Search Documents

By P. G. Hallof

Only recently has the term Induced Polarization found its way into geophysical literature. Schlumberger first mentioned the possible use of the induced polarization effect in one of his early papers. Later, induced polarization was the subject of several university theses, such as Seigel's at the University of Toronto and Bliel's at the Michigan School of Technology. In addition, a group at the New Mexico School of Mining and Technobgy has done work on induced polarization. There is very little to be found in print on the subject of induced polarization. Several papers have been presented at meetings, the 1958 AIME and SEG* conventions, for instance, on laboratory measurements of the effect and theoretical considerations useful in the interpretation of field results. This paper is the first attempt to present actual field results which show the usefulness of induced polarization as a prospecting technique. There are several phenomena that can cause polarization when electrical current is passed through the ground. In a paper presented at the 1958 SEG* meetings Professor T. R. Madden of M. I. T. demonstrated that only two of these gave rise to appreciable effects. The first is a result of the membrane and diffusion effects in a sandstone that contains appre- ciable amounts of clay minerals. The unbonded charges associated with the clay mineral forma material that passes positive and negative ions with different mobilities. When current is passed through such a system for some period of time, polarization results. The second phenomenon, which gives rise to very much larger polarization effects, is the one used in the new prospecting technique. These effects are a result of the blocking action or polarization of metallic or electronic conductors in a medium of ionic solution conduction. This electrochemical polarization, called "the over-voltage effect" by electro-chemists, occurs whenever electrical current is passed through a volume of rock which contains metallic minerals such as base metal sulphides. This polarization at metallic interfaces in ionic solutions depends upon the chemical energies necessary to allow the ions to continue the flow of current by giving up or receiving an electron from the metallic surfaces. The energy stored in this reaction isanalogous to that stored when a condenser is charged. If a d. c. current flowing through such a system is interrupted, the polarization can be detected as a small, decaying current that flows after the applied current is discontinued. The decaying potential measured is a result of the current flow caused by charges returning to their equilibrium positions from the positions they assumed under the applied potential field. Because of the polarization, there is an excess of change at each metallic interface. There is an alternate method of measurement of the induced polarization effect. The electrical

Jan 1, 1961

By Michael Hoch, Walter C. Wyder

The Cr-Ni system was investigated between 900" and 1400°C and 45 to 100 wt pct Cr. The Cr-Fe system was studied between 1200" and 1385°C and 70 to 100 wt pct Cr. Powdered alloy compacts were produced from high-purity chromium, nickel, and iron poulders. The compacts were sintered in an argon atmosphere and then machined into small, 0.030-in. diam cylindrical specimens. These were then heated by induction in the high-temperature X-ray diJfractwn camem under a helium atmosphere and irradiated with copper Ka radiation. From the results of the high-temperature X-ray diffraction patterns it can be concluded that chromium exists only in the bcc form, and that no eutectoid reaction occurs in the Cr-Ni system in the temperature interval 900" to 1400°C. The X-ray diffraction patterns are in agreement with the Cr-Ni phase diagram of Bechtoldt and Vacher, and Williams. It is possible that chromium undergoes one or more allotropic transformations between room temperature and its melting point. Most of the evidence was gathered from the study of the chromium-rich ends of the Cr-Ni and Cr-Fe binary systems. All the investigations rely heavily on indirect methods: thermal analysis, electrical resistivity, and micro-graphic inspection of quenched samples. In the present work the chromium-rich side of the Cr-Ni and Cr-Fe binary systems is studied, using high-temperature X-ray diffraction techniques. Thus the coexistent structures can be observed directly at temperature. PREVIOUS INVESTIGATIONS ~ansenl shows two possible Cr-Ni phase diagrams 1) a simple eutectic [Liquid =a-Cr(bcc) + y-Ni(fcc)], 2) a eutectic [Liquid+ P-Cr(fcc) + y-Ni(fcc)] and euctectoid [p-Cr(fcc) ==a-Cr(bcc) + yNi(fcc)]. The latter is based on the work of Grant and co-workers.2 Stein and rant'" placed the eutectoid composition at 1215°C and 68 wt pct Cr; their diagram is shown in Fig. l. Similarly, Sully3 also discusses the two proposed diagrams. Price and Grant,4 working on an isothermal section of the Cr-Ni- Fe ternary diagram at 1300°C, made no mention of a ß-chromium phase (fcc). The ß-chromium structure was also reported by Misencik 5 in the Cr-Nb(Cb) system. Williams 6 studied the Cr-Ni system using precipitation techniques. His work included the chromium and nickel solvus lines below 1250°C. He reported no ß structure nor any eutectoid reaction. The solvus lines which he produced were very similar to those of Jette, et al 7 below 1000°C. He concluded that Grant and coworkers2 had misinterpreted their data, and that effects which they had reported were actually due to the rapid and extensive precipitation of the nickel-rich phase. Bechtoldt and vacher8 used sintered powdered alloy compacts in an attempt to find the ß phase. They used metallographic and room-temperature X-ray diffraction techniques and also failed to detect the fcc chromium phase. They attributed the low slope of the chromium solvus at approximately 1150°C as the probable cause of the abundant precipitation obtained. They also stated that the precipitation was the probable cause for the abrupt discontinuities in the thermal analysis and electrical resistivity data which led to the conclusion that a eutectoid reaction existed. Fig. 1 also shows their diagram. Grigor'ev and coworkers9 investigated the polymorphic changes of chromium in the Cr-Ni phase diagram. Using standard microstructural and thermal analysis techniques, they published a phase diagram which contained five polymorphic forms of pure chromium and four eutectoid reactions. They stated that the room-temperature bcc chromium transformed to a fcc structure at 930°C, to bcc at 1300°C, to hcp at 1650oC, and then finally to bcc at 1830°C. The eutectoid reactions were placed at 850°, 960o, 1140°, and 1220°C. Also to be noted was the fact that the uppermost phase, the bcc above 1830°C, was different from the upper phase of Grant and coworkers,2 the fcc above 1840°C. Their eutectoid reactions, temperatures and compositions fall

