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By A. B. Kinzel, Thomas R. Cunningham

Silicon, unfortunately, is not in the same category as some other metals with respect to the absolute value of the highest purity material prepared. Tucker, in England, and Becket, in this country have developed procedures for the purification of silicon, and Becket's process has made industrially available silicon of a purity of 99.8 per cent or better. However, even the term "silicon metal" may be a paradox to some people, although not more so than the term "amorphous" as applied to silicon. These terms come from commerce, and "metal" is used to distinguish industrially high-purity silicon from ferrosilicon, silicon-aluminum, and other high-silicon alloys. Alloys of iron and silicon with 95 per cent Si or less are known as ferrosilicon, with a designation of silicon content where necessary, arid the term "silicon metal" is invariably applied to the grades containing 96 per cent Si and higher. The Becket method of purification was referred to in a monograph on the Alloys of Iron and Silicon, and the Tucker procedure was described in some detail in that publication.' In order to get silicon of still higher purity, a sample, prepared by the Becket method, analyzing 99.84 per cent Si, 0.020 Fe, 0.016 Al, 0.005 Ca, 0.025 C, 0.033 per cent 02, 0.006 H2, 0.006 N2, and 0.001 per cent Mn, was crushed to pass a 100-mesh sieve and further purified by a modification of Tucker's procedure. This modification differs from Tucker's method in that after treatment the 100-mesh alloy was centrifuged to remove the last traces of acid. Our directly determined analysis of this purified sample shows: Si, 99.952 per cent; Fe, 0.009; Al, 0.012; Ca, 0.003; C, 0.006; or 99.982 per cent. Silicon by difference equals 99.97 per cent. The variation between silicon by difference and silicon as directly determined is important. Although Tucker mentions the amount of insoluble matter in commercial silicon both before and after his treatment, he does not mention the existence of carbon in the alloy; nevertheless, he reports silicon by difference. Any final figure as to purity obviously results from agreement between direct determination and

Jan 1, 1940

By Terje Preber

Undisturbed sampling of shale has always been difficult. As pert of a comprehensive subsurface investigation for a nuclear power plant in northwestern Illinois, the Maquoketa shale, which contains seams of argillaceous dolomite, was sampled using different coring techniques. Since the Maquoketa shale is extremely fissile, careful sampling preservation by both lateral and vertical confining was utilized. The samples were tested to determine both static and dynamic properties. A relationship between void ratio and compression index, swell index, and swell pressure ratio was established. Correlation was found between the dynamic properties and both undrained shear strength and confining stress. Based on the results of the sampling and testing programs, recommendations for sampling and sample preservation techniques are given. INTRODUCTION Undisturbed sampling and preservation of samples of weathered, fiasile shale is often a very difficult task. The often erratically varying degree of weathering with depth complicates sampling and makes reproducibility of testing results difficult. Therefore, the testing of weak, weathered rock very often yields a wide variety of test results with large data scatter. The reproducibility of teat results usually associated with water-deposited soils is seldom, if ever, obtained. The testing and sampling program described in this paper was part of a comprehensive subsurface investigation for a nuclear power plant in northwestern Illinois. The sampling, preservation and testing program of shale samples taken from the Maquoketa shale are described, and, in particular, the different sampling techniques and sample preservation procedures are evaluated with respect to their effectiveness. The samples obtained by these procedures were subjected to a comprehensive testing program, including both static and dynamic testing in order to provide input for soil-structure interaction analysis. GEOLOGY The Maquoketa Shale Group is of Ordovician age and is part of the Cincinnatian Series. The area where the shale samples were taken was in a broad sea far from sources of clastic sediments during most of Ordovician time. However, during Cincinnatian time when large deltas in the Appalachian region were being formed, clastic sediments from the east dominated the sedimentation ii. Illinois, resulting in formation of the shale and dolomite shales of the Maquoketa Shale Group (Willman et al., 1975). The geologic unit sampled consists of a greenish gray to gray silty shale containing numerous 1- to 12-inch (2.5- to 30.5-cm) thick interbeds of argillaceous dolomite. The dolomite comprises up to 40 percent of the profile studied. The shale

