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By Avnulf Muan, P. V. Riboud

The effect of Cr2O3 on melting relations of iron oxide at oxygen pressures slightly above those prevailing in contact with metallic iron has been determined. Liquidus and solidus temperatures of wüstite are raised by the addition of Cr2O3, from 1385°C for pure iron oxide to 1420°C at the peri-ledie point where wüstite, iron chromite, liquid, and gas coexist in equilibrium under the atmospheric conditions used in the present investigation (CO2/H2 = 1). It has been shown in a previous investigation1 that the liquidus and solidus temperatures of iron oxide are drastically increased by the addition of Cr2O3 under the relatively oxidizing conditions prevailing in air. This is to be expected in view of the easy substitution of cr3+ for Fe3+ in crystalline oxide structures which are stable at high oxygen pressures, as demonstrated for instance by the completeness of the solid solution series Fe2O3-Cr2O3 at high temperatures (>1000°C). The stable phase of iron oxide at oxygen pressures approximating those prevailing when metallic iron is present is wüstite. This phase, although commonly represented by the simplified formula FeO for sake of convenience, in reality has a defect structure in which a part of the iron ions are present as Fe3+. It is to be expected that at least a limited amount of cr3 ions will substitute for Fe in this structure when Cr2O3 is added to wüstite. Depending on the ease of this substitution in comparison with that of cr3 substitution for Fe in iron oxide-Cr2O3 liquids under the same atmos- pheric conditions, the liquidus and solidus temperatures of wüstite may increase or decrease upon addition of Cr2O3. The methods of establishing these melting relations and the results obtained are presented in the following. I) EXPERIMENTAL METHOD 1) General Procedure. The quenching technique was used in this study. Oxide mixtures were heated at chosen constant temperatures in an atmosphere consisting of equal parts of CO2 and H2 until equilibrium was established among gas and condensed phases. The samples were then quenched in mercury to room temperature, and the phases present were determined by microscopic and X-ray investigation. 2) Preparation of the Mixtures. Starting mixtures were prepared by weighing and thoroughly mixing Fe2O3 and Cr2O3, or wüstite and Cr2O3. The Fe2O3 and Cr2O3 used were "Baker Analyzed" reagent grades, whereas wüstite of composition was synthesized by reducing Fe203 at 1325°C in an atmosphere consisting of equal parts of CG andHz. In order to avoid contact with crucibles, the equilibration runs were made with small pellets suspended from thin (-0.004-in.) platinum wires. Mixtures made from FOs and Cr203 were readily pelletized at a pressure of 500 atm in a 9.5-mm die, whereas mixtures made from wüstite and Cr203 when treated identically were too weak for handling. In order to obtain a stronger product, these pellets were sintered by heating for 2 min at -1200°C in the same atmosphere as was subsequently used for the equilibration runs (CG/H2 = 1:1). During the sintering, these pellets were wrapped in thin (0.0004-in.) platinum foil, which was stripped off before the equilibration runs. In order to reduce the time needed for equilibrium to be attained, preliminary equilibration of relatively large pellets of each mixture was carried out at -1200°C for 4 to 12 hr. Smaller pellets

Jan 1, 1964

By C. Land, R. Hultgren

Heat contents of four Cr-Ni alloys were determined in a diphenyl ethev calorimeter. Aside from ferromagnetic effects, Kopp's law of additivity of heat capacities is approximately fol-lowed, in disagreement with earlier results of A. W. Foster. In 1934 Foster1 reported heat-capacity measurements of dilute solutions of chromium in nickel, primarily as a study of the effect of alloying on the ferromagnetic Curie temperature. He found that, apart from the Curie temperature effect, the general level of heat capacities was reduced 10 pct by the addition of 1 pct Cr; 20 pct by the addition of 2 pct Cr. His measurements of pure nickel essentially agreed with accepted values. These results indicate that small amounts of dissolved chromium cause an increase in the Debye temperature of nickel, presupposing a change of frequency of interatomic bonding vibrations which is much larger than should be expected. If Foster's results were verified, therefore, they would have important implications for bonding theory. The only other heat-capacity measurements in this system seem to be those of Taylor and Hinton,' who studied anomalies which they attributed to super-lattice formation at 25 at. pct Cr. At temperatures above the anomaly, Taylor and Hinton found heat capacities at this composition were quite normal, approximately obeying Kopp's law of additivity. EXPERIMENTAL WORK In order to verify or disprove the remarkable results of Foster, the heat contents of four dilute solid solutions of chromiunn in nickel were measured in a diphenyl ether calorimeter. This instrument, described elsewhere,, operates on the principle of the Bunsen ice calorimeter, but uses diphenyl ether as the working substance. Diphenyl ether melts at the convenient temperature of 26.S°C and supplies a more sensitive measure of heat than ice. The hot sample, in an atmosphere of argon, is dropped from a furnace at a measured temperature into a chamber which is surrounded by a mixture of solid and liquid diphenyl ether. The heat from the hot specimen melts some of the solid without chang- ing the temperature of the calorimeter. The amount of solid melted, and therefore the number of calories released by the specimen, is measured from the increase of volume of the mixture, which pushes mercury down a graduated capillary tube. The apparatus has been standardized against the known heat content of pure platinum. Heat loss during the dropping of the specimen was estimated by comparing the heat content of an empty platinum capsule with a solid platinum ball of the same radius and degree of polish of the surface. Repeated tests demonstrate the precision of measurement to be closer than *0.3 pct. Smoothed experimental results are listed in Table I. The tabulated values for pure nickel are taken from kelley, several measurements were made which agreed closely with this tabulation. For chromium, however, no similar agreement was found. The values tabulated were taken from a thorough study of chromium with the diphenyl ether calorimeter which will be published elsewhere.= Suitable plots of the data showed the expected ferromagnetic anomalies in the low-chromium alloys, while the 11 pct alloy shows no ferromagnetic anomaly, but a different, small anomaly below 900°K. This is perhaps the same anomaly found in CrNi, which was once attributed to superlattice formation,' but is probably due to some other cause, such as antifer-

