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EDITORIAL comments on the anthracite report of the Federal Fact-finding Coal Commission, which became public on July 5, together with an analysis of its more important conclusions, will be found on another page of this issue. In this place, only a few extracts from the report, bearing more directly on technical matters, can be quoted, for lack of space. COST OF MINING Mining cost, as it stands on the books of each mining company, represents the average cost of the total output, all sizes, of anthracite. Egg coal has at least five times the market value of barley, but these' sizes are mined together and their costs can not be separated. Mine costs directly reflect the conditions under which these deposits of coal are recovered. Even within the few counties in which anthracite is found there is a conspicuous range of natural conditions. The distinc-tion between the Northern, Middle, and Southern field, or, as they are also termed, the Wyoming, Lehigh, and Schuykill regions, is primarily geologic and topo-graphic, but the effects of the natural conditions largely control costs. The contrast is great between Some of the level-lying beds of moderate but fairly constant thickness under the broad Wyoming Valley, where mining and underground haulage present relatively simple problems to the engineer, and the steeply pitching or overturned and faulted beds of variable thickness in the Schuykill field, where crushed coal' and treacherous roof multiply the difficulties of mining; and increase the unavoidable waste. Even more direct is the connection between geologic processes and the, differences in the character of the coal as mined, the varying proportions of large and small sizes demanding differences in preparation and resulting in different average prices realized for the product of the mines.

Jan 8, 1923

By N. A. Gjostein

The self-diffusion coefficient D, for a surface near the (100) plane in copper was determined by means of the Mullins theory of thermal grooving, and was found to obey the Arrhenius relationship, and Do = 6.5 x 10' sq cm per sec. Suppression of surface diffusion by chemisorbed impurities encounters difliculties as a satisfactory explanation for the large Q, and Do. Instead, a model is presented which indicates that Q,, as determined by a mass-transport technique, may involve both the energy needed to form an adsorbed atom from a ledge in the surface as well as that for the movement of the adsorbed atom.; LITERATURE reviews1-3 indicate that the mechanism of self-diffusion on metal surfaces is not clearly understood. The lack of experimental data on the temperature variation of the surface self-diffusion coefficient DJ has contributed greatly to this situation. Radioactive tracer techniques4-rn have been used to measure Ds, but for many years only Nicker-son and Parker8 had determined (for polycrystalline silver) an activation energy B, and a frequency factor Do for the surface self-diffusion process. Even in this case, a mechanism could not be clearly inferred because it was suspeted7 that a contribution from volume diffusion was not taken into account by the investigators. Some later work by Li and parkere on polycrystalline gold, in which they obtained essentially the same results as for silver and in which volume diffusion could be accounted for, seems to invalidate this criticism. In 1957, Mullins10'11 developed the theory for the thermal grooving process. This advance has opened a new and promising technique for measuring the surface self-diffusion coefficient Ds. Recognizing that a thermal groove may form by several different mass transport processes, Mullins first consideredlo the cases where a) the groove forms by evaporation and condensation or b) by diffusion along the groove surface, in either case, in a system where a metal surface is in contact with only its dilute vapor phase. In a later paper," he extended the treatment to cases where the groove forms by volume diffusion into c) the solid phase or d) by mass transport through a passive gaseous phase at 1 atm pressure. The time dependence of the groove dimensions and the shape of the groove profiles predicted by Mullins' treat-

