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By Brison Robertson, W. P. Fishel

The carbide-forming tendencies of the various steel-alloying elements, or their affinities for carbon, is a subject that has received considerable attention, but little more than a probable arrangement of the elements as to their carbide-forming tendencies has been proposed. The physical properties of alloy steels depend upon the relative proportions of the elements present and their combinations. one important phase of this subject is the distribution of carbon between the various elements present. The distribution of car. bon between iron and other elements evidently sill depend upon: (I) the affinity of each for carbon; (2) the relative atomic masses of the elements present; and (3) the possible formation of compounds between the alloying and iron and between the elements themselves, In ternary steels the case is simplified, especially in systems in which the element and iron form no compounds, In such systems iron and the alloying element are competing for the carbon present. In this work the distribution of carbon between titanium and iron has been studied by measuring the relative amounts of iron carbide and titanium carbide present ill a series of annealed steels in which the ratio of titanium to carbon extended from 0.527 to 4.61. Ten Fe-Ti-C alloys, weighing about 250 grams each, were prepared by melting under a Vacuum, in an Induction furnace, Armco iron, carbon-free ferrotitanium (25 per cent Ti), and pure carbon. Vacuum melting prevented the formation of titanium oxides and nitrides, which would the the problem. The melts were made in graphite crucibles lined with sintered magnesium oxide. The ingots were the in the furnace under a vacuum and "'ere then completely annealed at 950°C. The determination of the amount of titanium carbide present was based upon the established insolubility of titanium carbide in boiling dilute (1:4) sulphuric acid, and the complete solubility Of free titanium and titanium-iron compounds in this acid. High-carbon ferrotitanium, which had been treated to remove free Ti and Fe. was found to be completely insoluble in the acid; and the carbon-free ferrotitanium used in making the alloys was found to be completely soluble. Others have reported the insolubility of titanium carbide in sulphuric and hydrochloric acids. Turnings from the ingots were digested with boiling sulphuric acid (1:4) until all action had ceased. The carbide residue was filtered off and analyzed for titanium, and in some cases for carbon. This represerifs the titanium that was united with carbon The filtrate from the carbide residue contains the portion Of the titanium that was in solid solution in the ferrite. Titanium

Jan 1, 1945

By Gerhard Derge, Arthur H. Grobe, Harold Markus

The high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as tcrne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys. 1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. Apparatus and Method The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from M to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. + 0.1". Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By Harold Markus, Arthur H. Grobe, Gerhard Derge

The high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as tcrne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys. 1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. Apparatus and Method The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from M to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. + 0.1". Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By Arthur L. Christenson, Clarence E. Jackson

IN the establishment of the relationship between weldability and hardenability, two methods have been employed in correcting for the grain growth produced in the heat-affected zone: first, the hardenability calculated from chemical composition1 may be corrected to the grain size observed in an actual weld,2 or, second, a hardenability test may be made on the steel quenched from a temperature high enough to produce a grain size comparable to that found in the heat-affected zone.3 In order to obtain grain sizes in the end-quench hardenability bar comparable to those resulting in the base metal from the welding cycle, a quenching temperature of 2100°F. has been used. In studies of the end-quench hardenability specimen quenched from 2100°F. instead of from a lower temperature of 1700°F., it is important to ascertain the relative cooling rates for various distances along the bar. It is a question as to whether the cooling occurs at the same rate or whether there is any significant difference from the standard cooling-rate curve published by Jominy and confirmed by others.4,5 This paper reports experimental evidence concerning the effect of quenching temperature on the cooling rates in the end-quench hardenability test. The effect of quenching temperatures on cooling rates has been studied by a number of investigators.6,7 French has considered this effect from both theoretical and experimental aspects. In French's studies on complete quenching of spheres and rounds, an increase in the quenching temperature caused an increase in the cooling rate at 720°C. at the center of the specimen. The center cooling velocity also has been shown to be dependent upon the surface per unit volume for the type of specimens studied; the velocity of cooling increases with an increase in the surface per unit volume. Three methods of indicating the rapidity of cooling of a body of metal during a quenching operation have been proposed: I. The time it takes for the metal to cool from the quenching temperature to a temperature halfway between the quenching. temperature and the temperature of the quenching medium (half-temperature time): Grossmann, Asimow and Urban7 justify the use of this criterion by the fact that the half-temperature time includes the temperature and time of incubation as well as the zone of formation of pearlite and, further, the data so derived accord very closely with experimental values. 2. The time interval the metal remains in a given temperature range; for example,

