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By C. H. Li, R. J. Stokes, T. L. Johnston

The phenomenon of solid-solution strengthening has previously been studied in a number of binary alloy systems.1-8 There has been, however, very little information published concerning the strengthening effects of specific solutes in magnesium alloys. Schmid and his coworkers9,10 investigated the behavior of aluminum and zinc in binary and ternary magnesium-alloy single crystals, but this work was done before high-purity materials were readily available. Workers at the Dow Chemical companyH reported increases in the critical resolved shear stress upon alloying magnesium single crystals with zinc and indium. Recently, Hardie and parkins* investigated the extent of hardening produced by the addition of various solutes to poly crystalline magnesium. The present work was undertaken to provide data on the strengthening effects of a number of solutes in high-purity magnesium, for the purpose of supplying further experimental information which might be useful in describing a general mechanism for solid-solution strengthening. To simplify interpretation of the results, the mode of deformation was limited to basal slip, through the use of single crystals. EXPERIMENTAL PROCEDURE Magnesium and magnesium binary-alloy single crystals containing indium, cadmium, thallium, aluminum, and zinc were prepared in the form of l/2-in.-diam rods, approximately 8 in. long, using a modified Bridgman technique in which the crystals were slowly cooled from the melt in a steep temperature gradient, in an atmosphere of helium. It was found that a solid-liquid interface travel speed of about 0.7 in. per hr consistently produced single crystals. The poly crystalline starting materials for the preparation of single crystals consisted of 1/2-in.-diam extruded rods, prealloyed to the desired composition. The unalloyed magnesium and magnesium-indium extrusions were furnished by the Dow Chemical Co. The other alloys were prepared at the Rensselaer Polytechnic Institute Metallurgical Laboratories. Some preliminary studies of the strengthening effect of indium were conducted at room temperature using a constant rate of tensile loading of 1040 g per min. Stress was applied to the crystals by means of a simple 5:l lever arm. The lever was loaded by a constant rate of flow of shot into a receptacle suspended from the long arm of the lever. Plastic flow was detected by an electrical resistance strain gage cemented to the surface of the crystal normal to the minor axis of the predicted glide ellipse. The crystals were acid machined to produce tensile specimens with a reduced section between the grip ends, with an additional step in the center of the reduced section to compensate approximately for the slip-retarding effect of the strain gage. The balance of the single crystals were extended in an Instron tensile tester. This machine employs a synchronously driven screw and automatically records applied load as a function of cross-head separation. It became unnecessary therefore, to employ a strain gage to detect deformation or to acid machine a reduced section. Preparation for testing reduced merely to chemical cleaning of the surface, thus minimizing the amount of handling and probability of accidental damage to the crystals. The rate of elongation employed in all the tests was 0.002 in. per min, corresponding to a strain rate of approximately 0.0004 per min. EXPERIMENTAL RESULTS The investigation confirmed the finding of many workers that the yield strength of hexagonal metal crystals is strongly orientation-dependent. This is illustrated in Fig. 1, in which o, the tensile stress required to produce gross plastic flow in eleven unalloyed magnesium crystals stressed at a constant rate of loading is plotted as a function of sin X, cos Ao where X, is the angle between the

Jan 1, 1960

By A. L. Titchener, M. B. Bever

The stored energy of cold work was investigated in drawn gold-silver wires by tin-solution calorimetry as a function of strain, strain rate, initial grain size, and temperature of defornation. The energy expended in the deformation process was measured. Hardness was also measured and was correlated with the stored energy as a function of strain and strain rate. Mechanisms of energy storage are discussed. THE variables which determine the amount of energy stored in a metal during cold work are of two kinds: those involving the metal and its condition and those involving the process of deformation. For example, the stored energy differs between one metal and another and between different degrees of purity of a single metal. It also depends on the nature of the deformation process and particularly the extent, rate, and temperature of deformation. Most investigators have reported the stored energy as a function of strain (or some similar geometric parameter) or of the energy expended during deformation. In general the stored energy increases with strain, rapidly at first, but more slowly at large strains until a saturation level is reached. Information about the effects of other variables, however, is limited. Some data are available on the dependence of the stored energy on the purity of a metal1 and on the composition of

