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By E. J. Dulis, R. M. Fisher, K. G. Carroll

IT is well known that ferritic steels containing more than 15 pct Cr when subjected to temperatures in the range of 700" to 1000°F exhibit increasing hardness and decreasing ductility. The phenomenon has been widely termed the "885 °F embrittlement," after the temperature of most marked effect.'.' In view of the excellent review articles available in the literature3-6 only a brief account of experimentally established facts need be given here. The extent of changes in physical characteristics during embrittlement depends on chromium concentration and time at temperature, higher alloy content and longer time both promoting more rapid and extensive changes. In a 27 pct Cr steel, changes in impact strength and in angle of fracture in bending can be detected after only a 1 hr exposure at 885°F; after 50 hr this steel becomes quite brittle. Hardness increases slowly with time during thousands of hours exposure and may attain a maximum hardness number twice as large as that of the unexposed steel. Microstructural changes accompanying embrittlement have been described as an initial widening of grain boundaries followed by eventual darkening of ferrite grains. Embrittled steels etch more readily, e.g., the weight loss of a 27 pct Cr steel in acid solution may occur at a rate one hundred fold greater following exposure at 885 OF. Marked changes which accompany embrittlement have been observed in electrical resistivity, specific gravity, and magnetic coercive force. Changes in physical properties may be readily removed by heating at temperatures above the embrittling range, such as a treatment at 1100°F for 1 hr. It has frequently been noted that the 885 °F embrittlement suggests precipitation on a submicro-scopic scale of a chromium-rich constituent, the nature of which has not been revealed by X-ray diffraction. Progressive broadening of the body-centered cubic diffraction lines during embrittlement has been observed," and recent observations by Lena and Hawkes' upon single crystals have shown early asterism in X-ray photographs, disappearing within an hour at 900 °F. Many workers have ascribed8-13 the phenomenon to a precipitation of a phase (FeCr), which is known to cause embrittling effects at temperatures much higher than 885°F. Two general observations, however. suggest that a precipitation cannot be responsible for the 885°F phenomenon: 1—prior cold work greatly enhances a formation, whereas it scarcely affects the 885 °F embrittlement, and 2—the presence of an alloying element such as nickel or manganese may have an effect on the 885 °F embrittlement which is opposed to its effect upon a formation. The slight enhancement of a formation and 885°F embrittlement observed in the presence of elements with strong carbide and nitride forming tendencies' is probably a consequence of lessened chromium depletion of the matrix. The bar graph in Fig. 1 shows a typical example, taken from two 27 pct Cr steels used in this work, of the hardness after exposure for 10,000 hr at 900°, 1050°, and 1200°F. Steel A (0.03 pct C, 3.13 pct Mn) showed marked hardening at 900" and 1200°F, whereas steel B (0.12 pct C, 0.63 pct Mn) exhibited only the 900°F hardening. The cr phase was found in steel A at the higher temperatures but not in steel B. Presumably a formation is enhanced by the low-carbon and high-manganese concentrations in A," Thus there are two distinctly different hardening phenomena present which cannot both be ascribed to v precipitation without invoking a transition phase possessing remarkable properties. Materials A number of chromium steels exposed for long periods (5000 to 34,000 hr) at 900°F, as well as unexposed samples of one of the steels, were available for this investigation. Table I gives the chemical compositions and aging treatments of these steels. In addition to these steels exposed in the elevated temperature test furnaces of the National Tube Division, a number of high-chromium steels were heated for short periods in small laboratory air furnaces and lead baths. Supplementing these commercial steels, a sample of high-purity (0.018 pct C, 0.002 pct N) 28 pct Cr iron, exposed 1000 hr at 887°F. was furnished by the Union Carbide and Carbon Corp. In addition, an alloy of iron and chromium of high purity containing 46 pct Cr was used. This

Jan 1, 1954

By R. F. Mehl, M. L. Swanson, J. P. Hirth, G. M. Pound

The sorption of zinc in a-brass was investigated. By analyzing the elliPtically polarized light reflected from the surfaces of a-brass solid-vapor couples, their optical constants and surface compositions were determined. It was shown that the surface compositions approached an equilibrium value exponentially with time. The bulk diffusion coefficient, surface diffusion coefficient and condensation coefficient for a-brass solid-vapor couples were calculated near 350°C from the experimental results. It has been assumed during various diffusion experiments with bimetallic solid-vapor couples (Dunn,1 Seith and Kraus,2 Jenkins,3 Balluffi and Seigle,4 and others) that the surface composition of such couples reaches its equilibrium value immediately. Although this assumption is probably valid at elevated temperatures, it is certainly not expected to be confirmed at lower temperatures.* consequently, it was decided that a fundamental experiment, designed to solve this problem as well as to examine all aspects of bimetallic sorption, would be the investigation of the rate of approach to equilibrium of the surface composition of solid-vapor couples. The sorption (i.e., adsorption, absorption, and desorption) of metals is obviously dependent on the state of the metallic surface and substrate. Much recent theoretical8"9 and experimental10-12 work on condensation and evaporation of pure metals has shown that the surface contour in atomic dimensions is a critical factor in sorption, so that any deformation or contamination13,14 of the surface exerts a profound influence. It is also known that absorption or diffusion occurs much more rapidly along grain were and in other deformed regions. Thus an effective sorption experiment must utilize a strain-free and clean surface, or at least a clearly defined and reproducible surface state. A mechanically polished surface is in a highly deformed17-l9 state. Because the degree of this deformation is uncertain, it is clear that for most experimental purposes a strain-free (i.e., etched, chemically polished, or electropolished) surface is desirable. Although adsorbed gas molecules on metallic surfaces are unavoidable even in the highest vacuum,20 oxide films can in some cases be removed by suitable vacuum annealing. Electrolytically polished and annealed surfaces, being relatively without strain, smooth and free of bulk oxides, were considered adequate for the present sorption experiments. Measurement of the surface composition of a solid-vapor couple presents a unique problem. Since experiments to determine the approach to equilibrium of the surface composition must be performed at temperatures where diffusion is very slow, solute penetration is so small that conventional analytical methods are unsuitable. An optical reflectivity method utilizing a polarization spectroscope was employed because of the relatively small penetration (~200A) of visible light in metals. By this method, elliptically polarized light reflected from the metal surface was analyzed and compared with that reflected from samples of known composition. The a phase of the copper-zinc system was