Jan 1, 1943

By L. D. Fetterolf, G. T. Mahler, W. M. Peirce, R. K. Waring

UNTIL recently, the only commercial method of producing magnesium has been fused salt electrolysis, despite a considerable amount of experimental work on the direct reduction of magnesium oxide. In this early work, a number of investigators demonstrated that magnesium oxide would react with any one of several reducing agents to produce magnesium vapor, but that the mixture of magnesium oxide and reducing agent must be heated to a high temperature even in a vacuum. In particular, it was demonstrated that silicon and aluminum are effective reducing agents and that when either of these is used the magnesium vapor can be condensed to massive metal. In spite of this knowledge, no successful commercial reduction process was developed, at least in this country, because of the operational difficulties imposed by the requirement of high temperature and vacuum and because of the high cost of the reducing agent. The outstanding experimental work done by Pidgeon, who carefully reviewed all of the known methods of making magnesium and then selected ferrosilicon reduction, overcame some of the operational difficulties. The process developed by Pidgeon comprises briquetting a mixture of calcined dolomite and reducing agent, pre-heating the briquets to about 600°C. in an externally heated alloy retort, reducing the MgO with silicon in an evacuated horizontal alloy retort heated externally to about 1150°C., and condensing the magnesium vapor to a solid in a cold extension of the retort projecting beyond the fr6nt of the furnace. A major advantage of Pidgeon's process is that the retort is not cooled down between charges. Earlier investigators had used apparatus that necessitated cooling and reheating of the retort between charges. Early in January 1942, when the War Production Board was considering the Pidgeon process for quickly increasing the production of magnesium, The New Jersey Zinc Co. offered to have a research investigation of the process carried on, with the hope of assisting in its further development. This offer was accepted, and a two-retort pilot plant was built at Palmerton and put in operation on Jan. 29, 1942. An intensive investigation of certain phases of the process was carried out in the ensuing four months. This investigation was completed in the last part of May 1942, and the pilot plant was then shut down. Subsequently, The New Jersey Zinc Co. was requested to have further development work done on the process, and a more extensive investigation was undertaken in August I942 under contract with the War production Board and under the super- vision of the War Metallurgy Committee. This paper describes the phases of the investigation that are thought to .be

Jan 1, 1944

By D. Weinstein, F. C. Holtz

AS a possible method of improving the elevated temperature strength properties of zirconium, an investigation was initiated on the feasibility of producing a dispersion-strengthened material. Because of the high reactivity of zirconium, its high solubility for oxygen, and the stability of the Zr-0 solid solution, the major problem in such a development is choice of a suitable dispersant. Thus, in the present investigation we were concerned primarily with the stability of various dispersants in the zirconium matrix. The experimental procedure consisted of blending powders of zirconium and a dispersant, followed by cold compaction and extrusion. The best available source of -325 mesh zirconium powder contained between 1500 and 3500 ppm Oz; to this material, powders of zirconium carbide (5 p max), vanadium carbide (5 p max), alumina (0.03 p average), lan-thana (0.8 to 2 p), ceria (0.8 to 2 p), yttria (0.8 to 2 p), calcia (44 p rnax), or thoria (0.6 to 0.8 p) were added in amounts of 7 vol pct and compacted at 65 tsi. A cylindrical compact having a density between 70 and 80 pct of theoretical and dimensions of 1 in. diam by 1-114 in. high was thus produced. After canning in copper, these billets could be extruded (5: 1) on a 54-ton capacity, slow-traverse hydraulic press with the billet temperature at 1550°F and the extrusion die at 900°F. However, lack of densifica-tion of some of the extruded billets necessitated ratios of at least 23 :1. Ultimately, all billets were successfully extruded at 1500°F to 0.190 in. diam (32 :I), fully dense rods using a 200-ton capacity press and a ram speed of 90 ipm. The microstructures of as-extruded Zr-7 vol pct LazOS and Zr-7 vol pct Y2Os are shown in Fig. l(a) and (c), respectively. These structures are similar to all the as-extruded materials and consist of an elongated, single-phase zirconium matrix dispersed with oxide or carbide particles. Very little porosity is observed, and the interface between matrix and particles appears satisfactory. The size and distribution of particles, however, are not ideally of the type desired for dispersion strengthening. Since the primary study was of particle stability with respect to zirconium, no attempt was made to overcome agglomeration during powder blending and fabrication. Some areas exhibit fine, well-distributed particles; undoubtedly, a small proportion is submicroscopic and has the