Jan 1, 1962

By T. R. Ingraham

The thermal decomposition of Nickel (II) sulfate was examined by determining the total pressure of SO3, SO2, and O2 developed over a sample when it was heated in an evacuated system fitted with a Pyrex-bellows mercury manometer. The equilibrium pressures were combined with previously published data on the oxide and sulfide systems to establish a predominance volume diagranz for the Ni-S-O system over the normal range of roasting temperature and gas composition used in the treatment of nickel minerals. The protective coating of NiSO4 which forms on the oxide during roasting, and which causes the sulfation reaction to almost cease, may be disengaged readily by temperature cycling. When nickel sulfide is roasted in air, either nickel sulfate or nickel oxide may be formed by altering the experimental conditions. Because of the differing stabilities of various metal sulfates and oxides, possibilities exist for separating some of the constituents of mineral mixtures by the technique of selective sulfation and oxidation roasting. The experimental information required to make reasonable predictions of the possibilities of this technique is incomplete and, in some cases, in conflict. As part of a general program of providing some of the required information, a study EXPERIMENTAL Materials, Apparatus, and Procedure. Fisher certified reagent-grade nickel sulfate hexahydrate was used in the source material for both nickel sulfate and nickel oxide. The manufacturer's analysis indicated: 0.001 pct Fe, 0.005 pct Cu, 0.003 pct Co, 0.001 pct C1, other 0.15 pct. The material was dehydrated, before use, by heating at 420°C for 5 hr. The oxide was prepared by roasting the sulfate in an open tray in a muffle furnace for 10 hr at950°C. Preliminary experiments which were made by thermogravimetric analysis and X-ray diffraction analysis established that only one crystal form of nickel oxide and one of nickel sulfate were involved in the equilibrium shown in Eq. [I]. The apparatus used in the experiments was described previously.1,3 The main feature is a corrosion-resistant, flexible Pyrex bellows which is used to protect the mercury in a u-tube manometer. Before a run was begun, the apparatus was washed thoroughly with hot hydrochloric acid and water and dried by heating under vacuum. The mixed sulfate -oxide sample was contained in a platinum bat rest-

Jan 1, 1967

THE Johnson award for 1926 was given to T. L. Joseph for his experimental work on blast-furnace operation. When the Bureau of Mines undertook its experimental blast-furnace investigation in 1919, a number of operators and metallurgists were doubtful as to the practicability of small-scale tests. Several pre-vious attempts, outside the Bureau, to operate small furnaces had been unsuccessful. However, pig iron was produced in three and four-ton furnaces during the first half of the nineteenth century. The operation of a small furnace did not therefore seem an impossible task. This point of view, together with a realization of the importance of problems connected with the pro-duction of pig iron, prompted the Bureau to undertake this work. Such problems as the feasibility of using charcoal briquets as a fuel, the application of oxygen enriched blast, and the use of new ores and raw ma-terials, in general, can be investigated only at consider-able cost on full sized furnaces, while with an experimental furnace they can be conducted at a com-paratively ;small, cost. The results of small-scale tests are sufficient to determine whether the problem. War-rants the expenditure required for a trial on a com-mercial scale. The accompanying photographs and chart show the various stages of the experimental furnace development. Some idea of the size and shape of furnaces which were tested can be had from the development chart. In oper-ating furnaces A to F, a series of changes were made to increase hearth temperature. Perhaps the most im-portant change was the position of the tuyeres with respect to the bottom of the hearth. The height of the tuyeres above the hearth was gradually increased and the hearth diameter decreased. It was shown by this series of furnaces that metal and slag are the chief source of heat supply to the crucible. For this reason there is a minimum rate at which these materials can be brought into the hearth of a small furnace if it is to function properly. The rate of slag "and metal fall are determined by the burden on the furnace and the rate of blowing. Due to lack of funds necessary to provide ample blowing equipment, hot blast stoves, essential mechani-cal features, and to meet operating expenses, it. was necessary to work with much smaller furnaces, such as G to K shown in the chart. The particular object of these tests was to study the extent to which reactions could be speeded up by decreasing the size of the stock. One decided change, noticed at the beginning of this series of tests, was the effect which coke size had on the production of a strongly reducing gas. Furnace G, 22 in. high, operating on coke crushed to pass 10 mesh, made a gas richer in carbon monoxide than did fur-naces A to F, operating on run-of-the-oven coke.

