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By A. R. Troiano, E. A. Steigerwald, F. W. Schaller

The kinetics of crack propagation in a hydrogenated high-strength steel at subzero temperatures indicated that cracking progressed in a discontinuous fashion. The delayed failure process thus involves a series of crack initiations rather than the continuous growth of a single crack. The incubation time required for the initiation of delayed failure was controlled by the diffusion of hydrogen. The activation energy for the process was 9120 cal per g-alom. As the test temperature was lowered the incubation time constituted a greater percentage of the total tinze to fracture, and al -50°F the incubation and fracture times were essentially coincident resulting in instantaneous, catastroplzic fracture. A unique feature of hydrogen embrittlement is the delayed failure process in which the material fails under the action of a sustained load even though it is capable of supporting a higher load for a finite period of time.')' Delayed failure of steel and titanium is characterized by an incubation time, preceding the initiation of a crack in a highly localized region, and the subsequent growth of the crack to ultimate failure.3-5 The kinetics of crack growth in hydro-genated high-strength steels have been studied through the use of resistance measurements and have an important bearing on the mechanism of delayed failure. Delayed failure is believed to be merely a facet of hydrogen embrittlement in which sufficient time is allowed during a test for hydrogen diffusion. The current theories employed to explain hydrogen em-brittlement can be grouped into two types. one6-8 explains the embrittlement on the basis of the pressure exerted by molecular hdrogen in lattice voids or defects while the other9-10 attributes the embrittlement to the influence of hydrogen in the lattice. The mechanism used to explain the nature of the crack kinetics in delayed failure is based on the stress-induced diffusion of hydrogen to the area of maximum triaxiality.3 When the hydrogen concentration in this region reaches a critical value, a crack is nucleated. This initial crack propagates instantaneously until stopped by the higher fracture stress of the adjacent material of lower hydrogen content. The continuation of cracking must then await the further diffusion of hydrogen to the new region of triaxiality near the base of the crack where another initiation will occur. From this mechanism it follows that crack propagation is nothing more or less than a series of initiations with limited fracture. The purpose of this investigation was to examine the kinetics of crack growth in an effort to determine whether or not the process was discontinuous. Studies of crack propagation were conducted at low temperatures to retard the diffusion of hydrogen which is presumed to be the rate controlling process in delayed failure. MATERIALS AND PROCEDURE Specimen Preparation—A commercial heat of air-craft quality SAE-AISI 4340 steel, designated as Heat G, was furnished by the Republic Steel Co. in the form of %-in. hot-rolled bars. The material had the following chemical analysis: Composition of 4340 Steel—G Heat C Mn Si Ni Cr Mo 0,395pct 0.82pct 0.29pct 1.76pct 0.85pct 0.25pct Notched tensile specimens with less than a 0.001 in. radius, Fig. 1, were used throughout the investigation. The specimens were heat treated to a 230,000 psi strength level according to the following sequence: a) Normalize bar stock at 1650°F for 1 hr, b) Stress relieve at 1200°F for 4 hr and furnace cool,

Jan 1, 1960

By Harry K. Ihrig

Jan 1, 1947

By Harry K. Ihrig

Jan 1, 1947

By George S. Koch

Since 1882, world zinc production has increased. In contrast, US zinc production rose until about 1915, but since then has remained nearly constant, with a slight tendency to decrease. Production from the Tri-State district, the largest early source of zinc in the US, has gone down steadily; this decline has been balanced by a growth in the rate of other districts. These changes in US production are due to economic, not geological, factors. Recent exploration has located large minable ore bodies: additional deposits will undoubtedly be found in the stratabound carbonate rock and volcanogenic environments. A statistical analysis of the exploration effort in the Middle Tennessee district indicates that new discoveries can be expected there. Thus, the US is in an early stage of the production cycle for zinc. Of major mining districts in the US, only the Tri-State is exhausted under current economic conditions; large zinc resources of low-grade material, which would repay mining at higher prices or improved technology, are known to exist in that district .