Jan 1, 1963

By Gerald Edmunds

In a paper1 before this Institute in 1940, the writer reported that the surface orientation texture of zinc and cadmium differed from the texture existing within the casting, in that basal planes were parallel to the surface. He was unable to rationalize the , origin of this surface texture. It is conceivable that the surface orientation texture is influenced by the atomic force fields, which are different at the surface and within the body of metal. It was considered that a radical changc in the surface against which the metal is cast might alter the surface texture. In trial of this, zinc has been cast against a surface of molten lead, but the same result has been obtained—i.e., (001) parallel, ± 2oo, to the surface—as was obtained when it was cast against air, Transite or iron.' Into the bottom of an open cast-iron tray, 7 by 14 in. by 2 in. deep, preheated to about 275°C., about 1/4 in. of lead, then 1/2 in. of zinc was poured, and the whole was covered with an electric heater to enforce freezing from the bottom upward. After a lapse of time sufficient for the zinc but not the lead to solidify, the zinc slab was raised free of the molten lead. The bottom surface of the zinc casting was coated with a thin layer of lead. A specimen of the slab 136 in. square was metallographically polished to flatten it and remove the slight film of lead, and the orientation was determined by the method used before,' with the result stated above. Some determinations have also been made on other metals, as follows: Surface orientation determinations were made on the 3/8-in. diameter grip section of two 1/4-in. diameter aluminum-alloy die-cast tensile bars and on a 1/8 by 1/2-in. flat aluminum-alloy die-cast tensile bar. None of these three aluminum die castings exhibited any preferred orientation at the surface. A brass die casting (nominal composition: 60 Cu, 37.75 Zn, 1.00 Sn, 1.00 Pb, 0.10 Al, 0.15 Si) furnished by C. S. Smith was also examined. The surface showed a random orientation of alpha and beta. Summary A zinc casting solidified against a molten lead surface was found to have the same surface orientation texture, (001) parallel to the surface, as other zinc and cadmium castings. Aluminum and alpha-beta brass die castings were found to have random grain orientation textures at the surface. Acknowledgment The X-ray determinations were conducted by M. L. Fuller.

Jan 1, 1945

By J. W. Craig, H. L. Walker

Industry has for many years recognized the dependence of certain mechanical and physical properties. as well as workability, upon grain size variations in brass. Although the dependence of properties upon grain size has been recognized there are not many instances where a planned program of testing has been conducted and where the only intentional variable has been grain size. In particular the literature is limited with respect to the effect of grain size on the endurance limit, though there are many industrial applications where the brasses are subjected to cycles of repetitive stresses. Literature A number of the physical and mechanical properties of a given brass sheet, in the annealed condition, will depend upon: (I) The ready-to-finish grain size before final rolling, (2) the percentage deformation by cold working, and (3) the time and temperature of annealing. The first and second variables affect the recrystallized grain size, and the third variable affects the coalesced grain size. Gibbsl has shown the effect of two different ready-to-finish grain sizes upon the tensile strength and hardness of deep drawing brass strip after a definite amount of cold rolling. The smaller the ready-to-finish grain size, the higher the tensile strength and hardness, but with lowered ductility, Gibbs also demonstrated, for a given time and temperature of anneal, that the tensile strength, hardness, and elastic limit are higher for the smaller ready-to-finish grain size, but the elongation is lowered. Townsend and Greena112 have reported data which show that cold working increases the tensile strength, hardness, and load carrying ability of deep drawing brass sheet under reversed stress. Greenall and Gohn3 have reported data which show that the smaller grain sizes have higher tensile strength and hardness properties, and the data also show that increased cold working increases the tensile strength and hardness properties of deep drawing brass sheet. Kommers4 has reported data for tests of brass of known ready-to-finish grain size, a specific amount of cold reduction, and annealed at different temperatures above and below the recrystallization temperature. Kommers' results indicate that annealing below the recrystallization temperature does not change the tensile strength and hardness properties, but the endurance limit may be increased from 22,000 to 28,000 psi. The increased endurance limit is explained as resulting from the reduction of internal stresses by a stress-relief anneal. Burghoff5 and associates have reported data on creep tests, over

Jan 1, 1949

By H. E. Dunn, C. M. Cosman, J. H. Brennan

Up to the beginning of World War I, the American ferro-alloy industry was in its infancy and largely dependent on Europe. During that War, capacity was over expanded. Later recovery and commercial and scientific development have resulted in an industry which in 1957 produced 1.8 million tons of ferro-alloys. THE ferro-alloy industry is today an important element of the industrial structure of the United States. Its output is valued at almost half a billion dollars annually and its products are basic not only to National defense but also to the peacetime standard of living. This has not always been so. The ferro-alloy industry from late in the last century has grown from small beginnings, nurtured by the demand for stronger, tougher materials; by the search for steels capable of absorbing severe impact loads and resisting corrosive media and high temperatures; and also by the need for electrical and electronic specialties. Conversely, the ferro-alloy industry has grown because it developed improved steels and alloys by extensive research, and because it was able to show to steel makers the advantages accruing from the more extensive and the more economical use of alloying elements. The industry has grown in scope from producing a few grades of ferro-alloys of the more common metals-manganese, chromium, vanadium, silicon, titanium, tungsten, and molybdenum-until there are today some 150 compositions of ferro-alloys available to the steel maker, including such elements as columbium, zirconium, and boron. In 1912 the industry produced 360,000 tons of alloys valued at about $12,000,000, while 1957 production figures show an output of 1.8 million tons worth $440,000,000. In the United States, the history of an industry is largely the history of the companies making up this industry; hence, this paper will briefly trace the development of the most important ferro-alloy-producing companies. Quite varied have been the reasons that caused the different companies to move into the ferro-alloy field; the Willson Aluminum Co., seeking methods of producing aluminum, succeeded with the production of calcium carbide, and their developing electric furnace skills led them to the production of ferro-silicon and ferrochromium alloys. Willson was the predecessor of the Electro Metallurgical Co. of Union Carbide. Two Pittsburgh undertakers, interested in vanadium as an alloying agent for steel, set about to find a mine and, ranging as far as Peru, fathered American Vanadium Co., the predecessor of Vanadium Corp. of America Experiments of the