Jan 3, 1927

By L. S. Darken, H. A. Wriedt

THE constitution diagram of the iron-copper system derived by Daniloff' exhibits, at the iron-rich end, phase fields similar to those of the iron-carbon diagram. At 1484° 1094°, and 850°C there are, respectively, a 6-y-L peritectic, a y-E-Lperitectic, and a a-y-E eutectoid. The phase designated E is copper-rich, containing 4 pct Fe or less according to the temperature. The composition of copper-saturated ferrite (a-solid solution) has been determined previously only twice as a function of temperature. By electrical conductivity measurements, Buchholtz and Köster2 found 3.4 pct Cu in ferrite at a eutectoid temperature of 810°C. They represented the composition of saturated ferrite by the equation, log (%Cu) = 4.32-4125 (1/T) Gregg and Daniloff3 reported that Köster later modified his opinion, raising the indicated eutectoid temperature to 833 °C and the copper content of eutectoid ferrite to 3.7 pct. The literature contains several indications4-7 that the work of Köster and his co-workers is not reliable. Norton,8 using an X-ray method, found that 1.4 pct Cu dissolved in ferrite at the approximate eutectoid temperature of 850°C and that the solubility decreased to about 0.3 pct at 700°C. Below 700°C his experimental data show almost no change in solubility. These findings, although inconsistent with the work of Ruer and Goerens4 and of Smith and Palmer,7 have been used generally since their publication. In investigations involving the observation of arrests in temperature during continuous heating or cooling the precise location of the eutectoid temperature has been obscured by a large hysteresis. The more reliable work 579 where the results are not effected by this hysteresis indicates a eutectoid temperature between 840° and 850°C. The foregoing discrepancies, along with a few observations in this Laboratory relating to the precipitation of copper from ferrite, prompted us to rein-vestigate the lower temperature portion of the Fe-Cu system. In this investigation the solubility of copper in ferrite was obtained by the chemical analysis of high-purity iron equilibrated with copper-silver alloys. This method eliminated the necessity for retaining by a quench the physical state of the specimen existing at the equilibration temperature. EXPERIMENTAL The reaction of the iron with the copper alloy was

Jan 1, 1961

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute, since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1" to 2°C. per min. with or without slow stirring (Fig. I). By this method the lead-rich end of the lead-alltimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the liquidus curve of the binary alloys did not intersect at the euteotic temperature. An equivalent effect mas observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent in- vestigation by Pellini and Rhines,1 who determined the eutectic temperature to be 2 51.5°C. The observation that the curves of primarY crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomeilon by assuming the existence of a compound Sb4pb. He felt that supercooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3 the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature Of 2500 to 252°C. at a rate Of coo1ing of about 6°C. Per min. Abell Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic only 11 .4 to 11.5 per cent antimany. (Previous analyses by Stead4 .in 1891 gave 13 per cent.) Weaver,ll however, reported in 1935 that cooling cunres indi-

Jan 1, 1944

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute, since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1" to 2°C. per min. with or without slow stirring (Fig. I). By this method the lead-rich end of the lead-alltimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the liquidus curve of the binary alloys did not intersect at the euteotic temperature. An equivalent effect mas observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent in- vestigation by Pellini and Rhines,1 who determined the eutectic temperature to be 2 51.5°C. The observation that the curves of primarY crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomeilon by assuming the existence of a compound Sb4pb. He felt that supercooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3 the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature Of 2500 to 252°C. at a rate Of coo1ing of about 6°C. Per min. Abell Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic only 11 .4 to 11.5 per cent antimany. (Previous analyses by Stead4 .in 1891 gave 13 per cent.) Weaver,ll however, reported in 1935 that cooling cunres indi-