Jan 1, 1960

By E. Parthe, J. P. Pemsler

TWO references can be found in the literature concerning the ternary system uranium-tantalum -carbon. C. H. Schramm, P. Gordon, and A. R. Kaufmam reported in this Journal1 on the existence of the ternary carbide "UTa10C4." They also report a second face-centered-cubic carbide phase in the system U-Ta-C, which they denote as "white" phase. The publication includes a reproduction of a Debye-Scherrer powder photograph of "UTa10C4" and a list of the sin2 0 values of this compound. H. Nowotny, R. Kieffer, F. Benesovsky, and E. Laube2 report the complete solid solubility between TaC and UC with a B1 structure. Since the ternary phase "UTa10C4" lies very close to the binary system Ta-C, and the established phase Ta2C with a C27 structure had not been mentioned by Schramm et al., it was thought worthwhile to compare the patterns of "UTa10C4" with Ta2C. The strong lines of the given pattern were indexed on a hexagonal unit cell with the approximate cell parameters a = 3.09A and c = 4.93A. These are the values reported for Ta2C in the literature.3 The correspondence between reported and calculated sin2 8 values may be studied in columns 4 and 5 of Table I. The agreement is fair, but there remain weak lines which cannot be assigned to the hexagonal unit cell. The extinctions correspond to those of Ta2C, but a comparison of the calculated and observed intensities of the Ta2C lines (columns 2 and 3) with those of the corresponding lines of "UTa10C4" (column 6) show occasional deviations. To clarify this situation, four new samples were prepared. The compositions of these samples were chosen in such a way as to observe any existing ternary phase in the system TaC-UC-U-Ta. The samples were arc melted in an inert atmosphere and annealed at 1100°C for 36 to 72 hr. Compositions of the samples determined by chemical analysis are given along with the results of X-ray investigations in Table 11. The following conclusions may be drawn from these data: a) No ternary compounds occur in the section TaC-UC-U-Ta of the ternary system Ta-U-C. The "white" phase reported by Schramm et al. corresponds to a solid solution between TaC and UC. Only one three-phase field exists: C27-B1-A2. (Both tantalum and ? uranium have body-centered-cubic A2 structures.) The a uranium observed in sample 4 transformed from the high-temperature ? phase on cooling. b) The phase Ta2C with a C27 structure extends into the ternary system. "UTa10C4" is, therefore, a uranium-enriched Ta2C. Good agreement is ob-

Jan 1, 1960

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N',N'-tetraacetic acid and N'-(2-hydroxyethyl)ethylenediarnine-N,N,N '-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1'9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH's in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH's. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By A. W. Schlechten, R. P. Abendroth

Jan 1, 1960

By I. Plaskin

Interaction of sulfide minerals and native metals I with reagents in flotation is largely determined by particle-surface changes resulting from action of the medium and dissolved gases. A number of early studies were devoted to the selective action of various gases on minerals.' Mc-Lachlan' paid attention to oxygen as the most active gas affecting flotation properties of sulfide minerals. Opposing views were expressed concerning the influence of sulfide oxidation on xanthate flotation: Taggart3 recognized the positive influence of oxygen, and I. W. Wark4 rejected it. Shvedovh ffered the hypothesis of partial oxidation. As to the influence of such gases as hydrogen" and carbon dioxide on mineral floatability, opinions also differed. Effect of Oxygen on Sulfide Mineral Flotation: Research on the influence of oxygen and other gases on the floatability of sulfide minerals and native metals has been carried out at the Institute of Mining of the USSR Academy of Sciences in

Jan 1, 1960

By R. W. Baldwin

As used in geophysical exploration, the term overvoltage applies to secondary voltages set up by a current into the earth which decay when the current is interrupted. These secondary effects may be measured by pick-up electrodes. The term induced polarization has often been employed to describe this same phenomenon. In its own operations Newmont Exploration Ltd. commonly uses the word pulse. The basis of this method in prospecting is that metallic particles, sulfides in particular, give a high response, whereas barren rock, with certain exceptions, gives a low response. Overvoltage has been tried in searching for many types of mineral occurrence but has been most successful in outlining the widespread disseminated mineralization associated with porphyry coppers. History:' Newmont Mining Corp. has been interested in overvoltage since 1946, when Radio Frequency Laboratories of Boonton, N. J.. drew the company's attention to phenomena observed in the laboratory. At the instigation of A. A. Brant further model studies were undertaken, and the first tests were performed in 1947. Tests at San Manuel, Ariz., in 1948 were very encouraging, clearly demonstrating that the method could be used to distinguish scattered sulfides at depth. H. 0. Seigel followed up the San Manuel work with a study to determine the phenomena involved.'