Jan 1, 1961

By Henry R. Joesting

DURING the past year and a half, the Territorial Department of Mines in Alaska has conducted a modest experimental program for the purpose of determining the extent to which magnetic and resistivity methods can be used in interior Alaska in connection with prospecting, mining and geological studies. Since little information is available concerning previous work,1,2 and since conditions differ considerably from those in most other regions, it was considered advisable to make a general study of the possibilities and limitations of the two methods, rather than a detailed study of any single problem. PROBLEMS One of the most serious handicaps to prospecting and geological study in interior Alaska, especially in the mature regions, is a cover of unconsolidated deposits ranging in thickness from a few feet to several hundred feet. These deposits, some of which are permanently frozen, consist of silt with varying proportions of vegetation and windblown material in the valleys and of residual deposits on the hills.3,4 The problems treated here are caused by the existence of this overburden: I. Location of buried placers. 2. Determination of depth and areal distribution of permanently frozen and of thawed unconsolidated deposits. 3. Location of water-bearing beds under unconsolidated deposits. INSTRUMENTS AND METHODS Magnetic and direct-current resistivity methods were used because they are relatively simple, rapid and inexpensive and because generally they are well suited to the study of the problems indicated. The instruments used were a vertical Schmidt-type magnetometer and a direct-current resistivity instrument similar to those used by the Geophysical Branch of the U. S. Geological Survey.5 For placer surveys with the magnetometer, a sensitivity of about 25 gammas per scale division was found suitable. For resistivity studies of frozen and thawed overburden and of underground water, the Lee partitioning method6 was found to be most generally suitable. In the Lee method a central potential electrode is placed midway between the two potential electrodes of the Wenner four-electrode configuration.7 Nonpolarizable electrodes were made from unglazed porcelain pots about 10 cm. high and 5 cm. in diameter. In order to retard evaporation of the electrolyte the sides of the pots were glazed, inside and out, with clear Duco lacquer. For resistivity work in cold weather, a nonfreezing electrolyte consisting of equal parts of ethylene glycol and a saturated water solution of copper sulphate proved satisfactory. Stainless steel rods of 3/4-in. diameter made excellent current electrodes because their bright finish enabled good ground contacts to be made.

Jan 1, 1941

By B. A. Cheadle, C. E. Ells

The ovienlalion of hexagonal a-zirconium crystals in cold-drawn Zircaloy-2 tubes and in both as-extruded and heat-treated Zr-2.5 wt pcl ND tubes has been rrleasured using the inverse Pole - figure technique. Uniaxial tensile tests hare shown the Zil-caloy-2 lubes to hare highly anisotropic delovmation behavior whereas heat-treated Zr-2.5 wt pet Nb tubes are nearly isotropic. The differences in deformation behavior are esbloilred from the observed textures of the tubes and the deformation systems known to oberate in Zircnloy,-3. Tlze vcsults lead to an explanation of the high effective strain observed fov the Zircaloy-2 tubes as colrzpared to heat-treated Zr-2.5 wt pet Nb tubes in restrained end burst tests at 280° to 300°C. THE Zr-2.5 wt pct Nb alloy. when heat-treated by quenching from temperatures slightly below the (a + p)/P phase boundary and subsequently aged at 500°C, has tensile strengths about 50 pct greater than those of 20 pct cold-worked Zircaloy-2.1 There is. therefore, considerable economic incentive to replace Zircaloy-2 with the heat-treated alloy in some in-reactor applications. notably for pressure tubes, where strength is a prime consideration. However, when tubes of Zr-2.5 wt pct Nb fabricated by extrusion and drawing prior to heat treatment were subjected to restrained end-burst tests at 300 °C. the circumferential expansion at failure1 was only 10 pct that of cold-drawn Zircaloy-2 tubes in similar tests,2 Table I. This result was not predicted from uniaxial tensile tests in which the ductilities of the two materials were quite similar.' The detailed requirement for ductility in pressure vessels has not yet been worked out. and comparison of the relative merits of cold-worked Zircaloy-2 and heat-treated Zr-2.5 wt pct Nb is further complicated by the irradiation-induced loss of ductility and hydrogen pickup each will undergo from reactor operation.1,2 Nevertheless. the lower circumferential expansion of the Zr-2.5 wt pct Nb tubes raised serious doubts on the advisability of their use as pressure vessels. For this reason, an investigation to determine the cause for different ductilities of the two types of tubes was initiated. From a study of uniaxial tensile properties and crystallographic orientation it has been found that the fracture ductilities observed in the burst tests can be related directly to the crystallographic ori-

