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By Walter P. Jenny

I. The Reducing Action of Carbon and of Hydrocarbons,. .. 445 11. Protective Action of Carbon and of Hydrocarbons,. 451 111. Contributory Action of Carbonic Acid Gas,..452 IV. The Stability of Carbonic Acid and of Water,..453 V. Occurrence of Carbon and the Carbon-Compounds,. 455 VI. The Occurrence of Carbon, Alone,.... VII. The Occurrence of Carbon Combined with Hydrogen,. .. 460 VIII. The Relative Reducing Power of Minerals,..487 I. The Reducing Action of Carbon and of Hydrocarbons. Carbon has long been recognized as one of the most powerful reducing agents in the deposition of ores. Investigations, made by myself, of the zinc- and lead-deposits in Southwest Missouri, in the region centering about Joplin, where the formation of the metallic sulphides has been due to the action of bitumen, carbonaceous shales and bituminous coal, have afforded abundant evidence that the solid oxygenated hydrocarbons, particularly when in fine powder and in suspension in the waters circulating through the ore-bodies, are the most energetic and powerful reducing agents known. Bitumen, liberated by the decomposition of the ore-bearing limestone, is found in the Joplin mines in all degrees of fluidity and hardness, dependent on the amount of oxidation it has undergone. From semi-fluid maltha it grades into partly oxidized mineral-pitch, which, by further oxidation, changes to hard asphalt, finally breaking up, from continued absorption of oxygen, into a fine powder resembling in appearance powdered coal. In this condition oxidized bitumen, from its light gravity, is transported readily in suspension in the underground circulating-waters. Bituminous coal and black carbonaceous clays and shales occur as surface formations, often in intimate association with

Jan 1, 1903

By Royal B. Jackman, Carle R. Hayward

Two comprehensive papers have appeared regarding the forms of copper that occur in smelter slags, one by Frank E. Lathe1 and the other by C. G. Maier and G. D. Van Arsdale.2 These authors comment on other published results and draw conclusions from their own investigations. The development of X-ray examination of minerals and improvement in high-power microscopic methods make it possible today to get additional evidence by means that were not available to earlier investigators. The present work was confined to reverberatory slags obtained from five different plants. Some definite conclusions were reached regarding the forms of copper present in these slags. In most cases these agree with some of the findings of Maier and Van Arsdale but new methods of attack were used in the investigation. Conclusions of Previous Investigators Various important conclusions reached by previous investigators are summarized in the following paragraphs, arranged chronologically. William A. Heywood:3 Slag losses increase with grade of matte but with the same grade of matte losses decrease as the acidity of the slag increases. Lewis T. Wright:' Slag losses are only partly due to prills of matte. It is suggested that part of the copper is dissolved in the slag. J. Parke Channing9 A considerable part of the copper enters the slag as silicate or oxide and not as sulfide. C. A. Grabill:6 Slag losses are both physical and chemical. Physical losses, due to poor settling, gas flotation and slight differences in specific gravity, are small under normal conditions. Chemical losses may- be due to formation of oxides or to solution of metals and sulfides. The last is considered the most important. John W. James:' The copper in converter slag is largely the oxide and as such enters the reverberatory slag when converter slag is added to the charge.

Jan 1, 1934

By T. J. Woods

Tars paper deals with the origin, definition and prevention of scabs an semifinished rolled-steel product. Mold coatings, which are considered essential in scab prevention, were found to be effective only in relation to the ingot surface of semikilled and killed steels and not necessary for the rolled product. That is to say, the scabs on ingots caused by having been cast in uncoated molds are eliminated in the soaking and rolling operations, therefore are not present on the rolled product. This fact, which is contrary to the average opinion, was established after extensive and thorough experiments had proved the ordinary conception of the origin of scabs to be incorrect. This subject may be of little or no concern to steel plants producing small ingots for the manufacture of small billets and bars, except as it may be of interest in showing why their surface troubles with scabs do not exist on the product of heats with normal pouring practice. But to the producer of large ingots to be rolled into slabs for large plates used in shipbuilding, it is a very important subject. DEFINITION OF A SCAB The generally accepted opinion is that the individual scabs present on rolled products (as shown by Fig. I) are considered to have been individual splashes on the ingot surface. This opinion was found to be incorrect. Experiments showed that there were no individual scabs on the product that had appeared as individuals on the ingot surface. The single scabs seen are either pieces of a shell that is present near the bottom of all top-cast ingots, or a veneer that may be present on any part of an ingot improperly poured, as when the stream strikes the mold wall. This definition is based on a detailed study of scabs and their characteristics in which the following have been found true: Location.- On the product of heats poured without trouble, scabs, if present, are always on the product that corresponds to the bottom end of the ingot, and usually occur in clusters, This is true whether molds are coated or not. Shape.-There is no regularity as to shape, size or thickness. It is sometimes possible to separate a few pieces and place them together, like pieces of a jigsaw puzzle, indicating that at one time they had been united as one piece. If individual splashes were the origin of scabs, the foregoing would not be true. Instead, the splashes, which occur throughout the pouring of the ingots, would be present uniformly over the entire product and there would be considerable similarity in the shape and thickness of the scabs. EXPERIMENTAL WORK Our experimental work was conducted on 200-ton heats of semikilled plate steel tapped into an oval ladle 15 ft. high. All ingots were top-cast direct into 24 by 54 by 82-in. molds, straight-sided, set on fat stools. Two separate studies were made about one year apart, each study extending