Jan 1, 1960

By F. R. Wadleigh

There are in commercial use today in the United States various classifications of coal, each based on one or more characteristics. The bases of these classifications may be described as follows: GeNeRaL Basis Examples 1. Geological By seams and basins (local). 2. Chemical By constituents, as determined by analysis—ash, volatilc, slilfur and hcating value. 3. Combustion Characteristics As frce-burning, smokeless, character of ash. 4. Carbonization Characteristics Coking, noncoking. 5. Physical Characteristics Splint, soft, hard, block. 6. Geographical States, Fields, Counties, Districts. 7. Sizes By dimension or name. 8. Company Names Producing or sales company names, as "C. C. B. Pocahontas," etc. 9. Trade Names, copyrighted or not 10. Uses Gas, steam, coking, locomotive, fuel, bunkers, etc. 11. Use Methods Stoker coal. 12. Pools (Tidewater Exchanges) Analyses Size Seams Railroads Uses Structure Districts There are also classifications founded on more than one basis, as follows: 1. Geographical and Geological. By locality of mines (State, District, County) and seam. Examples: Cambria County, Miller Seam, New River, Sewell Seam. 2. Geographical and Chemical. Alabama medium volatile. 3. Combustion Characteristics and Ash Content. Free-burning, red ash (anthra- cite). 4. Carbonization Characteristics and Analysis. Noncoking, high-volatile, low sulfur. 5. Physical and Carbonization Characteristics. Splint, noncoking. 6. Size and Use. ¾-in. gas coal; domestic sizes (prepared sizcs); stcam sizcs. 7. Company Name and Seam. Consolidation Co., Elkhorn. 8. Size and Analysis. Low-volatile run-of-mine; low-volatilc slack. 9. Sizes—size of screen and name. 6 by sin. lump. 10. Chemical and USP. High-volatile steam. 11. Geographical and Use. Youghiogheny gas. 12. District, Size and Use. Pittsburgh gas l¼-in. lump. ,

Jan 1, 1930

By John Henderson

Densities of melts 0f the lime-iron oxide-silica system in contact with solid iron have been measured by the maximum bubble pressure method in the temperature range 1250° to 1440°C and the composition range 0 to 40 mol pct lime, 15 to 100 mol pct iron oxide, and 0 to 55 mol pct silica. Densities range from 4.65 g cm 3 for wustite at 1440°C to 2.75 g cm-&apos; at 1350°C for a melt containing 30 mol pct lime, 20 mol pct iron oxide, and 50 mol pct silica. The results are interpreted in terms of a postulate that the melts can be regarded as a random array of oxygen ions in which regions of local order exist to satisfy the coordination requirements 0.f the cations. An understanding of the nature of metallurgical slags is basic to the development of a sound theoretical description of heavy metallurgical extractive and refining processes. Because these liquids are complex, direct measurements of their properties has not thrown much light on their structure. This has led to the approach of measuring the properties of simpler liquids, and building up their complexity until slag compositions are reached. In this way the density of liquid iron silicates was measured in a previous study1 and the present work represents a further stage in this synthesis. EXPERIMENTAL The technique used in the measurement of density was the maximum bubble pressure method. Details of the apparatus and procedure were similar to those previously reported,&apos; with the exception that a constant voltage transformer was used to supply the power input to the furnace and six silicon carbide resistance elements were used in place of the molybdenum winding. With these modifications melt temperature could be maintained within 1 centigrade degree during the course of a run. The silica used to prepare the melts was washed natural quartz ignited at 1000°C; wustite was prepared by air-melting A.R. grade ferric oxide in an iron crucible and lime was prepared by air ignition, at 1000°C, of weighed quantities of A.R. grade calcium carbonate, previously air-dried at 110°C. The finely ground constituents were intimately mixed in a glass ball mill prior to melting. Temperatures quoted are accurate to * 5°C and the standard deviation of the density values, calculated by the method of least squares, ranged from 0.5 to 1.8 pet. However, replicate determinations of density on different melts of the same nominal composition at the same nominal temperature did not vary by more than 1 pct, Table I, and this figure has been taken as an estimate of the accuracy of the density results. The density of carbon tetra-chloride was also measured as a check on the absolute performance of the experimental method. At 20°C a value of 1.593 * 0.002 g cm"3 was obtained; this compares with the literature value2 of 1.595 g cm"3. Results of experiments designed to measure the dependence of the density of lime-iron oxide-silica melts, in contact with solid iron, on composition and temperature are shown in Table I. Because iron sometimes precipitated in the sample during quenching, the Fe203 chemical analyses were only poorly reproducible and should be taken as a guide rather than as absolute values. Fig. 1 shows the data from various sources for the density of liquid iron silicates and Fig. 2 shows isodensity contours at 1410°C for lime-iron oxide-silica melts, calculated by graphical interpolation of smoothed curves drawn through the experimental results, together with the 1400°C results of Adachi and ogino3 and Pope1 and Esin.4 Fig. 3 shows the isothermal variation with composition of the volume of melt per gram ion of oxygen at 1410°C and Fig. 4 shows regions in which the temperature coefficient of this volume is negative, positive, or negligible (<0.005 cm3 deg-I). DISCUSSION a) Disparity Between Reported Density Results. Consider the system iron oxide-silica, the results for which are summarized in Fig. 1. Although there is some difference in the temperatures at which the various densities apply, this difference is not sufficiently large to account for the observed discrepancies. The reliability of the present results for the low-silica region has been confirmed by measurement of the density of liquid wustite by three different techniques. At 1410°C the density measured by a balanced-column method was 4.55 g cm"3, by a combination balanced-column and gas-densitometer method 4.59 g emd3, and by a pycnometer method 4.53 g cm"3. Schenck, Frohberg, and Hoffermann&apos; have also reported a value of 4.55 g cm"3 for the density of liquid wustite at 1400°C. It must be concluded, therefore, that neither Pope1