Jan 1, 1963

By J. L. Jorstad

The hypereutectic Al-Si alloys 390 and A390 have wear characteristics superior to any of the more common aluminum casting alloys. This excellent wear resistance, coupled with good mechanical properties, high hardness, and low coefficient of thermal expansion, has made these alloys candidates for the all-aluminum internal combustion engine, the application for which they were primarily developed. A390 alloy is intended for sand and permanent mold casting, and requires a lower iron ccxltent (0.5 pct maximum) than its die casting companion 390 alloy (0.6 to 1.1 pct Fe). The 17 pct nominal silicon in these alloys provides sufficient quantities of the hard primary silicon phase to assure a high degree of wear resistance, yet little enough of this phase, to minimize the casting and m achining problems associated in the past with the hypereutectic alloys. The mechanical and physical properties of 390 and A390 alloys are competitive with the best of the common aluminum casting alloys with the exception of low ductility. This low ductility is not considered a detriment, since in many applications these alloys replace cast iron. Corrosion resistance is similar to the standard alloys 380 and 333. Numerous parts, of varying degrees of complexity, have been cast of alloys 390 and A390, including engine blocks and heads. The deviations from normal good handling and casting practices that are required for the alloys are those associated with the presence of the primary silicon. To obtain optimum strength and machinability, the molten alloys should be treated with phosphorus to refine the primary silicon phase. Care must be exercised to properly control the pouring temperature and rate in order to minimize primary silicon growth and segregation. AUTOMOTIVE engineers have for years recognized the advantages of lighter weight and better heat transfer that aluminum could offer as material of construction for engine blocks. These advantages alone, however, are insufficient justification for acceptance of aluminum engines by the automotive industry. To be acceptable, an aluminum engine first must pass all tests to which cast-iron engines are subjected, and, in addition, must represent no cost penalty in manufacturing. None of the conventional aluminum casting alloys have sufficient wear resistance to withstand the tests to which cast iron is subjected as a cylinder bore material, and recent attempts to manufacture aluminum engines with cast-in-place iron sleeves could not compete costwise with the equivalent cast-iron engine. The prerequisite to an acceptable aluminum engine seemed to be a casting alloy with a high degree of wear resistance that would eliminate the necessity of cast-in iron sleeves or liners. The hypereutectic A1-Si alloys 390 and A390 have met this challenge.' Combined with modified pistons and a patented cylinder bore surface finish,2 the performance of these alloys in more than 1300 cold start and cold scuff tests, over 3500 hr of dynamometer wear and endurance tests, and more than 350,000 miles of road tests leaves no doubt as to the feasibility of running on bare aluminum cylinder bores. ALLOY DEVELOPMENT The desirable characteristics of the hypereutectic A1-Si alloys have been recognized for some time. Their excellent wear resistance and low coefficient of thermal expansions have been used to advantage in the production of diesel-type pistons in Europe and to a limited extent in this country. The major contributor to the good wear resistance of these alloys is the extremely hard primary silicon phase in the microstructure. Although the percent silicon used experimentally has been much higher, most commercial alloys have ranged from about 14 to 25 pct. Generally, as the silicon content is increased, wear resistance increases, and the coefficient of thermal expansion decreases. With increases in silicon, however, machinability and cast-ability tend to suffer. The development of a satisfactory aluminum engine block material at Reynolds involved the testing and evaluation of many alloys, covering a wide range of silicon contents and numerous variations of iron, copper, magnesium, manganese, and other alloying additions. Castability, mechanical and physical prop-

Jan 1, 1969

By T. S. Plaskett

A striated structure perpendicular to the growth axis was observed by the copper-decoration tech-nique in dislocation-free, .float-zoned silicon crystals. The striations, which were spaced about 100 p apart, fitted the relationship d = f/u , where d is the spacing, f is the growth rate, and u is the crystal rotation rate. Each stria was resolved into an UNDOPED silicon crystals pulled from quartz crucibles by the Czochralski technique usually exhibit a striated structure perpendicular to the growth axis.'-' This structure has been attributed to oxygen segregation, with the oxygen being introduced from the quartz crucible. If the crucible is rotated, the level of oxygen contamination has been reported as high as 10° atoms per cu cm.10 These striations are similar to solute striations commonly observed in doped Czochralski-grown crystals. The periodic nature of the striations is caused by a periodic variation in the growth rate",12 which is attributed mainly to thermal gradients in the melt.13 A finer striated structure14 attributed to constitutional supercooling is sometimes observed between the coarse striae. The oxygen striations have been observed by infrared transmission techniques,' by the copper-decoration technique,' by X-ray diffraction microscopy,6-8 and by 9 p absorption measurements3 on crystals pulled from the melt both with and without dislocations. In this investigation float-zoned dislocation-free crystals were examined by the copper-decoration technique. The level of oxygen for float-zone material is less than 1016 atoms per cu cm the lower limit of detection by 9 p absorption measurement. EXPERIMENTAL TECHNIQUE The crystals were grown by the float-zone process with the rf heating coil outside of the quartz envelope containing the silicon. All float zoning was done under an atmosphere of purified helium. The Dash technique15 was used to grow the crystal dislocation-free. This involves growing the crystal initially with a diameter between 2 and 3 mm and at array of starlike precipitates of copper. The strucLure was not .found at the surface tor a depth of about 1.5 mm, or in a region of similar width ahead of a dislocation network. The structure is postulated to consist of vacancy clusterings or dislocation loops. very rapid rates, about 20 mm per min, for a distance of about 3 cm. The diameter of the crystal is then increased to the diameter of the source of silicon, which in this case was about 19 mm. Because of the arrangement of the apparatus, the zone was passed downward rather than upward, contrary to the standard float-zoning practice. Also, the source was rotated rather than the seed. ziegler17 has made dislocation-free crystals by a similar technique but has passed the zone upwards. The starting material was zone-refined and had a p-type resistivity of 150 ohm-cm. The major impurity was boron; the total impurity excluding the boron was reported by the supplier (Dow-Corning) to be typically less than 2 x 1013 atoms per cu cm. The crystals were examined by the Dash copper-decoration technique18'19—a method in which about 10" atoms per cu cm of copper are diffused at a temperature between 900" and 1000°C into silicon which is then quenched to room temperature. On quenching, the copper precipitates on crystalline defects which are then visible when viewed by transmission infrared microscopy. The photomicrographs shown were taken either of the infrared image tube screen or directly on infrared film. All sections prior to decorating were chemically polished and, for some sections, given a sirtlZ0 dislocation etch-pit examination. After decorating, the samples were mechanically polished. RESULTS A photomicrograph, taken in transmission of a decorated cross section, is shown in Fig. 1. The portion of the section shown is near the surface of the crystal. The entire cross section showed no dislocation etch pits after being given a Sirtl etch treatment. It is seen that the copper precipitated randomly. Each precipitate, as has been reported by others, was found to have a starlike structure.