Jan 1, 1965

By Paul B. Crawford, Bobby L. Landrum

Electrical model studies have been made of the effect of unsymmetrical vertical fractures on production cnpacity. The study war restricted to the case of two vertical fractures originating at the well and extending out into the reservoir for various distances and orientations. The ratio of the short fracture length to the long fracture length was varied from 0.1 to 1.0 in successive studies. The angle separating the two fractures was varied from 0 to 180 degrees. The most effective fractured patterns were obtained when the fractures were oriented 180 degrees. It was found that when the total fracture length was equal to 0.2 of the drainage radius, the increase in production capacity may vary from approximately 1.55 to 1.95. depending upon the ratio of the short fracture length to the long fracture length and the angle separating the two fractures. If the total fracture length were 0.5 of the drainape- radius. poroduction cavacitv., increases varving 1.95 to 2.65 were observed, depending on the angle between the fractures and the ratio of the .short fracture length to the long fracture length. The fractured well production capacity decreased aPproxin?ately I to 10 per cent as the angle separating the fractures was varied from 180 to 90 degrees. It was dependent on the particular fracture. The commercial application of reservoir fracturing techniques has caused an interest to be expressed in the effect of vertical and horizontal fractures on production capacities. Some data have indicated that substantially vertical fractures may be created in some reservoirs. It is believed that the fractures are possibly unsymmetrical, that is, one fracture may extend due north 100 ft and a second fracture on the opposite side of the well may extend south or southeast only 50 ft. The total fracture length, ratios of the lengths and angles of separation may vary considerably. For this reason variations in these factors were considered. The study was restricted to the case of two vertical fractures originating at the well and extending out into the reservoir. It is not known that such will occur in a reservoir, but the results may be of value in interpreting or studying fracturing applications. PROCEDURE An electrical model was used in this study of the effect of unsymmetrical vertical fractures on production capacity, A wooden tank 30 in. in diameter and approximately 2 in deep was coated with paraffin wax. A copper band was situated at the periphery and a single wire electrode was positioned at the center of the tank. The ratio of the reservoir radius divided by the

Jan 1, 1956

By O. N. Cole, R. E. Davis, T. D. Brotherton

Pvfoperties of rubidium and cesium are compared with those of other alkali metals. Methods for the preparation of rubidium and cesium metal are reviewed briefly, ad hazards and safety precautions required in handling rubidium and cesium metal are described. SimPle methods for handling laboratory quantities of elemental rubidium ad cesium under oil and under argon are illustrated. CESIUM and rubidium were both discovered by Bunsen and Kirchoff in the years 1860 and 1861. Cesium was discovered while Bunsen and Kirchoff were making a spectrographic study of spring water from Durkheim, Germany. It was the first element discovered by this technique. The element was given the Latin name "caesius" for sky blue because of the color it imparted to flames. Elemental cesium was first prepared by Setterberg in 1881 through electrolysis of a molten mixture of cesium and barium cyanides.' In 1861, Bunsen and Mirchoff discovered rubidium while making a spectrographic study of the alkali content of lepidolite ore from Saxony. Two prominent dark red lines appeared in the spectrum and so the element was named "rubidius" or dark red. In 1861 Bunsen and Kirchoff first prepared elemental rubidium through the electrolysis of molten rubidium chl~ride.~ The alkali metals are very similar in their chemical and physical properties. They are the most active metals, and all exhibit a single oxidation state of one. They are so reactive that they are never found in nature in the elemental state. The reactivity of he metals increases with atomic number. Rubidiurn and cesium ignite spontaneously in air and react explosively with water. This extreme reactivity makes necessary special equipment and techniques for the safe preparation and use of the metals. The cation: of Group IA can be separated from the metallic cations of other groups with relative ease, but the separation of the individual alkali cations is much more difficult because of their close chemical similarity. This close chemical and physical similarity of alkali metals can be inferred from the atomic radii, oxidation numbers, and ioni-zation potentials shown in Table I. A difficult but the most practical physical method of separating the elemental alkali metals from one another is by distillation. Only lithium has a boiling point sufficiently far-removed from the boiling points of the other alkali metals to make this method of separation feasible without elaborate and expensive equipment. This method is not used, however, for lithium because it possesses sufficient chemical dissimilarity from the other alkalies for it to be separated relatively easily as lithium hydroxide monohydrate or as lithium carbonate. Francium, the last member of the group, has no known stable isotopes. The naturally occurring