Jan 1, 1962

By E. B. Spice

Although much may be learned about the economics of cold weather operations by studying successful mining ventures in southern and central Canada, it is the purpose of this article to extend the study by considering only permafrost areas. Geographically this means most of the country north of the 60th parallel. In this area, at the present time, only five Canadian companies are carrying on routine and successful mining operations on a year-round basis. However, there have been some score of unsuccessful ventures, and a number of properties in the development stage show promise of being producers. Problems of cold weather are worthy of study. It may be pointed out that successful mines in this area face problems of isolation and costly transportation as well as cold weather. To reach valid conclusions, consider the development of a mythical mineral deposit located on the 65th parallel in the heart of the barren lands; problems of isolation and transportation will be ignored.

Jul 1, 1956

By J. D. Defilippi, E. M. Gilbert, K. G. Brickner

FCC chromium-manganese-nitrogen (Cr-Mn-N) steels differ from most other fcc materials in that these steels undergo a ductile-to-brittle transition. Transformation to martensite is considered to be responsible for this behavior in some metastable Cr-Mn-N steels. However, very stable Cr-Mn-N steels also exhibit a ductile-to-brittle transition. The results of this study indicate that deformation faulting is the probable cause of the brittle behavior of stable Cr-Mn-N steels. Deformation faulting accounts for the ductile behavior of these steels in a tension test at -320°F and brittle behavior in an impact test at -320°F. Deformation faulting also accounts for the toPological features observed on the fracture surfaces of impact specimens of these steels. FACE- centered- cubic chromium-manganese-nitrogen (Cr-Mn-N) steels differ from most other fcc materials in that these steels undergo a ductile-to-brittle transition. Many Cr-Mn-N steels transform to martensite during deformation,l-5 and several investigatorsl-3 have suggested that the brittle behavior of these steels is caused by martensite formation. However, very stable Cr-Mn-N steels also exhibit brittle behavior. Schaller and Zackeyl reported that a very stable Cr-Mn-N steel (less than 3 pct martensite formed at -320°F) exhibited a transition temperature higher than that for steels in which large volume fractions of martensite formed during testing. The explanation given by Schaller and Zackey for this observation was that in the very stable steel the martensite, because of its higher interstitial content, was more brittle than that formed in their other steels. This explanation was questioned by Tisinai and samans4 and Baldwin.6 Moreover, because the toughness of stainless martensite at cryogenic temperatures is generally very low, this explanation does not account for Thompson's7 observation that small additions of nickel (1 to 3 pct) greatly improve the toughness of high nitrogen (0.35 pct) Cr-Mn-N steels. The present paper summarizes the results of an investigation of the low-temperature brittleness in very stable Cr-Mn-N steels. The importance of the mode of deformation on the toughness of these steels is discussed. Table I. Compositions of the Steels Invertigated, Pet Steel C Mn P S Si Ni Cr N - A 0.09 14.70 0.018 0.011 0.47 0.22 18.40 0.54 B 0.12 14.90 0.001 0.008 0.48 0.14 17.80 0.38 C 0.12 14.95 0.004 0.005 0.62 3.95 18.43 0.38 MATERIALS AND EXPERIMENTAL WORK The compositions of the steels investigated are shown in Table I. Steels A and B had compositions within the limits of a proprietary Cr-Mn-N stainless steel,* whereas Steel C was similar in composition to the proprietary steel except for its 3.95 pct Ni content. All steels were hot-rolled to 1/2-in. thick plate. The plates were subsequently annealed for 1 hr at 2000°F and water-quenched. Standard longitudinal and transverse Charpy V-notch impact specimens were machined from the annealed plates. Duplicate longitudinal and transverse impact specimens were tested at 212", 80°, 32", 0°, -100°,-160°,-200°,-256", and -320°F. Longitudinal tension-test specimens were also machined from the plates and tested at a crosshead speed of 0.05 in. per min at the aforementioned temperatures. The fractured impact and tension-test specimens of all three steels were examined to determine whether martensite had formed during testing. Magnetic, X-ray, electron-diffraction, and electron-microscopy techniques were used to detect the presence of martensite in the highly deformed areas of these specimens. Metallographic examination of highly deformed areas of impact and tension-test specimens revealed the presence of dark-etching bands, such as those shown in Fig. 1. These bands were observed only in deformed samples and were thought to be associated with the low-temperature brittleness of the Cr-Mn-N steels. Accordingly, a sample 1 in. wide by 3 in. long was cut from the 1/2-in.-thick plate of Steel C. This sample was surface-ground to a in. and then cold-rolled 60 pct at -320°F. Thin foils were prepared from the cold-rolled sample and examined in a JEM electron microscope. Brightfield, dark-field, and selected-area diffraction techniques were used to determine the cause of the dark-etching bands. Fractographic experiments were also performed. Impact specimens Of Steels A, B, and C were broken at -320oF, and the fracture surfaces of these specimens were immediately shadowed with carbon. The carbon replicas were examined in a Siemens electron microscope, and attempts were made to correlate the topological features of the fracture surfaces with the deformation mechanisms that could be occurring during an impact test of these steels.