Jan 1, 1943

By Matti J. Saarivirta

Two new precipitation hardening copper-base alloys, Cu-1.5pct Ti-2.5 pct Sn and Cu-1.5 pct Ti-2.5 pct Sn-0.4 pct Cr were developed. High strength and medium conductivity are obtained by solution annealing and subsequent heat treatment. Combination of solution annealing, cold working, and heat treatment increases the strength further. Good elevated temperature strength and ductility makes these alloys superior to copper-beryllium-cobalt alloys. A considerable amount of research work is being done throughout the world to develop new and improved copper-base alloys. In many cases, the object is to develop alloys having a combination of high electrical and thermal conductivities, and high strength. The problem is complicated by the fact that any alloying element added to increase strength, invariably decreases conductivity. Among the few commercial precipitation hardening type copper-base alloys, the Cu-Be-Co alloys are best known. These alloys are used in many applications that require good spring characteristics cornbined with high strength and moderately high electrical conductivity. They can be formed readily after solution annealing, then heat treated to obtain high strength and conductivity. Because of the relatively high cost of the Cu-Be-Co alloys, considerable research has been aimed at developing new lower cost alloys having similar properties. As far as is known today, the binary Cu-Ti alloy is the only one whose properties are

Jan 1, 1962

By O. N. Carlson, H. A. Wilhelm, J. M. Dickinson

On the basis of microscopic studies, melting-point observations, and X-ray analyses, a phase diagram is proposed for the Cb-V system. A complete series of solid solutions is formed with a minimum in the solidus at 1810°C near 35 wt pct Cb. No compounds or intermediate phases were found in the system above 650°C. THERE is an ever increasing need for better structural metals and alloys for use in nuclear reactors. In addition to the normal properties of engineering structural materials, such as high temperature strength, resistance to corrosion, and fabric-abil~ty, the nuclear properties of the material must be considered. In a nuclear reactor it is important to conserve neutrons, so a material which removes these neutrons from the reaction excessively is considered to have unfavorable nuclear properties. In nuclear-reactor design the engineer must have nuclear as well as other data available on alloys in order to make a wise selection of materials. Due to the fact that many of the common structural materials have undesirable nuclear properties, it is vital that new alloys of metals having more favorable nuclear properties be investigated. Columbium and vanadium are both high melting metals, both exhibit resistance to chemical attack, and no great difficulty is encountered in fabricating them into desired shapes. With proper treatment both metals can be cold rolled extensively without failure. In addition they have desirable nuclear properties for certain types of reactors. Therefore, the alloys of columbium and vanadium should be of interest in the atomic energy program. Since an alloy-development program is enhanced by a knowledge of the phase equilibria of the components, this investigation was undertaken to establish the phase diagram for the Cb-V system. According to the Hume-Rothery rules for alloying,' the chemical similarity, crystal structure, and atomic-size factor are favorable for a complete series of solid solutions for this system. Both elements are in the same family of group V of the periodic table and thus are quite similar chemically. The crystal structures of columbium and vanadium are compatible for extensive solid solubility, since both have body-centered-cubic structures. The atomic diameters of columbium and vanadium are 2.85 and 2.62Å, respectively. This difference of slightly more than 8 pct is well within the 15 pct maximum difference allowed for extensive solid solubility. Experimental Procedures Source of Materials: Columbium powder and sheet trimmings were obtained from the Fansteel Metallurgical Corp. According to the manufacturer the metal contains less than 1 pct impurity. An analysis of the metal showed approximately 1800 ppm C in the powder while the sheet trimmings contained less than 500 ppm C. Spectrographic analysis showed minor amounts of Ca, Cr, Fe, Mn, Si, Ti, V, and Zr in both forms of the columbium. No commercial source of vanadium having the ductility and purity desired was available to the authors at the beginning of this investigation. As a result, all of the vanadium used in this study was prepared by the bomb reduction of vanadium pen-toxide with calcium employing the method reported by Long.' Yields of massive vanadium normally were about 80 pct. Chemical analysis of the vanadium prepared in this manner showed the presence of 200 to 500 ppm N and 800 to 1000 ppm C. Minor amounts of Ca, Fe, Mn, Si, Zr, Cr, and Cb were detected by spectrographic analysis. This vanadium metal was ductile and was cold rolled into 5 mil sheet. Annealing was not necessary during this rolling and the metal retained its cold-rolling characteristic after are-melting. Preparation of Alloys: The Cb-V alloys were prepared by melting pieces of vanadium sheet togethel-with columbium in the form of sheet or pellets of powder. The melting was carried out under argon in conventional arc-melting equipment employing a tungsten electrode and a water-cooled copper crucible. Each alloy was remelted three or four times, inverting the alloy after each melting in order to assure complete mixing. Alloys normally were obtained as round flat disks, weighed approximately 70 grams, and had roughly the shape of a disk 1 1/2 in. in diameter and 1/4 in. thick. Half of each alloy