Jan 1, 1960

By W. M. Tuddenham, R. J. P. Lyon

In many areas surrounding the orebodies in mining districts rocks have been bleached and altered by the ore-forming solutions and have been oxidized during later weathering processes. A number of the rock-forming silic-ates have been broken down to clay, sericitic micas and chlorites have been developed, and pyrite may be found hundreds of feet outside the economic limits of the orebody. These halos of altered ground are prime targets used by geologists in many districts to delineate promising sites for drilling. Both in the field and in the laboratory it is often difficult to map these mineralogical changes in the halos in detail without numerous petrologic examinations. The secondary minerals are generally fine-grained, and since conversion of one mineral to another is often progressive, many alteration processes have not proceeded to completion (feldspars to clay to sericite mica). Qualitative detection of these minerals is difficult; quantitative determination is frequently impossible.

Jan 1, 1960

By A. E. Gorum, J. Washburn, E. R. Parker

Experimental evidence was obtained in support of the idea that cleavage fracture can be initiated by dislocation pile-up. The high ductility of MgO crystals when tested in bending comPared to their relative brittleness in tension was explained on the basis that large pile-ups are more likely in a tension specimen. CLEAVAGE fractures have been a problem of major concern for many years. A number of large steel structures have failed in a brittle manner, usually suddenly and without warning; often the failures occurred for no obvious reason and at nominal stress levels well within the generally accepted range. A great deal of data have been collected about factors that contribute to failures,1 but the physics of the fracture process has never been revealed. cottrel12 has recently developed a theory of brittle fracture in ductile materials which was based upon the concept that dislocations moving on two intersecting planes can unite to form a crack nucleus. This theory accounts for the known effect of grain size and for the effect of testing temperature. There has, as yet, been no experimental evidence published that would substantiate this or the earlier theories based on stress concentrations due to piled-up dislocations. The study reported herein was conducted to obtain information that would either substantiate or disprove the

Jan 1, 1960

By H. Conrad

The strain hardening associated with the creep of magnesium single crystals at room temperatu.Je was investigated by shear tests in which the direction of stressing was reversed a number of times after creep in a <100> direction. The strain hardening was strongly anisotropic; the largest amount occurring in the direction of flow and the least 180 deg to this. The time law for creep changed from a parabolic type to logarithmic for the first and subsequent reversals of stress. For a given stress the creep strain decreased significantly for the first and second reversals and then only slightly for subsequent reversals. The logarithmic creep constant a changed in a similar manner. A linear relationship was observed between the creep strain for a given reversal and the stress. The slope for the third reversal yielded a strain hardening coefficient 12 to 16 times greater than that observed for unidirectional flow. Al-though no recovery was observed upon resting at room temperature, the hardening resulting from stress reversals could be completely removed by heating to 450" C. PREVIOUS work1.&apos; indicated that the creep rate of magnesium single crystals tested in the temperature range of 78" to 364°K decreased with time. This was attributed to an increase in internal stress resulting from an accumulation of dislocations at internal obstacles. The object of the present investigation was to further evaluate the nature of this hardening by conducting tests in which the direction of stressing is changed after previous creep in shear in a given slip direction. Previous to 1950 three investigations indicated that a Bauschinger effect3 occurred for single crystals as well as polycrystals brass in tension compression,

Jan 1, 1960

By W. C. Lacy

The last crop of graduates from our colleges and universities who sought employment in the mineral industries found that they needed to hustle to find a job. There was no longer a list of waiting employers to choose from. Some of them became discouraged and drifted into other fields; many are still looking for employment. Word has gotten around that there are no jobs available in the mineral industries, and enrollment in the various colleges of mines and mineral industries has started to drop. Even established professional men are finding themselves suddenly out of work because of unstable metal prices and rising costs. All these people-students beginning to search for a career, young engineers not yet established-face the same problem: "What is the future of the mineral industries, and what type of training will best qualify the scientist or engineer for this changing field?" This question was posed to a number of leaders in different phases of the industry. Their comments are summarized as a guide to those considering a career in the finding, extraction, or beneficiation of mineral products.

Jan 1, 1960

By H. B. Charmbury, D. R. Mitchell

Everyone in the coal industry from top management to the preparation engineer is vitally interterested in recovering as much salable coal as possible from the run-of-mine product. Coal losses from a preparation plant occur in the solid refuse material being discharged from the plant and in the bleed-off slurry from the water circuit. The refuse is generally hauled from the plant in solid form by trucks, conveyors, or aerial trams to the refuse or culm banks or it may be crushed and transported by hydraulic methods to refuse ponds or dams. The loss of coal in refuse material and the extent of this problem has been covered in another paper. The loss of salable coal in the plant bleed-off slurry is one of the water circuit problems in coal preparation plants. Slurries originate at various places in the processing circuits and are usually disposed of by transportation to waste ponds known as slurry ponds. Even though the combustible material discharged as slurry and refuse from the plant is labeled a loss, the loss must only be considered temporary. There is a tendency at the present time to examine refuse and slurry losses and to reprocess these materials to recover valuable coal.