Jan 1, 1982

By Stanley J. LeFond

Jan 1, 1985

By Paul M. Tyler

MUCH information concerning pegmatites which was thought to be true a few years ago has been proved false, and what is now actually known about some pegmatites is not true of many others. The erratic and seemingly unpredictable structure and variable composition of this class of mineral deposits has been widely emphasized. Even parts of the same pegmatite body exhibit marked differences in texture, mineral composition, width, and attitude. Constructive geological thinking in respect to pegmatites now aims to establish general laws rather than to stress the confusing diversity of features having no special economic significance.

Jan 9, 1953

By J. M. Locke

BRÜCKNER's revolving cylinders for roasting ores, etc., are now used at a number of the mills in Colorado and New Mexico, for the purpose of roasting and chloridizing silver ores, with highly satisfactory results, even from those cylinders of small size, erected before the many improvements of recent date. As examples of the larger improved cylinders, reference can be made to those erected at the Tennessee Reduction Works, Silver City, Grant County, New Mexico, and those which were built, in 1871, at the celebrated Caribou Silver Mill and Mines, Colorado, a mining enterprise which has proved so satisfactory as to have been lately sold to a Holland company for an enormous amount. These cylinders, as now constructed by Messrs. Lane & Bodley, of Cincinnati,, Ohio, are shown in Plate III, in which Fig. 1 is an elevation in perspective, Fig. 2 a longitudinal, and Fig. 3 a trans¬verse section. Fig. 4 is a sketch of a mill, with Brückner's cylinder. The exterior of the cylinder is a shell of boiler iron, 12 feet long by 5 feet 6 inches in diameter. The ends are partially closed with similar material, leaving in the centre a circular opening about 2 feet in diameter, bounded by a flange projecting several inches.. Upon one side is placed an opening closed by a hinged door. Upon the outside of the cylinder are bolted three bands, as shown in Fig. 1, in which the section of the first is square, and that of the third semi¬circular; the second, or middle band, is a strong spur gear. Passing through the cylinder are six pipes parallel to one another, in a plane at an angle of 15° to the axis of the cylinder; these pipes also lie in this plane at an angle of from 30° to 35° to the longitudinal, axis of the plane, as shown in Fig. 2, where the internal arrangement of the cylinder is seen, a perforated diaphragm being formed through part of the cylinder by means of perforated plates placed between

Jan 1, 1874

By R. V. Norris

In a former paper on this subject,' I summarized Murgue's theory and experiments, and presented a large number of tests of mine-fans, stating some conclusions, " more or less warranted by the evidence," as to design, capacity and efficiency. Since that time the very valuable report of Mr. M. Walton Brown: Committee on Mechanical Ventikators, Institution of Mining Engineers, has appeared, and I have made additional experiments which tend to clear up some points in connection with this subject. Design and Tests of the Luke-Fidlbr Colliery Fan. The Luke-Fidler fan (see Figs. 1, 2 and 3), built to replace an old wooden fan at a very fiery colliery, presents some pecu-

Jan 1, 1905

By N. A. Stockett

SOUTHEAST Missouri is the largest and oldest lead-producing district in the United States. For the year 1941, the statistical picture of pig-lead production, stated in short tons (partly estimated by the Engineering and Mining Journal) is as follows. [Tons World production 2,000,000 United States production 460.000 Southeast Missouri production 242,000] The consumption of primary lead in the United States in 1941 was approximately 900,000 tons, or almost double the country's production. The largest previous year's consumption in the United States was 718,000 tons, in 1926. The largest quantities of lead are used for cable sheathing, storage batteries and white lead. During 1941 tetraethyl lead for auto and aviation gasoline consumed 50,000 tons of lead. The entire lead production of Southeast Missouri is now mined by the St. Joseph Lead Co., whose dominant position as the largest producer in the United States of lead directly from ores is best shown by the fact that in 1941 it produced approximately 31 per cent of the lead production of the United States from its mines in southeast Missouri, where 22,000 tons of ore, averag¬ing over 3.00 per cent lead, is mined per working day. It is known that lead was mined at Mine La Motte, Madison County, Missouri, by Renault in 1723. Other white men and Indians probably did some mining prior to that time. Since 1865, the recorded production to Jan. 1, 1942, shows that the St. Joseph Lead Co. and the various other companies that have operated in St. Francois County mined lead ore, which, after milling and smelting losses produced 5,00,000 short tons of pig lead. About 95 per cent of the present lead production of Southeast Missouri is mined in St. Francois County. The northern part of this area is 60 miles south of St. Louis. The remainder of the lead is obtained at Mine La Motte, about 25 miles southeast from the center of the producing area in St. Francois County. PROSPECTING In this district, most of the ore is discovered by surface and underground diamond drills and by prospect drilling underground with rock drills. Each 2-ft. length of the cuttings from these Jackhamer prospect holes is assayed for lead. These holes are marked and the records are entered on maps. It has been found that close drilling--100-ft. centers of holes, and sometimes less-is necessary in order to locate most of the smaller commercial ore bodies, many of which previously had been missed by drilling the areas with holes spaced 200-ft. centers or more.