Jan 1, 1955

By C. C. Clark, J. S. Iwanski

The purpose of this investigation was to study mi-crostructural changes that take place in a commercial nickel-chromium-iron alloy, such as Incoloy "901," over long periods of time at temperatures up to 13 50°F and to correlate such changes with creep-rupture properties. of the alloy. In the course of the investigation, some microstructural changes were observed which correspond to microstructural alterations found in previous studies of Inconel "X." Microstructural phases have been identified in both alloys with the aid of electron and X-ray diffraction and an electron probe microanalyzer. The materials used in this investigation were from commercial heats of the following chemical composition: Pct Cr Pct Ni Pct Mo Pct Fe Pct Cb Incoloy "901" 12.51 43.67 5.72 Bal. -Inconel "X" 14.61 73.44 - 6.61 1.02 Pct A1 Pct Ti Pct Mn Pct Si Pct C Incoloy "901" 0.10 2.46 0.46 0.24 0.05 Inconel "X" 0.70 2.43 0.51 0.36 0.04 Long-term creep-rupture tests were conducted on Incoloy "901" at temperatures of 1000°, 1200°1 and 1350°F. A summary of these results is shown in Table I along with the results of a long-term creep-rupture test conducted on Inconel "X" at 1500°F. The heat treatments given the specimens are also shown in Table I. When the creep-rupture results on Incoloy "901" are compared with shorter-tertn data, there is no evidence of any undue deterioration of the creep-rupture strength with time, nor is the elongation decreased more than would be expected from the influence of time alone. INCOLOY "901" PHASE IDENTIFICATION Microscopic examination of the Incoloy "901" specimens reveals a dark etching grain boundary constituent in the specimen which was under test for about 11,500 hr at 1000°F. This grain boundary constituent was seen to increase in size as the test temperature was increased to 1200" and 1350°F, Figs. 1, 2, and 3. Simultaneously, an acicular structure of definite crystallographic orientation appears within the grains of the 1350°F specimen, Fig. 3. Under examination with the electron microscope, a fine precipitate is observed in the 1200 °F specimen. Fig. 4. It becomes considerably larger in the 2850-hr 1350°F specimen, Fig. 5. In a few areas the precipitated particles have been replaced by, or transformed to, small needles or platelets. After 7380 hr at 1350°F, Figs. 3 and 6, the needles are much larger and have replaced nearly all of the fine precipitate. X-ray diffraction studies detected the presence of hexagonal Laves phase and hexagonal n phase (Ni,Ti) in the 1350°F specimens, Table 11. Only the Laves phase was detected by X-ray diffraction in the 1200°F specimen and none was detected in the 1000°F specimen. In this latter specimen, however, the small quantity of precipitate in the grain boundaries (presumed to be Laves phase) precludes its detection by X-ray diffraction. Composition of the hexagonal Laves phase is not yet known, although its diffraction

Jan 1, 1960

By J. E. Burke

Recent investigations have elucidated many of the phenomena of the grain growth process, but have also revealed some conflicting and unexplained results. Beck and his co-workers 1,2,3 have shown that grain growth continues with continued heating at one temperature until the average grain size approaches the thickness of the specimen. Plotting the logarithm of the average grain diameter, D, against the logarithm of the annealing time, t, they find the straight line relationship given by the equation: D = Ktm [,] with possible small deviations at short annealing times. K and n are constants at constant temperature. On the other hand, Wa1ker4 finds that, in alpha brass) the rate of growth falls off more rapidly than indicated by Eq i after long annealing, so that an equilibrium grain size is approached. Burke5 showed, using Walker's data, that time and temperature for grain growth are apparently related through an activation energy, H, according to the relationship: ] where h and tz are the annealing times necessary for the average grain size to increase from Do to D at temperatures T1 and T2 and R is the gas laws constant. In the case quoted, H had the value 60,000 cal per mol. The apparent validity of this relationship, at least up to 700°C, and the approximate value of H were later confirmed by Beck3 The results obtained by Beck Kremer, Demer and Holzworth2 for aluminum and aluminum-magnesium alloys could not be satisfied by such a relationship, since the slope of the isothermal curves increased with increasing temperature. These data indicate and Beck, Holzworth and HuV ater demonstrated expcrimentally that the only apparent factor controlling the rate of grain growth at constant temperature is the grain size. While many of the phenomena have been elucidated, a reasonably quantitative explanation of the process is lacking. There exists uncertainty even as to the primary driving force for grain growth, although there is a considerable body of indirect evidence that the interfacial energy of the grain boundary is responsible.7,8,io Making implicit use of this assumption, several authors14,16 have pointed out that grain boundaries should migrate toward their center of curvature. Harker and Parkerg have advanced this concept furthest, and show that one can expect grain boundary migration to occur only when the grain faces are curved, or when they meet at non-equilibrium angles. When the face is curved toward a grain A, for example, the atoms in the surface of grain B, on the other side of the boundary7 are on the average more surromded by the atoms of their lattice than the atoms on the surface of grain A. Because of thermal motion, the atoms at the interface will sometimes be attached to grain A and