Jan 1, 1965

By N. H. Emmons

An interesting development of copper blast-furnace construction has been brought about in adapting the blast-furnace to be a "burner" for sulphuric acid making. When the Tennessee Copper Co. first decided to construct an acid-plant, the standard type of brick-top furnace, supported by structural steel, was the only one in use at its plant. All the tests for temperature and strength of gas had been made on these furnaces, and had been satisfactory. When, however, the acid-plant was put on the flue, and the flue had to have a damper put in it to force the gas into that plant, troubles began. The furnaces were fairly tight, and for a few months the work was quite satisfactory. Fig. 1 shows the old type of furnace-top used at the start. It was soon found that this top would not stand the temperatures, particularly when dampered back, as was necessary to force the gas into the Glover towers. The structural steel, of which the furnace skeleton was constructed, warped and twisted so badly that it was not safe to use the furnaccs. This effect is shown by Fig. 2, which is a photograph of old No. 4 furnace, after the brick-work had been removed. It became apparent that a new type of top mas necessary and the engineering force was started on the design of a new furnace-top, with the result that a low top, with brick-lined flues at each end below the feed-floor, leading to the main concrete dust-chamber, was constructed. This furnace, No. 7, is shown in Fig. 3. The charging-doors are made of cast-iron sections, three sections to a door, and three doors to a side. A door to the furnace was made of east copper, but the heat was great that the copper bent readily, due to the jarring of its

Jan 1, 1911

By RICHARD MAIZE

IN this critical period of our history, the coal industry of the nation, faced with many obstacles, performed its work safely during the first ten months of 1943. Thousands of the younger mine workers were inducted into the armed forces of our country and in many instances their jobs have been filled by others without much if any experience and training. This situation alone would seem to be sufficient to interfere with the safe and orderly operation of the industry but the Government's demand for a substantial increase in coal tonnage over that produced in normal times introduced a hazard which always accompanies speed, regardless of the skill of the worker.

Jan 1, 1944

By C. O. Lee, R. H. Feierabend, Z. W. Bartlett

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.'.' Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.' Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.'.' Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.' Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

DESPITE the fact that American brimstone production has increased 2 ½ times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.1,2 Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.4 Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the caprock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1952

By S. E. Bronisz, Dana L. Douglass

a Uranium was deformed by cold rolling, and the effects of this plustic deformation on the microstruc-ture of the metal were observed by the technique of transmission elecbon microscopy. The recrystalli-zation of selected cold-wmked samples was also studied by this method. The samples were prepared for examination by electrolytic thinning in a standard metallographic electrolyte which has not been previously reported as being used in producing thin foils of uranium. The microstructural changes observed in the a uranium were generally similar to those seen by optical microscopy. The changes in the microstructure of a uranium following cold work and recrystallization treatments have been the subjects of several studies employing optical and X-ray techniques.12-19 These studies indicated that twinning was the redominant mode of deformation at room temperature20 and that the regions of high energy associated with the deformation twins were preferred sites for the initiation of recrystallization.15,18, Recently several workers have prepared thin foils of uranium suitable for examination by transmission electron microscopy.'-lo The foils thus prepared have been used to study fission fragment damage; a particular dislocation reaction,' and gas precipitation." At this laboratory the microstructural changes occurring during the cold working and recrystallizing of a uranium samples have been studied by using transmission electron-microscopy techniques. The foils used in this work were electrolytically thinned in a polishing bath not reported previously in the literature as being used for this purpose. EXPERIMENTAL PROCEDURE The uranium used in this investigation was depleted a uranium sheet 4 mils thick. The results of a spectrochemical analysis of this material are shown in Table I. The as-received uranium was cut into strips, 1 in. wide by 5 in. long, and annealed in vacuo at 600°C for 2-1/2 hr. The resulting microstructure consisted of relatively uniform, equiaxed grains having diameters of 10 to 50 p. Cold Working. The cold-worked samples were prepared by rolling several of the annealed uranium strips to various thicknesses. The strips were reduced 3.5 ± 0.5, 6.0 ± 0.6, 10.0 ± 0.5, 19.5 ± 1.0, and 28.5 ± 2.0 pct in thickness. It was not possible to achieve these reductions with a single pass through the rolling mill, so the strips were turned end for end during the rolling procedure. The cold-rolled strips were stored in dry ice until samples from them could be thinned and examined (within 24 hr after rolling). Annealing. The samples used in studying the re-crystallization behavior of a uranium were obtained by annealing sections of the strips which had been reduced 10.0 and 28.5 pct. These samples were sealed in evacuated Pyrex capsules and were annealed in a tube furnace at temperatures from 200" to 600°C and for times from 1/2 to 2 hr, see Table l. Thinning: The samples from the rolling and heat treatments were prepared for examination in the electron microscope by electropolishing in a bath composed of 25 g chromic acid, 133 ml glacial acetic acid, and 25 ml water. This electrolyte has been used and recommended for preparing specimens for optical metallography It was necessary to mask the edges of the sample with a stop-off paint in order to prevent preferential attack in these areas. The paint used was made by dissolving polystyrene in benzene. The electrolytic cell consisted of a cylindrical stainless-steel cathode placed in a beaker containing the electrolyte, with the sample as the anode positioned at the cell axis. The temperature of the electrolyte was held below 15°C by cooling with liquid