Jan 1, 1943

Jan 1, 1896

By E. A. Gulbransen, J. W. Hickman

INTRODUCTION DURING the past two decades considerable progress has been made in the art of manufacturing heater alloys. The conventional iron-chromium-nickel alloys have been improved by the addition of small quantities of other elements. Up to the present time, to our knowledge, there has not appeared a systematic study of these alloys where the newer tools of investigation have been brought to bear on the problem. It is not yet clear what roles the additional elements play in increasing life time in usage. As a first approximation one might guess that elements such as manganese, silicon, zirconium, calcium and aluminum would aid in the formation of a protective film on the alloy surface, thus retarding the oxidation rate and increasing lifetime. If these additional elements do form protective oxides in the outer surface of the oxide film, it may be possible to identify them by means of reflection electron diffraction. It is also possible that the additional elements may not diffuse to the surface but may remain at the interface between the oxide and the metal. Then, too, the major elements in the alloys undoubtedly form oxides which are stratified on the surface. If the minor elements concentrate in a layer in contact with the substrate where they undergo oxidation and if this oxide film offers resistance to the diffusion of iron, chromium and nickel ions, then the lifetime of the heater element might be expected to increase. It is also possible that preferential reduction in the diffusion rates of the several ions may occur to such a degree that oxides may form in the body of the film and on the outer surface which are different from those that would normally form if the additional elements were not present. The use of transmisson electron diffraction may aid us in interpreting these phenomena. Up to the present time all of the factors which influence the lifetime of a given heater element are not definitely known. Among these are: (I) The rate of oxidation of the alloy. This may be dependent upon the composition and the physical state of the alloy. (2) The stability of the structure of the coating which forms. Transitions from one structure to another or solid phase reactions resulting in a change of composition may occur. The tendency of the film to adhere to the substrate when heated and cooled successively will be important. (3) The evaporation of various constituents from the alloy such as the removal of carbon by oxygen in a decarburization reaction. With these possibilities in view, an electron diffraction study of the oxides occurring on six different nickel-chromium alloys was undertaken with the hope that the results of this study could be correlated with oxidation rate studies as determined by means of the vacuum microbalance method1 and with

Jan 1, 1948

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

By William D. Klopp

A study was conducted of the tensile and creep properties of are-melted and electron-beam-melted tungsten over the temperature range 2250° to 4140°F. The tensile and creep strengths vary with pain size, the finer -grained materials being stronger. The activation energy for transient creep at 2250° to 3500°F is 95,000 cal per (g)(mole), while that for steady creep at 3300o to 4000°F is 141,000 cal per (g)(mole). At 2875o to 3300°F the apparent activation energy for steady creep decreased with decreasing temperature. It is suggested that cross slip is rate controlling during transient creep, while dislocation climb is rate controlling during steady creep above 3300° F. ALTHOUGH considerable data have been generated on the high-temperature tensile properties of powder-metallurgy tungsten,1 relative few data have been published on the properties of are-melted2 or electron-beam melted tungsten.3 Furthermore, the available data show a fairly large amount of scatter at high temperatures. The effects of structure and purity have not yet been defined, aside from observations that high-purity electron-beam (EB)-melted tungsten3 and single-crystal-plasma-flame tungsten4 are weaker than less pure powder-metallurgy tungsten. The creep behavior of powder-metallurgy tungsten has been studied, but no data are available on the creep behavior of tungsten consolidated by melting. Green5 found that powder-metallurgy tungsten exhibited linear creep at 4082° to 5072°F with an activation energy of 160,000 cal per (g) (mole). The similarity of this activation energy to that of 153,000 cal per (g)(mole) for volume self-diffusion6 suggests that recovery of strain hardening by dislocation climb is rate controlling in this temperature range. In studies at 4800°F, Sutherland and Klopp7 concluded that grain size significantly affected the creep behavior of commercial powder-metallurgy materials. This grain-size effect was suggested by sherby,8 although the opposite relation had been reported for aluminum.' The purpose of the present study was twofold: first, to provide baseline data on high-temperature tensile and creep properties of are-melted and EB-melted tungsten for concurrent tungsten alloy studies, and, second, to determine the phenomenolo-gical effects of structural and purity variables on the high - temperature mechanical properties of tungsten. EXPERIMENTAL The are-melted tungsten materials were prepared by melting sintered 1-1/4-in.-diam electrodes into 2-1/2-in.-diam by 5-in.-long ingots. The are-melting facility has been described previously.' Eight ingots were melted, machined, and hot-extruded at