Jan 1, 1964

By Thomas T., Read

SUGGESTIONS that existing schools give instruction bearing on the mineral industry, or that schools for that purpose should be established in the United States, began to be made early, and it would require too much space to catalogue them all. Some of the more important may be mentioned to indicate their general character. In the "advertisement to such parents as have now (or expect to have) children prepared to be educated in the College of New York," which appeared in the New York Mercury of June 3, 1754, Samuel Johnson, the first president of King&apos;s College, the predecessor of Columbia, said that it was the "design of this college to instruct and perfect the youth," among other things, "in the arts of Numbering and Measuring of Surveying, and Navigation and Geography. . . . and in the Air, Water and Earth around us, and, the various kinds of Meteors, Stones, Mines and Minerals, Plants and Animals; and in the knowledge of all Nature in the Heavens above us, and of everything useful for the Comfort, Convenience and the Elegance of Life . . . " Though the concept that natural science should be used to enlarge the bounds of human life was thus implicit at Columbia from the very beginning (John Stevens graduated from it in 1768, James Renwick in 1807, Horatio Allen in 1823, and A. W. Craven in 1829), it was only during the period of Renwick&apos;s professorship of Natural and Experimental Philosophy and Chemistry (1820- 1853) that much attention was given to applied science.* Among the Austin papers, published by the American Historical Association,2 there is a draft in Stephen F. Austin&apos;s handwriting of a proposed memorial from the legislature of Missouri to Congress, not only urging "the propriety and utility

Jan 1, 1941

By J. H. Westbrook, R. W. Guard

The influence of a number of alloying additions on the structure and hardness of Ni3Al (?&apos;) has been studied. Three general effects have been observed.. solid-solution hardening, strain aging, and defect hardening arising from deviations from stoichiometry. The solid-solution hardening phenomena are complicated relative to binary terminal solid solutions due to the possibility of virtually independent substitution for the component elements and to the concomitant effects of strain aging. In many superior nickel-base high-temperature alloys the elevated temperature strength is attributable to the presence of a dispersion of Ni3A1 (?&apos;) in a solid-solution matrix. Examples of such alloys are Inconel X-550, Inco 713, Waspalloy, and Nimonic 80. It is, therefore, appropriate to seek a further understanding of the properties and alloying behavior of this compound. Ni3Al, the compound most rich in nickel in the nickel-aluminum binary system, was first detected by litakal but not established with certainty until the much later studies of Bradley and Taylor&apos; and Alexander and Vaughan.3 More recently the mechanism of formation was clarified by Floyd4 who showed that Ni3Al is the product of a peritectic reaction at 1395°C between the melt and the compound NiAl in agreement with the original suggestion of Alexander and Vaughan.3 Ni3Al has the ordered face-centered-cubic or Cu3Au structure in which the nickel atoms occupy the face centers and the aluminum atoms the cube corners, a0 = 3.570A. Despite earlier reports to the contrary. the compound apparently remains ordered at least to 1000oC.5 It exists over a narrow range of compositions (-3 pct wide) whose limits and temperature dependencies thereof have been reviewed recently by Taylor and Floyd.&apos; Most previous workers have found Ni3Al to be both hard and brittle7,8 although Maxwell and Grala8 obtained 2.5 to 6 pct tensile elongation at room temperature and Alexander and vaughan3 described the material as "hard and tough" on the basis of observations made while preparing metallographic specimens. In a recent study one of the present authors found that although considerable intergranu-lar brittleness was evident: individual grains of a coarse-grained inert atmosphere arc-melted specimen were readily deformable.l0 The same study also showed Ni3Al to have an anomalous temperature dependence of hardness in that such a curve exhibits a number of peaks between room temperature and 800°C which could not be associated with any microscopically observable precipitation reactions or polymorphic transformations. It was, therefore, proposed in the present study to elucidate the anomalous high-temperature strength behavior and to examine the solid-solution alloying of this compound and the effects of such alloying on hardness. Sample Preparation and Experimental Procedure-Samples, both of pure Ni,Al and of various alloyed solid solutions based on Ni3Al, were prepared by arc melting 100-g buttons in an inert atmosphere arc furnace. All buttons were heat treated for 4 hr at 1275oC and examined metallographically for homogeneity. Microstructures were typically homogeneous and single phase with ASTM grain size about 1 and unusually clean grain boundaries. Chemical analyses showed good correspondence (within a few tenths of a percent) with intended compositions. Microindentation hardness data were obtained from room temperature to 800°C in vacuo using a balanced-beam type loading system in an instrument to be described in detail elsewhere." In general a 100-g load, a loading rate of 1 mm per min and an indentation time of 15 sec were used. Various indenter materials were used according to the materials bein tested because of specimen-indenter interaction. Fl Measurements of the Vickers-type indentations were made at room temperature. Hardness-temperature curves were run at least twice on each sample to ensure that surface work-hardening effects had been eliminated." Precision lattice-parameter measurements were made on powder samples using a back-reflection