Jan 1, 1949

Discussion of the paper of Archer E. Wheeler and Milo W. Krejci, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 1831 to 1880. BRADLEY STOUGHTON, New York, N. Y.:-I would like to ask Mr. Krejci whether they have tried mixing coke dust with the lime in those converters and, if so, if any advantage has been found. It has been a very great advantage in the steel converters where coke dust has been mixed with the lime near the tuyeres. Of course the agent that causes the corrosion at that point is oxide of iron, and coke seems to prevent the formation of the oxide of iron and so protect the tuyeres. It would be interesting to know if it had the same effect in the copper converters. MILO W. KREJCI:-We have never tried it here. At Anaconda the tuyere section was formerly put in by mixing magnesite with tar and ramming that into the tuyere section, but they have abandoned that. Might I ask how you would apply the coke dust? How get it into the tuyere section ? How hold it there ? BRADLEY STOUGHTON :-The coke dust is mixed with silica and clay and then rammed in and burned. I suppose in your converters it would be mixed with the magnetite or magnesite and then agglomerated with the material in place. MILO W. KREJCI:-We never tried it here. PROF. JOSEPH W. RICHARDS, South Bethlehem, Pa.:-I would like to ask how thick this deposit of magnetite is on the lining. How thick a layer would be practical ? MILO W. KREJCI:-About 21 in. would be sufficient. SOLOMON LE FEVRE, Mineville, N. Y.:-I was interested to hear of the use of magnetite in connection with the copper smelter. I am interested in the mining of magnetite, but was not aware that it had been used at all' by the copper metallurgists.

Jan 11, 1913

By Philip D. Pearson

CALAND Ore Co.'s dredging program has reached the halfway mark. The goal is to remove more than 160 million cu yd of lake bottom material overlying the iron orebody in Falls Bay of Steep Rock Lake, Ont. Two large dredges were constructed to remove this overburden, a layer of soil about 90 pct varved clay some 400 ft thick. Moisture content of the clay is high-approximately at the liquid limit of the soil. A few years ago, searching for additional reserves of ore, Inland Steel Co. looked toward Canada and the newly developed Steep Rock iron range. To this end an option agreement was signed Dec. 30, 1949, between Steep Rock Mines Ltd. and Caland Ore Co. Ltd., a wholly owned subsidiary of Inland Steel. Several drilling programs were conducted between this date and Jan. 1, 1953, when a 99-year lease was signed covering an area of 1249 acres. This lease calls for ore production to begin in 1960, with full production of 3 million tons per year by 1969.

Jan 8, 1957

By Richard H. Jahns

GRANITIC pegmatite deposits are the chief source of commercial feldspar, sheet mica, beryllium, tantalum-columbium, and lithium minerals, and certain types of kaolin. They also have yielded significant quantities of cassiterite, gems, scrap mica, molybdenite, tungsten minerals, uranium-thorium and rare-earth minerals, and zircon, either directly or as the sources of placer deposits. The output from pegmatite mines in the United States is small as compared to other mineral products in terms of bulk or value, and much of it comprises minor metals and nonmetals. Nevertheless, pegmatite minerals play a vital part in domestic industrial economy, particularly in the ceramic and electrical industries. Numerous special purpose uses also are important, even though they require small quantities of raw materials. Never was United States dependence upon pegmatite mining more clearly emphasized than during World War 11, when greatly expanded demands and uncertainties of foreign sources of supply caused much concern. Such commodities as beryl, tantalite, and sheet muscovite remained high on the critical list for months at a time, and for some minerals there was a real struggle to achieve and maintain a favorable ratio of supply to demand. Satisfactory stock piles of certain sizes and qualities of sheet mica, for example, were not built up until late in 1944, when wartime requirements already had begun to level off or even to decrease. Production of all the strategic pegmatite minerals from domestic deposits during World War I1 constituted only 10 pct or less of the total domestic consumption of these minerals, but the importance of this contribution should not be minimized. Domestic production often represented the difference between increase and further reduction of existing stocks of commodities already in seriously short supply, and in the early stages of the war it was the only assured source if imports were cut off. During the recent war period, the U. S. Geological Survey carried on a program of pegmatite studies in the New England and Southeastern States, in the Black Hills area of South Dakota, in the Rocky Mountain region of Wyoming, Colorado, and New Mexico, and in various parts of Washington, Idaho, Utah, Nevada, Arizona, and California as shown in Fig. 1. Several papers and reports already have appeared as an outgrowth of this work,'-= and others are in preparation. This paper outlines some results of data obtained by the writer during the period 1942 to 1946, when he was engaged in studies of pegmatites in the Southeastern, Southwestern, and Rocky Mountain States. Beryllium Minerals Beryl is the present commercial source of beryllium metal and beryllium compounds, which are used in ceramics, in the preparation of X-ray tubes and fluorescent lamps and screens, in special processes of paint and textile manufacture, and in the optical systems of some electrical instruments. The metal also is used in nuclear physics, chiefly as a source of neutrons. Beryllium is alloyed with aluminum for certain light-metal uses and is a constituent of some nickel and iron alloys. Currently the chief demand, however, is for copper-base alloys, which are exceptionally resistant to fatigue and wear, are responsive to hardening treatments after