Jan 1, 1970

By J. W. Pugh, J. D. Nisbet

THIS study of the ternary has been made as one phase of a metallurgical investigation which began nearly four years ago in the General Electric Company's Research Laboratory in Schenectady, N. Y. The objective of this program is the discovery of new metallurgical information which will lead to the development of better high-temperature materials. Combinations of the four pure base elements—iron, chromium, nickel, and cobalt—are being studied at the present time. It is essential in an investigation such as this to know as much as possible about the constitutional diagrams involved. The study of the iron-chromium-nickel system has been made to this end. Preliminary Explanation of Experimental Procedure: In all, fifty-five alloys at steps of 10 at. pct were made for the investigation of this ternary. Several ternary alloys in the chromium rich corner had to be omitted because their extreme brittleness made testing impractical. All alloys were vacuum melted with hydrogen reduction and centrifugally cast. The apparatus and technique of this process has been described in detail by Nisbet.1,2 The purity of the alloys prepared in this way is considered to be quite good. Impurities are listed as follows: Pct Carbon.............................0.02 Oxygen................................0.02 Nitrogen.........................0.005 Magnesium..................0.03-0.05 Sulphur...........................trace Hydrogen....................trace Phosphorous..................trace Silicon........................ trace After casting, all samples were given a homo-genization treatment which consisted of holding them for 15 hr at 1150°C (2100°F) and water quenching. Testing was begun with the samples in this condition. The tests employed in the study of this system were (1) dilatometer, (2) hardness versus aging temperature, (3) tensile strength and elongation versus temperature, (4) microstructure analysis, and (5) electrical resistance versus temperature. Dilatometer tests were made at the rather rapid heating rate of 1093°C (2000°F) in one hour on a Bristol-Rockwell type instrument. Hardness data were taken on specimens cooled from 204", 427", 649°, 760°, 871°, 982°, and 1093°C under conditions which are thought sufficient to bring the specimens to equilibrium in all but the cases of the very sluggish transformations. Electrical resistance data for several specimens were taken for both heating and cooling conditions in a vacuum furnace especially designed for this work by D. W. Bainbridge, formerly of this laboratory. Provisions were made for heating and cooling standard specimens at a constant rate, while autographic records of resistance and temperature were made simultaneously. Micrographs of all the alloys were made in the quenched condition. Some question may exist as to how such physical values as hardness, tensile strength, and elongation were interpreted to indicate a change in phase. Original data were recorded on physical property versus temperature graphs, each of which was made from the data of a single alloy (fig. la). From these, another series of graphs were plotted with the physical property as a function of composition for constant temperatures (fig. 1b). Sharp deviations in the slope of these composition versus hardness curves often indicate a change in phase. The example of fig. 1 will serve to describe this experimental technique. The plotting of a single point from graph "a" to graph "b," and finally to the phase diagram "c," is illustrated. The location of the point on graph "b" is indicated as point (1). If all the alloys of the A-B binary system were solid solutions at temperature X, the hardness in this curve would be expected to rise at a fairly even rate as A is diluted with B to a maximum at some intermediate value between A and B, as

Jan 1, 1951

Jan 1, 1959

Coal production during 1963 amounted to 446 mil- lion tons, an anticipated increase of about 6% over the 1962 production of 422 million tons. Electric consumption was 207 million tons, a continuation of its upward trend with an increase of about 7%. The metallurgical market consumed 77 million tons: the industrial market, 96 million tons; and the retail market, 26 million tons. Exports were 46 million tons. Modernization continues in the coal industry as it approaches the mid-1960's. The industry has shown a keen desire to explore and pursue new developments, new concepts and new managerial methods and techniques that have become so vital and important for industrial well-being.