Jan 1, 1963

By Clark L. Corey, Bogdan Lisowsky

Electrical resistivity, X-ray line positions, degree of order, and microstructures have been investigated for Ni-A1 alloys near the Ni3Al composition. The results indicate that Ni3Al undergoes disordering between 1250oC and the mp; also supersaturated y, produced in y + y' alloys by gas quenching, is extensively ordered prior to y' (Ni3Al) phase separation. The latter reaction, if not both, must follow the cooperative phenomena model. Shifts in line position as a function of quench-indulced super satulration are shown. Lattice pavarneters of equilibriunz and nonequilibrium phases are given. THE objective of this investigation was to determine the mechanism and kinetics of the reactions which occur in Ni3A1 and hypostoichiometric Ni3A1 alloys. The results are of particular significance relative to pre-precipitation phenomena. Early work on Ni-A1 binary compositions near the Ni3A1 composition (13.6 wt pct Al) has been adequately reviewed by Hanssen,1 whose phase diagram is presented in Fig. 1. williams2 verified the suggestion made by Taylor and Floyd3 and others4 that y', Ni3A1, may precipitate coherently on (100) planes of the y phase (see Fig. 1 for phase nomenclature); he further suggested a two-step precipitation mechanism consisting initially of probably short-range ordering followed by actual precipitation of y'. The precipitation stage in low-aluminum hypo-eutectic compositions has been studied by a number of investigators;*"7 short-range order or "zone" formation have been suggested as explanations for various diffuse X-ray scattering effects. The ordering reaction in Ni3A1 alloys is characterized by a) a very rapid rate of ordering in nonstoi-chiometric compositions, b) absence of a disordered phase region for the stoichiometric compound, y', or Ni3A1, c) precipitation phenomena as a dominant aspect in hypoeutectic alloys, and d) an increase in elec-trical resistivity on ordering.' The latter two factors were found by Newkirk to characterize ordering in Co-Pt, for which an extensive and detailed analysis was made.' An electrical-resistivity increase on ordering has also been reported for cuAu3.10 PROCEDURE Ni-A1 alloys in the form of 1300-g chill-cast ingots were prepared by vacuum melting electrolytic nickel and high-purity (99.99 pct) aluminum. Very small heats prepared from high-purity carbonyl nickel, supplied through the courtesy of Dr. Goff of the Naval Research Laboratory, were used for comparison with the larger ingots and no differences were noted. The cast material was homogenized in purified argon for a minimum of 72 hr at 1200°C and water-quenched from 1350°C. Compositions studied are given in Table I. The 10 pct A1 alloy was both hot- and cold-rolled. X-ray superlattice line intensities and peak positions were obtained from -270 mesh filings, using CuK, radiation with a LiF crystal monochromat adjusted to receive both 01 and a2. One-degree slits and a 1/8 deg per min scan rate were used to record line traces. A standard tungsten powder, obtained through the courtesy of G.E. Research Laboratory, was used to calibrate line positions.

Jan 1, 1968

By Harry M. Mikami

Chromite is the only ore mineral of metallic chromium and chromium compounds and chemicals. Because of this fact, chromite and chrome ore are used synonymously in trade literature. In commercial market quotations, chrome ore is the term commonly used. Chromite per se, because of properties imparted by its chromium content, is used in refractories and in special purpose molding sands for metal casting. There are many other minerals containing some, generally minor, amounts of chromium, but none are commercial sources of the element (Thayer, 1956). Chromium and chromite have many diverse uses that, directly and indirectly, critically affect vast segments of our modern industrial system. Most important are probably the metallurgical applications wherein chromium is a component of heat-, abrasion-, corrosion-and oxidation-resistant and high-strength alloys of many types. Stainless steels are the largest volume category of chrome-bearing alloys. Chromium chemicals are used in leather tanning, in pigments, dyes and mordants, printing, chemical process industries, photography, pharmaceuticals, metal plating, pure chromium metal production, and for many other purposes. Chromite is a necessary constituent in basic refractories indispensable for the production of steel, copper, cement, and glass. Under present conditions, the US and North America, with the possible exception of Cuba, have no commercial ore reserves. There are chromite deposits, as will be described, but they would be used only under highly abnormal conditions if all outside sources were cut off for an extended period. All chromite used in the US is imported from the eastern hemisphere in which are contained the principal world reserves. The main suppliers in 1980 were the Republic of South Africa (43%), the USSR (21% ), the Philippines (12%), Albania (11 %), Turkey (8%), and others (5%). The strategic nature of chromite is obvious. End Uses-Grades and Specifications As noted before, the three principal uses for chromite are metallurgical, refractories, and chemical with a fourth minor use as foundry molding sand. For metallurgical applications chrome ore is first reduced in electric carbon arc furnaces to various types of ferrochromium alloys. There are high, medium, and low carbon ferrochromiums with carbon ranging from 0.01 up to 10%. Chromium itself ranges from 50 to 73 %. Ferrosilicon chromium and ferrochromium-silicon grades have chromium from 33 to 67% and silicon from 3 to about 48%. Since iron is reduced with chromium, the Cr:Fe ratio of the ore will determine the ultimate grade of the ferrochromium whereas carbon and silicon can be controlled during processing. MgO, A12O3, CaO, and excess SiO2, are removed in slag. A small amount of pure chromium metal is prepared by alumino-thermic and electrolytic processes from essentially iron-free chrome components that have been made via the chemical route. The higher grades of ferrochromium with chromium in the 66 to 73% range can only be made from ores with not only high chromium content, but low iron, i.e., high Cr:Fe ratio. These ores, conventionally termed metallurgical grade, have Cr2O3 contents of 45 to 56% with Cr: Fe ratios of 2.5 to 4.3. A standard composition is generally 48% Cr2O3 and 3:1 Cr:Fe ratio. Very high grade ores are often blended with lower grades even with the high iron chemical grade. For some ferrochromiums, additions of high alumina refractory grade are used as slag conditioners to facilitate smelting while still contributing chromium values. A lower grade ferrochromium, the high carbon charge chrome, has become the predominant grade in use today for making chromium-bearing steel alloys. This

Jan 1, 1983

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.' and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~' have reported the structure of