Jan 1, 1960

By P. Chiotti, G. R. Kilp

Thermal, metallographic, vapor pressure, and X-ray data were obtained to establish the phase diagram for the zinc-zzrconiz~m system. Five compounds corresponding to the stoi-chiometric formulas ZrZn, ZrZn,, ZrZn,, ZrZn,, and ZrZn14 were observed. All these compounds, with the exception of ZrZn2, which melts congruently at 1180°C under constrained zinc-vapor conditions, undergo pexitectic reactians. The temperature at which the zinc vapor pressure is I atm for a series of alloys was determined from vapor-pressure measurements. The data obtained are summarized in the construction of a I-atm-pressure phase diagram and a phase diagram corresponding to a pressure of less than 10 atm. THE purpose of this investigation was to establish the phase diagram for the zinc-zirconium system. Thermal, metallographic, vapor pressure, and X-ray data were employed in determining the phase regions. Partial investigations of this system have been conducted by Gebhardt1 and Carlson and Borders.&apos; Carlson and Borders studied the high-zirconium region and established the existence of a eutectic at 69 wt pct Zr with a melting point of 1015°C. The terminal phases of the eutectic horizontal were shown to be an intermetallic compound ZrZn and a solid solution of ß zirconium containing 21 wt pct Zn. The ß solid solution decomposes into ZrZn and a zirconium at 750°C. The eutectoid composition is given as 15 wt pct Zn, and the solubility of zinc in a zirconium at temperatures below 750°C is indicated to be negligible. Gebhardt studied the zinc-rich region and observed a lowering of the melting point of zinc from 419.5" to 416°C and temperature horizontals at 545" and970°C. Some preliminary observations by Chiotti, Ratliff, and Kilp were reported by Hayes.2 pietrokowsky3 has reported the compound ZrZn2 to have a cubic MgCu2 structure with ao = 7.396A. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc or Baker analyzed reagent granulated zinc, both 99.99 pct pure and hafnium-free iodide-process crystal bar zirconium obtained from the Westinghouse Electric Corp. The zirconium contained 200 ppm Fe, 200 ppm Si, 100 ppm C, and minor amounts of other impurities. The zirconium was milled or machined into thin chips or shavings. These were cleaned with a nitric-hydrofluoric acid solution, rinsed with water, and acetone, and dried just prior to their use in alloy preparation. The granulated zinc was similarly cleaned using dilute nitric or hydrochloric acid. Weighed quantities of these materials, 20 to 30 g total, were mixed and pressed at 20,000 to 70,000 psi to give relatively dense compacts. During the early part of this investigation the pressed compacts were placed in MgO-15 wt pct MgF, crucibles which were then sealed inside of quartz ampules. The compacts were given various prolonged heat treatments prior to their use for thermal analyses, or vapor-pressure measurements. Because of expansion of the compacts and the relatively high zinc vapor pressure it was difficult to heat to the melting temperatures of the alloys without failure of the quartz ampules. Homogenization at temperatures below the melting temperature gave brittle, porous alloys unsuitable for metallographic examination. It was also difficult to prevent condensation and segregation of zinc on the colder parts of the quartz ampules during heating and cooling operations. These problems were eliminated to a great extent by the use of tantalum crucibles. Tantalum proved to be a satisfactory container with little or no reaction between the alloys and the tantalum. Small tantalum thermocouple wells were successfully welded in the bottom of these crucibles. Pressed compacts were sealed inside the tantalum crucibles by welding on preformed caps under an argon atmosphere. Heat treating and differential thermal analysis were combined into a single operation. The experimental sample assembly is shown in Fig. 1. This assembly was enclosed inside a stainless-steel tube heating chamber which could be evacuated and filled with an inert gas. The thermocouple leads were brought out of the heating chamber between two rubber gaskets used to provide a vacuum seal for the water-cooled head. Most of the compounds in this system undergo peritectic decomposition. After heating above the temperature of a particular peritectic horizontal the sample was cooled to just below the peritectic temperature and held at temperature for several hours. The sample was then reheated through the peritectic temperature and the size of the thermal arrest, if still present, compared with the one previously obtained. If the thermal arrest was not characteristic for the alloy composition being investigated its magnitude diminished and repeated cycling and annealing eventually eliminated it. The peritectic thermal arrests characteristic of a particular composition were established in this manner.