Jan 2, 1964

Aamot, Olav Crone, Chem. Engr., Norsk Elektrokemisk, Kongensgt. 18, Oslo, Norway. '29 Abbott, Clarence E., V.P., Charge of Raw Materials, Tennessee Coal, Iron & R. R. Co., 1242 Brown-Marx Bldg., Birmingham, Ala. '04 Abel, Raymond L., Prof., Dept. of Pet. Refin., Univ. of Pittsburgh ..Pittsburgh, Pa. '28 Abel, Walter D., Cons. Engr 364 S. Cloverdale Ave., Los Angeles, Calif. '32 Abele, Louis T R.F.D. 1, Adamsville, Ohio. '31 Abell, Leo M., Ore Dressing Investigator, School of Mines Adelaide, S. Australia. '31 Abenius, Hakan V., Mine Supt., Bolidens Gruvaktiebolag Boliden, Sweden. '37 Aborn, Robert H., Asst. Met., Research Lab., U. S. Steel Corp., Lincoln Highway, Kearny, N. J. '19 Abraham, W. E. V., East India United Service Club, 16 St. James' Sq., London, S.W. 1,, England. '28

Jan 1, 1937

Discussion of the paper Of JAMES JOHNSTON, presented at the New York meeting, February, 1914, and printed in Bulletin No. 85, January, 1914, pp. 107 to 133. CHAIRMAN E. GIBBON SPILSBURY.-I would like to call attention to the fact shown in this paper that less than five years or perhaps seven years ago nobody had thought it possible to cyanide with success silver ores. The cyaniding of silver and gold ores was first of all started in Mexico, and gradually extended to this country in the case of the silver ores alone. The average extraction, I think, for the metals in Mexico, in the case of the silver ore, is less than 85 per cent., whereas here, in the case of a very complex ore, carrying a high percentage of sulphur and arsenic, and other objectionable elements, the ore has been treated so as to extract an average of 95 per cent. of the silver contents of the ore. It is really a phenomenal revolution in the metallurgy of silver ores which has been demonstrated and worked out at the Nipissing mines. GEORGE A. PACKARD, Boston, Mass.-I would like to suggest a slight modification, perhaps, of the statement which is made that no one considered cyaniding of silver ores up to five, or perhaps seven years ago, because in 1897, when I was at Mercur, Utah, one mill near there was operating on silver ores. It did not operate very successfully from a commercial standpoint, because they did not have a great deal of ore, but the extraction, I was told, was very satisfactory, and I am quite confident that it was, because, as suggested by the name, Chloride Point, the ores were silver chloride ores, and of course very easily soluble. Some years before that, in 1892, I made some tests myself. I spent three months making tests on more or less complex silver sulphide ores at Virginia City, Mont., and while our tests on the plain sulphide ores, finely ground, were quite successful, on account of the presence of a small amount of copper we did not work out a satisfactory solution of the problem at that time; although since then a cyanide plant has been erected and for at least eight years these ores have been treated by cyaniding at Virginia City, and the mill is still in operation. The period of five to seven years should, therefore, be modified considerably, in justice to the pioneers in the cyanide processes. REGINALD E. HORE, Toronto, Ont., Canada.-I hoped that there would be metallurgists from Cobalt here to present and discuss Mr. Johnston's paper. In their absence a few remarks from me may help to make clearer to you what they have accomplished.

Jan 6, 1914

By Charles Dorrance

Culm is a general term used in the anthracite regions for many years to denote a mixture of coal, bony coal and impurities which is sent to the refuse-banks. Thus, 35 years ago culm contained the pea and buckwheat sizes of anthracite; but to-day, and as mentioned in this paper, culm is used specifically to denote the material which passes through the smallest screen in the anthracite-breaker. The smallest size of commercial anthracite is known as No. 3 buckwheat, barley, or bird's-eye coal, and is ordinarily made through a round-punched plate having openings & in. in diameter, and over a round-punched plate with openings 3/32 in. or 1/16 in. in diameter. Thus culm will consist of coal, bony coal, slate, gravel, iron pyrite, etc., ranging in size from 3/32 in. down to dust. Other local terms for culm are " slush," " silt," and " dirt." The first experiments towards the utilization of anthracite culm by briquetting, and the first briquetting-work done in this country, were in 1872 at Port Richmond Piers, Philadelphia, Pa., by E. F. Loiseau.1 Clay was used as a binder and the finished briquette was water-proofed with shellac, etc. Excessive cost was given as the reason for discontinuing work at this plant.

Jan 1, 1912

By J. W. R. Rayner

THE conventional method of making water gas involves individual plants for the separate carbonization of coal to coke and the subsequent gasification of coke with steam. The process demands lump coke, preferably made from the best quality of coking coals. The ash in the coke should have a high melting point and the gasification process suffers a loss of efficiency when cokes with low ash-melting points are used. In Britain, these coals are generally the most expensive and they are readily available only in certain localities. The coals not suitable for making lump coke, or yielding only poor quality coke, are much more widely available and are generally cheaper. DEVELOPMENT OF ALTERNATIVE PROCESSES In Germany, processes have been developed and operated commercially for the production of water gas from very low-rank coals such as brown coal and lignites, but much less effort has been spent on processes to use coals of intermediate rank, which are widely available in Britain. The brown-coal processes use coal in the form of either dust or briquettes. The most successful of the dust-gasification methods is the Winkler process, which made a substantial contribution to German oil production during the war. It uses coal in the size range 0 to 8 mm and the fuel bed is blown with a mixture of oxygen and steam at a rate high enough to give it a characteristic boiling motion or, in present-day phraseology, at a rate more than sufficient to fluidize it (Fig. 1). Air cannot be used to provide the heat required for gasification, for vari¬ous reasons. In the first place, to make the process continuous by mixing air and steam would involve the production of a lean gas containing much nitrogen. If a separate blow were used, a large amount of potential heat would be lost because the blow gas in such a process would contain a very high percentage of carbon monoxide. Oxygen is necessary therefore and oxygen remains relatively expensive for use in gasification. In the Winkler generator, formation of clinker caused by local overheating does not occur, because of the mobility and high heat transfer of a fluidized bed. These properties of fluidized dusts have been used most successfully.