Jan 1, 1965

Jan 4, 1976

By C. G. Rhodes, D. Kramer

The kinetics of precipitation of transient a phase during the transformation in U-16 wt pct Mo between 400° and 550°C were studied using quantitative metallography and electrica1 resistiuity measurements. The volume percent of a phase goes through a maximum in time, corresponding to a critical degree of progress of y' formation. prior to its re-solution after prolonged annealing. The fastest rate of a precipitation oc-cuvs at 500°C with a concomittant lowest peak of 9.5 vol pct a. At 450°C, 14 vol pct a, greatest fov any temperature, was observed after 24 hr witlz an associated slowest rate of formation. a precipitation at 400°C ceases after approximately 160 hr and the amount of a present remains unchanged after long times at temperature; no y' was observed metallographically at this temperature. IN the U-Mo system at 16 wt pct Mo, an ordering reaction takes place below 600°C, see Fig. 1, whereupon the random bcc solid solution, y, transforms to the ordered bct phase, y'."2 The new unit cell is constructed of three old unit cells somewhat distorted. While attempting to study the kinetics of this transformation it was observed that an unexpected phase was precipitating out early during the transformation anneal reaching appreciable amounts before disappearing after long times. The y' appeared in the presence of this new phase and after long times constituted the whole sample. Owing to the high optical activity of this unexpected phase under polarized light, it was suspected to be the a phase. Subsequent X-ray powder pictures confirmed this belief. The kinetics of a phase formation and disappearance is the subject of this paper. EXPERIMENTAL PROCEDURE A) Alloy Preparation. Alloys for this study were prepared by vacuum induction melting normal reactor grade uranium and 99.5 wt pct Mo pellets in thoria crucibles. Two ingots were prepared, and sections of the top and bottom of each ingot were chemically analyzed for uranium and molybdenum content. The results of the analyses appear in Table I. B) Metallography. Samples of 16M were wrapped in tantalum foil, sealed in evacuated (5 X 10"6 mm of Hg) quartz capisules, and annealed at 1110"C prior to being transferred directly to the transformation temperature. They were examined metallographically after increasing times to determine the progress of the transformation at 400°, 450°, 500°, and 550°C. The samples were prepared for metallographic examination by mechanical polishing with diamond paste and electrolytic polishing with a solution of glacial acetic acid and chromic acid. Since the y' phase is tetragonal, its presence can be detected by viewing the sample in polarized light. To increase the contrast between y' plates, the samples were electro-etched in a 10 pct oxalic acid solution. To reveal a phase in bright field (it can be seen in polarized light in the "as-polished" state), the samples were electro-etched in a solution of citric acid and nitric acid. To determine the vol pct a phase, a variation of the one dimensional systematic point count method as described by Hilliard and cahn3 was used. The

Jan 1, 1962

By Michael Perch, Charles C. Russell

Nearly 95 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69,9, and in 1938 it was 61.3, To produce a net ton of pig iron 1959 lb. of coke was required in ,1940 and 1760o lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1942