Jan 1, 1984

By C. C. Clark, J. S. Iwanski

The purpose of this investigation was to study mi-crostructural changes that take place in a commercial nickel-chromium-iron alloy, such as Incoloy "901," over long periods of time at temperatures up to 13 50°F and to correlate such changes with creep-rupture properties. of the alloy. In the course of the investigation, some microstructural changes were observed which correspond to microstructural alterations found in previous studies of Inconel "X." Microstructural phases have been identified in both alloys with the aid of electron and X-ray diffraction and an electron probe microanalyzer. The materials used in this investigation were from commercial heats of the following chemical composition: Pct Cr Pct Ni Pct Mo Pct Fe Pct Cb Incoloy "901" 12.51 43.67 5.72 Bal. -Inconel "X" 14.61 73.44 - 6.61 1.02 Pct A1 Pct Ti Pct Mn Pct Si Pct C Incoloy "901" 0.10 2.46 0.46 0.24 0.05 Inconel "X" 0.70 2.43 0.51 0.36 0.04 Long-term creep-rupture tests were conducted on Incoloy "901" at temperatures of 1000°, 1200°1 and 1350°F. A summary of these results is shown in Table I along with the results of a long-term creep-rupture test conducted on Inconel "X" at 1500°F. The heat treatments given the specimens are also shown in Table I. When the creep-rupture results on Incoloy "901" are compared with shorter-tertn data, there is no evidence of any undue deterioration of the creep-rupture strength with time, nor is the elongation decreased more than would be expected from the influence of time alone. INCOLOY "901" PHASE IDENTIFICATION Microscopic examination of the Incoloy "901" specimens reveals a dark etching grain boundary constituent in the specimen which was under test for about 11,500 hr at 1000°F. This grain boundary constituent was seen to increase in size as the test temperature was increased to 1200" and 1350°F, Figs. 1, 2, and 3. Simultaneously, an acicular structure of definite crystallographic orientation appears within the grains of the 1350°F specimen, Fig. 3. Under examination with the electron microscope, a fine precipitate is observed in the 1200 °F specimen. Fig. 4. It becomes considerably larger in the 2850-hr 1350°F specimen, Fig. 5. In a few areas the precipitated particles have been replaced by, or transformed to, small needles or platelets. After 7380 hr at 1350°F, Figs. 3 and 6, the needles are much larger and have replaced nearly all of the fine precipitate. X-ray diffraction studies detected the presence of hexagonal Laves phase and hexagonal n phase (Ni,Ti) in the 1350°F specimens, Table 11. Only the Laves phase was detected by X-ray diffraction in the 1200°F specimen and none was detected in the 1000°F specimen. In this latter specimen, however, the small quantity of precipitate in the grain boundaries (presumed to be Laves phase) precludes its detection by X-ray diffraction. Composition of the hexagonal Laves phase is not yet known, although its diffraction

Jan 1, 1960

By R. D. Pehlke, J. V. Gluck, R. L. Louvet

A study has been made of the effect of small additions of bismuth on the activity of zinc in dilute solution in molten tin. Free-energy interactions have previously been determined between zinc and various third elements where the solvents were molten bismuth or molten lead.'-4 In both of these solvents, the activity of zinc exhibits a strong positive deviation from ideal behavior (at 550°C y° for zinc in lead is 11.4 and for zinc in bismuth is 3.0). The present work, using tin as the solvent, is an extension to a case where the positive deviation is considerably diminished (y°Zn at 550°C is 1.63). Several previous investigators have studied the Zn-Sn binary system; however, little data is available in the range below 0.1 mole fraction zinc.5= Previous high-temperature galvanic cell studies in the Sn-Zn-Bi ternary system included the determination by Gluck and Pehlke of interactions in the bismuth-rich corner1 and separate investigations of the central region by Oleari and Fioriani6 and by Ptak and Moser.7 Yokokowa et al.8 conducted Knudsen effusion studies in the central region; however, their experiments at 625°K were conducted somewhat below the present experimental temperature range. Their results indicated an increase in zinc activity with the addition of bismuth. The present series of experiments was conducted in galvanic cells represented as follows: Zn Zn++ in LiCI-KC1 eutectic Zn + Bi in Sn (pure reference (fused salt electrolyte) (molten alloy) standard) The experimental apparatus. a multi-electrode system employing alumina crucibles and contained in a Vycor tube under a helium atmosphere, has been described previously, as have been the experimental procedures, precautions, and the methods of data reduction.1-4,- The experimental measurements were made over the range from 450° to 650°C. Between thirty and forty measurements were made in each run. The linearity of the electromotive force vs temperature relations was verified by linear regression techniques. The correlation coefficients exceeded 0.99. The experimental results summarized in Table I include the interpolated electromotive force at 550°C and the temperature dependence of electromotive force. Only results from stable and consistent cells containing more than 0.025 mole fraction zinc are reported. Attempts to run cells at 0.01 or 0.02 mole fraction zinc were not satisfactory. This is attributed to the closeness of the free energies of formation of the chlorides of tin and zinc. Calculations employing Wagner and Werner's criteria for displacement reactions10 indicated that reduction of the zinc content to 0.01 mole fraction places the cell near the borderline concentration for a 1 pct error in measured potential. The compositions shown in Table I are the actual weighed-in amounts. Previous experience has indicated that compositional changes during the running of a stable cell are negligible.' Over the range of compositions studied for the binary alloys, the activity coefficient of zinc was essentially constant indicating that Henry's law is followed to 0.05 mole fraction zinc. The temperature, OK, de-