Jan 1, 1953

By Samuel B. Christy

As is well known, the ore at New Almaden is cinnabar. Native quicksilver occurs also; but, as a rule, in small quantities only. Pyrite occasionally accompanies the ore. Bitumen is quite common,

Jan 1, 1885

By J. C. Trantham, J. W. Marx

From 1955 to 1958 the Phillips Petroleum Co. conducted a series of small scale counterflow combustion field tests in a tar sand about 60-ft deep and 6 to 12-ft thick near Bellamy, Mo. A total of seven different well patterns, including conventional five-spots and seven-spots plus a 15-well line drive pattern and a 10-well radial pattern, were employed. Electric heaters, gas burners and wellbore fuel packs were tested as counterflow ignition devices. Direct drive ignition followed by reversal to counterflow operation was not possible in this case because of formation plugging by the semi-solid tar during the direct drive phase. Sustained counterflow burning was achieved with wellbore fuel packs under conirolled conditions which permitted close correlation of fire front velocity, air velocity, air-oil ratios and yields for a wide variation in process parameters. The tar in place was about 10' APl with a reservoir viscosity greater than 500,000 cp. The composite oil prodlcct was 26' API with a viscosity in the range of 5 to 15 cp. Vertical sweep efficiency in the line drive pattern was essentially 100 per cent, with no evidence of gravity segregation. Original tar in place ranged between 800 and 1,000 bbllacre-ft, specific rock permeability averaged about 800 md before burning and effective air pemeability with residual oil and water in place (at the time of ignition) averaged 250 md. The volume of oil recovered during stabilized line drive counterflow burning represented about 67 per cent of the volume of tar originally in place in the burned out zones. A minimum was found when air-oil ratios were plotted against formation air velocities, and a limiting air velocity existed below which the counterflow fire front reversed and burned back over its own trajectory, using the residual coke left behind. INTRODUCTION Early in 1955 the Phillips Petroleum Co. began preparations to field test counterflow underground combustion as a method for producing oil from high viscosity hydrocarbon deposits, such as bituminous (tar) sands. At that time all published information on the use of underground burning io increase oil recovery was based on the direct drive process, in which the fire front moved through the formatim in the same direction as the injected air stream. Such direct burning is not applicable to many heavy oil sands or to most tar sands because the heat-thinned native hydrocarbon congeals in the cold rock ahead of the fire front forming a gas permeability block which smothers the combustion. Laboratory experiments first demonstrated that this permeability blocking would not occur if the fire front and the air stream moved in opposite directions. In this counterflow (reverse) burning process the heated heavy oil or tar is driven back through the combustion zone. Here thermal cracking produces relatively light hydrocarbon products which pass through the heated rock behind the fire front (largely in the vapor phase) and are incapable of causing a gas permeability block.' Exploratory wring revealed that consolidated bituminous sandstones with a combination of tar saturation, permeability, thickness and depth favorable for experimental field testing existed at several points in western Missouri. By the fall of 1955, a test site for determining technical feasibility of the counterflow process under field conditions had been selected near Bellamy, Vernon County, Mo. — about fifty miles north of Joplin. The pay zone was too thin and too shallow to constitute a commercial prospect, but these same factors permitted controlled experimental operation with a small compressor installation and with a large number of monitor wells. These were needed for adequate observation of the underground phenomena at reasonable cost. RESERVOIR CHARACTERISTICS The reservoir chosen for the experimental field tests was a 124 thick section of tar sand extending from 49 to 61 ft subsurface, with shale and siltstone laminations sealing the top and bottom. This section was part of a larger 30-ft thick tar sand deposit which extended both above and below the test zone. Core analyses showed that the 12-ft sand was effectively subdivided into two approximately equal sections, with the lower zone being consistently more permeable than the upper zone. The most significant laboratory core data are summarized in Table 1. The line drive test which is the principal subject of this report utilized only the lower 6-ft thick zone, with the upper zone regarded as part of the 55-ft overburden. WELL PATTERNS The over-all field test program involved a total of seven different well patterns, including conventional five-spots and seven-spots plus a 15-well line drive pattern and a 10-well radial pattern. In some of the tests the full 12-ft zone was employed; in other cases only the more perme-

