the Sieverts&apos; Law line, and by the visual observation of the formation of the new phase on the surface of the melt. There were, however, a few differences in apparatus and technique as described below. The oil manometer used by Rao and parlee&apos; to measure low partial pressures of nitrogen was not employed. The present authors sought to avoid as much as possible the exposure of the liquid alloy to low total pressures of gas during the 6 to 10 hr long runs because of the heavy iron evaporation-loss errors involved. This was achieved, partly by keeping evacuation times to a minimum with fast pumping but largely by the use of two burettes, one for argon and one for nitrogen, and using them to equilibrate the alloy with mixtures of argon and nitrogen rather than nitrogen alone. Each run involved a careful sequence of operations. After melting, de-

Jan 1, 1963

By W. P. Lass

The purpose of this article is not only to describe the plant and method of cyaniding the Treadwell concentrates, but to present some of the results of the experimental work obtained in the past three years for the Alaska-Treadwell Qold Mining Co., at Douglas Island, Alaska, under the direction of F. W. Bradley, Consulting Engineer, and Robert A. Kinzie, General Superintendent, of the affiliated companies. At the time the experimental work was undertaken the concentrates were being shipped to the smeltery at Tacoma, Wash., and the cost for treatment of 3-oz. (gold) concentrates was $11.95 per ton, divided as follows : Smelting-charges,......... $4.00 Loading, freight, insurance, etc., . 2.89 Interest due to time loat in transit and in settlement,... 0.05 Loss due to settlement for 95 per cent. of the gold at $20 per ounce, 6.01 Total,...$11.95 From the experimental work described later, it was estimated that 96 per cent. extraction could be made by treatment on the ground, and that the cost, when treating 80 tons per day, would be $3.25 per ton, divided as follows : Per Day. Per Ton. Labor,. $86.16 $@.827 Chemicals,.76.60 0.960 Power and steam-heat,... 67.60 0.845 Marketing-, refining- and other charges, . 49.36 0.617 Totals,.. $2.59.72 $3.250 Adding to this total the 4 per cent. treatment-loss, which on 3-02. concentrates amounts to $2.48, gives a total cost of $5.13 per ton. Comparing this with $11.95, the cost when shipping to the smelter, leaves a net gain of $6.22 per ton by the local

Jan 1, 1912

By J. H. Bechtold, R. Kossowsky

1 HE superplastic behavior of the eutectoid A1-78 wt pct Zn alloy has been thoroughly investigated by Back-ofen et al.&apos; The superplastic elongations and the marked resistance to necking were rationalized in terms of high strain rate sensitivity. In a subsequent paper2 superplastic behavior was formulated to show Nabarro-Herring diffusional creep as rate controlling at low strain rates, giving way to a dislocation climb process at higher strain rates. In a paper devoted to an interpretation of superplasticity in two-phase alloys, Packer and sherby3 have included the results of an examination of the structure of an Al-Zn eutectoid specimen before and after superplastic deformation. No significant change in grain size or directionality was observed in the deformed microstructures. This one observation led the authors3 to suggest that con- tinuous recrystallization or grain boundary migration was responsible for superplasticity. The purpose of this note is to report our observations on the superplastic behavior of the Al-Zn eutectoid alloy which differ in certain respects from works previously reported. Following Hayden et al., the results are discussed in terms of dislocation climb as the important factor during superplastic deformation. A heat of nominally high (99.995) purity 22 wt pct A1-78 wt pct Zn was induction-melted and cast into a 0.5 by 6 by 12 in. slab. The slab was heated to 350°C and rolled to 1/8-in.-thick plate. The plate was then cold-rolled to 0.040-in. thickness, annealed at 35OaC, and rolled to the final thickness of 0.020 in.* Speci-

Jan 1, 1969

By H. K. Shearer

Oil production in north Louisianat in 1939 was 25,249,640 bbl., a decrease of 11.2 per cent from 1938. The only important increases in production were in the Cotton Valley and Shreveport fields, but Caddo, Homer, Sligo and Zwolle also made slight gains. Greatest decreases were in the Lisbon and Rodessa fields. Xatural gas production of 313,333 million cu. ft. was an increase of 5.6 per cent over 1938. The increase was accounted for in the Monroe field, while all other fields showed only minor variations from the production of the previous year. Well completions in 1939, as compared with 1938, were as follows: The decline in number of completions was due entirely to lack of proved areas for drilling, and would have been greater except for a revival of interest in the old Caddo shallow field. A majority of the wells completed during the year were in various old, shallow fields, so the average depth of drilling was much less than in several preceding years, notwithstanding a few very deep tests. No new fields were discovered, the only wildcat well reported as a producer being a very small oil well in northwestern De Soto Parish, which is of no apparent commercial importance. Deep gas-distillate production in the Cotton Valley formation was opened at Lake Bistineau and Lisbon, and oil at Shongaloo, but all these wells were too small to encourage additional drilling. Extensions and Developments Caddo Field.—More active drilling was donc in the 36-year old Caddo field in 1939 than in any of the newer fields, with completion of 133 oil

Jan 1, 1940

By H. K. Shearer

Oil production in north Louisianat in 1939 was 25,249,640 bbl., a decrease of 11.2 per cent from 1938. The only important increases in production were in the Cotton Valley and Shreveport fields, but Caddo, Homer, Sligo and Zwolle also made slight gains. Greatest decreases were in the Lisbon and Rodessa fields. Xatural gas production of 313,333 million cu. ft. was an increase of 5.6 per cent over 1938. The increase was accounted for in the Monroe field, while all other fields showed only minor variations from the production of the previous year. Well completions in 1939, as compared with 1938, were as follows: The decline in number of completions was due entirely to lack of proved areas for drilling, and would have been greater except for a revival of interest in the old Caddo shallow field. A majority of the wells completed during the year were in various old, shallow fields, so the average depth of drilling was much less than in several preceding years, notwithstanding a few very deep tests. No new fields were discovered, the only wildcat well reported as a producer being a very small oil well in northwestern De Soto Parish, which is of no apparent commercial importance. Deep gas-distillate production in the Cotton Valley formation was opened at Lake Bistineau and Lisbon, and oil at Shongaloo, but all these wells were too small to encourage additional drilling. Extensions and Developments Caddo Field.—More active drilling was donc in the 36-year old Caddo field in 1939 than in any of the newer fields, with completion of 133 oil

Jan 1, 1940