Jan 1, 1969

By A. B. Cox, L. W. Wark

In an earlier paper1 measurements of contact angles due to the effect of xanthates on mineral surfaces were reported. The solutions in which these measurements were made differed widely from those of modern flotation circuits. It is intended, however, by introducing, one at a time, the other principal reagents of flotation, to approach gradually the solution composition of flotation liquors. The work now described is an attempt to determine the effect of one of the most important of these reagents—namely, sodium cyanide—on the establishment of air-mineral contact. The work has been carried out for the following companies: Broken Hill South, North Broken Hill, Zinc Corporation, Electrolytic Zinc of Australasia, Mount Lyell Mining and Railway, and Burma Corporation. Since the effect of cyanide is inseparably connected with the alkalinity, the results cited below deal with the mutual effects of alkalis and cyanide. Alkalis alone exert a significant effect on the air-mineral contact but comparatively large amounts are required. Since the addition of a small amount of cyanide greatly decreases the degree of alkalinity necessary for the suppression of contact at surfaces of any of the minerals experimented with (except galena) and since alkalis are rarely used alone in practice, little attention has been paid to cyanide-free solutions. It was shown in the previous paper that, excluding the dixanthogen effect, whenever contact was practicable at all in an ethyl xanthate solution the angle of contact was 60". There is, therefore, less necessity to measure equilibrium contact angles; in fact, the experiments herein described have generally been conducted with a view to determining whether contact is possible and not to measuring the actual value of the contact angle. The separations which have generally to be effected in dealing with complex sulfide ores are: (1) galena from sphalerite, pyrite, etc.; (2) sphalerite from pyrite and/or gangue minerals; (3) copper minerals from pyrite and gangue minerals; (4) pyrite from gangue minerals; (5) chal-

Jan 1, 1935

By Luther Lennox

DURING the last few years, one of the great problems in the milling of all ores has been that of crushing. This subject involves not merely the cost of the operation, but also the selection of the proper degree and character of crushing to yield the best metallurgical results on the given ore. Considering the diversity of machinery, one is led to wonder at the variety of crushing methods employed, even when realizing that metallurgy demands varying products. In an attempt to investigate the relative crushing resistances of a number of ores now being milled in this country and Alaska, the management of the Portland mills requested samples of average mill-run of ore from various companies. The request met with a ready response, indicating the desire of all operators to gain information on the subject. The difficulties involved in this investigation were numerous, lack of time for outside problems during this strenuous period being a serious one. Also, we were unable, in the time, to obtain a correct 150-mesh . screen; in the screen analyses tabulated and plotted herewith, the 150 mesh screen was used merely to protect the 200-mesh screen, not to ascertain points on the curves.

Jan 8, 1918

By John M. Tinsley, Calvin D. Saunders, H. K. van Poollen

In the past few years much con-sideration has been given to the evaluation of the effect of hydraulic fracturing on the productivity of wells. Generally, these studies included the evaluation of fracturing materials, fracture extension and formation damage due to the use of various fracturing fluids. Only little consideration has been given to the characteristics, and in particular the flow capacity, of the fracture itself and its effect on well productivity. This paper presents the results of laboratory investigations pointed toward fie evaluation of the efficiency of various fracrures with special emphasis on the flow capacity of these fractures. Data presented in this paper are the results of both an electrical model study and physical testing. Under consideration are (I) effect of overflush, (2) premature production of well after treatment, (3) "tailing-in" with coarse sand near the end of the treatment, (4) effect of propping agent size and concentration, (5) reduction in effective frac-ture permeability caused by formation caused by formation fines, silt and clays, and (6) effect of various fluids on formation strength and competency. The results of this investigation indicate that the flow capacity of a fracture is affected by any or all of the various parameters mentioned above. The authors believe that a better understanding arid utilization of these factors should result in more efficient formation fracturing. INTRODUCTION Hydraulic fracturing has become almost a standard practice of many companies for stimulating production from old and new wells. Although most companies utilize this service, techniques of application vary widely between companies and areas. Probably too often when a well in an area responds favorably to a particular technique all future wells in the same area are treated in a similar manner. Possibly a modification of the technique would result in a further production increase. Variables, of which many are extremely difficult to evaluate from field results, hamper the selection of procedure changes. Attempts are being made by a number of organizations to analyze statistically treating techniques from production data. This is a very worthy and necessary approach but very possibly laboratory investigations may aid in evaluating some of the variables which tend to affect the results of a fracturing treatment. Some of the factors cannot be studied from practical field experience and only laboratory tests can show the possibilities which might exist. One of the factors which appears to be of major concern today is the flow capacity of the created fracture and how it can be changed. Papers on this general subject have been primarily concerned with the size of propping agent and the extent of fracture. Papers have also been written on the possible permeability damage to formations by fracturing fluids. In addition, it might be possible that another type of flow restriction is prevalent. This would be a restriction of flow through a sand-packed frac- ture caused by foreign materials integrating within the propping agent. This paper presents preliminary data obtained in an attempt to evaluate the effect of some factors affecting flow through sand-packed fractures. No attempt is being made to offer a fracturing technique adaptable to all areas and conditions, but to furnish data tending to show the possible effects which might be caused by variations in procedures and materials. PROPPING AGENT PERMEABLLITIES A hydraulically induced fracture containing sand as a propping agent may theoretically be classified as a packed-sand system. The flow of fluids through such packed systems has been the subject of much research. Although there have been numerous methods proposed for the evaluation of such systems, most writers agree on the general properties affecting their flow capacity or permeability. These properties include porosity, particle size, sphericity and the roughness of the particle. In some methods of evaluation . the particle size and sphericity terms are combined to produce an equation which is a function of the surface area of the particles. In this study the permeability of various fracturing sands was both measured and calculated. The apparatus for the permeability measurements consisted of a 52-in. Lucite tube with a 2.5-in. ID. A screen and drain plug were fitted in the bottom of this tube to retain and hold the sand in place while allowing fluid flow. Two pressure taps consisting of thin, highly perforated