Jan 1, 1965

By R. D. MacDonald, John Dasher, A. M. Gaudin

ION exchange is a widely used unit operation in water treatment and elsewhere in chemical industries. It has occasionally been used in hydro-metallurgy for treating plating, pickling, and rayon wastes Concerning ion exchange in extractive hydrometallurgy—for treating ore leach solutions— the literature prior to the Geneva Conference has given only hints."-" Yet most of the ore leach plants now being built or completed in the last three years use ion exchange for this purpose. Most of these plants are used for extracting uranium. The overall process for leaching low grade uranium ores and the history of its development have been given in the authors' previous papers.',' The object of this paper is to discuss certain engineering aspects of the new application of ion exchange to recover dissolved values from ore leach solutions. Necessarily the illustrations will be taken from the first application—to uranium metallurgy. Although ion exchange processes have been devised in which separation of spent residue from pregnant liquor is not required, as in the RIP process,"-'I only ion exchange operation, in which the resin is contacted with a clear solution, will be discussed in this paper. Uranium exists in acid leach liquors mainly as the cation UO," and can be adsorbed completely by cation exchange resins, but the adsorption is not selective as other cations such as Fe++, Fe+++, Al+++, Mg++, Mn", and Ca++ are also adsorbed. Uranium, however, forms complex anions with sulfate, phosphate," Carbonate"~"~ and even with chloride if the solution is strong enough.15 These anions can be adsorbed by anion exchange resins. The strong base anion exchangers have a very strong preference for these complexes and hence this adsorption is very selective. In this paper, the examples concern acid sulfate leach liquors from which uranium is adsorbed as UO,(SO,),-% and UO,(SO,),". Materials and Equipment Ion Exchange Material—Ion exchange materials include natural and synthetic; organic and inorganic; cationic and anionic; and weak, intermediate, and strong varieties. They consist of fragments or beads normally in the size range —16 to $50 mesh. The newer varieties have been developed to have greater stability, chemical strength, and/or capacity than earlier varieties. The resin used for uranium recovery is a strong base anion exchanger.* To make * Such as Rohm and Haas Amberlite IRA-400 series, British Permutit DeAcidite FF. Permutit lonac SE. and Dow Nalcite SAR. this resin, styrene plus a few percent divinyl benzene are polymerized into long chains with occasional cross links. This resin in bead form is then reacted to introduce quaternary amine groups onto most of the aromatic rings.' These resins are water-avid gels of specific gravity of about 1.1, which shrink and swell by osmosis when the ionic content of the surrounding solution is changed. The beads which are shown in Fig. 1 can be broken like an onion by rapidly replacing 15 pct H,SO, with water. This organic gel can also be broken by mechanical handling as by a centrifugal pump. Otherwise it is remarkably stable. It is unharmed by fairly strong acid or alkali, oxidizing or reducing agents, and heat up to 70°C. The strong base resin when completely in the chloride form (with a chloride anion on each quaternary amine group) holds over 107 g of C1- per dry kg. As all these chloride ions can be displaced by other anions, the resin has an exchange capacity of over 3 g equivalents per dry kg. However, the resin is sold and used by moist volume. The moist resin contains about 50 pct water, weighs about 43 lb per cu ft, has 40 pct voids, and an exchange capacity of over 1 g equivalent per liter of bed volume. Ion Exchange Equipment—Ion exchange equipment used for recovery of uranium from leach solutions is substantially identical to that developed for water treatment and other applications.'" The resin beds are held in closed tanks or columns which, in the uranium plants, have been standardized at 7 ft diam and 12 ft high. The resin bed

Jan 1, 1958

By J. P. Denny

The constitution of the Ga-In system was determined by thermal methods. An experimentally determined metastable equilibrium line (an extension of the indium-rich liquidus) was obtained. The various alloys were studied metallographically using polished samples obtained by a casting method. These low melting alloys required a special dry-ice assembly to maintain a suitable temperature. RECENT interest in alloys that are liquid at room temperature has led to rather extensive investigation of gallium-base alloys. Widely distributed over the earth, gallium could be produced in substantially larger quantities than at present, if a significant demand existed.' One study' has established its presence in 12 out of 14 zinc blends, in all of 15 aluminum ores, in 4 out of 12 manganese ores, in 35 out of 91 iron ores, and in all of 7 magnetite ores. It occurs as a rule in minute amounts, however, leading to high extraction costs. Recent quotations run from $2.50 to $7.50 per g. During the course of the present investigation, portions of the system Ga-In have been redeter-mined, and the results of this study are presented herein. Thermal and metallographic methods have been employed. Lecoq de Boisbaudran, the discoverer of gallium, conducted the first investigation" on Ga-In alloys in 1885. The temperatures of incipient melting, and of completion of melting, were determined at four alloy compositions. In 1936, Hansen' constructed a eutec-tic-type phase diagram for the system Ga-In, based on . work. The existence of a Ga-In compound was regarded as improbable by Hansen, and subsequent investigations are in agreement. French, Saunders, and Ingle3 conducted a more complete study of the system in 1938, using thermal methods. Their phase diagram is a eutectic type, containing a unique concave-upward liquidus. The solid-solution range of gallium in indium was reported as 9.5 pct by weight, and that of indium as less than 1 pct, at the eutectic temperature. The eutectic composition, determined as being bracketed by the compositions showing a true horizontal at the eutectic temperature (16°C), was reported as 76 5-0.5 pct Ga and 24 i 0.5 pct In. Experimental Procedure The preparation of Ga-In alloys is simplified by the low melting points involved. Various compositions were prepared by melting in pyrex tubes, using a cover of distilled water or parafin to prevent the alloys from wetting the glass wall. In all cases, the melts were homogenized. by stirring. Where possible, both cooling and melting curves were determined. The extensive undercooling of gallium was found to prohibit a satisfactory cooling-curve analysis of gallium-rich alloys, however, and transition points on the gallium side of the eutectic could be determined only by melting curves. The inverse rate method of thermal analysis proved to be most satisfactory and was used to a great extent. Various heating and cooling rates were used, ranging from 0.2" to 5.0°C per min. Low temperature melting analyses were conducted within a constant temperature bath, maintained at about 70 °C. The alloys were solidified (under water or paraffin) within a pyrex tube, using dry ice; the tube was then sealed within a cold Dewar flask, the unit transferred into the constant temperature bath, and periodic temperature readings taken. The high temperature melting-curve determinations and all cooling-curve determinations were made in a vertical tube furnace. At near-eutectic compositions, the furnace was placed within a refrigerated room held at —20°C. Accordingly, the furnace on cooling approached —20°C asymptotically and permitted the determination of those phase transitions occurring below room temperatures. Temperatures were measured with a 30-gage iron-constantan thermocouple, immersed directly in the alloy. To prevent contamination of the melt, the leads and junction were coated with Lucite, applied by painting with a solution of Lucite in ethylene dichloride. Electromotive force measurements were made with a Leeds and Northrup precision potentiometer, type 8662. The couples were calibrated against the boiling point. of water and, at lower temperatures, against a calorimeter thermometer having a Bureau of Standards certificate. The melting points of gallium and indium used in the present investigation were determined as 29.-77° and 156.1°C, in good agreement with previously reported values of 29.78°C° and 156.4"C.' The spec-