Jan 1, 1952

By James O. Lewis

Gravity drainage is the self-propulsion of oil downward in the reservoir rock. Under favorable natural and operational conditions, it has been found to effect recoveries comparable to water displacement. With modern technical knowledge, the operator can often make a choice between dissolved gas drive, water drive and gravity drainage as the principal recovery agent in a reservoir. It is desirable that the opeator be able to determine which of the three agents will be most effective under each set of conditions. So far, gravity drainage has received less consideration than the other two. In this paper. an endeavor is made to set forth some of the principles of gravity drainage, to point out the types of reservoirs favorable for it, and to show how it may be applied in them. Field examples are described and discussed. Introduction Since early in the history of the oil industry, it has been recognized that gravity is one of the three important natural forces for expelling oil from the reservoir rock. As knowledge of the technology of oil recovery progressed, ideas changed with respect to the relative importance of the three forces and with respect to the manners in which they functioned. For a time, disproportionate emphasis was placed on the importance and function of gas and the need for conserving gas pressures. More recently, disproportionate emphasis has been placed on encroaching edge water. Only lately has there been evidence that the function and importance of gravity was to receive due consideration. Study of this neglected phase of oil recovery is needed to round out our knowledge of reservoir behaviors and to gain a balanced viewpoint of the interplay of forces that may operate in varying importance in reservoirs. The purpose of this paper is to discuss mainly in a qualitative way, the functions of gravity, to present some concrete instances where it has been important and to raise some questions that should be investigated further. Oil-recovery Agents The important natural agents for effecting oil recovery that may be originally available in a reservoir are gas, both dissolved in the oil and free in gas caps, encroaching edge water and gravity. Each of these agents can act in a dual capacity—physically to overcome the surface energies that hold the oil within the pores and mechanically to overcome viscous . resistance and to propel the oil through the porous reservoir rock to the wells. Advancing edge water displaces the oil from the pores and lifts it updip to structurally lower wells. Gravity drains the oil from the pores and flows it downdip to the wells. Gas displaces oil from the pores, entrains it in the gas stream and flows it to the wells, but gas in solution also affects the physical properties of the oil and thus can influence oil recovery by the other agents, whether or not the mechanical energy in the gas is utilized. Of the two functions of these agents, the more important is the ability to dis-

Jan 1, 1944

By E. S. Bumps, H. D. Kessler, M. Hansen

The titanium-rich end of the Ti-AI phase diagram has been determined to the compound TiAI3 (62.7 pct Al), thus joining the aluminum-rich portion previously investigated by others and completing the diagram. Micrographic analysis and X-ray diffraction were the chief methods used to determine the phase relationships. THE Ti-Al phase diagram has been investigated as part of a program on titanium phase diagrams for the Wright Air Development Center. Included in the available information concerning the phase relationships in titanium-rich Ti-A1 alloys is a brief statement by Brown' that: "aluminum raises the transformation temperature to 1000°C (183Z°F)." This observation is interesting in that it is the first example of a metallic alloying component raising the transformation temperature of titanium, and consequently widening the field of the a solid solution. Busch and Freyer' presented resistivity data which indicated the formation of titanium-rich solid solutions of 1 and 3 pct A1 alloys prepared by powder metallurgy methods. Duweza found that there is only one other intermediate phase other than the known compound TiA1, (62.7 pct Al). This phase, designated as y, is of variable composition; its crystal structure is of the AuCu type and is therefore based on the composition TiAl (36.02 pct Al). Earlier work on the constitution of the aluminum-rich alloys has been reviewed by Hansen, and need not be discussed here. The tetragonal crystal lattice of TiAl,, as found by Fink, Van Horn, and Budge," was confirmed by Brauer." Recently, Schubert7 has reported that TiA1, is homogeneous within a limited composition range; however, the solubility limits were not given. The Ti-A1 phase diagram as presented in. this paper was determined by micrographic analysis of alloys containing from 1 to 62 pct Al, annealed at and quenched from temperatures between 700" and 1400°C. The phases and phase ranges investigated extend to the compound TiA1, (62.7 pct Al) to join the aluminum-rich end of the system determined by other investigators, thus completing the diagram. Methods of Investigation Preparation of Alloys: Iodide titanium, 99.9+ pct pure, obtained from the New Jersey Zinc Co., and high-purity (99.99+ pct) aluminum sheet from the Aluminum Co. of America were used to make up alloy ingots weighing 10 to 20 g. Detailed descriptions of melting techniques have been presented previously for work on the Ti-Mo and Ti-Cb> nd Ti-Si" phase diagrams. Briefly, the melting practice consisted of arc melting an accurately weighed charge in a copper block crucible insert in a non-consumable tungsten electrode furnace, under helium at atmospheric pressure. All ingots were carefully weighed after melting to detect possible losses. Comparison of weight before and after melting showed no appreciable weight changes. Also, chemical analyses were in close agreement with nominal compositions, Table I. The diagram as presented is, therefore, based on nominal compositions. Alloys were prepared having the following nominal aluminum contents: 1 ... 36 (1 pct increments), 38, 40, 41, 42.5, 44, 45, 46, 47.5, 49 . . . 64 (1 pct increments), 67, 70, 80, and 90. Ingots with up to 14 pct A1 were cold-pressed various amounts in order to increase the rate of attaining equilibrium structures on heat treatment. The amount of cold deformation that could be applied decreased with increasing aluminum content, until alloys containing 12 pct A1 or more cracked after only a few percent deformation. Annealing Treatments: Samples annealed at temperatures of 700" to 1000°C were sealed in