By Arthur F. Taggart

PROGRESS in a technical art is of several kinds. It springs .from many diverse sources. It comprises invention, mechanical improvement, operating advance, analytical study, education. Invention is, by definition, a relatively great, essentially individual step, taken quickly. Operating advance is the slow, cumulated march of practice; in contrast, it moves at the pace of the tortoise, but over, the years its effects rival and, in some cases, surpass those of invention. Mechanical improvement- is a usual concomitant of the reduction of invention. to operating practice; thereafter it is a primary tool of operating advance. Analytical study is the process of mental digestion of the fruits of invention and practice. Its purpose is to render these into a form assimilable by the art as a whole, and by the perennial crop of would be practitioners. Education, disseminating the results of such study, consolidates and maintains the positions gained. Thus, slowly at first, but continuously accelerating, the tide of progress grows- to flood. Such growth, in mathematical parlance, is expressible in the general form y = mxn, where x is time, n is some positive number greater than one, m is another positive number, and y is the state of the action at instant x. When n is 2, the readers will recognize the graph of the equation as one branch of the familiar square parabola, whose property it is to become parallel to the y-axis; i.e., to move at an infinite rate, in that never-never

Jan 1, 1947

By A. S. Yue

The movphology of the Mg-32 wt pct Al eutectic has been studied as a function of freezing- rate and temperature gradient. At slow freezing rates a lamellar eutectic was formed; whereas, a rod-like eutectic was generated at fast rates. The inter-lamellar spacing increased as the freezing rate decreased in aggreement with theoretical predictions. Lamellar faults, morphologically similar to edge dislocation models in crystals, were responsible for the subgrain structures in the eutectic mixture. A linear increase in fault density with freezing rate was observed. Fault concentl-ations of the order of 10 per sq cm for a range of freezing rates from 0.6 to -3.0 x 10 cm per sec were estimated. The transformation from lamella?, to rod-like morphologies was determined experimentally to be dependent on the freezing rate and independent of the temperature gradient. Moreover, the number of rods formed per- unit cross-sectional area increased exponentiallv with increasing freezing rote. BRADY' and portevin2 classified eutectic structures into lamellar, rod-like, and globular according to the morphology of the solid phases present. Although this classification is quite descriptive, very little has been reported on the details of the mechanism by which the eutectic structures are formed. Recent work by Winegard, Majka, Thall, and chalmers3 and by chalmers4 on lamellar eutectic solidification suggest that the maximum thickness of the lamellae decreases with increasing rate of solidification due to inadequate time for lateral diffusion. scheilS and Tiller' have shown theoretically that the lamellar widths indeed depend on the solidification rate. However, there has been no experimental evidence to support the theory. Chilten and winegard7 have studied the interface morphology of a eutectic alloy of zone-refined lead and tin. They found that the lamellar width decreased as the freezing rate increased in agreement with the theoretical predictions of scheils and Tiller.' More recently, Kraft and Albright' have investigated the microstructures of the A1-CuA12 eutectic as a function of growth variables. They observed lamellar faults present in the lamellar eutectic, similar to edge dislocation models in crystals. Furthermore, Kraft and Albright reported that they could not designate which extra lamellar was responsible for the formation of a lamellar fault even under electron microscopic magnification. In this paper, the morphology of the Mg-A1 eutectic structure is described. The effects of freez- ing rate on the interlamellar spacing and on the lamellar fault density are presented in detail. The transformation from lamellar to rod-like eutectics is discussed in terms of the freezing rate and the temperature gradient. EXPERIMENTAL PROCEDURE The experimental details of alloy preparation, the decanting mechanism and the determinations of the freezing rate and the temperature gradient have been reported elsewhere. Measurements of plate-edge angles were made with a microscope. The true angles used to determine the interlamellar spacings were determined by a two surface analysis technique.'' Since the decanted interface structure does not represent the true eutectic morphology on the solid,g all measurements were made from an area in the solidified bar behind the interface. Measurements of the apparent interlamellar spacings between the two phases of the eutectic were made on a photographic negative by means of a calibrated magnifier. Each value listed in Table I represents the average of thirty measurements on one negative. In general, these measurements are approximately equal with an error of less than pct. The average rod diameter for each specimen was also measured on a magnified photomicrograph. Each value of the diameter represents the average of fifty measurements. RESULTS AND DISCUSSION The experimental observations and their discussion to be presented here are restricted to the morphology of the eutectic structure and to the effects of the freezing rate and the temperature gradient on the solidification of eutectics. INTERLAMELLAR SPACING It has been shown previouslyg that the micro-structure of the decanted interface and the longitudinal section of the Mg-A1 eutectic is characterized by the presence of both lamellar and rod-like morphologies. The lamellae become more regular as the freezing rate is decreased. A three-dimensional photomicrograph representing a perfect lamellar morphology is illustrated in Fig. 1. The lamellae of the top and longitudinal sections of the specimen are regularly spaced while those in the transverse section are not quite straight and parallel. Their parallelism is slightly distorted because fault lines producing a discontinuity are present. A method for calculating the interlamellar spacings A, is described in Appendix 1. The true