Jan 1, 1953

By S. E. Bronisz, R. E. Tate

s-plutonium samples possessing a strong growth texture have been produced by allowing them to transform under pressure from p to a. A fiber texture with [010] parallel to the pressure axis results. The textured samples are expected to be useful in determining the effects of crystallographic orientation on the physical properties of a plutonium, and initial results of measurements of resistivity and mechanical properties are described. THE crystal structure of a plutonium1 is mono-clinic, P21/m, and many of the metal's properties should reflect the crystallographic anisotropy. Unfortunately, it has not yet been possible to grow useful sizes of single crystals of a plutonium. Therefore, few of plutonium's orientation-sensitive properties have been determined as a function of crystallographic orientation. One way to gain information about at least some of the orientation-dependent properties is to study a highly textured sample. Such samples have been produced by cold rolling a plutonium,2 but they are necessarily very small in one dimension. We have now successfully used two other techniques to produce highly textured samples, not limited to small thicknesses. METHODS OF PRODUCING PREFERRED ORIENTATION The texture is produced by causing the plutonium to transform from ß to a while under pressure. It was observed by Gardner3 that applying a compres-sive load during the transformation resulted in the formation of columnar grains of a plutonium, and Cramer4 observed a similar structure in some diffusion couples rolled in the P phase. Neither of these workers, however, investigated the subject beyond these observations. The more flexible of the two methods developed is that of compressive loading. The technique is to enclose a sample of plutonium in a die assembly before applying the load. It is possible, of course, to dispense with the die and simply press the sample between two platens. In this case, however, the unrestrained sample deforms during the pressing, making it difficult to maintain the load and to control the final sample thickness. This compressive loading technique has been used on specimens ranging from 1/4 to 3 in. diameter, with height-to-diameter ratios ranging from 5 : l to 1:6. The procedure begins with loading the sample, a right cylinder of a plutonium, into the pressing die. Plastic deformation of the sample while it is being pressed is minimized by machining the sample so that its diameter is nearly the same as that of the die barrel. Then the loaded die assembly is placed in a vacuum pressing can that fits on a hydraulic press. After a vacuum is achieved the die assembly is heated to 180°C and equilibrated. The load is then applied and the specimen and die are allowed to cool to about 40° to 50°C before the pressure is removed. The resulting sample is composed of rod-shaped a -plutonium grains, the rod axes being parallel to the cylinder axis and the pressing direction. Photomicrographs of the oriented structure are shown in Fig. 1. Although most of the specimen is composed of grains whose rod axes are parallel to the cylinder axis, a thin, peripheral layer consists of rod-shaped grains whose rod axes are perpendicular to the cylinder axis. Presumably, the highly plastic nature of p plutonium leads to approximately hydrostatic conditions during the initial stages of the P — a transformation under pressure. At this time, the grains in the peripheral layer would have grown parallel to the local force direction. During the latter stages of the transformation, the accompanying volume contraction would have eliminated the radial forces, leaving only the axial force and resulting in the growth of the observed structure. The growth texture did not form without the application of pressure. Attempts were made to produce the texture by repeating the standard temperature cycle without

Jan 1, 1965

By W. Hodge, A. F. Haskins, R. M. Evans

Refractory boron compounds are shown to resist corrosion by molten zinc. Coatings were made from ferroboron and manganese boron by several methods: welding, hard facing, and pack diffusion; and techniques of coatings are very important. Mechanical failure of the diffusion coatings can be partially eliminated by applying them to type 416 chromium steels rather than carbon steels. Welded coatings made with a tungsten arc are better than those made by other welding methods. Sintered compacts of mixtures of iron and chromium borides developed strengths of about 30,000 psi. They resisted corrosion of zinc at 600°C and oxidation at higher temperatures. MOLTEN zinc rapidly attacks common metals of construction. The rate of attack is greatly amplified at temperatures over 500°C. However, there are many applications where it is necessary, or at least advantageous, to use metal construction, such as for galvanizing pots and zinc smelter equipment. Condensers and agitator linings used in continuous zinc smelting processes are eroded and corroded by violently agitated molten zinc. Pumps, tubing, and other parts to permit transfer of molten zinc would be desirable in many zinc handling operations. The development of metallic materials which are resistant to molten zinc also might permit its use as a heat-transfer medium in modern high efficiency power plants. In reviewing previous work on zinc-resistant metals, it was evident that most of the available data refer to corrosion at temperatures just above the melting point. Tungsten and high Mo-Fe alloys containing more than 80 pct Mo resist corrosion by molten zinc.', ' Imhoff states that because chromium is not attacked by zinc, chromium plating improves galvanizing pot life." Nitrided cast iron has been used in die-casting machines' where the molten alloy is 96 pct Zn and 4 pct Al. Other metals that have been suggested as of possible value for zinc resistance are columbium, tantalum, and titanium.V he corrosion of steel by zinc has been discussed by many authors,z, "2 None of these materials resisted corrosion by molten zinc at the temperatures used in this investigation, i.e., 600" to 700°C. I. Exploratory and Resistant-Coating Tests To make a study of zinc-resistant metals, exploratory tests were conducted to sort out roughly those materials which seemed most worthy of further development. This preliminary study included both solid metals and surface coatings. Exploratory Corrosion Tests in Molten Zinc—In initiating a study of this problem, numerous samples of metals and alloys were evaluated by dynamic corrosion tests made at 440 °C. Each metal was tested in its most readily available form, which, because of shape and size, was often unsuited for standard corrosion testing. The equipment used for dynamic corrosion testing of all materials, except in a few initial experiments, is shown in Fig. 1. Samples were tied to tungsten rods with tungsten wire, immersed in the zinc, and revolved at 12 rpm about the circumference of a 4 in. diam circle. Speed of travel was about 12.5 fpm. The molten zinc was protected from oxidation by an atmosphere of carbon monoxide, or, at a later period in the program, by a 9:1 mixture of nitrogen and hydrogen. When the effect of both molten metal and atmosphere was desired, the zinc level was lowered. Special high grade zinc was used in all of the corrosion tests. Corrosion losses for materials tested are shown in Tables I and 11. Whenever the materials were available in suitable form, the losses are reported in mils per year. It was recognized that weight losses on irregularly shaped specimens did not show the corrosion rate but the important consideration—poor resistance to corrosion—could be determined readily.