Jan 1, 1967

By Y. Baskin

Solid-solubility relationships in the Pseudobinary systems UAS-UP, UAs-US. UAS-UC, aid UAs-UN were investigated. The first two systems exhibit complete mutual solubility, whereas the component compounds in the other two systenzs are immiscible. The above information, together with solid-solubility data joy six additional pseudobinary systems , were analyzed for compliance wilh the Hurrze-Rothery rules for rnetallic systems. The relative size difference of the component nonmetal atoms was found to be the dopainant jactor determining the extent of solid solubility between the NaC1-type uranium compounds. The anionic and covalent radii of the nonmetal atoms appear to be inadequate for these systems, but compuled radii based on rare earth compounds yield consistent results for the uranium compounds. THE actinide elements, like metallic elements of the transition and rare earth series, readily form binary compounds with nonmetallic elements of groups IV, V, and VI of the periodic table. Of particular importance are the NaC1-type equiatomic compounds with carbon, nitrogen, sulfur, phosphorus, and arsenic. The uranium members of this family of compounds have high melting points, are essentially stoichiometric, and exhibit various amounts of mutual solubility. Thus, they are of interest for investigating the factors governing the extent of solid solubility. Previous investigators have determined the solid-solubility limits in the pseudobinary systems between the compounds UC, UN, US, and UP. Anselin et a1 .' reported complete miscibility in the system UC-UN. Baskin and shalek 2 and Allbutt et a1.3 reported that UP and US exhibit complete mutual solubility. Shalek and white4 reported partial miscibility in the system US-UC. At 1800°C the maximum solubility of UC in US is 40 mol pct, but that of US in UC is 4 rnol pct. shalek5 found limited solubility in the system US-UN; the maximum solubility of UN in US is 11 rnol pct at 1800°C, while that of US in UN is only 0.3 mol pct. White and askin 6 found very limited miscibility in the system UP-UC at 1800°C. Approximately 7 mol pct UC is soluble in UP, but there is no solubility of UP in the monocarbide. Phase relations in the pseudo-binary system UN-UP were investigated by askin.' Approximately 0.7 mol pct UN is soluble in UP at 1800°C, while UP is immiscible in UN. The present study was carried out to explore the extent of terminal solubility in the systems UAs-UC, UAs-UN, UAs-US, and UAs-UP. This information, combined with existing data, provided a sufficient basis on which to determine the factors governing solid solubility in pseudobinary systems containing NaC1-type uranium conpounds. I) EXPERIMENTAL 1) Materials. The compounds UC and UN were obtained from the Kerr-McGee Corp. and United Nuclear Co., respectively. The US, UP, and UAs were synthesized by reacting finely divided uranium with H2 S, pH3, or AsH3 gas at low temperature (300° to 500°C), followed by homogenization in a vacuum at moderately high temperatures (1400° to 1700°c).8-10 The materials were essentially stoichiometric, with the exception of UC, which exhibited a C/U ratio of 1.05. Oxygen was the major contaminant in these compounds, ranging from 0.05 wt pct in US to 0.30 wt pct in UC, and it was generally combined with uranium to form UO2. The UO2 content in these materials was usually of the order of 1 wt pct, and did not exceed 2 wt pct. Furthermore, no evidence was found for a high-temperature reaction between uranium dioxide and any of the compounds. Chemical analyses of equilibrated compositions in the systems UAs-UP and UAs-US showed that the non-metal atom to uranium ratios averaged about 1.01, and that the oxygen contents ranged from 0.06 to 0.22 pct. However, the small deviations from stoichiome-try or the presence of minor oxygen impurities do not invalidate the conclusions to be drawn from this study. 2) Experimental Procedures. The component compounds in powdered from were blended in the desired proportions for 5 hr in the ball mill that consisted of stainless-steel balls in a plastic container. Chemical analyses indicated very little metallic pickup from the blending operation and virtually no increase in oxygen content. The pellets were pressed in a 0.270-in.-diam steel die under 40,000 psi pressure. One wt pct of stearic acid dissolved in CCl 4 served both as a binder and as a die lubricant. Chemical analyses revealed that the stearic acid left no carbon residue in the sintered samples. The pellets were sintered in vacuum in an unsealed tantalum crucible. The temperature, measured with a calibrated optical pyrometer, was maintained at 1800" + 30°C for 3 hr. This was sufficient time for attaining equilibrium as no change occurred in either the lattice parameters or the sharpness of the X-ray patterns when samples were annealed for longer periods of time. The pellets were cooled with the furnace. Debye-Scherrer powder patterns were taken at room temperature with a 114.59-mm-diam Norelco powder camera and CuKor radiation (CuGI = 1.5405A). Unit cell dimensions were determined from a Nelson-Riley extrapolation to the high-angle reflections. The values for were precise to k 0.001A. 11) RESULTS X-ray and met allographic investigation revealed that complete mutual solid solubility exists in the pseudobinary systems UAs-UP and UAs-US. The lattice parameter vs composition plots, Fig. 1, show a

Jan 1, 1968

By R. W. Newcomb

THE constancy of calibration, and to a great extent the life, of a thermoelement is dependent on the suitability of the primary protecting tube in which the wires are mounted, particularly when used at high temperatures. An ideal thermocouple protecting tube would be com-posed of materials that would not contaminate the thermoelement wires contained in it-one that would remain absolutely gas-tight ,it all temperatures of usage, that will not be attacked by gases, or other surrounding agencies, that is not destroyed by heat, that withstands sudden and extreme temperature changes, that affords a high degree of mechanical protection and does not deform at high temperatures, that is a good heat conductor and obtainable in small diameters so as to keep down lag factors. It has not yet been possible to produce tubes of any known mate-rials that will meet all of these conditions. In selecting protecting tubes, therefore, one should be chosen the characteristics of which best fit it to the particular conditions of usage. Frequently conditions are such that two tubes have to be used, a primary gas-tight protecting tube inside of a secondary protecting tube, because certain agencies will attack the primary gas-tight tube unless it is guarded by the outside tube.