By Aureal T. Cross

THIS paper is a review of the published literature on research in coal geology, principally exclusive of resource studies, which appeared or became available during 1950 and the latter part of 1949. This report is not to be construed as being complete. The papers referred to in the bibliography are those among many more, which were read either in full or in abstract. Undoubtedly other papers were published' which either escaped the author's notice or were not available to him. Those which were seen in abstract only (about one fourth of those listed) were not available in time for the inclusion of more than a notice. An outline of all papers listed in the bibliography has been arranged by subjects and reasonable subdivisions with some papers cited under more than one subject. Most papers are indexed according to the principal subject of discussion or research only as to an unusual or noteworthy section of the entire report. There will likely be some disagreement as to the quality or merit of some of the papers selected and the specialist may be supercritical of the outline or organization of papers in his field. It may be that attention has occasionally been drawn to papers reporting old information or conclusions of questionable value. Conferences and Meetings One of the best indications of the growing interest in coal geology problems in the United States is the increasing number of times this- field has been the focus of attention at conferences and meetings. Notable among these are the joint meeting of the Society of Economic Geologists and the Geological Society of America at El Paso, November 1949, at which the principal thesis was concerned with low rank carbonaceous fuel deposits, especially of western United States. Among the papers given which are already available were those presented by Barghoorn,16 Parry,180 Roe,153 and Parks.162 At the annual meeting of the Botanical Society of America in New York, December 1949, a joint meeting of the Paleobotanical and Microbiological Sections was held for which a symposium on Microbiology in Relation to the Geologic Accumulation of Organic Complexes was 'organized. Publication of the six papers presented by Ralph G. H. Siu, Elso S. Barghoorn, Irving Breger, Claude E. ZoBell, James M. Schopf, and A. C. Thayson is anticipated. At the regular meetings of the Paleobotanical Section at the same time, several other papers of interest reported on coal ball studies, partial coalification of petrified wood, and floras. In Chicago, April 1950, a symposium on Applied Paleobotany was held by the Society of Economic Paleontologists and Mineralogists in conjunction with the American Association of Petroleum Geologists. The five papers presented at this meeting dealt with the use of Paleozoic plant microfossils for stratigraphic work, J: M. Schopf, Devonian-Mississippian fossils of the black shales, Aureal T. Cross, Mesozoic plants of stratigraphic value, Th. Just, plant microfossils of the Tertiary, L. R. Wilson, and studies of the Brandon lignite, Elso S. Barghoorn. Early publication of these in the Journal of Paleontology is expected. The Nova Scotia Research Foundation and the Nova Scotia Dept. of Mines sponsored an excellent 3-day conference in June 1950, which, dealt with several aspects of coal geology. Papers on coal classification, P. A. Hacquenbard, structure and sedimentation problems in Nova Scotia, T. B. Haites, new techniques of thermal analysis, W. L. Whitehead, geochemical investigations of Nova Scotia coals, Irving Breger, the role of fossil plant spores in coal correlation and the stratigraphy of the coal-bearing strata of the Appalachian Region, Aureal T. Cross, were given. Some discussions of these papers by those in attendance were recorded, and the entire proceedings is being prepared for publication. In September 1950, an unusual 3-day field conference was held by the Ohio and West Virginia Geological Surveys under the sponsorship of the Coal Geology Committee. This study of the stratigraphy sedimentation, and nomenclature of the Upper Pennsylvanian and Permian coal-bearing strata of southeastern Ohio, southwestern Pennsylvania, and northern West Virginia .was augmented by two discussions on associated rocks (clays and shales) and stratigraphic nomenclature at Wheeling, and Morgantown, West Va. An extensive guidebook was prepared, and transcriptions of the Morgantown meeting were made. As a follow-up of the September field conference, a round-table discussion 'was held on this general topic at a special open meeting of the Coal Research Committee in conjunction with the November meeting of the Geological Society in Washington. Short prepared statements to invite discussion were given on each of several topics by L. M. Cline, Carl O.