Jan 1, 1962

By I. Fatt

Networks of resistors are used as analog computers to obtain relative permeability and resistivity index curves for networks of tubes. These curves have all of the characteristics of those obtained on porous media and, therefore demonstrate the validity of the network of tubes model. INTRODUCTION In paper I' of this series the network model was shown to give information on the structure of porous media that could not be obtained from the bundle of tubes model. The agreement between the capillary pressure characteristics of a network of tubes and those of typical porous media does not prove the validity of the network made. The bundle of tubes model, although it gives less information, also shows this agreement. In this paper the flow properties of a network of tubes are shown to be in agreement with flow properties of porous media. The flow properties of the bundle of tubes model are not in adequate agreement with those of porous media. The dynamic properties of porous media, such as fluid permeability and electrical conductivity, have been found experimentally to be more sensitive functions of structure and pore size distribution than are the static properties such as porosity and capillary pressure characteristics. The network model can, therefore, be best tested by comparing the dynamic properties of a network of tubes with the observed properties of porous media. All static and dynamic properties of a completely valid model must agree with the observed properties. The most commonly measured sensitive dynamic properties are the relative fluid permeability and the relative electrical resistivity. Experimental measurements of these dynamic properties on sandstone, sintered glass, sintered alumina, and soil are reported in the petroleum and soil science literature. These properties were chosen, therefore, for the test of the network model. In the network model, relative permeability is the permeability of the network when some of the tubes are not conducting fluid, relative to the permeability when all tubes are conducting fluid. Similarly, the relative resistivity is the electrical resistivity of the network of tubes when some of the tubes are filled with a nonconductor. relative to the resistivity when all tubes are filled with the electrical conducting fluid. Single Size Tube Network The simplest porous medium is one in which all pores are of the same size. Such media can be approached by packing beds or columns of uniform size particles of sand, glass, or metal. The model of such medium in this study is a network of single size tubes. The network form, the ß factor, is usually not known for real porous media. If the validity of the network model can be established, then the study of the flow properties

Jan 1, 1957

By N. Tiner

IN an article on magnesium and its alloys, Gann and Winston1 stated that manganese has a limited solubility in the liquid state. W. Schmidt2 showed a diagram according to Joseph Ruhrmann indicating that the solubility of manganese in liquid magnesium falls from about 2.65 per cent at 790°C. to about 0.5 per cent at 695°C. The curve was extrapolated to show zero solubility at the melting point of pure magnesium (Fig. I): This work suggested that at the lowest manganese contents it was not possible to detect either a eutectic or the formation of a solid solution, so that manganese was stated to be present in the structure as large individual crystals. Two years after the presentation of these results, Gann3 brought evidence to show that some manganese is capable of dissolving to form a solid solution, any excess of manganese present then assuming chiefly the form of small blue-gray particles scattered throughout the primary magnesium crystals, occasionally in clusters but seldom at the boundaries. He presented micrographs of cast alloys containing o.1, 0.4 and 1.0 per cent manganese that show a small amount of coring around the individual particles due to solid solution, and indicate that the location of the manganese particles is closely associated with the original dendritic structure of the primary crystallization. He also pointed out that the amount of manganese that can be dissolved in magnesium depends on the amount of other alloying elements present, the effect of the second alloying element being to decrease the amount of manganese retained in the alloy. E. Schmid and G. Siebe14 have determined the solid solubility of manganese and its variation with temperature by means of precision X-ray diffraction measurements. They found that the solubility is 3.4 per cent at 645°C and decreases to practically zero at 200°C. It is apparent that the X-ray diffraction measurements of Schmid and Siebel are not in agreement with the results of Ruhrmann as presented by Schmidt. This disagreement, and also the lack of data on magnesium-aluminum-manganese and magnesium-zinc-manganese systems, led the author to the present investigation, to determine accurately the liquid solubility of manganese and its variation with temperature. EXPERIMENTAL METHOD The experimental method for making solubility determinations consists of saturating the molten magnesium or the alloys with manganese at various temperatures and analyzing the dip samples taken from these melts. Melting is carried out in a cylindrical steel pot heated by an electric resistance furnace. The pot had a metallic outside coating to protect the steel against oxidation, and a graphite inside lining to prevent the contamination of the melt by prolonged contact with iron. The inside diameter of the pot was 4 in. and the depth 12 inches.

Jan 1, 1945

By P. C. Claspy, P. H. Smakula

The electro-optic coefficients of LiNbO, and KTao.,5Nboe3,O3 (KTN) have been experimentally determined at the HeNe laser wavelengths of 0.6328, 1.15, and 3.39 µ. The coefficients were calculated fronz the retardation induced by an applied electric field. The retardations were measured by observing one or move transmission maxima and minima as a function of the applied field, and by measuring the retardation directly with a Babinet-Soleil compensator. The values obtained agree quite well with those previo~lsly reported by others. Extinction ratios as high as 3000:l have been observed. Resistivities and Curie temperatures have also been measured. Light-induced optical inhornogeneities in LiNbO, repovted by others have been observed. CONSIDERABLE interest has recently been shown in the electro-optic properties of LiNb03 (Refs. 1 and 2) and KTN.3, 4 These crystals have a number of advantages over such well-known materials as KDP. These advantages include: 1) the infrared transmission of KTN and LiNb03 extends to 5 p whereas that of KDP cuts off at 1.5 p ; 2) driving voltages required for modulators using these materials are considerably lower than those required for KDP. After first discussing some theoretical considerations of the electro-optic effect, we will report the results of measurements of the dc electro-optic coefficients of these materials at wavelengths of 0.6328, 1.15, and 3.39 p. THEORY The generalized equation for the electro-optic effect can be written: Although lattice polarization is the fundamental variable, rather than the applied electric field, we follow the convention of expressing the linear electro-optic effect in terms of the applied field. For LiNbO the quadratic terms are negligible. Since KTN has a center of symmetry the rijk tensor is 0. After applying the usual symmetry considerations and index contractions,* the rijk and gijkl tensors can be expressed as follows: LiNbOaT If field directions are now chosen, the change in refractive index and the angle between the induced optic axes and the crystallographic axes can be found. The induced rotations of the principal axes of the index ellipsoid for fields in principal crystallographic directions are given in Table I. Since KTN is initially isotropic, the principal axes in the zero-field condition are parallel to the crystallographic axes. The induced retardations are given in Table 11. EXPERIMENTAL We obtained the various electro-optic coefficients by measuring the induced retardation as a function of