Jan 1, 1960

By B. N. Webber

During World War II the Pocos de Caldas bauxite deposits of Minas Gerais in Brazil yielded some 60,000 tons. Since then they have maintained a small but almost continuous production. Known for many years, the deposits have been reconnoitered by a number of geologists,1-4 but no dimensional study has been possible because there have not been enough exposures to show clearly the depth, bedrock, and habit of occurrence. The deposits are somewhat unorthodox in their occurrence mainly on steep slopes of mountainous terrain. Although the parent rocks are a sequence of alkalic intrusions that bauxitize readily under the proper conditions, bauxitization has not been the dominant weathering process in the area. It is limited to certain localities where important volumes of bauxite have formed by laterization of several rock types, each yielding a distinctive type of bauxite. Bauxitization may be observed in several stages and in both direct and indirect cycles of formation. The deposits are unique in being of demonstrably recent age, so that the conditions under which the bauxite formed are essentially those of the present time. The bauxitization sequence is postulated in Fig. 1. Pocos de Caldas district is situated at approximately 21" 50&apos; south latitude and 46" 30&apos; west longitude in southwestern Minas Gerais, near its boundary with the state of Sao Paulo. It lies within the Eastern Plateau physiographic province of Brazil, occupying a prominent highland area that rises some 2000 ft above the surrounding country. The central portion of the Pocos de Caldas highland is characterized by gently undulating topography, with generally sluggish drainage, and is surrounded by a rim of hills rising above 1000 ft above it. In cross section the highland resembles a truncated cone with a depressed central area. The rim has been sculptured into a more prominent and abrupt topographic pattern than the central area, and streams that are of low to moderate gradient in the central plateau plunge over the rim in a spectacular series of cascades and falls. GEOLOGIC SETTING The Pocos de Caldas highland owes its physiographic expression mainly to the differential erosion of a complex intrusion of alkalic rocks into gneiss and sandstone. Erosion was guided somewhat by faulting. The highland is almost circular, and its limits, except in one locality, coincide with the periphery of the intrusion. The alkalic intrusions largely control its shape and extent, aided by some subsidence through faulting of the central portion. The mountainous rim of chilled phase, the later intrusions, and the indurated intruded rocks have resisted erosion more effectively than the central portion of the intrusion, which is composed of more coarsely crystalline alkalic rocks that form a central basin in the highland. Gneiss and sandstone are found coincident in elevation with the topographically highest intrusions. BAUXITE TYPES Most of the bauxite, which varies in physical type, is on the top and steep slopes of the northern rim. The only alumina mineral is gibbsite, definitely crystalline but iron-stained unless of secondary origin. Clay particles occurring with the bauxite are kaolinite. Some types of bauxite are an index to their origin. There are four general physical types of bauxite or bauxite laterite: 1) Surface Rubble: This partly nodular and partly fragmented type, usually less than 3 ft thick, results from surface weathering of massive bauxite or may form by superficial enrichment of nodular bauxite with a clay matrix when the interstitial clay is removed by surface runoff.

Jan 1, 1960

By E. R. Stover, J. Wulff

A tentative 870°C isothermal section, the solidus equilibria, and the solubility of Tic and graphite in the nickel solid solution have been determined with arc-cast specimens. Each of the Ni-Ti intermetallics forms two-phase fields with Tic; only Ti,Ni has a measurable solubility for carbon. A quasi-binary eutectic exists between Tic: and a titanium-rich nickel solid solution; ternary eutectics occur on either side, with TiNis or with graphite. Graphite is in equilibrium with a nickel solid solution containing a ratio of Ti/C which increases below the solidus. DURING the past decade, titanium-carbide cermets containing nickel or cobalt alloy binders have been widely studied for high-temperature and wear-resistant applications. Recent work has emphasized control of the carbide grain size and distribution2&apos;s and the thermal exparision match between the phases/ The present study was initiated to determine the phase compositions during the sintering or infiltration process, and during subsequent heating. Although the effects of additives and impurities in commercial compositions are important, it was necessary to consider first the pure ternary, Ni-Ti-C. Emphasis was placed on the nickel corner, since the nickel solid solution is the continuous phase in compositions having highest strength. Early metallographic work by Zarubin and Molkov- showed that solid solubility at either end of the section Ni-Tic is small. Edwards and Raine reported that nickel dissolves between 3 and 5 wt pct Tic at 1250° C, on the basis of microstructures of annealed, vacuum-melted powder mixtures. Although the solubility of nickel in Tic has not been measured, Tic formed by the menstruum process in liuid-iron solution contains as little as 0.06 wt pct Fe. BINARY SYSTEMS The most recent determinations of the three binary systems are summarized in Fig. 1. Titanium carbide (6) is predominant among the binary phases, and it melts above the boiling point of nickel. The Ni-C binary is based on separate liquid solubility&apos; ) and solid solubilitylo measurements. The eutectic temperature, 1328OC, is taken from the solidus determination described below. However thermal analysis data by Morrogh and williams also show eutectic arrests in this vicinity in the absence of supercooling. The Ni-Ti binary is taken from the work of Poole