Jan 1, 1962

By Alan Morris

In a previous paper1 the results of cutting tests on free-cutting brass rod were reported. Investigation was made of the effects of variation in lead content, microstructure and cold drawing. The author's reply to the discussion of that paper includes a study of the directional cutting properties of drawn and annealed rod. The present paper records the results of tests made on series of samples in which the tin, iron and copper contents have been varied. The apparatus used and method of testing are described in detail in the previous paper. The machine is of the pendulum-operated milling type used and described by Airey and Oxford.2 Angular readings of the height to which the pendulum rises after falling from a fixed position, both when a cut is made and when the pendulum swings freely, give the basis for calculation of the energy consumed in making a cut. Careful weighing of the sample before and after cutting gives a measure of the amount of metal removed. The results are expressed in footpoiinds per cubic inch of metal removed, and have been called "unit cutting energy." In the course of the discussion of the author's earlier paper, W. B. Price reported large-scale tests involving some 50,000 lb. of material. These tests indicated that the addition of as much as 0.6 per cent of iron and 0.25 per cent of tin had apparently no adverse effect on the highspeed cutting characteristics of the rod. The rod also contained a small amount of nickel. The test results reported here tend to confirm his observations. Effect of Variation in Tin Content The castings for this series were made 2 by 1 by 9 in. and were processed as follows: 1. Castings were annealed at 500" C. for 7 hr. 2. Cold-rolled to 0.700 in.

Jan 1, 1933

By Charles H. Fettke

The Bradford field of northwestern Pennsylvania and adjacent portions of New York state has attracted world-wide attention in recent years on account of the remarkable success that has been attained in the application of water-flooding as a means of increasing the extraction of oil from a pool that had almost reached the economic limit by ordinary production methods. It is one of the few large oil fields in which artificially conducted water drives have thus far proved successful, although many attempts have been made to apply them elsewhere. As detailed a knowledge as possible of the character of the producing sand in this field is therefore of considerable interest, not only from a scientific but also from a practical standpoint. Outside the Bradford field, such knowledge should aid operators in determining whether or not their sands are amenable to flooding. In the Bradford field itself flooding operations are not uniformly successful over the approximately 85,000 acres of productive area, due in many instances primarily to variations in sand conditions. A knowledge of just what these variations are would often be a great aid in overcoming the difficulties, or else would save considerable sums of money which might otherwise be wasted in experimenting in areas where the chances of success are very small. Realizing that more precise information in regard to the nature of the reservoir rock was essential to improvements in the methods of oil recovery, the Northwestern Pennsylvania Oil Producers Assn., by private subscription of its members, took a core of the Bradford sand from a well 1/2 mile west of Custer City, Pa., during the spring of 1925. The Forest Oil Co. also took a core of the same sand from a well about 8 miles east of Bradford at that time. The cores were submitted to the United States Geological Survey for study and A. F. Melcherl has published the results of porosity determinations on the Custer City core.

Jan 1, 1929

By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton' reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler' stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

By W. J. Reagan

The problem of increasing output and decreasing percentage of rejections is a vital one in the manufacture of steel of any kind. The making of basic open-hearth steel for use in rolled steel wheels, tires for locomotive and car wheels, and forgings of various kinds, is a highly specialized industry. The increase in weight of railway rolling stock of all kinds, and the high speed that the public demands of transportation facilities, make it imperative that steel for use in this class of material shall be of the highest quality obtainable. During the past few years it has been the writer's good fortune to have opportunity to study the defects in basic open-hearth steel, and also the results obtained by various changes in open-hearth practice, on such defects. The opportunity for study and the details available are rarely found in the manufacture of steel of any kind. It seems reasonable to assume that many of the results determined here can be applied to the production of steel of other types with a decided improvement in quality, a decrease in the percentage of rejections and an increase in output. All of the material described is basic open-hearth steel with the following range of analysis: carbon, 0.50 to 0.85 per cent.; phosphorus and sulfur, 0.04 max.; silicon, 0.15 to 0.35; manganese, 0.50 to 0.75. All of this material is bottom-cast, therefore tapping and pouring temperatures are higher than in top-cast production. Ingots used in this type of work are of standard length with varying diameters. The ingot is known as duodecagonal, or twelve-sided. The standard body length is 88 in. and the hot top length, 14 in. Fig. 1 shows a typical ingot of this type. The diameter varies from 13 to 30 in. Ingots for special forgings, which cannot be made in molds of standard size, are made in molds of various sizes and designs. These ingots are sliced cold, into blocks of various lengths, depending upon the weight of the forging to be made. Fig. 2 shows the ingot after coming from the slicing lathe. Jusf sufficient metal remains between blocks to hold the ingot in one piece while it is being removed from the lathe; then steel wedges are inserted between the blocks and the blocks are broken apart. This affords abundant opportunity for inspection, as the interior of the