Jan 1, 1968

By S. G. Valentine

BLAST-FURNACE blowing engines are broadly of two main types: either steam- or gas-driven reciprocating engines, or turbine-driven rotary engines. Some results of experience with a furnace blown by an engine of the latter type may be of sufficient general interest to relate. The first engine of this type was installed at Oxford Furnace, New Jersey, before the writer's connection with this plant, in March, 1910. This furnace uses chiefly New Jersey magnetites and had been in blast seven months on its old engines when the turbo blower was started. It was 80 ft. high by 17 ft. 6 in. bosh and 11 ft. hearth diameter. It is of interest to see from the records what happened when the turbo engine was put to work. But of course, as the old blowing equipment was rather antiquated, consisting of two I. P. Morris engines with air cylinders 72 by 72 in., in good running order, however, it is evident that the comparison between their work and that of the turbo blower cannot be interpreted as being between machines that were respectively of equal excellence as representatives of their types. Still the results were gratifying and -interesting. The records show that, with the old engines blowing 13,630 cu. ft: of air per minute, measured by piston displacement, the furnace was working up about 480 tons of stock per 24 hr. and producing an average of 132 tons per day and a maximum of 166 tons. The rotary blowing engine installed was a General Electric Co. machine, the driving end being a Curtis steam turbine and the air end a six-stage rotary compressor, all running at about 1,500 to 1,600 rev. per minute, and having a capacity of 25,000 cu. ft. of air per minute up to 25 lb. pressure, and equipped with an automatic constant-volume variable-speed governor. After running this blower, for a period equal to that covered above by the old engines, at an average rate of 15,000 cu. ft. of air per minute, the furnace worked up an average of about 592 tons of material and produced an average of 170 tons per day. Thus, on an apparent increase of 10 per cent. in the air volume there was an increase of about 23.5 per cent. in the materials worked up and of about 28.8 per cent. in the product. For the first calendar month's operation of the turbo blower, on an average of 15,040 cu. ft of air per minute, there is

Jan 2, 1914

By C. E. Westley, R. R. Beebe

Recent works by Plaksh et al.,1,2 Glembotsky,3 and others have renewed interest in the effects of oxidation on the surface activity of the sulfides. Since considerable supporting data are available on galena-potassium ethyl xanthate, this system is being studied at South Dakota School of Mines and Technology by contact angle measurement, using the technique of McGlashan and McLeod.4 The contact-angle method is well adapted to investigation of the influence of small amounts of oxygen on the establishment of a stable contact angle on galena in potassium ethyl xanthate solution. Samples of massive galena containing less than 0.001 pct Cu, 0.001 pct Ag, and 0.01 pct Zn are mounted in castable plastic and ground and polished manually in a glove box containing the desired proportions of oxygen and purified nitrogen. Oxygen and nitrogen contents of the test atmosphere are determined with an Orsatt analyzer. In this way a reproducible surface is created in contact with whatever oxygen concentration is desired. Water and all reagents are prepared and stored in the test atmosphere. An absorbent is used to control carbon dioxide that might be present. Final polishing is done with levigated alumina on a glass plate. The prepared sample is placed in the test solution and transferred to the contact angle apparatus in a sealed box, and the test is conducted while both sample and solution are maintained under a slight positive pressure of the test atmosphere. Table I gives the results of contact angle measurements made at various 02-Nz concentrations.5 Each value of contact angle is the average of at least six individual measurements made with different bubbles at different locations on the sample surface. A period of 20 to 25 min has been found by preliminary tests to be sufficient to permit develop- ment of maximum angle, and all measurements are made after at least this much time has elapsed. Exposure of prepared samples to pure water under the test atmosphere before exposure to the xanthate results in a small but measureable and consistent reduction in contact angle. This is particularly true in the oxygen-deficient atmospheres; for example, at 2.2 pct O2 such water contact reduces the average angle about 8" from that obtained by immediate testing in xanthate. The general trend of increasing contact angle with increasing oxygen concentration corresponds to the results of Plaksin et a12 The absence of diminish-ment of contact angle at very high oxygen concentration has been attributed to the high concentration of xanthate per unit of galena surface: At oxygen concentrations below 1 pct (the limit of accuracy of the Orsatt analyzer), no contact angle is obtained. Furthermore, no contact angle is obtained at any oxygen concentration in the absence of xanthate. This result seems to be in disagreement with those cited by Plaksin.1 Further work on the interaction of galena and potassium ethyl xanthate or a similar collector as influenced by oxygen is contemplated. The true nature of the interrelation is as yet unknown. For example, it is not known whether the governing oxygen reaction is with the mineral, with the reagent, or with both.