Jan 9, 1919

By Charles A. Anderson

Arizona and western New Mexico contain 17 of the 25 leading copper mines in the United States. Production of molybdenite, lead, zinc, and by-product gold and silver is important. Precambrian ore deposits are largely limited to the Yavapai Series in central Arizona and most of the metal production has come from massive sulfide deposits, dominantly pyritic but containing different amounts of chalcopyrite, tennantite, sphalerite, and galena. Their origin has been interpreted by some geologists as hydrothermal replacement of schist, and by others as syngenetic deposits later metamorphosed. Most of the important ore deposits are of Mesozoic and early Tertiary age, dominated by the porphyry copper deposits spatially related to stocks, plugs, sills, or dikes of quartzbearing porphyritic to granular rocks. Host rocks for these deposits include the associated intrusive rocks, Precambrian schist and granitic rocks, Paleozoic limestones, Mesozoic(?) porphyritic andesite, and Mesozoic arkose and siltstone. Chalcopyrite and pyrite are the dominant hypogene sulfide minerals in the porphyry copper deposits, accompanied by minor molybdenite. The Questa deposit in New Mexico is largely molybdenite. Supergene sulfide minerals are chalcocite and minor covellite. Some ore bodies consist largely of hypogene sulfides, some are dominantly supergene sulfides, and others are mixed hypogene-supergene sulfides. Supergene oxide-copper minerals locally are important. Intense hydrothermal alteration accompanied the metallization in all of the porphyry copper deposits; five types are recognized, ( 1) propylitic, (2) argillic, (3) potassic, ( 4) quartz-sericite (without clay), and (5) lime silicate. The origin of the closely spaced fractures that contain ore minerals in intersecting veinlets is debatable; some geologists favor tectonic forces and others suggest cooling of magma or shrinkage due to alteration. Breccia pipes, veins, and limestone replacements account for some important deposits of Mesozoic and early Tertiary age, and presumably these are genetically related to the various intrusive rocks of this age. The St. Anthony deposit of Cenozoic age in southeastern Arizona is unique, consisting of a lead-zinc vein associated with later molybdenum and vanadium oxide-minerals. Cenozoic manganese deposits in western Arizona are an important resource in the Artillery Mountains, but the extent to which they may be exploited is a metallurgical and economic problem.

Jan 1, 1968

The Board of Directors, at its meeting on March 22, 1918, extended an invitation to the American .Institute of Metals to become the Institute of Metals Division of-the American Institute of Mining Engineers in accordance with the terms of By-Law VII. This invitation was presented to the membership of the American Institute of Metals for letter ballot, and, at the meeting of the Board of Directors of the American Institute of Mining Engineers on April 26 191 ,it-was reported that the replies had been in favor of accepting the invitation. The American Institute of Metals therefore becomes a division of this Institute and the members thereof are entitled-to all privileges of regular

Jan 6, 1918

By G. W. Healy, J. C. Schottmiller

Molten silicates were found to exist in the Cr-Si-0 system at temperatures above 1450°C. one atom of oxygen is readily removed from CrzOs in the presence of Si02 at 1700°C, forming a silicate melt. Steam-hydrogen ratio measurements made at this temperature indicate that the free energy of the reaction: Cr20s(c) + Hz = 2CrO (in Si02 -saturated melt) + H20 is approximately 5600 * 1500 cal. A deep-blue chromous silicate, probably Cr2Si04, forms from these melts at about 1400" to 1500°C, and is characterized by.its distinctive X-ray diffraction pattern and optical properties—distinct pleochroism and high refractive indices. THE question of the state of oxidation of chromium in slags has vexed metallurgists for many years The experiments of Koerber and Oelsenl suggested the probable presence of divalent chromium in silica-saturated slags equilibrated with high-chromium melts. Hilty and coworkers2 had also found chromium at lower valency, as Cr304, in inclusions formed from oxygen-saturated Fe-Cr melts with as little as 10 pct Cr. In both cases, disproportiona-tion of the lower oxide to CraO3 and chromium was found to occur to a greater or lesser extent, depending upon the rate of cooling from the high temperature. The work on Cr304 was sufficiently detailed for chipmans to derive its thermodynamic properties, but Oelsen's experiments in the silicate system were not extensive enough since most of his runs were made with slags containing large amounts of manganese oxide in addition to iron and chrome oxide and silica. The present study describes experiments carried out to map out an approximate liquidus diagram in the CrzOs, "CrO", SiOa portion of the Cr-Si-0 system, and to measure the partial free energy of solution of oxygen in the system. EXPERIMENTAL 1) Approximate Melting-Point Determinations. Preliminary trials showed that when an equimolar mixture of Cr20s and SiOa was treated with hydrogen in the temperature range 1500" to 1600°C, copious amounts of steam were evolved, and a low-melting liquid formed which could be quenched to a blue, crystalline, material having a distinctive X-ray diffraction pattern. It was found that the identical material could be produced by heating intimately mixed, finely divided Cra03, Cr, and SiOa, held in a tungsten crucible, under purified argon. Thus, it was possible to prepare mixtures containing any desired proportions of chromium, silicon, and oxygen, pel-letize them, heat to temperature in the furnace shown in Fig. 1, and observe, after cooling, whether the pellet remained unchanged or showed signs of incipient, partial, or complete melting. 2) Free Energy of Solution of Oxygen. This was studied by measurement of steam-hydrogen ratios for the reaction: H20 (gas) + O (dissolved in charge) + Ha (gas) The experimental method chosen was to prepare a