Jan 1, 1960

By T. A. Rickard

The notion prevails that writing is a knack, that the skilful use of the pen is a gift of nature. This is an error. Dogberry may be responsible for it; he said: "To be a well-informed man is the gift of fortune, but to write and read comes by nature". Because Dogberry said it, we may be sure that Shakespeare thought otherwise. Ability of any sort may be partly innate, but my own observation and experience lead me to conclude that most of the easy writers have become so by constant practice. As I recall the names of men successful with the pen, I remember that most of them have written a great deal and have taken particular pains to improve their style. The suggestion that proficiency in the difficult art is a happy accident provokes a sardonic smile. The larger part of the great writing in our literature is the result of persistent effort. An easy fluency has been the undoing of many; their flamboyant and fantastic scribbling has proved as perishable as froth. This criticism applies to technical writing also; in order that a technical description or discussion may hold the interest of the reader, at least long enough to cause him to read it to the end, the writing must be done carefully and systematically; otherwise it will fail in its purpose of conveying information. Clearness is absolutely essential. "It is not enough to use language that may be understood; it is necessary to use language that must be understood."* The purpose of writing, at least of that which is meant to be read by others, is not only to express ideas but to communicate them. Lack of perspicuity may prove as %ad as

Jan 1, 1931

By Frank W. Dickson, George Tunell

Five hot spring areas of the western United States show evidences of present day deposition of HgS; two also show evidences of accompanying Sb2S3 deposition. Sulfide minerals are depositing at or near the surface from hot waters that differ for each spring ai:ea in amount and kinds of dissolved matter. All the springs contain dissolved substances that act as buffering agents and that cause increased alkalinity with increasing temperature. Transport of Sb2S3 is possible in H2O and in boron and sulfide solutions. Increasing alkalinity and temperature enhance stibnite solubility. Quantitatively important transport of HgS appears restricted to alkaline sulfide solutions that contain HgS2=. Elemental mercury probably forms in deep hot waters because HgS breaks down into mercury and sulfur above 200°C, and free S is removed by reaction with water. Elemental mercury should accompany HgS2= in solutions that were at 200°C or higher. Cinnabar deposits from saturated alkaline sulfide solutions because of combinations of temperature decrease, dilution, oxidation, and reactions with wall rock: Amedee Hot Springs, Boiling Springs, and Coso Hot Springs are areas in which HgS is the only sulfide deposited. Hot waters at Amedee and Boiling Springs are supersaturated with HgS or transport colloidal HgS. Steamboat Springs waters deposit mainly silica and stibnite, but they have deposited HgS recently. Sulphur Bank waters deposit mostly stibnite and some HgS. The hot-spring waters of all springs represent highly modified deep water. Field and laboratory studies support the concept of transport of HgS in moderately alkaline sulfide solutions as HgS2=. Fluctuating deposition of stibnite and cinnabar reflects availability of sulfide or variations in deep-source HgS and Sb,S,. Silica and HgS dissolve mutually in alkaline sulfide solutions, and cinnabar and quartz would be expected to deposit simultaneously. Free mercury given off by hot-spring waters would impregnate country rocks.

Jan 1, 1968

By ROBERT E. HARDWICKE

THE QUESTION of whether the production of oil should be limited to market demand has been constantly discussed during the last two years. Oil men, legislatures and courts have reached highly conflicting conclusions. Opponents of limitation to market demand assert that it is a scheme of the big purchasing companies to fix prices and to create a monopoly. Proponents, on the other hand, declare that such a limitation is necessary to prevent physical waste and that the effect on prices is merely incidental. A brief review of market demand legislation will disclose the confusion existing. The laws of Oklahoma,&apos; prohibiting waste of oil and gas, specifically&apos; authorize limitation to market demand as a method of preventink such waste. These laws and the proration orders based thereon have been upheld by the Supreme Court of Oklahoma, by several three-judge Federal District Courts, and by the Supreme Court of the United States.&apos; Kansas has a similar law3 but no case has been found which discusses its validity. About a year ago the California Legislature passed a comprehensive conservation act, generally known as the Sharkey Bill giving authority to restrict production to an amount representing current requirements for use, taking into consideration oil and products in storage. This may be considered as equivalent to limitation to market demand. The Act was defeated upon referendum vote after a hard fought campaign in which it was charged that the Act would result in destruction of the independent operators.