Jan 1, 1953

By T. B. Massalski, C. S. Barett

THAT metals and alloys of the body-centered-cubic structure tend to become unstable at low temperatures is so nearly universal that any exceptions are worthy of special attention. Studies of the exceptions may disclose unrecognized examples of metastability or may shed light on the nature of some of the factors that stabilize the body-centered-cubic phase. Among the structurally analogous body-centered-cubic 3/2 electron compounds, the ß-phase in the Cu-Zn system deserves further attention for, although this phase is known to undergo partial mar-tensitic transformation on cooling below room temperature to the temperature of liquid nitrogen when the composition is less than about 42 wt pct Zn, it does not transform on cooling .when there is more than this amount of zinc present.1-4 The present authors recently found that an alloy containing 48.35 wt pct Zn could be transformed, however, if deformed severely at room temperature or lower temperatures.V his discovery led to the suggestion that the jerky flow of ß-brass single crystals6 and some of the unusual temperature variations of the yield strength and hardness are due to strain-induced transformation during the tensile tests. The present investigation is an extension of that work to cover the entire available range of compositions of Cu-Zn ß-phase alloys and certain interesting compositions of the ß-phase in the Cu-Zn-Ga system. Particular attention is given to the structure of the transformation product resulting from cold work, which is found to vary with alloy composition, and to the temperature range in which transformation can be induced in the various alloys. The composition limits of the body-centered-cubic phase in the Cu-Zn system, based on a recent review by Raynor7 and the precision determinations of Beck and Smith: are shown in Fig. la; in the ß region the alloys are disordered and in the ß region they are ordered. The rate of ordering is so rapid that a high degree of order is found in any of these alloys immediately after quenching. Experimental The nine binary and four ternary alloys of this investigation were prepared from cathode copper (99.99 pct purity), electrolytic zinc (99.99+ pct), and gallium (99.98+ pct). All alloys were cast in transparent Vycor tubing, homogenized at temperatures between 800° and 890°C, and quenched in water. Ternary alloys were cast in small amounts (-5 g) to predetermined compositions to fall along a line of constant electron concentration in the ternary system. Changes of weight during the casting operation of the ternary alloys were not greater than 1 part in 2500 from the intended nominal weights and therefore their compositions were accepted without chemical analyses. All binary alloys were cast in larger amounts (100 to 150 g), homogenized, and hot rolled after preheating to 800°C. The central portion of the rolled strip of each alloy was annealed for eight days and quenched in brine. All binary alloys were analyzed chemically. The compositions, heat treatments, and metallographic appearances of all alloys are tabulated in Table I. Various samples were subjected to heat treatment or cold work at several temperatures and were then examined metallographically or by means of X-rays. Specimens about 6x6x3 mm in size were examined metallographic ally to confirm the presence of the ß-phase after quenching. Cold work was introduced by fastening each sample between two pieces of steel, cooling the assembly to the desired temperature, and transfering it rapidly to a vise where moderate or severe compression was immediately applied. Cold working at liquid helium temperature was done by a chisel-shaped tool mounted on an X-ray spectrometer, described elsewhere.% A!! metal-

Jan 1, 1958

By H. A. Wriedt

A method of calculating activities in binary systems having miscibility gaps is described. The method, which applies only to the phase in which the gap occurs, is exact when the function defined by the equation varies linearly with composition. Analytical and numerical solutions (as a function of the conjugate phase compositions) are presented for two coefficients A and B from which the thermodynamic activities can be calculated. Deviations from Henry's law, calculable by the method presented, are shown graphically for the particula~ case of the component i at the edge of the miscibility gap more remote .from pure component i. For symmetrical gaps, the deviation from Henry's law at this gap edge becomes smaller as the gap becomes wider, The interrelation of gap location, the direction of departures from Henry's law and the occurrence of maxima and minzma in these departures is discussed in some detail. Values for a and for activity calculated from phase diagrams show fair to excellent agreement with corresponding experimental values in the Al-Zn and CaO-SiO2 systems. WHEN structurally similar phases, B and 6, lie at the sides of a two-phase region in a constitution diagram, it can be assumed that, stably or metast-ably, they will become completely miscible at a higher temperature. The B and 6 phases are particular composition ranges of a single B6 phase region with a miscibility gap. Below, as above, the critical solution temperature, the free energy of formation of the 06 phase is a continuous function of composition through the range of the miscibility gap. It is the purpose of this paper to use this continuous free-energy function in order to develop a simple method for computing the thermodynamic activities in the B6 solution of a binary system. To make these calculations it is assumed that the function ai, familiar from Gibbs-Duhem integrations and defined by the equation