Jan 1, 1930

By S. D. Baumer, P. M. Hulme

IN the late thirties, the National Carbide Co. cooperated with C. E. Wood, of the U. S. Bureau of Mines, in his investigation of the relative merits of various desulphurizers, including soda ash, caustic soda, and calcium carbide. Laboratory tests showed that carbide, when it could be made to react, is an excellent desulphurizing agent for molten iron. Sulphur content can be driven to lower levels and higher extractions obtained with carbide than with actionsany of the more common reagents. Wood's results1 are shown in Table I. Unfortunately, as the Handbook of Cupola Operation puts it, the chemical fact that carbide is a good desulphurizer was of only academic interest because it was found to be extremely difficult to devise a practical means to make it react with molten iron. Calcium carbide is formed in the electric furnace at 4000°F and above, and its softening point is probably at least 500 °F above the usual working temperatures encountered in iron and steel practice. Consequently, carbide does not form a true slag but floats as a dry powder on top of the metal and only a very small portion of it ever comes in actual contact with the iron. Stirring with a rabble, or pouring the metal over the carbide, increases the efficiency only slightly. Extractions of 20 to 30 pct can be obtained in this manner, but conventional soda slag treatment can do better than this and do it more cheaply. All attempts to lower the melting point of carbide in order to obtain a reactive, liquid slag have so far proved fruitless. Directly under the arc in a metallurgical electric furnace, carbide becomes highly reactive. Excellent sulphur removal can be obtained without any slag other than a thin layer of carbide." imilarly, good results are obtained by adding small amounts of carbide to the finishing slag in double-slag arc furnace practice. To react a liquid with a solid, it is axiomatic that the liquid has to wet the solid before anything can happen. If the solid is heavier than the liquid, the problem is easy, but it becomes more difficult when the solid is much lighter than the liquid, as in the case of carbide and liquid iron. Wood recognized this problem and solved it in a unique fashion. The results shown in Table I were obtained by spinning the carbide beneath the surface of the molten iron by means of a refractory centrifuge. This technique allowed each particle of the finely divided carbide to come into intimate contact with the metal and to be wetted thereby. Wood's centrifuge technique was successful in the laboratory where it achieved excellent and consistent results. Some attempts were made to expand this method to commercial practice, but serious difficulty was encountered in obtaining a refractory centrifuge head that would be economically feasible. About this time the war intervened and the project lay dormant for several years. In 1944, it was revived. It was suggested that the carbide could be blown into the metal with a carrier gas in an attempt to eliminate the necessity for the expensive and brittle centrifuge. The idea was first tried out in a fairly large ladle of iron using natural gas as the carrier. Considerable sulphur was removed, but it was quite obvious that the use of natural gas was not practical. Attempts then were made to blow carbide into molten iron using, in turn, nitrogen, argon, carbon dioxide, air, and oxygen. The latter two gases proved unsatisfactory. Calcium evidently prefers oxygen to sulphur because in the tests calcium oxide and carbon dioxide were produced, the sulphur still being untouched in the iron. Nitrogen, argon, and carbon dioxide gave much better results, although the efficiencies and extractions were erratic, and only a few isolated tests approached the results obtained by Wood. Table II shows typical results obtained with these gases. The sulphur removals were interesting, sometimes even encouraging, but it is evident that such erratic behavior could not be tolerated in commercial practice. A number of different types of equipment, such as sand blasting machines, refractory guns, and the like can used to blow the solid into the metal. All types required relatively large quantities of gas in order to maintain the flow of solid carbide through the system and into the metal. It was observed that the bubbles of gas breaking through the surface of the metal contained quantities of unreacted carbide. The liquid metal never came in contact with these particles and if it cannot wet them it cannot react with them. The initial work had shown that carbide had great possibilities as a desulphurizer. In practice

Jan 1, 1952

By Lawrence B. Wright, Lester G. Morrell

On the steep slopes of the Kootenays, 15 to 20 miles south of Nelson, B. C., are a number of ore occurrences (Fig. 1). One that has many features of mining and geological interest is the Ymir Yankee Girl Gold Mines Limited. Discovery of this property was made in 1899 at an outcrop on the hillside, some 2500 ft. above the village of Ymir. This proved to be a branch vein 20 ft. long leading to two main veins, the Yankee Girl and the Spur (Fig. 5). The ore pattern as now delimited shows a remarkable increase in ore area with depth below the outcrop. This recent development is of interest particularly in view of the fact that the property was nearly condemned, professionally. Another interesting feature, which has a bearing upon its history, is the persistent excess of tonnage produced from period to period over visible reserves. This is not ascribed to lagging mine development, but to detailed vein characteristics, which we will endeavor to make clear by giving a description of the veins and their surroundings. HISTORY AND PRODUCTION Little interest_was_evidenced-in this-distriet until the building of the railway in 1893 provided easy access and the discovery of the Ymir mine in 1896 attracted attention. As a result, the Ymir Yankee Girl group of claims was staked in October 1899. In 1907, an American syndicate took over the property and subsequently extended the 50-ft. drift and opened the present 400 and 540-ft. levels. In 1908, the Syndicate, without recording any shipments in the meantime, dropped its lease, which was taken up by H. L. Rogers, who bonded the Yankee Girl group. Rogers shipped 2622 tons of ore, mainly from the uppermost stope in the mine, which is reported to have yielded