Jan 1, 1932

By H. T. Sumsion, A. U. Seybolt

The results of an investigation of vanadium-rich V-O solid solutions are presented, indicating the structure and lattice parameters of two solutions, a and ß, and their approximate temperature-composition existence. The a solution is the terminal body-centered cubic one, and contains up to 3.2 atomic pct 0. The ß solution has an ordered body-centered tetragonal structure, is formed at 1270°C, and exists from about 15 to 22 atomic pct 0. From the evidence available, the various phase boundaries have no appreciable temperature dependence. Evidence has been found for a polymorphic transformation in pure vanadium at 1550°C. IN an earlier investigation&apos; dealing with the preparation of pure vanadium by calcium reduction of the oxide, it was found that small amounts of oxygen drastically reduced the ductility of the metal. Because this effect was so marked, it was decided to make a study of the solubility of oxygen in solid vanadium. This report deals principally with this solubility and the nature of the phase relationships in the vanadium-rich region, particularly at temperatures below 1300 °C. However, during the investigation enough data on the V-0 system were obtained to make it appear worthwhile to present a tentative phase diagram up to the composition VO. The only significant prior work found on this system are the contributions of Klemm and Grimm,&apos; and Mathewson et al.3 Klemm and Grimm prepared a wide range of V-O compositions by powder techniques including the compositions VO.l, VO.2, VO.3 and VO4 (9.1, 16.8, 23, and 28.6 atomic pct 0, respectively). The first three compositions were found to consist of a body-centered tetragonal solid solution, while the last also showed lines of VO (NaCl structure). They found that the parameter c, increased and the parameter a, decreased with increasing concentration of oxygen. For their composition VO.27, or about 16.8 atomic pct O, they cite the values a, = 2.948A, c, = 3.53A, and c/a = 1.2. Klemm and Grimm made no attempt to determine the solid solubility limit nor to construct a phase diagram. They did, however, give some data on the homogeneity range of VO, and they proposed a structure for the body-centered tetragonal solid solution; these points will be taken up later. Materials and Preparation of Samples The vanadium used in this investigation was prepared in the laboratory by the method previously mentioned.&apos; A typical analysis is as follows: Fe, 0.007 pct; Si, 0.02; Ca, 0.06; C, 0.224; O2, 0.044; N,, 0.0017; H2, 0.003; and V, 99.34 ±0.3 (assay). The vanadium assay is probably low by about the error given. The impurities total about 0.36 which, if subtracted from 100, gives a purity of about 99.6. At the time material was being prepared for this work no suitable technique was available for melting vanadium without appreciable contamination. The procedure adopted therefore was to cut the calcium-reduced regulii into slices which were then rolled to strip about 0.025 in. thick for oxygen diffusion. Pieces of rolled vanadium of approximately 0.025xY4xl in. and weighing about 0.3 g were suspended in a vertical fused-silica tube which was part of an ordinary gas absorption apparatus. The silica tube was heated by an electric resistance-tube furnace which could be raised around the silica tube or lowered away from it as desired. This apparatus had no novel features which require detailed description. Other than the silica tube and furnace, it consisted of a glass system evacuated by a liquid nitrogen trapped mercury diffusion pump, a mercury-operated gas burette, a McLeod and a Pirani gage, and a mercury manometer. It was also equipped with suitably located stopcocks for isolating various parts of the system; the vacuum ordinarily attained was between 10" and 10-6 mm of mercury. Oxygen generated by decomposing MnO2 was passed through anhydrous magnesium perchlo-rate before introducing it into the gas burette and thence to the absorption chamber.