Jan 1, 1960

By R. D. Pehlke, J. F. Elliott

The equilibrium pressure of nitrogen gas over pure silicon metal and silicon nitride has been measured in the temperature range 1400° to 1700°C. From the experimental data, the standard free energies and enthalpies of formation of Si3N4(a) have been calculated as functions of temperature over the above temperature range. Utilizing data in the literature and the results of this investigation, the specific heat, molar enthalpy, molar entropy, standard enthalpy of fornation, and standard free energy of fornation are estimated for the temperature range 298° to 1400°C. THE high-temperature thermodynamic properties of many metallic nitrides are not well established at present. This is a serious deficiency because nitrogen and nitride-forming metals are important alloying additions to steels, and knowledge of the interaction between nitrogen and these elements is essential to a better understanding of the behavior of steels. Metallic nitrides also are used as refractory materials. Consequently, the investigation reported here was undertaken to provide more complete information on the standard entropy and free energy of formation of silicon nitride. The experimental technique provided a direct measurement of the equilibrium pressure of nitrogen gas in the range of 1413 to 1700°C for the reaction: 3 Si(1) + 2N2 (g) = Si3N4 (a) [ 1 ] and below 1413oC for the reaction: 3Si(c) + 2N2(g) = Si3N4(a) [2] APPARATUS The experimental system consisted of a crucible assembly, a reaction chamber, and a gas supply and vacuum system. The Crucible Assembly which contained the equilibration specimen and molybdenum radiation shields with a susceptor for induction heating is shown in Fig. 1. Two covered, high-purity alumina crucibles, one nested within the other, contained the susceptor, shields and specimen. Central openings in the upper shield and crucible covers permitted on optical pyrometer to be sighted into the central cavity of the specimen. The specimen itself was a 5/8 OD by 1-in.

Jan 1, 1960

By J. F. Havard

Gypsum is a useful industrial mineral found abundantly on the earth&apos;s crust. It is inexpensive to mine and process, and its calcined products have a wide range of readily controllable properties such as strength, density and setting time. It has proven to be such a useful material indeed, that ten American companies, operating some 57 calcining plants in 25 states in 1958, produced or imported in that year a total of 13,649,000 tons of the crude mineral valued at $39,361,000, which they then converted into manufactured products with a value of $329,070,000. Gypsum (CaSO4.2H2O) is calcium sulfate with two molecules of combined water, which are responsible for most of its useful properties. It is closely associated in most deposits with anhydrite (CaSO4), which contains no combined water and has limited commercial value in the United States. Man has long recognized the useful qualities of gypsum. It was utilized by the Egyptians in the construction of the pyramids and, later, by the Romans for important structures. Many of the ancient peoples prized gypsum for artistic and ornamental purposes, carving statuary from alabaster and making casts with plaster. The tabular variety, selenite, was used for windows, and the light transmitted through these windows reminded people of light from the moon (selene), hence the name selenite. The use of gypsum continued through the Middle Ages and into modem times. Benjamin Franklin was a famed exponent of gypsum because he applied ground gypsum to clover fields in the form of large letters which later read, in the more luxuriant growth, "land plaster used here." Gypsum is still used as an effective conditioner for some soils, but in recent decades, particularly in North America and Europe, it has become much more important as a major material for the building industry. Description Gypsum and anhydrite are closely associated minerals. Gypsum is found in a number of forms: massive rock gypsum, alabaster, selenite, satin spar, and gypsite. Anhydrite is found as massive rock or as smaller bodies or isolated crystals included in gypsum. Massive Rock Gypsum comprises most of the commercial gypsum and occurs as a sedimentary rock, interbedded in most places with shale, limestone or dolomite. This rock is soft and crystalline. Its color is white or shades of gray, pink, yellow, brown or other colors. Alabaster is a pure, compact and fine-grained variety suitable for use in sculpture or turning into artistic forms; it may be white or selected for attractive coloration. Selenite is gypsum crystallized in flat, transparent, flexible foliated plates, found in clays or in surface vugs in gypsum. Satin Spar is a fine silky fibrous variety with the axes of the crystalline fibers perpendicular to the vein or joint in which it has formed. Gypsite is an earthy mixture of gypsum with clay and sand in secondary formations; it is sometimes useful as a soil conditioner and has been used in making base-coat plasters. Pure gypsum contains 20.9 pct combined water, 46.6 pct sulfur trioxide (SO3) and 32.5 pct lime (CaO). Standard specifications (American Society for Testing Materials Designation C 22-50) read that minimum purity for material to be called gypsum is 70 pct CaSO4.2H20. Most of the commercial gypsum is 85 to 95 pct pure as produced. Impurities in