Jan 1, 1961

By Gerald Edmunds

IN a paper1 before this Institute in 1940, the writer reported that the surface orientation texture of zinc and cadmium differed from the texture existing within the casting, in that basal planes were parallel to the surface. He was unable to rationalize the origin of this surface texture. It is conceivable that the surface orientation texture is influenced by the atomic force fields, which are different at the surface and within the body of metal. It was considered that a radical change in the surface against which the metal is cast might alter the surface texture. In trial of this, zinc has been cast against a surface of molten lead, but the same result has been obtained-i.e., (001) parallel, ±20°, to the surface-as was obtained when it was cast against air, Transite or iron.1 Into the bottom of an open cast-iron tray, 7 by 14 in. by 2 in. deep, preheated to about 275°C., about ¼ in. of lead, then) ½ in. of zinc was poured, and the whole was covered with an electric heater to enforce freezing from the bottom upward. After a lapse of time sufficient for the zinc but not the lead to solidify, the zinc slab was raised free of the molten lead. The bottom surface of the zinc casting was coated with a thin layer of lead. A specimen of the slab 1 ½ in. square was metallographically polished to flatten it and remove the slight film of lead, and the orientation was determined by the method used before,1 with the result stated above. Some determinations have also been made on other metals, as follows: Surface orientation determinations were made on the 3/8-in. diameter grip section of two ¼ -in, diameter aluminum-alloy die-cast tensile bars and on a 1/8 by ½ -in. flat aluminum-alloy die-cast tensile bar. None of these three aluminum die castings exhibited any preferred orientation at-the surface. A brass die casting (nominal composition: 60 Cu, 37.75 Zn, 1.00 Sn, 1.00 Pb, 0.10 Al, 0.15 Si) furnished by C. S. Smith was also examined. The surface showed a random orientation of alpha and beta. SUMMARY A zinc casting solidified against a molten lead surface was found to have the same surface orientation texture, (001) parallel to the surface, as other zinc and cadmium castings. Aluminum and alpha-beta brass die castings were found to have random grain orientation textures at the surface. ACKNOWLEDGMENT The X-ray determinations were conduced by M. L. Fuller.

Jan 1, 1945

By Charles Trotter

AN instrument has recently been developed for determining the inclination and azimuthal direction of boreholes. This instrument is known as the Tro-Pari Instrument and is the invention of C. Trotter and G. Pajari of Sudbury, Ontario. DESCRIPTION The instrument is characterized by a unit mounted in gimbals and provided with a clockwork mechanism to clamp a compass to indicate azimuthal direction and simultaneously to clamp the unit in its plumb position to indicate inclination (Fig I). By means of a timing ring suitably calibrated in 5-min divisions, the unit may be set to lock after a lapse of time sufficient to allow the placing of the instrument at the desired point in the drill hole where readings are to be taken. The maximum time lapse obtainable with the instrument designed for use in EX or AX size holes is 1 hr 30 min which is considered to be ample time to lower to the greatest depths that may be drilled with this size of equipment. Larger sizes could be developed for larger diameter holes such as BX and NX sizes or the larger oil-well sizes and a correspondingly greater time lapse could be provided for. Up to the present time only the EX-AX size has been built. OPERATION Assuming a borehole is to be surveyed at 1000-ft depth and assuming it will take 30 min to lower the instrument to this depth, the timing ring is rotated through seven divisions which represent a time lapse of 35 min (5-min leeway) and is then returned to its zero position. This operation imparts energy to a spring which drives the clockwork mechanism. Simultaneously the compass needle is freed to swing to its magnetic north-south position and the encased mechanism is freed to hang plumb within a semicircular portion of the frame which is graduated in degrees after the fashion of a protractor. This semicircular protractor portion has a V-shaped notch at each degree division of its inner periphery. The instrument, now in its free position, is inserted in a bronze container made to suit the size of hole to be surveyed (Fig 2). Soft rubber washers are provided within the container to prevent undue shock. The container is connected to the drill rods with three 5-ft lengths of brass or aluminum alloy rods separating it from the steel rods in order to prevent distortion of the magnetic field. The assembly is then lowered to the desired point where readings are to be taken and is allowed to remain at rest until a period of time has elapsed slightly in excess of the time for which the timing ring was set. In the example cited above, when the 35 min has elapsed the compass needle is locked in its north-south position and the protractor locking pin is extruded and locks in the V notch opposite its plumb position. The device may now be removed from the borehole and it will remain in this locked position in spite of jarring or shak-

Jan 1, 1947