Jan 1, 1954

By R. M. Waterstrat, E. C. van Reuth

BINARY- alloy phases having the A15-type crystal structure have been described as occurring at a simple and more or less invariant stoichiometric composition (A3B) which corresponds to the relative number of atoms occupying each of the two crystallographi lattice sites in this structure.1,2 It is frequently assumed, therefore, that each crystallographic site is occupied exclusively by one kind of atom. In most cases, however, there have been insufficient experimental data to establish whether atomic ordering is, in fact, complete. Recent studies have shown that binary A15-type phases are sometimes stable over an appreciable composition range3&apos;&apos;* and, occasionally, the composition range of stability does not even include the "ideal" A3B stoichiometric composition.5-7 We have observed the existence of nonstoichiometric A15-type phases in the binary systems Cr-Pt and Cr-Os. This has not been reported in previous work on these alloy systems.1,8-11 A series of alloys, each weighing approximately 30 g, was prepared by are-melting in an Ar-He atmosphere using 99.999 pct Cr, 99.999 pct Os, and 99.99 pct Pt as starting materials. Each alloy was melted four times with a total weight loss of less than 1 pct. The stoichiometric (A3B) alloys were sealed in evacuated quartz tubes and annealed at 1200°C for periods of time ranging from 3 days to 2 months. Examination of the alloy microstructures revealed that little change had occurred over this time interval and it was therefore assumed that the microstructures were fairly representative of equilibrium conditions. No evidence of contamination was observed although there was apparently some loss of chromium which was confined to a thin layer at the surface of the specimens. The quartz tubes were quenched from the annealing temperature into cold water. X-ray diffraction and metallographic examination of the stoichiometric alloys revealed an estimated 10 to 30 pct of second phases which were tentatively identified as phases previously reported in these binary-alloy systems.8-11 A second series of alloys was prepared by mixing -325 mesh metal powders having a nominal purity of 99.9 pct and compressing these mixed powders in a cylindrical die at a pressure of 43,000 psi. These alloys, each weighing 15 g, and some of the arc-melted alloys were annealed in a high-temperature vacuum furnace heated by tantalum strips at a pressure of 10-8 Torr and were rapidly cooled by turning off the furnace power. X-ray and metallographic examination of both series of alloys served to establish the composition ranges of the A15-type phases. Although some chromium losses occurred during the vacuum annealing, they were largely confined to a thin layer on the outer surfaces of the samples. It was established that the A15 phases occur in the Cr-Pt system at 21 ± 1 at. pct Pt after 1 week at 1200°C and in the Cr-Os system at 28 ± 1 at. pctOs after 1 day at 1400°C (see Table I). We also observed that an arc-melted stoichiometric (A3B) alloy in the Cr-Ir system was single-phase (A15-type) in the "as-cast" condition in agreement with previous work.8,13 In addition we obtained a sample of the Cr-Os A15-type phase from Argonne National Laboratory. This alloy contained less than 1 pct second phase12 and was submitted to a density measurement. The density measurement yielded a value of 11.14 g per cu cm in comparison to a theoretical value of 11.25 g per cu cm calculated using the observed lattice constant (4.6806Å) of this alloy. The uncertainty in measurement was 0.1 pct but the sample may have contained some cracks or minor imperfections which could account for the low experimental value. We have also studied the atomic ordering in these phases by means of integrated line intensity measurements using thick, flat, rotating powder samples and CuK a radiation in an X-ray diffractometer. We have obtained order parameters of 0.90 for the Cr-Pt phase, 0.89 for the Cr-Ir phase, and 0.64 for the Cr-Os phase using the formula: where s is the usual Bragg and Williams order parameter, ra is the fraction of chromium atoms in A sites, and FA is the fraction of chromium atoms in the alloy. The values obtained are estimated to be accurate within ±4 pct. If the unusually small value for the order parameter of the Cr-Os A15 phase were due to the existence of lattice vacancies on the "B-atom" sites, then a density of 10.04 g per cu cm would be expected in contrast to the observed value of 11.14 g per cu cm. We, therefore. conclude that the fraction of lattice vacan-

Jan 1, 1967

By C. W. Parmelee

THE ideal fuel for burning ceramic wares is the one that, among other characteristics, has little or no sulfur. For that reason wood was long considered the most desirable fuel but its high cost has practically eliminated its used except in regions where it is very abundant or other circumstances warrant its choice. The fuels commonly employed are natural and producer gas, oil, and coal. The last named is undoubtedly the most important, not only in this country but abroad. Occasionally anthracite is used but the larger part is bituminous. The quality of the coal used depends on the kind and the value of the products being manufactured. For some materials, such as common brick, hollow block, etc., the quality of the coal is of less importance than in the manufacture of polychrome terra cotta, pottery, porcelain, etc. It is obvious that in burning clays that contain notable amounts of pyrite, marcasite or gypsum, as is the case with many common clays, the sulfur content of the fuel is of much less importance. The permissible amount of sulfur in the coal used will depend on the kind of product being manufactured. "A good sample&apos; of coal commonly used in pottery ovens has something like this quantity of sulfur." PER CENT. Total sulfur 1.20 Sulfur in the ash 0.11 Volatile sulfur a 1.09

Jan 9, 1919

By H. B. Bell, P. C. Lidster

A study has been made of the use of ThO2-Y2O3 solid electrolytes to determine activity of chromium in Fe-Cr and Ni-Cr alloys in the temperature range 1300° to 1700°K. This method has been shown to give results which agree with the best vapor pressure measurements. SEVERAL investigations1"5 have been made of chromium activities in Fe-Cr alloys. Most of these have been made by vapor pressure measurements using knudsen cell techniques while one has been made using gas equilibration with H2/H2O gas mixtures. In the present investigation electromotive force measurements have been made on this system using a thoria yttria solid electrolyte. This system was -chosen to establish the technique of measurement at low oxygen potentials, before extending it to Fe-Ni-Cr alloys. The cell used was Pt Cr • Cr2O3 ilThO2 • Y2O3 llalloy • Cr2O3 IPt Since the oxygen pressure of the chromium-chromic oxide mixture lay in the range 10"19 to 1027 atm in the temperature range investigated, thoria yttria electrolytes were used. It was soon found during the investigation that considerable care was required to prepare satisfactory electrolytes and a study was made to find the best method of preparing pellets of TI1O2-Y2O3 solid solution of as near theoretical density as possible. Various compositions in the range 2 to 15 mole pct Y2O3 were studied but the experimental measurements were made with electrolytes containing 4 to 5 pct Y2O3. The method of preparation finally adopted was to use thorium oxalate and yttria as raw materials. The thorium oxalate was decomposed at 900°C for 6 hr to give a reactive powder. This powder was then mixed with the appropriate amount of yttria and ground in an agate mortar for about 4 hr. The powder was moistened with absolute alcohol as a lubricant and pressed in a metal die at a pressure of 7 tons per sq in. The pellets were then heated at 1100°C for 24 hr followed by 24 hr at 1250°C. After this firing cycle the material was reground and repelleted and again fired at 1100° and 1250°C followed by heating for 7 days at 1600°C. It was found in later experiments that a further firing of 4 hr at 2000°C improved the density further and gave pellets of only 2 pct porosity. After firing, the pellets were polished on emery paper and finally with the 2 µ diamond paste. The polishing was followed by a final firing of 24 hr at 1500°C. Investigation showed that this final treatment minimized reaction between the electrolytes and chromium oxide. It was believed that this was because of a lowering of the surface energy of the electrolyte surface. Two types of investigation were carried out to check that the pellets were satisfactory oxygen ion elec-