Jan 1, 1956

By H. E. Cline

Mechanical properties of the eutectic between CoAl and cobalt were measured over a range of- temnperatures and strain rates for a variety of microstructures produced by directional solidification and by thermo-mechanical processing. Directional solidification led to rodlike, lamellar, and irregular microstructures. The unusually high volume fraction of the cobalt-rich rods and the lurge spacing of the rods were explained by the phase diagram. The hot-worked structure consisted of fibers of COAL in a cobalt-rich matrix. The roonl- tevlperature strength of the uvrought material increased with decreasing grain size but the 1000°C strength decreased with decreasing pain size. At high temperatures the directionally solidified tnaterial was stronger and less strain-rate-sensitice than the hot-rolled material. The fine-grained hot-worked ma-terial became superplastic at high temperatures, with tensile elongations greater than 850 pct, while at root temperature this material was ductile and impact-resistant because of the ductile matrix. Fracture occurred in the directionally solidified material at elevated temperatures by inter phase separation and at roorn temperature by cracks in the intermetallic phase. Growth of these cracks was impeded by the ductile cobalt-rich phase. It was found that the CoAl intermetallic remains ordered at elevated temperatures. DIRECTIONAL solidification of eutectic alloys has been used to produce structures consisting of parallel rods or lamellae. Although the spacing of the phases depends on the growth rate, it has been observed to be of the order of 1 µ in many eutectics. A strong intermetallic phase has been used to reinforce a ductile matrix in the rod eutectic A1-Al3Ni and the lamellar eutectic Al-Al2cu.1 The microstructure of the eutectics A1-A13Ni and A1-A12Cu remained aligned after samples of these alloys were exposed to temperatures just below their melting points for long times. Stability of the microstructure at elevated temperatures makes directionally solidified eutectics a candidate for high-temperature applications. Recently Thompson4 has developed the Ni-NiMo eutectic containing 40 pct NiMo lamellae, giving a tensile strength superior to nickel-base superalloys. Unfortunately, this eutectic oxidizes rapidly at elevated temperatures. By mechanically processing a two-phase structure, one may reach strengths as high as 700,000 psi, as demonstrated by drawn pearlite.5 In this case the strengthening mechanism was thought to be related to the fine substructure formed during deformation.5 However, a heavily worked structure may recrystallize and coarsen at elevated temperatures. Some worked eutectics such as Al-Al2Cu,6 Pb-Sn,7 and Sn-Bi7 have shown unusually large elongations in tension when tested at elevated temperatures. This phenomenon of large extension, called "superplasticity", was related to the fine grain size of wrought two-phase alloys at elevated temperatures. A mode of deformation of "superplastic" material has been shown to be grain boundary sliding,' which has also been observed during creep of polycrystalline materials.9 The Co-A1 system was chosen for this investigation after examining the phase diagrams of binary eutectics." The high melting point of 1400°C, the aluminum content which was expected to give oxidation resistance, and the properties of the intermetallic CoAl were the chief factors influencing this choice. This eutectic consists of a mixture of the intermetallic CoAl and a cobalt-rich solid solution. The intermetallic CoAl has a large range of solubility and a CsCl structure." From the similarity between CoAl and NiAl one would expect CoAl to be ordered at elevated temperatures; however, specific heat measurements" show a transition at 800°C. West-brookL2 has measured the hot hardness of CoAl and found a rapid decrease in hardness above 600°C. The tensile properties and stress rupture properties of as-cast CoAl-Co eutectic were measured by Ashbrook and wallace13 who report a room-temperature tensile elongation of less than 1 pct. I) EXPERIMENTAL A) Sample Preparation. Experimental materials were prepared by directional solidification, by hot working, and by powder processing. The starting materials were electrolytic 99.9 pct pure cobalt and 99.99 pct pure aluminum. 1) Directional Solidification. A vertical Bridgman apparatus heated by induction was used to directionally solidify cylindrical ingots $ in. in diam and 5 in. long. The apparatus was first evacuated and then an argon atmosphere was introduced to retard evaporation. The ingots were contained in an alumina crucible inside a graphite susceptor that rested on a movable water-cooled base. The base was lowered out of the induction coil at a constant rate. Eight of the ingots were solidified using a drive rate of 2.5 cm per hr, two of the ingots at 1.2 cm per hr, and one ingot at 10 cm per hr. The eutectic composition Co 10 wt pct A1 was used in all but one ingot which had the composition of the stoichiometric CoAl intermetallic, Co 32 wt pct Al. 2) Mechanical Processing. At 1000°C the eutectic Co 10 wt pct A1 is a mixture of an intermetallic phase, Co 21 wt pct Al, and a cobalt-rich phase, Co 5 wt pct Al.10 These phases differ from the stoichiometric CO 32 wt pct A1 and pure cobalt because of the large solubility of this eutectic at elevated temperatures." Four rectangular slab ingots, 4 by 1 by 12 in. high, of Co 10 wt pct Al, Co 5 wt pct Al, Co 21 wt pct Al, and Co 32 wt pct A1 were cast for hot rolling. The cobalt was first vacuum-melted, H2-treated for 20 min,