Jan 1, 1940

By Lawrence B. Wright, Lester G. Morrell

On the steep slopes of the Kootenays, 15 to 20 miles south of Nelson, B. C., are a number of ore occurrences (Fig. 1). One that has many features of mining and geological interest is the Ymir Yankee Girl Gold Mines Limited. Discovery of this property was made in 1899 at an outcrop on the hillside, some 2500 ft. above the village of Ymir. This proved to be a branch vein 20 ft. long leading to two main veins, the Yankee Girl and the Spur (Fig. 5). The ore pattern as now delimited shows a remarkable increase in ore area with depth below the outcrop. This recent development is of interest particularly in view of the fact that the property was nearly condemned, professionally. Another interesting feature, which has a bearing upon its history, is the persistent excess of tonnage produced from period to period over visible reserves. This is not ascribed to lagging mine development, but to detailed vein characteristics, which we will endeavor to make clear by giving a description of the veins and their surroundings. HISTORY AND PRODUCTION Little interest_was_evidenced-in this-distriet until the building of the railway in 1893 provided easy access and the discovery of the Ymir mine in 1896 attracted attention. As a result, the Ymir Yankee Girl group of claims was staked in October 1899. In 1907, an American syndicate took over the property and subsequently extended the 50-ft. drift and opened the present 400 and 540-ft. levels. In 1908, the Syndicate, without recording any shipments in the meantime, dropped its lease, which was taken up by H. L. Rogers, who bonded the Yankee Girl group. Rogers shipped 2622 tons of ore, mainly from the uppermost stope in the mine, which is reported to have yielded

Jan 1, 1940

By Philip D. Wilson

SPEED is essentiaI in this war program and it is hard to keep up with developments. When the title of this paper was chosen, the contemplated magnesium production for which plants were then under construction was some 200,000 tons of metal per year or sixty times the 3350-ton production in prewar 1939. A few- days later an analysis of the President's 185,000-plane pro-gram, incendiary bomb schedules, and the additional requirements of the Army. Navy and Maritime Commission made it apparent that a much greater amount of magnesium must be provided in 1943. The new figures are huge but the censor will not per-mit their disclosure.

Jan 1, 1942

By P. B. Baxendell, R. Thomas

Work on the calculation of vertical two-phase flow gradients by Cia. Shell de Venezuela has been based mainly on the "energy-loss" method proposed by Poett-mann and Carpenter in 1952. The "energy-loss-factor" correlation proposed by Poettmann and Carpenter was based on relatively low-rate flow data. This correlation proved inapplicable to high-rate flow conditions. In an attempt to establish a satisfactory correlation for high rates, a series of experiments was carried out at rates up to 5,000 BID in Cia. Shell de Venezuela's La Paz field in Venezuela, using tubing strings fitted with electronic surface-recording pressure elements. As a result of these experiments a correlation between energy-loss factor and mass flow rate was established which is believed to be applicable to a wide range of conduit sizes and crude types at high flow rates (e.g., above 900 BID for 27/8-in. OD tubing). It is anticipated that the resulting gradient calculations will have an accuracy of the order of % 5 per cent. At lower flow rates the energy-loss factor cannot be considered as constant for any mass rate of flow, but varies with the free gas in place and the mixture velocity. No satisfactory correlating parameter was obtained. As a practical compromise for low flow rates, a modification of the curve proposed by Poettmann and Carpenter was used. In practice this was found to give gradient accuracies of approxirnately ± 10 per cent clown to flow rates as low as 300 B/D in 27/8-in. tubing. INTRODUCTION Production operations in Cia. Shell de Venezuela's light- and medium-crude fields are principally concerned with high-rate flowing or gas-lift wells. Under these conditions the analysis of well performance, the selection of production strings and the design of gas-lift installations are vitally dependent on an accurate knowledge of the pressure gradients involved in vertical two-phase flow. Initially, attempts were made to establish the gradients empirically as done by Gilbert,' but the results were not reliable due to scarcity of data over a full range of rates and gas-oil ratios. Several methods of calculation based on energy-balance considerations were attempted, but the computations were cumbersome and the results cliscouraging. In 1952 a paper was published by Poettmann and Carpenter' which proposed a new approach. Their method was also based on an energy-balance equation. but it was original in that no attempt was made to evaluate the various components making up the total energy losses. Instead, they proposed a form of analysis which assumed that all the significant energy losses for mutiphase flow could be correlated in a form similar to that of the Fanning equation for frictional 1osses in single-phase flow. They then derived an empirical relationship linking measurable field data with a factor which, when applied to the standard form of the Fanning equation, would enable the energy losses to be determined. The basic method was applied in Venezuela to the problem of annular flow gradients in the La Paz and Mara fields" This involved establishing a new energy-loss-factor correlation to cover high flow rates and, also, some adaptation of the method to permit mechanized calculation using punch-card machines. The final result was 1 set of gradient curves for La Paz and Mara conditions which proved to be surprisingly accurate. With the encouraging results of the annular flow calculations, several attempts were made to obtain a corresponding set of curves for tubing flow. Here, unfortunately, little progress could be made. The original correlation of Poettmann and Carpenter was based on rather 1imited data derived from low-rate observations in 23/8- and 27/8-in. OD tubing. It did not cover the higher range of production rates, and extrapolation proved unsuccessful. A new correlation covering high flow rates was required, but this proved to be extremely difficult to establish since tubing flow pressure measurements at high rates did not exist—due to the difficulty of running pressure bombs against high-velocity flow. The necessity for reliable tubing flow data increased with the development of the new concessions in Lake Maracaibo, where high-rate tubing flow from depths of 10,500 ft became routine. Thus. it was decided to set up a full-scale test to establish a reliable energy-loss factor for tubing flow conditions. A La. Paz field light-oil producer with a potential of approximately 12,000 B/D on annular flow was chosen. To obtain full pressure gradients, a special tubing string was installed which was equipped with electronic surface-recording pressure measuring devices,