Jan 1, 1962

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By W. V. Green

The creep-rupture behavior of commercial powder-metallurgy tungsten rod is reported for temperatures of 2250°, 2500°, 2700°, and 2800°C, stresses up to 7000 psi, and times up to 4 hr. The temperature dependence and the stress dependence of creep rates are evaluated. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher stress results reported by pugh.4 THE tensile strength of single-crystal wire1 and of polycrystalline wire2 have been measured by Goucher. More recently Bechtold3 and pugh4 have studied the mechanical properties of tungsten rod between room temperature and 1200°C. Since tungsten has the highest melting point of all metals, it should retain useful strength to very high temperatures, and should find many applications in missiles, rockets, and so forth. Therefore, the mechanical usefulness of polycrystalline tungsten rod was investigated in the 2250" to 2800°C temperature range by short-time creep-rupture tests. MATERIALS TESTED Creep specimens were machined from 1/2-in. round commercial tungsten rod which was manufactured from powder by cold pressing, sintering, and hot swaging. Purity reported by the vendor was 99.95 pct W. Spectrochemical analyses showed "traces" (less than 0.01 pct) of silicon, iron, and titanium, and "faint traces" (less than 0.001 pct) of calcium and manganese. Carbon content was 30 ppm and nitrogen content was 70 to 110 ppm. No oxygen analysis was obtained. Room-temperature stress-strain tests on the as-received tungsten gave badly scattered results. Threaded end specimens broke at the threads. When these specimens were retested using shoulder grips, the specimens broke at the shoulders. No fractures occurred in the gage lengths. The fracture stresses were: 127,000; 137,000; and 154,000 psi for three specimens which fractured at the shoulders. The microstructure of the as-received tungsten rod is shown in Fig. 1. SPECIMENS USED Fig. 2 shows the two types of creep specimens tested. The threaded-end type specimen, which was used in most tests, had a 3/4-in. gage length and 1/4-in. gage diam. The cone-end specimen, which was used primarily to investigate the effects of a smaller gage diameter and the practicability of the modified grips and specimen, had a 3/4-in. gage length and a 1/8-in. gage diam. In both cases, the gage length terminated at 0.005-in. high shoulders which served as fiducial marks for optical strain measurements. Surface finish on the gage length was 16 µ-in. rms. Creep rates and rupture times were not significantly different for the two types of specimens and were not affected by electropolishing the specimens before testing. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.5 In it the specimen is held vertically by grips of similar material and on the axis of a cylindrical tungsten or tantalum heater-tube. The specimen is loaded by means of the specimen grips, a pull rod (which is sealed to the chamber lid by a vacuum-tight bellows), a mechanical lever system, and hanging dead weights. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. An optical system views the incandescent specimen through slits in the radiation shielding and heater-tube. The optical system projects an enlarged image of the specimen gage length on a ground-glass screen. Periodic gage-length measurements are made on this image with two cathetometers. Thorium oxide coatings on the specimen threads or conical end surfaces completely prevented diffusion-welding of specimens to grips, and were used

Jan 1, 1960

By Craig R. Barrett, Jack L. Lytton, Oleg D. Sherby

The types of substructures developed during high-temperature creep of (110)[001]-oriented polycrys-talline Fe-3.1 pct Si were examined by electroetching of dislocation sites. Edge dislocations were observed to accumulate adjacent to grain boundaries and poly-gonize perpendicular to their glide planes to form a "Pile-up" of nearly parallel tilt boundaries. The dislocation density developed within the grains during steady-state creep was found to increase with increasing stress. The formation of periodically spaced groups of edge dislocations along grain boundaries was observed, and it was proposed that these formed to relive bending stresses at grain boundary shear .faults. Grain boundary serrations developed at these faults, and it was suggested that this was a result of localized grain boundary migration at the polygonized groups. THE authors have conducted a series of high-temperature creep tests on (110)[001]-oriented poly-crystalline Fe-3.1 pct Si sheet. The creep specimens were examined at various stages of creep by means of electrolytic etching of dislocation sites using the chrome-acetic acid solution developed by Morris.' Hibbard and Dunn2 have demonstrated that the etch pits produced with this technique correspond to single dislocations. It is the purpose of this paper to present and discuss the dislocation substructures which were formed during high-temperature creep at constant stress. EXPERIMENTAL PROCEDURES The polycrystalline Fe-3.1 pct Si sheet employed in this study contained a (110)[001] texture. This texture was quite strong, and the elastic properties of the sheet closely approached those of a single crystal of iron.3,4 A typical analysis in weight percent for this material is 3.1 Si, 0.1 Mn, 0.003 C,

Jan 1, 1965

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.' The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By Leo Horvitz