Jan 1, 1944

By E. W. Dewing

The solubility of A14C3 in cryolite melts has been determined by holding the melt with aluminum in a graphite crucible for 4 hr at temperature, quenching the crucible in water, and analyzing the frozen salt by CH4 evolution. The solubility is given by log(wt % Al4C3) = 1.298 -1.l74 (wt ratio NaF/AlF3) independent of temperature in the range 985" to 1080°C. Additions ofA1203, .NaCl, CaF2, or LiF up to 10 wt pct do not affect the solubility, provided that LiF and CaF2 are replaced by equivalent NaFin calculating the ratio. The variation with ratio can be accounted for quantitatively on the hypothesis that the Mechanism of solution is Al4C3 + 2AIF3 = 3Al2CF2 since the solubility varies as (aAIF3) 2/3; Mechanisms involving C", C2- , AlC- , A12C2+, and Al2CF+are re-jected. At ratios above 1.5 truces of c;- are also present. It was noticed some years ago in this laboratory that carbon specimens made cathodic in a cryolite bath decrease in diameter over a period of time.' It was also found that cryolite which had been melted with aluminum in a graphite crucible was sometimes yellow, and that A14C3 could be seen intimately embedded in the cryolite crystals. CH, could be recovered by acid attack. There was thus reason to believe that A14C3 had a genuine solubility in molten cryolite, and the object of this work was to measure it. EXPERIMENTAL AND RESULTS A graphite crucible, 2 in. ID and 2.5 in. deep with a close-fitting lid, contained about 150 g of cryolite (plus additives) and about 20 g of 99.99 pct pure Al. It was placed in a vertical Inconel furnace tube, covered with refractory brick to provide thermal insulation, and the top of the tube was roughly sealed with disks of asbestos paper. An alumina tube led argon down to the level of the top of the crucible to expel air, and an alumina sheath with a Pt-10 pct Rh ther-mocouple inside was positioned between the crucible and the wall of the Inconel tube. The tube was heated in an electrical resistance furnace for the desired length of time; the refractory bricks were then removed, and the crucible was lifted out with tongs and quenched in water. After such a crucible was broken open it could be seen that its inner surface was yellow owing to the presence of A1,C3, and sometimes needle-like crystals could be observed (at X75 magnification) growing out into the nielt. It was concluded that Al,C, had been present as a separate phase when the crucible was at tenlperature and that the melt had been saturated: in

Jan 1, 1970

By S. F. Emmons

Br far the greater number of the members of this Institute are men who are engaged in the strenuous work of the technical part of their profession, and find little time for the abstract scientific work which is less distinctly practical and pecuniarily emunerative. There is, however, a small but increasingly numerous class whose members devote themselves to broad geological problems which underlie the systematic development, and whose work, theoretically, ought to precede and form a basis of that of their more practical brethren. These are the so-called mining or economic geologists, who are, for the most part, connected with State or National geological surveys. From the character of their work, the life of these men necessarily follows rather different line's than that of most of their colleagues, and is not generally familiar to them. It seems admissible, therefore, that to the life of a prominent member of this class, who died during the past year, having literally sacrified his life to his work, a more extended notice should be given than the relatively small number of his contributions to the Transactions might seem to justify. George Romans Eldridge, son of Ellery and Sarah (Mathews) Eldridge, was born on Cape Cod at Yarmouth, Mass., Christmas day, 1854. His boyhood education in the public school at Yarmouth was followed by a six years' course in the Public Latin School at Boston, from which lie entered Harvard Uni¬versity in 1872, being graduated with the highest rank in his class in the natural sciences in 1876. During his college course he spent the summers of 1875-6 at Cumberland Gap, Ky., as volunteer aid to Prof. N. S. Shaler, who was then in charge of the State Geological Survey of Ken¬tucky. This vacation work, undertaken by him rather as a pastime, gave him his first leaning toward geology. Soon

Mar 1, 1906

By E. A. Gulbransen, W. S. Wysong

The behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a a Or as an important component in alloys in high temperature Oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a micro-balance study of the following problems: (1) the oxidation behavior in the ternperature range of 25 to 550°C (') the reduction with pure hydrogen Of thin Oxide films formed On tungsten, and (3) the volatility Of thin Oxide films On tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the Oxide to to ratio is greater than one, the oxide is not considered protective, ('1 the meta1 readily Oxidizes at temperatures from 30" to 55o°C (3) the oxides WO² and WO³ are reduced at temperatures as low as 500°C. by hydrogen, and (4) the Oxide WO3 is volatile at temperatures from 800 to 1100°C. Literature The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°c. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides, Schei14 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bed-worth's5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.? They have reported that WO3 is the stable oxide in contact with the metallic substrate up to approximately 600°C while wo³ forms first at 7oo°c. Hagg and Magneli8 have recently reported a study of the lattice structures . observed in the tungsten oxidcs using the X-ray diffraction method. In addition to an a-phase WO3 and a '-phase WO2, they reported the existence of two new phases. A 8' phase, homogeneous between