Jan 1, 1970

By Paul. D. Merica

I LIKE to look upon the award this year also as a recognition of the importance of metallic materials of construction to the engineer and of the active progress which I believe is continually being made in almost all branches of that field today. It has been said that metals are the material backbone of industry and technology. Well in that case, I suppose we metallurgists are industry&apos;s bonesetters. And it is possibly not inappropriate that we should occasionally give some atten¬tion to those bony structures of our industrial activities upon which engineers in other fields hang their manifold and striking creations. What is going on in the field of metals development? Well, in the first

Jan 1, 1938

By A. Muan

Liquidus data are presented for mixtures in the ternary system FeO-Fe2O3-SiO2 in equilibrium with a gas phase with O2 pressures ranging from 10-10.9 to 1 atm. Data obtained are combined with previously published data to construct lines of equal 02 pressures and lines of equal CO2/H2 mixing ratios along the liquidus surface. Courses of crystallization of selected mixtures under conditions of constant total composition, constant O2 pressures, and constant CO2/H2 mixing ratios are discussed. PHASE equilibrium studies of silicate systems where iron is one component are complicated by the fact that iron readily occurs in three different states of oxidation: Fe3+, Fe2+, and Fe0. Success or failure in work with iron silicate systems is to a large extent dependent on control of the oxidation state of iron and all investigations therefore must be carried out under carefully controlled atmospheric conditions. Silicate systems containing only strongly electropositive metals (like Na+, Ca2+, Mg", etc.) can, for simplicity, be treated as condensed systems, that is, the gas phase can be neglected and the phase relationships discussed in terms of the phase rule written in the well known simplified form P + F = C + 1. In the case of iron silicate systems, however, the composition of the condensed phases varies with the gas composition, and a complete picture of phase relationships can be obtained only by varying the gas composition over a wide range. In order to understand the phase relationships in the more complicated multicomponent silicate systems with iron oxide as one of the constituents, a knowledge of the ternary system FeO-Fe2O3-SiO2 is essential, since it constitutes a bounding portion of all such systems. It was with this in mind that the present study was undertaken. Previous Work A considerable amount of work has been done on various aspects of the chemistry and metallurgy of systems containing silica and iron oxides. The two bounding binary systems FeO-Fe2O3 and FeO-SiO2" The first attempt to obtain information on phase relationships of iron oxide-SiO, mixtures at different 0, pressures was made by Greig.&apos; Darken" determined the melting points of iron oxide on solid silica under various atmospheric conditions. Darken did not determine experimentally the composition of the melts at liquidus temperatures but discussed very ably the principles involved in applying the phase rule to the system. In a recent study Schuhmann, Powell, and Michal8 determined experimentally the liquidus surface of a portion of the ternary system and combined the new information with data in the literature to construct a phase diagram. Their method was briefly as follows: Homogeneous mixtures with various contents of SiO2, FeO, and Fe2O3 were made up by melting together stock mixtures in various proportions. Samples of the homogeneous mixtures, the compositions of which were determined by chemical analysis, were then heated in platinum crucibles in an inert atmosphere until equilibrium among the condensed phases was achieved. The samples were quenched to room temperature and the phases present determined by microscopic examination. Assuming that no change in composition takes place during the equilibration run in inert atmosphere, the liquidus surface can be determined, but no information is obtained regarding the partial pressures of 0, of the gas phase in equilibrium with the condensed phases. The author&apos;s method, to be described in the next section, permitted the location of points at the liquidus surface as well as a calculation of the corresponding partial pressures of O2. Experimental Method General Procedure: The standard quenching technique was adapted for a study under controlled variable atmospheric conditions. Premelted mixtures of silica and iron oxides in platinum envelopes were held at constant temperature under chosen atmospheric conditions until equilibrium was reached among solid, liquid, and gas phases. The sample was then quenched to room temperature, the phases present identified, and, for the most significant runs, the composition was determined by chemical analysis. The corresponding partial pressure of 0, was calculated from known equilibrium constants of the gas reactions occuring in the furnace atmosphere. Materials: Starting materials were oxides of commercially highest available purity; cp silicic acid was dehydrated by heating to 1350°C for 6 hr and cp Fe2O3 was dried at 400° C for the same length of time. Samples of 10 g were made up by mixing