Jan 1, 1968

By A. E. Bibb, F. W. Kunz

A platelet form of zirconium hydride was found in zirconium and ZY-1 wt pct U single crystals containing hydvogen in the range of 50 to 100 ppm. The habit planes for the hydride plateletg in the zirconium crystals were found to be {1012}, {1121}, and (1122) while the habit planes in the ZY-1 wt pct U crystals were {1121), {1123}, and (1.231). With the exception of the {1231} plane, these have been identified as the twin planes in zirconium. The different effect of hydridc on the mechanical puoperlies of zirconium at high and low strain rates has been explained in terms of the defornzation mechanism and the habit planes of the hydride. ZIRCONIUM and zirconium-base alloys are considered for many nuclear reactor applications, where the pick-up of hydrogen is a distinct possibility, if not an unavoidable occurrence. An excellent example of this is the absorption of hydrogen by zirconium and its alloys during aqueous corrosion, where as much as 30 pct of the hydrogen produced by the corrosion reaction is picked up by the metal. Under the proper conditions, the absorbed hydrogen would precipitate as zirconium hydride and consequently alter the mechanical and physical properties of the zirconium-base alloys. The knowledge obtained from a study of the crystallographic aspects of the hydride precipitation is necessary for the interpretation of the observed changes in the mechanical and physical properties. The deleterious effect of hydrogen on zirconium-base materials is not always observed in normal slow tensile loadings at or above room temperature, but becomes immediately obvious under impact loading, where the energy absorbed decreases with increasing hydrogen content,' and in notched specimens where triaxial loadings are attained.2 This effect is of serious consequence in the applications of Zr where shock loads or high strain rates are experienced. The purpose of this investigation was to determine the crystallographic planes of the Zr and Zr-1 wt pct U matrices upon which zirconium hydride will precipitate and to correlate these with the observed mechanical property data. PROCEDURE Crystal Growth—Single crystals of Zr and Zr-1 wt pct U alloy were used in this investigation. The Zr crystals were made from sponge that had a typical analysis as shown in Table I. Large grains were grown in this material by rapid cooling an arc-melted charge in a button furnace. This operation undoubtedly lowered the volatile impurity concentration below those listed in Table I. Back-reflection Laue patterns of these large grains showed the presence of considerable substructure and lattice distortion within each grain. It was found that an 18-day anneal in an argon atmosphere at 840°C (a high a heat-treatment) followed by furnace cooling, resulted in the further growth of the large grains and removed the detectable substructure ana lattice distortion. Equiaxed crystals with a cube edge of approximately 1/4 in. were produced in this manner. Large crystals of Zircaloy-2 (1.5 wt pct Sn, 0.15 wt pct Fe, 0.1 wt pct Cr, 0.05 wt pct Ni) also were produced by this technique but the large amount of substructure formed could not be removed by annealing. The Zr-1 wt pct U solid solution crystals were produced from an alloy rod consisting of Westing-house-Foote hafnium-free crystal bar zirconium and depleted uranium. The chemical analysis of the alloy is also given in Table I. Three-inch sections were cut from an 0.120-in.-diameter alloy rod and tapered to a fine point on each end. The samples were sealed in evacuated Vycor tubes, homogenized for 5 hr at 1000°C in the ß-phase field, and slowly lowered in a gradient furnace into the a phase (800°C), annealed for 60 hr at this temperature to produce grain growth and furnace cooled. This technique produced large grains approximately 1/2 to 3/4 in. long over the entire cross section of the rod, which were free of observable substructure. Metallographic examination up to X1000 did not show the existence of any second phase in these grains. Crystal Orientation—All crystals were abraded on fine emery paper to produce two flat surfaces 90 deg to each other. The crystals were analyzed by the standard Back-Reflection Laue technique to obtain the crystal orientation with respect to the abraded surfaces. The Back-Reflection Laue Photograms of all crystals used were clear and sharp indicating that the crystals were free from any substructure that could be detected by these means. Hydriding—Only samples containing four to five grains were used for hydriding. Samples that exhibited fine grained patches were discarded. The samples were hydrided using the following technique. After etching in 48 vol. pct HNO3, 48 vol. pct H2O, and 4 vol. pct HF (48 pct) solution, the specimens

Jan 1, 1961

By Henry A. Wriedt, John Chipman

Equilibrium in the reaction of hydrogen gas with oxygen in liquid nickel, iron, and their alloys has been studied at temperatures of 1500° to 1700°C. The equilibrium con^stant, 0/p, [% O], is greater in nickel then in iron by a factor of 45 at 1594 C. In the alloy steel range, the activity coefficient of oxygen is slightly increased by the presence of nickel. NICKEL is more resistant to oxidation than is iron, in both the solid and the liquid state. The solubility of oxygen,' however, is greater in nickel than in iron. The two metals and their liquid alloys constitute an interesting series of solvents in which the chemical behavior of oxygen can be studied by methods similar to those used for liquid iron.' Experimental Method The furnace assembly, including the tube for preheating the entrant gas, was the same as that described by Gokcen and Chipman. " controlled mixture of water vapor, hydrogen, and argon preheated to approximately the melt temperature impinged upon the surface of the liquid metal. The charge, weighing about 35 g, was held in an alumina crucible at constant temperature in the gas stream for a prolonged period, then quenched in a stream of cold helium, sampled, and analyzed for oxygen by the vacuum fusion method. The temperature of the liquid metal was measured by a Leeds and Northrup optical pyrometer which had been checked against a similar instrument certified by the National Bureau of Standards. The freezing point of electrolytic iron in hydrogen, taken as 153j°C, was used for frequent checks. This point and the emissivity determined by Dastur and Gokcen" established the transmissivity of the optical system. The emissivities of Fe-Ni alloys at 1535" are known from the experiments of Smith and Chipman,h nd it was assumed that the variation with temperature is parallel with that of iron. Recorded temperatures are probably accurate within k5"C. Preparation of Gas Mixtures—Since the ratio H,O:H, had to be much higher for nickel than for iron, it was found convenient to construct two separate systems for gas preparation. In both cases, the ratio of argon to the sum of the other two gases was at least 4, the proportion of hydrogen and water vapor being varied to produce H,O:H, ratios from 0.2 to 70. The primary purpose of the argon was to diminish the errors caused by thermal separation' in the gas phase. In addition, its presence lowered the saturation temperature required for a given H,O:H, ratio and minimized the difficulty of preventing condensation. Both systems were modifications of the one used by Dastur and Chipman.' For H,O:HI ratios greater than 2, welding-grade argon purified by passage over magnesium chips at 620°C was mixed with hydrogen produced in the electrolytic cell shown in Fig. 1. The design was based on a cell used by Bodenstein and Pohl," the important features of which area nickel wire cathode and sodium hydroxide solution as the electrolyte. The rate of hydrogen evolution was controlled by a calibrated ammeter and a rheostat in the circuit, the current efficiency being taken as 100 pct. Precise control of the argon flow rate at about 300 ml per min was achieved by means of a capillary flowmeter having a controlled pressure drop. The molar flow rate was measured volumetrically before each run, and a constant flowmeter setting was maintained thereafter. The A-H, mixture passed through a water saturator of the type previously described," the saturation temperature being maintained automatically with a fluctuation of k0.04"C. The tube between saturator and furnace was heated by a resistance winding. The system was of all Pyrex construction with the exception of the stainless steel tube containing magnesium chips. This was connected with the glass tubing at the upstream end by

Jan 1, 1957