Jan 1, 1952

New York Meets first Wednesday after first Tuesday of each month. DAVID H.-BROWNE, Chairman, JOHN H. JANEWAY, Vice-Chairman. F. E. PIERCE, Secretary, 35 Nassau St., New York, N. Y. P. A. MOSMAN, Treasurer. LEWIS W. FRANCIS. Boston Meets first Monday of each winter month. HENRY L. SMYTH, Chairman. . ALFRED C. LANE, Vice-Chairman. HENRY A. WENTWORTH, Secretary-Treasurer, 60 India St., Boston, Mass. ROBERT H. RICHARDS, ALBERT SAUVEUR. Columbia Holds four sessions during year. Annual meeting in September or October. FRANK A. ROSS, Chairman. RUSH J. WHITE, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P O. Drawer 2154, Spokane, Wash. FREDERIC KEFFER, FRANCIS A. THOMSON.

Jan 11, 1915

New Products Equipment

Jan 11, 1950

By Joseph B. Story, John T. Clarke

A modification, of the Kelvin bridge using an inductor was used to measure the conductivities of molten sodium chloride, calcium chloride, and mixtures thereof. A capillary-type four-lead fused quartz dipping cell was constructed. The effect of a small amount of potassium chloride on the conductivity of the melt was determined. IN the electrowinning of sodium and chlorine from sodium chloride in Downs cells, calcium chloride is added to the sodium chloride in an approximately equimolar amount to permit cell operation at a lower temperature. This lower temperature improves current efficiency and ease of operation, but decreases voltage efficiency by decreasing the electrical conductivity of the melt. A knowledge of the electrical conductivity of the Downs cell melt is necessary to the understanding of Downs cell operation, for the IR voltage drop across the melt is responsible for a significant part of the electrical power consumed by the cell. The work of previous investigators on fused sodium chloride-calcium chloride mixtures was reviewed from the standpoint of consistency with the results of others on the conductivities of the pure constituents. The electrical conductivity of pure fused sodium chloride has been established with accuracy by Van Artsdalen and Yaffe,1 by Edwards, Taylor, Russell, and Maranville,2 and by Lee and Pearson.3 It has also been studied by a number of other investigators.4-13 The best values for calcium chloride are believed to be those of Lee and Pearson,3 since the sodium chloride and potassium chloride conductivity values given by them check the best literature values. A number of other investigators have also reported values for calcium chloride.'-"."' Electrical conductivity data for fused sodium chloride-calcium chloride mixtures have been reported by Sandonnini,12 Vereshchetina and Luz-hnaya,18 Ryschkewitsch,11 Barzakovskii,5 and Alaby-shev and Kulakovskaya.15 Sandonnini reports no data at temperatures lower than 850°C. The conductivity values reported by Vereshchetina and Luz-hnaya, by Ryschkewitsch, and by Barzakovskii for pure sodium chloride and for pure calcium chlor- ide vary somewhat from the literature values believed to be best and the sodium chloride-calcium mixture data of these authors and of Alabyshev and Kulakovskaya (who give no data for the pure compounds) show significant variations. In view of these facts, it seemed that an investigation of the electrical conductivities of fused sodium chloride-calcium mixtures would be worthwhile. Apparatus Bridge System—The bridge used,in this investigation is diagrammed in Fig. 1. In general, the elaborations of this bridge over the simple Wheatstone bridge were for the purposes of a) eliminating lead resistances or making them accurately measurable, and b) eliminating major capacitative and inductive effects or balancing them against each other. Lead resistances in the lower arms of the bridge were kept as low as possible by making the leads short and of low resistance wire. This could not be done in the cell arm of the bridge because of the remoteness of the cell from the other bridge components and because of the high-resistance nickel or chrome1 wires used in the cell. Since maximum sensitivity is attained when the resistances of the four arms of the bridge are equal, 50-O resistors were used in the lower arms of the bridge when fused salt conductivities were being measured, and 1000-O resistors were used when the cell was being calibrated with normal aqueous KCl solution. The cell resistance was of the order of 50 ohms with fused salts and of the order of 1000 ohms with normal aqueous KC1 solution. The resistors used were non-inductive and accurate to 50.05 pct (General Radio Co. Types 500-C and 500-H). The lead resistance between point A in the cell and point E at the measuring resistor was eliminated by using the kelvin bridge principle; that is, the voltape drop across the lead from point A to point E was divided between the cell arm of the bridge and the measuring arm of the bridge in proporation to the resistaxes in the lower arms of the bridge.

Jan 1, 1958