Jan 1, 1949

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute. Since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1° to 2°C. per min. with or without slow stirring (Fig. 1). By this method the lead-rich end of the lead-antimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the' liquidus curve of the .binary alloys did not intersect at the eutectic temperature. An equivalent effect was observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent investigation by Pellini and Rhines,1 who determined the eutectic temperature to be 251.5°C. The observation that the curves of primary crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomenon by assuming the existence of a compound Sb4Pb. He felt that super-cooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3. the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature of 250° to 252°C. at a rate of cooling of about 6°C. per min. Abel, Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous, publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic contains only 11,4 to 11.5 per cent antimony. (Previous analyses by Stead4 in 1881 gave 13 per cent:) Weaver," however, reported in 1935 that cooling curves indi-

Jan 1, 1943

By Ronald C. Koo

SMALL additions of potassium, aluminum, and silicon as oxides (referred to as dope) to tungsten have been known for several decades to have a very large effect in raising the recrystallization temperature and altering the recrystallized grain morphology of heavily drawn wire. Previous investigations of this doping effect1 6 have led to various speculations but all failed to deduce unequivocally the physical state or the mechanistic influence of the dopant. Recently, walter7 has observed, by transmission electron microscopy, strings of "fine particles" in heavily rolled and annealed doped tungsten sheet and concluded that they were particles of mullite (Al6Si2013). His conclusion was inferred from the electron diffraction patterns of large particles ex-trated by carbon replication of fractured surfaces of slabs rolled from sintered ingots. That the strings of "fine particles" in heavily rolled and annealed sheet were also mullite was an assumption for which no evidence was presented. A similar investigation has been carried out in this laboratory over the past 2 years on a variety of tungsten wire: doped tungsten, and undoped tungsten, as well as 218 doped tungsten purchased from the Lamp Metals and Components Department of the G.E. Lamp Division. Although the electron microscope observations are similar to those reported by Walter, the writer has reached a different conclusion concerning the physical state of the dopant in annealed tungsten. The purpose of this communication is to present evidence that the strings of "fine particles" observed in transmission specimens are not mullite, but are voids. In the present investigation, tungsten wire, 0.88 mm in diam, was rolled into ribbon 0.2 mm by 125 µ thick. The ribbons were annealed in vacuo at a pressure of -1 x 10-5 Torr and then thinned electrolytically in a 2 pct KOH solution. Fig. 1 shows a typical transmissicjn electron micrograph of a sample annealed at 1700°C for 30 min which reveals rows of closely spaced voids having a light contrast (referred to as "fine particles" by Walter) aligned parallel to the working direction. Stereo micrographs (by D. Moon, Westinghouse Research and Development Center) have shown that these voids do not exist on the surfaces of the specimens as a result of thinning but are within the thin-foil specimens. The following experiments have been performed to verify that these are indeed voids. I) Effect of Annealing. Voids are absent in unannealed specimens and appear only after annealing. This behavior cannot be explained if they were solid particles such as mullite. Precipitation (in an unquenched specimen) upon annealing requires solute elements having decreasing solubilities with increasing temperature. Although the solubility of aluminum in tungsten does decrease with increasing temperature, precipitation requires a concentration in excess of 1.4 wt pct,8 which is at least two orders of magnitude higher than the aluminum content in doped tungsten. It is also unreasonable to assume that particles aligned in rows initially present in unannealed specimens were too