Jan 1, 1960

By Langtry E. Lynd

The predominant tonnage use of titanium is as a white pigment, in the form of rutile or anatase, which are allotropic modifications of titanium dioxide. Because of its whiteness, high refractive index and resulting light scattering ability, titanium dioxide is unequaled as a white pigment for paints, paper, rubber, and a wide variety of other materials. Consumption of titanium dioxide pigments for these uses has been rising steadily for many years, United States consumption in 1956 amounting to about 486,000 tons, worth $250,000,000. Production was off a little in 1957 and 1958. An outstanding development in the titanium field in recent years is the expansion of titanium metal production. Virtually nonexistent before 1948, United States production of pure titanium metal sponge reached a high in 1957 of about 17,200 tons, worth about $77,000,000. United States titanium sponge metal production in 1958 was cut back to about 4,600 tons because of reductions in military requirements. Another major use of titanium, in the form of the mineral, rutile, is for welding rod coatings. United States consumption of rutile for this purpose in 1958 amounted to about 11,000 tons, worth $1,100,000. Titanium-Bearing Minerals Although several minerals contain titanium as a major constituent, only a few of these occur in sufficient quantities and concentrations to be of commercial importance. These are ilmenite (FeTiO3), rutile (TiO2), and alteration products of ilmenite which have been referred to as weathered ilmenite, leucoxene, or arizonite. The other polymorphs of titanium dioxide, brookite and anatase, occur in a few deposits, of which only one has been of even minor importance. Considerable concentrations of titanite or sphene (CaTiSiO5) and perovskite (CaTiO3) are known, but do not compete with ilmenite and rutile deposits in grade or size. Rutile is very widely distributed as an accessory mineral in most rocks, but large deposits of commercial importance are rare. A few rock deposits have been worked for rutile but only one, in Virginia, is in operation (1959). Development of one in Mexico was discontinued recently. At present, the main sources of rutile are the beach and dune sands of Australia and Florida. A major use of rutile is for the manufacture of titanium tetrachloride, which is the intermediate compound universally used in titanium metal manufacture. Another main use of rutile is for welding rod coatings. Although the whiteness and brightness of titanium dioxide pigment is due to the high refractive index of rutile or anatase, natural rutile is too impure to be used directly as a white pigment, is too expensive to use for manufacturing pure oxide pigment, and is too scarce to provide the required tonnages. Instead, the cheaper, more abundant, mixed oxide of iron and titanium, ilmenite, which is readily decomposed by sulfuric acid, is used for manufacture of rutile and anatase pigments. Ilmenite is mined from both rock and sand deposits. Rock deposits contain ilmenite in massive or heavily disseminated form along with magnetite or hematite and are almost invariably associated with anorthositic and gabbroic rocks. Ilmenite also occurs as an accessory mineral in a great many igneous and metamorphic rock types. Concentrations of