Jan 1, 1956

By Paul F. Kerr

The uranium-producing areas near Marysvale, Utah provide an unusual group of veins and replacement deposits associated with a Pliocene-Oligocene intrusive and extrusive igneous complex. Aside from several scattered occurrences in older volcanics, uranium-bearing veins occur in intrusive quartz monzonite or granite and in nearby rhyolite. The veins in general trend within a few degrees of N55-65°E, are more or less vertical, and are found along the western margins of a quartz monzonite intrusive. The replacement deposits are found in rhyolite intrusives and also in the lower portions of rhyolite flows close to places where veins forming solutions rising through quartz monzonite came into contact with the rhyolite. At least 14 veins have been mined since uranium mining operations began at Marysvale some 16 years ago, while ore has been extracted through about 10 miles of underground workings. The active mmmg area is approximately 3000 feet long and in the central portion 1500 feet wide. Ores have been found over a vertical spread of almost 2000 feet, between the highest occurrence on Jungfrau Hill ( ca. 7200 feet) and the deepest discovery of ore in a drill hole near the Prospector Mine (ca. 5200 feet). Under existing mining and marketing conditions, mining along the veins in the main area appears to have reached an economic limit at about 500-600 feet below the surface. However, orebodies in the rhyolite and in the upper portions of veins close to the rhyolite are subject to active mining. Isotopic dates indicate that the uraninitebearing veins and replacements are late Miocene or Pliocene (ca. 10-13 m.y.), the rhyolite is Miocene (avg. 17.5 m.y.), and the quartz monzonite and granite intrusives are late Oligocene (23.6 to 26.0 m.y.). The older Bullion Canyon Volcanic Series which encircles the area is Oligocene (28 to 31.1 m.y.). Two generations of alteration occur: ( 1) Earlier alunitic veins and replacement bodies are found in the Bullion Canyon Volcanic Series, none of which have produced uranium; (2) Later argillic alteration associated with the introduction of uranium is found along veins, replacing glassy rhyolite dikes and replacing phases of the rhyolite.

Jan 1, 1968

By R. J. Colony

MINING geology does not lend itself - very readily to a review embracing "improvements in methods," as perhaps do shop practices or laboratory procedures. The "methods" used in mining geology are simply the application of geology to mining; winning the ore, the handling of material, mechanical appliances, all belong strictly to mining proper, and have no place in a review of geology as applied to mining. A comprehensive review would necessarily cover a .very broad field, which could be subdivided into many -parts. Only a few of these can be discussed here. .Those that have been suggested to the chairman indude :

Jan 1, 1930

By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan&apos; have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn&apos; have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5&apos;, Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By W. P. Frey

The briquet plant of the Lehigh Coal and Navigation Co., at Lansford, Pa., has previously been referred to.&apos; It has passed the stage of experiment and now rests on a foundation practically and financially sound. The purpose of this&apos; paper is to explain how success has been attained, and to set standards for the development of hard-coal briquetting which may eliminate future failures. All the conclusions are based on actual results, avoiding speculation and theory. Up to three years ago, the L. C. & N. Co. used coal-tar pitch as a binder in making hard-coal briquets. The plant operated with a monthly output of 300 to 600 tons and was unable to meet its own expenses. Naturally, no one was satisfied, especially as the ideals of a smokeless briquet were still unrealized. Then came the Dutch oil process, introduced in this country by the General Briquetting Co. of New York. This process uses as binder a small percentage of heavy residue of petroleum, which, being liquid, permits great economy of handling; it also did away with the most objectionable fumes of the former briquets. This oil2 is not absolutely smokeless; heating the fresh fuel to red heat liberates some low-volatile hydrocarbons, yielding a white smoke which is not objectionable. On the other hand, this oil adds to the briquet about 7 per cent. of volatile matter, giving the product a heating capacity equal to that of the best free-burning anthracite coal. The average silt used in the manufacture of these boulets averages 16.5 per cent. chemical ash, corresponding to 12,000 B.t.u. per pound of coal. The Hydrolene used as binder runs about 17,500 B.t.u. per pound, and approximately 7 per cent. of it enters into the mixture, hence 12,000 X 0.93..........................11,160 B.t.n. 17,500 X 0.07.......................... 1,125 B.t.u. Total.....................................12,385 B.t.u. per pound of briquets

Jan 1, 1918

By AIME

The following corrections (in italics and bold face) were received too late for the September issue of Transactions: Page 270, Abstract, line 1, spelling should be goethite. Page 270, column 1, authors&apos; box, authors&apos; affiliations should read: L. A. BAKER, formerly Principal Research Scientist, is Pellet Plant Superintendent, Cliffs Western Australian Mining, Cape Lambert, W. A., Australia. C. G. THOMAS is Experimental Officer, Minerals Research Laboratories, C.S.I.R.O., North Ryde, N.S.W., Australia. R. J. CORNELIUS and K. S. LYNCH are General Superintendent, Product and Process Development, and Superintendent, Pellet Plant, respectively, Hamersley Iron Pty. Ltd., Dampier, W. A., Australia. G. J. ARMSTRONG, formerly Chief Metallurgist, Hamersley Iron Pty. Ltd., is Mill Superintendent, Samin Ltd., Burra, S. A., Australia. Page 271, column 2, line 41, should read "highest possible spalling temperature and to adjust the. . :&apos; Page 275, column 1, line 1, should read "(LOI) figures are shown in Table 1 and vary from 2.61..." Page 275, column 1, line 16, spelling should be goethite. Page 276, column 2, line 6, should read "Predicting Grate Speed and Production Rate: The cor-..." Page 276, column 2, line 8, should read "basis of Blends A, B, C, D, and Plant Ore 1, shown in Table..." Page 276, Table 3, heading under "Prediction Method" should read Blend E. Page 277, column 1, line 38, should read "=293 tph of specification pellets (see Table 1 for loss-..." Page 277, column 2, replace caption for Fig. 14 with the following: Fig. 14-Example of calculation of hood temperature profile during downdraft free-water drying, given plant free-water drying time. Page 277, column 2, replace caption for Fig. 15 with the following: Fig. 15-Example of calculation of hood temperature profile during drying, given plant goethite drying time.

Jan 1, 1974