Microanalysis of near-surface soils for hydrocarbons is the basis of a method for locating gas and oil deposits. To substantiate this technique, evidence of vertical migration of hydrocarbons from petroleum accumulations is presented. Tabulated data relevant to hydrocarbon surveys conducted in several petroleum provinces are included. PEROLEUM and natural gas are composed principally of the saturated hydrocarbons ranging from methane, the lightest, to nonvolatile liquids and solids containing approximately thirty-five carbon atoms. A technique for locating buried accumulations of these hydrocarbons before drilling obviously requires that some of the hydrocarbons leave the deposit and migrate toward the surface of the earth where they may be detected in their original form. Earliest attempts to link near surface hydrocarbons to petroleum at depth were apparently made by Laubmeyer' in Germany and by Sokolov in Russia. These investigators collected samples of soil air from boreholes one to two meters deep and analyzed them for traces of hydrocarbons. They found that soil air over producing areas is richer in these constituents than is soil air over barren areas. Since 1936 work on petroleum exploration techniques of this type has been going on in this country. However, instead of determining hydrocarbon content of soil air collected in the field, investigators analyze samples of the soil itself for adsorbed and occluded hydrocarbons, which are released by suitable treatment and found in larger amounts than are the quantities reported for soil air. Difficulties often encountered in collecting gas samples in the field, moreover, are eliminated when soil is used as the sampling medium. Field Procedure: Sample locations are first surveyed over the area to be investigated. Care is taken to locate the stations at considerable distances from roads, pipelines, drilling wells, and other sources of contamination. The borehole pay be dug with a bucket-type hand auger or with mechanical drilling equipment. Lubricants are avoided in either case. When the desired depth is reached, a sample is brought to the surface, placed in a pint glass jar or can, and securely sealed. Sample containers are carefully labeled and delivered to the analytical laboratory. Generally a satisfactory sampling depth range is 8 to 12 ft. In some regions, however, satisfactory data are obtained from samples collected at much shallower depths. Such is the case, for example, in areas of west Texas where the limestone and caliche near the surface occlude hydrocarbons and prevent their rapid escape to the atmosphere. In carrying out broad reconnaissance surveys in search of large features, considerable time is saved by first taking samples one-fourth to one-half mile apart along profiles about one mile apart. If the analytical data indicate a hydrocarbon anomaly of interest, additional samples are taken to produce a more dense and uniform sampling pattern within the interesting area. This sampling program is particularly adaptable to areas that are sectionized. In areas covered with a network of roads, sampling along these roads facilitates the reconnaissance survey. Actual sampling density used depends upon areal extent of features expected. When flanks of piercement-type domes where accumulations may be only several hundred feet wide are sampled, stations are often no more than 200 ft apart. Analytical Technique: Of the hydrocarbons composing petroleum, only the more volatile would be expected to reach the surface of the earth. The analytical technique, therefore, was developed to determine only those constituents that exert a vapor pressure at room temperature. Actually, in near-surface soils, only a very small part of the hydrocarbons are heavier than pentane. Details of the analytical technique have previously been reported. Only a brief description of the methods will be presented here. A weighed portion of the sample, about 100 g, is first treated with an aqueous solution of copper sulphate and then with phosphoric acid in a partial vacuum. The copper sulphate prevents the reaction of the acid with carbides that may be present because the sample has been contaminated by auger particles. Such a reaction may produce spurious methane. The role of the acid is to decompose any carbonates present, thereby helping to release the hydrocarbons. The carbon dioxide is removed with potassium hydroxide and the flask containing the

Jan 1, 1955

By H. I. Aaronson

Isothermally formed plates of proeutectoid a, lengthen at approximately the rates predicted by the Zener-Hillert equation, indicating that their lengthening kinetics are controlled by the volume diffusion of chromium in the ß matrix. Solution annealing treatments in the vicinity of the transus introduce a second mode of transformation, in which the lengthening rate is at least 1.8 x 104 faster than predicted by this equation. Little or no volume diffusion appears to accompany the latter transformation. The Presence of oxygen is evidently a Prerequisite for the occurrence of this reaction. X HE effects of thermal history prior to the initiation of transformations which proceed by nucleation and diffusional growth are currently evoking considerable interest. The rate of nucleation (but not the rates of growth) of pearlitel and of bainite,2 and the over-all rates of aging reactions in Al-cu3 and Al-si4 alloys have been shown to be appreciably dependent upon thermal history in the solid-solution region"' or in the two-phase region prior to the onset of pre~ipitation.3,4 In none of these reactions, however, was the transformation mechanism changed by variations in the temperature-time path used to reach the reaction temperature. Preliminary experiments reported by M. K. McQuillan5,8 and a systematic investigation by Farrar and Margolin7 have disclosed that the transformation behavior of hypoeutectoid Ti-Cr alloys is considerably more sensitive to thermal history. Qualitative evidence strongly suggests that not only the rate of nucleation but also the rate of growth and even the mechanism of the ß — a reaction can undergo remarkable changes when a solution annealing treatment in the vicinity of the ß/a +ß, or transus temperature, is interposed between a high-temperature solution anneal (conventionallq at 1000°C) and the isothermal reaction treatment. The present investigation was undertaken in an attempt to ascertain the nature and origin of these effects. Study of the changes in the kinetics and morphology of the ß - a, reaction produced by varialtions in thermal history was the primary means employed for this purpose. EXPERIMENTAL PROCEDURE The compositions of the alloys used in this in~esti~ation are given in Table I. These alloys were homogenized for 5 days at 1050° C in evacuated (2 x 10 -5 mm of Hg), zirconium-gettered fused quartz capsules. The capsules themselves were enclosed in a porcelain chamber evacuated with a mechanical pump during the homogenization anneals. Upon completion of homogenization, the alloys were cooled to room temperature and then reheated to 550°C for 3 1/2 days in order to transform the alloys to a finely divided mixture of a and TiCr2, and thus provide an approximately constant initial mi-crostructure. Individual specimens were sealed in evacuated and internally gettered Vycor capsules and heat treated as previously described.8,9 EXPERIMENTAL RESULTS Ti-10.64 Pet Cr. This investigation was largely performed on the 0.64 pet Cr alloy. The "base"

Jan 1, 1962