By V. O. Struebing, K. A. Johnson, F. H. Ellinger, C. C. Land

The system Pu-Ce-(Pu,Ce)Co2 has been investigated by thermal, micrographic, and X-ray diffraction methods. The principal characteristics of this system were found to be: 1) a "eutectic" valley extending across the phase diagram from the 6 Pu/Pu3 Co eutectic at 408°C to the 7 Ce/Ce24Co11 eutectic at 42Z°C, the maximum temperature in the valley being 443°C; 2) three ternary inter mediate phases, each having an appreciable mutual solid solubility for plutonium and cerium; 3) eleven four-phase equilibria comprising one eutectic, four peritectics, and six Class II reactions; 4) a pseudobinary section between the ternary phase A and the y Ce solid solution, and another such section between the 6 Pu solid solution and the 77 phase (Pu3 CO) containing cerium in solid solution. ALLOYS of plutonium that are completely molten at temperatures in the vicinity of 500°C are of interest for use in the liquid state as fast reactor fuels. Since exploratory work1,2 on Pu-Ce-Co alloys had indicated that a "eutectic" valley extended across the ternary system between the Pu-co[6 Pu/n (Pu3co)] and the Ce-CO[? Ce/? (ce24co11)] binary eutectics, thus allowing alloys of any plutonium concentration to be selected within the temperature limitation, the present investigation was begun for the purpose of accurately defining the "eutectic" valley. However, when the existence of three ternary intermediate phases and the consequent complexity of the liquid-solid equilibria were discovered, the investigation was expanded to cover the complete system, except for the corner between the isomorphous series PuCo2-CeCo2 and pure cobalt. 1) EXPERIMENTAL The purities of the alloy components are given in Table I. Alloy buttons, each weighing about 5 g, were prepared by arc melting the accurately weighed components (±0.1 mg) under a purified He-Ar atmosphere. Weight loss as a result of melting was usually less than 1 part in 1000; therefore, the buttons were not chemically analyzed. One half of each button was re-melted by induction heating in vacuo in a magnesia crucible and furnace-cooled, so as to produce a somewhat coarser microstructure than that of the rapidly cooled arc-melted button. About 20 g of each alloy to be examined by thermal analysis were remelted in vacuo in a tantalum crucible of the inverted thermocouple well type. The thermal, X-ray diffraction, heat treating, and micrographic methods used in this investigation were essentially the same as have been described in earlier reports.3,4 Two etchants for these alloys were found to be satisfactory: A) 8 (parts by volume) orthophosphoric acid, 5 ethanol, and 5 glycol; B) 7 tetraphosphoric acid, 36 water, and 57 2-ethoxyethanol. Etchant A was used at 5 to 6 v for 15 to 20 sec, and etchant B was used at 10 v for 10 sec. 2) THE LIMITING BINARY SYSTEMS 2.1) Plutonium-Cerium. The phase relationships of this system have been investigated by Ellinger, Land, and Cramer,5 and by Selle and Etter.6 The over-all agreement of their phase diagrams is good, but there are some discrepancies in the positions of some phase

Jan 1, 1967

By S. S. Rumsey

Introduction IN order to realize the economies which would result in operating the mine pumps at the Chapin mine with electricity. generated by water power, the Oliver Iron Mining Co. recently installed a hydro-electric plant at the upper Quinnesee, falls on the Menominee river, and constructed a transmission line to the mine. On account of the large flow of water in the Chapin mine, and the great depth from which it has to be handled, it was necessary to make a thorough investigation of the merits of both the motor-driven centrifugal and motor-driven plunger pumps, in order that the most economical results as regards power, cost of installation, maintenance, and operation, be obtained. This investigation resulted in the selection of motor-driven centrifugal pumps, as the cost of the pumps and motors, installation, and maintenance was considerably lower, and the space required in the underground workings very much smaller, than for the plunger pumps. The overall efficiencies guaranteed by several of the centrifugal-pump manufacturers were so nearly those guaranteed by plunger-pump manufacturers that the saving in power which would result from the installation of plunger pumps did not justify their increased first cost and the increased cost of installation under the conditions prevailing at the Chapin nine. In order to substantiate the representations of the centrifugal-pump builders it was deemed necessary to insist upon a factory test of the completed units before shipment, the test to be conducted under conditions of head and capacity approximating as nearly as possible those under which the pumps would operate in service. Furthermore, it was considered necessary to demonstrate, by test, that there were no deficiencies in design or capacity of the pumps or motors before their final installation in the mine, as it would be extremely difficult to make alterations in the pumps or motors after they were installed.

Jan 10, 1914