Jan 1, 1964

By N. K. Chen, R. Maddin, K. T. Aust

Lattice rotations occurring on the tension and compression sides during the bending of molybdenum single crystals at room temperature were followed in detail. Observations were also made concerning crystallite rotations and slip traces. &apos;The results indicated the participation of (110) as slip planes and the<111>as slip directions. Crystallite fragmentation during bending was also noted. EVERAL investigations have been conducted on pure bending of face-centered cubic metals.&apos;-" Structural changes as a result of "bend-gliding," and the importance of bending and constraints during conditions of axial stressing, have been noted.&apos;," It was evident that the mechanism by which the bending deformation occurs is more complex than the case of simple shear. Studies of the bending of body-centered cubic metals from the aspect of the crystallographic mechanism appear to be lacking. Molybdenum single crystals therefore were subjected to deformation by bending in order to determine the reaction of the body-centered cubic lattice to bending stresses. It might be expected for the bending of single crystals that lattice rotation as represented by the axis of compression would proceed toward the pole of the active slip plane and that rotation of the tensile stress axis should indicate the slip direction.&apos; It was believed therefore that a study of the tension and compression sides of bent molybdenum single crystals should give data concerning the operative slip system. Specific problems which are pertinent to the overall picture of plastic deformation were also investigated, e.g., whether the constraints offered by pure bending give rise to the deformation band, and also the nature of the asterism occurring on the tension and compression sides during the stages of deformation. Experimental Procedure Eight single crystal specimens were grown from sintered molybdenum rods 143 in. diameter using the method described previously.6 The purity of this material was reported as 99.9 pct as described elsewhere.&apos; The specimens were % to 1/10 in. in diameter x 7 in. long, with single crystals approximately 1 to 2 in. in length occupying the entire center sections of each specimen. The specimens were elec-trolytically polished using an electrolyte of 300 cc methyl alcohol, 60 cc H2SO4, 130 cc HCl, and a current density of 4 amp per sq in. Each specimen was then loaded in a bending apparatus similar to that used by Yen and Hibbard,&apos; as shown in Fig. 1. The load was applied by means of a spring and screw arrangement through four ball-bearing surfaces set 1.5 in. apart. Either the inner two bearings or the outer two (A, B, Fig. 1) were attached to a movable steel plate (D) through which the load was transmitted. Since the apparatus was mounted on a track of the X-ray apparatus, the tension or compression side of the specimen could

Jan 1, 1954

By Wilbur S. Burbank, Robert G. Leudke

The impressive western San Juan Mountains of Colorado were carved by Pleistocene and Recent erosion from a thick blanket of Tertiary volcanic rocks that rests upon a basement of metamorphic, sedimentary, and igneous rocks ranging in age from Precambrian to Tertiary. These rocks record a long, complex, and fairly complete sequence of geologic events that have affected the region through much of geologic time. The geologic history of the region includes several periods of deformation, erosion, and igneous activity; closely associated with two of these periods were two periods of mineralization. The older of these was related to Late Cretaceous-early Tertiary (Laramide) intrusive activity, and its deposits occur in the older sedimentary units. The younger, of later Tertiary age and related to the widespread middle Tertiary extrusive and intrusive activity, is the chief concern of this paper. Tertiary volcanism built a great plateau surrounding the San Juan volcanic depression, a complex of subsided crustal blocks in the vent areas. The Silverton and Lake City cauldrons, nested within the larger depression, were domed by resurgent magma that created keystone grabens along the distended crests of the domed floors and many postcauldron radial and concentric fractures, dikes, and intrusive plutons within and marginal to the cauldron sites. The postvolcanic evolution of large quantities of gases, chiefly carbon dioxide and water, propylitically altered the rocks in and around the volcanic depression prior to the younger period of ore deposition. The ore deposits, localized mainly in the radial and concentric fractures about the cauldrons and in the associated graben faults, include fissure veins, chimneys, replacements, and disseminations in volcanic and underlying basement rocks. Fissure veins, constituting the major economic source, yielded precious- and basemetal ores. Most veins are compound with sphalerite, galena, and chalcopyrite; some veins contain silver-bearing arsenical sulfosalts and free gold. These minerals occur in predominantly quartz gangue. However, gangues composed of several manganese silicates and carbonates and relatively· barren of metals are abundant locally and probably originated by alteration of rocks at roots of faults and fissures during evolution of carbonatic solutions. The bulk of the ores are hypogene and probably had their source in deep parent magmas of the shallow eruptive rocks. Total production since the early 1870's has exceeded half a billion dollars in recovered metals, with a ratio of precious- to base-metal values of about 3 to 2. Since 1930, improvements in metallurgical treatment and mining techniques have increased the base-metal yield.

Jan 1, 1968