Jan 1, 1968

By M. K. Yen

The distortion of crystal structures referred to as "biege gleitung",1 "local curvature"2-4 and "deformation bands"5,6 is believed to be an unavoidable characteristic of deformed single crystals. The presence of asterism on Laue photograms of Al single crystals either deformed by pure shear7 or extended in a condition relatively free from the grip effect2 indicates strong evidence substantiating this point of view. The type of localized bending described in connection with the bending test of Al single crystals by Yen and Hibbard8 could conceivably exist either microscopically or submicroscopically in all types of deformation. The purpose of this note is to extend this idea to the postulate of a hypothetical "microbending site," as applied to the mechanism of slip in a general sense. The mosiac structure, as postulated by Darwin,9 is that crystals were actually composed of small blocks which have a linear dimension 10—4to 10-6 cm on the edge and deviate from each other by an angle of about one-tenth of a degree. The following discussion is based on the assumption that when slip is propagated from one mosaic block to the adjacent one, bending of the lattice at the region of their boundary is produced in order to maintain the continuity of the gliding process along a certain slip plane. Consider a two-dimensional diagram of two ideal mosiac blocks on the cross-section perpendicular to the slip plane and containing the active direction of slip. When an external force is applied, the localized bending or "microbending site," would be generated at the region as illustrated in Fig 1A at point B. A schematic diagram of a "microbending site," generated at a mosaic boundary, is illustrated in Fig IB. It may be seen that once the curvature of the bending site reaches sufficient magnitude, the interaction force encountered by pairs of atoms symmetrical with respect to the center of the bending is equal but opposite in sign. Consequently, the overall energy required to displace the atoms near the center is approximately zero.10"12 Based upon the finding that the misalignment between two mosaics is 0.1 degree,9 the assumption is made that "microbending sites" may possibly exist in the region where one plane will have one more row of atoms than an adjacent plane. It is probable that the origin of the bending site will be where the distance between two mosaic boundaries is "2d" as shown in Fig 1A at point B, where " d" is the interatomic distance. Thus, the distance between two "microbending sites" is in the range of about 600 interplanar spacings. In the case of aluminum, the spacing between two octahedral planes is about 2.33 A. The distance between two bending sites will be approximately 2.5 X 10"5 cm. It is interesting to note that according to Woods13 these values approach closely the size of the domains of a cold-worked metal whose minimum

Jan 1, 1950

By A. W. Ashbrook

There are essentially three main classifications for extractants: acidic, basic, and neutral. The acidic and basic are also referred to as cationic and anionic, respectively. Some extractants are shown in Table 11-1. Acidic Extractants Acidic extractants which are of use, because of cost and/or insolubility in water, are alkylphosphoric, sulphonic, aliphatic monocarboxylic acids and naphthalene derivatives.

Jan 1, 1978

By R. W. Harper, M. C. Fuerstenau, J. D. Miller

Data were obtained with hematite with octyl hydroxamate and oleate as collectors to determine the mechanism of collector adsorption and also to establish the roles that conditioning time and temperature assume in this system. The presence of hydroxy complexes of iron are apparently necessary for chemisorption of collector to occur, and it appears as if extended conditioning times and elevated temperature promote greater dissolution of the mineral and hence greater concentrations of hydroxy complexes. Data were also collected with two natural hematitic ores. With one ore that was ground to 70% - 15u, an addition of 0.4 lb per ton hydrox-amate resulted in a final concentrate recovery of 86% at a grade of 64% iron. Satisfactory concentrate grade could not be obtained with fatty acid under these conditions. The effect of conditioning time prior to the addition of collector was also examined with another ore. When the ore was conditioned for 3 min, 19% of the iron was recovered in the concentrate at a grade of 67% Fe. With a conditioning time of 7 min, 73% of the iron reported to the concentrate at a grade of 62% Fe. These products were obtained with an addition of 0.2 lb per ton hydroxamate. This ore also responded well to flotation with fatty acid. The use of potassium octyl hydroxamate as a collector for iron oxide has been the subject of an earlier study.1 From this initial study, it was suspected that hydrolysis of surface ferric iron was involved in collector adsorption. More recent work in other systems has shown that slight mineral dissolution, followed by hydrolysis of cations common to the mineral lattice, is apparently necessary, and that adsorption of these hydroxy com- plexes probably occurs prior to the adsorption of collector. In view of these facts, work has been continued on the hydroxamate-hematite and oleate-hematite systems to gain better insight into the mechanisms of collector adsorption on iron oxide. Microflotation experiments in conjunction with infrared analysis were used in this regard. In addition it was felt necessary to establish more clearly the responses that can be obtained from natural ores when hydroxamate is used as collector as compared to those obtained when fatty acid is used. Experimental Materials and Techniques Pure potassium oleate, potassium octyl hydroxamate, synthesized from hydroxylamine hydrochloride and methyl octanoate, and a distilled Tall Oil were employed as collectors. Conductivity water was used in the