Jan 1, 1960

By E. P. Sadowski, R. J. Raudebaugh

A study of micro structural characteristics of a 30 pct Cr, 42 pct Ni, 26 pct Fe alloy has been correlated with its behavior in creep and rupture tests at 1400°, 1600°, and 1800°F. Nitrogen pickup observed at 1600" and 1800°F was associated withfissur-ing of specimens prior to fracture. IN studying the high-temperature characteristics of a nominally 30 pct Cr, 42 pct Ni, 26 pct Fe alloy certain anomalies were observed, namely: The alloy had greater stress rupture and creep strength at 1800" than at 1600° F for time periods beyond 550 hr. As placed in test, this alloy was nonmagnetic. After test, some specimens were found to be fairly magnetic. The gain observed in magnetic response was not solely a function of time and temperature of testing. This is a report of the observations and a recounting of the results of studies made in an attempt to explain the behavior of the material under investigation. MATERIAL AND PROCEDURE All test material was taken from a production size heat of an experimental alloy melted and processed using commercial practice and having the following percentage composition: C Fe Cr Ni Ti 0.05 25.83 30.13 41.59 0.41 Al Mn Si S Cu 0.42 0.75 0.45 0.011 0.34 The material was tested in two conditions, namely mill-annealed and grain-coarsened. Mill annealing, which consisted of heating to about 1900° F in a continuous furnace for about 30 min and air cooling, gave a grain size of ASTM 8 and finer. To produce the grain-coarsened condition, mill-annealed material was soaked for 2 hr at 2050°F in a laboratory furnace and air cooled. This resulted in an ASTM grain size of 4 to 5. Rupture tests were carried out at 1400, 1600, and 1800° F in accordance with ASTM procedures. In tests where only rupture life and elongation at fracture were determined, specimens of 0.252 in. diam and 1 in. gage length were used. In tests where creep curves were obtained, specimens were of 0.375 in. diam and 4 in. gage length. Several of the tests under relatively low stress were discontinued short of rupture. Three low-stress tests are still in progress at this writing. Structural changes which occurred during testing were determined from examination of the tested specimens by light microscopy and X-ray diffraction. Diffraction pattern recordings were made with a diffractometer using copper radiation on samples heavily etched in a picric-hydrochloric

Jan 1, 1960

By A. D. Rich

The term "bleaching clay" or "bleaching earth," as used in the oil industries, refers to clays that in their natural state, or after chemical or physical activation, have the capacity for adsorbing coloring matter from oil. There are three common types of bleaching clays: fuller&apos;s earth, activated clays, and activated bauxite. Fuller&apos;s earth, or naturally active clay, is prepared from bentonites (see Chap. 5) that possess natural activity. It is not activated commercially; in fact, earths of this type ordinarily do not respond satisfactorily to acid activation. Fuller&apos;s earth is prepared in pulverized as well as granular form for use in the contacting and percolation processes, respectively. Acid-activated clays also are of bentonitic origin. The basic raw clay, however, is of a type that has a very low natural activity but is highly activable by treatment with mineral acid. Commercial acid-activated clays generally possess several times the decolorizing power (bleaching efficiency) of the best quality of fuller&apos;s earth. The former are prepared commercially only in the pulverized grade because of the difficulties in obtaining a satisfactory granular product, and hence are used only in the contact process. Activated bauxite is made by heat-treating bauxite ore, which in its natural state has very little natural activity. The commercial product is prepared in granular form for use in the percolation process on petroleum oils. For the most part, bleaching clay is used commercially in the decolorization of animal, vegetable and petroleum oils, fats and waxes. It is applied in two ways: (1) by the percolation method and (2) by the contacting method. Percolation refers to the passage of oil through a bed of granular clay whereas contacting refers to direct agitation of oil and pulverized clay followed by removal of the clay from the oil by filtration. In either case, the decolorizing effect is obtained by intimate contact between the liquid oil and the solid adsorbent. Petroleum oils are treated commercially by either the percolation or the contact process. Animal and vegetable oils are treated by the contact process only. Composition The raw clays from which both fuller&apos;s earth and acid-activated clays are prepared are composed of hydrous aluminum silicates containing varying quantities of magnesium, iron, calcium and other elements. These raw materials are usually nonswelling bentonites derived from volcanic ash or lava by weathering and hydrothermal chemical reactions. The bentonites have as their chief mineral constituent montmorillonite, which has the formula [(OH)4Si6A14O20•nH2O], according to Grim. (See Chap. 5, ref. 6, p. 91.) The underlying reasons are not fully known for the natural activity of the fuller&apos;s earth type of clay and its usual failure to further activate with mineral acid in contrast to the natural inactivity of the activatable type of clay. However, it may be said that the bentonites that are responsive to the acid-activation treatment generally have not undergone any drastic metamorphism. The chemical composition is not a reliable means of discrimination between a nonactive, a naturally active, and a nonactive but activable clay, therefore it is not possible to forecast the ultimate quality of a clay on the basis of the raw-clay analysis alone. Table 1 gives typical analyses of representative clays of the foregoing classifications.

Jan 1, 1960