Jan 1, 1971

By F. T. Selleck, H. H. Reamer, B. H. Sage

An experimental investigation was made of the effect of temperature upon the three-phase pressure associated with the propane-water and propene-water systems when hydrates were present. In addition, the characteristics of the propane-propene-water system were established over a limited range of ternperatureo under conditions such that hydrate was formed. The hydrate phase for this system may he a solid solution and the distribution of propane and propene in it is similar to that found in the coexisting hvdrocarhon liquid phase. INTRODUCTION A knowledge of the characteristics of hydrates of the hydrocarborrs encountered in industrial practice is of importance in connection with the design of process equipment. Villardl.1,2 carried out early studies of hydrates, and de Forcrand1 con-sidered the more probable compositions of the hydrates of hydrocarbons. Hammerschnid1 presented information about the propane-water and the isobutane-water systems. Scheffer5 studied the hydrate of hydrogen sulfide in detail, and de For-crand reported on the hydrates of krypton, argon, and xenon.1 Roberts and co-workers1,2 determined the nature of the hydrates formed in the methane-water and ethane-water systems. Carson and Katz10 studied the methane-propane-water, methane-pentane-water, and the methane-hexane-water systems in the four-phase region. The results of this rather extensive investigation indicated that the paraffinic hydrates formed solid solutions. The experimental evidence now available does not Support the existence of hydrates of the pentanes-antl-heavier hydrocarhons but it cannot be stated with certainty that such hydrates are not formed. Stackelherg. 11,12,13 made extensive studies of the crystal structure of paraffinic hydrate; by means of x-ray techniques and found that hydrates poses; a definite structure and composition. The existence of such a Structure does not preclude the firmation of Solid solutions of hydrates in aqueous systems containing two or more hydro-carbon~. Wilcox, Carson and Katz" reviewrd the information on the hydrates of importance in the processing of natural gas and presented data concerning their formation from natural gas. Kobayashi and Katz1' made studies at high pressure of the Hydrate of methane. and Unruh and Katz"' investigated hy-drates in mixtures of carbon rlioxide and methane. Frost and Deaton contributed to the knowledge of the composition of the paraffinic hydrates The irregularities in the experimental results were several times the expected uncertainties. This experience confirms the behavior encountered by other investigators indicating that hydrates tend to occlude water during their formation, thus rendering difficult the direct measoremeut of their composition. Miller and Strong2 investigated a number. of paraffinic hydrates from the standpoint of their possible application to (, the industrial storage of gas. Powel1 studied the effect of solutes upon the decomposition temperature of paraffin hydrates. Marked lowering of the decomposition temperature at a given pressure may he obtained by the use of such additive agents as ethylene glycol, urea. and sodium chloride. APPARATUS AND METHODS Two method* were here employed to study the behavior of hydrates. The first involved a glass capillary within which the hydrocarbons and water were confined over mercury. The second made use of a double-ended weighing bomb technique." The glass capillary equipment has been described elsewhere.'" A schematic drawing of it is presented in Fig. 1, where the arrangement of the agitator and mercury reservoir is shown in some detail. The lower part of the glass capillary, D, was enlarged to afford space within which the fluids used in the investigation could he stored at low pressures after their introduction through the valve. G. The temperature of the capillary was controlled by the circulation of a hydrocarbon oil of low viscosity from the agitated bath, B, through the vacuum jacketed column. C. The pump, A, was employed for the circulation of this oil. A relatively clear view of the capillary tube, D, was obtained through the vacuum jacket. Mercury was introduced into the lower part of the vessel, E, from

Jan 1, 1952

By Gerald Edmunds

THE liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the com- position of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. APPARATUS By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 1 ¾ in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 18 ½ in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By G. Sachs, S. I. Liu

Introduction In a previous investigation on the effects of repeated strains of large magnitude on the aluminum alloy 24 ST, it was found that the reduction in ductility by straining in tension was partially restored by a subsequent compression.&apos; As illustrated by the dashed line in Fig I,$ the ductility (e~) retained after prestraining in tension by a certain amount (el) and measured in a subsequent tension test is represented by a straight line sloping down under 4s°. If a compression of the same magnitude as the first tension is inserted (€2 = — €1) between prestraining and final testing in tension, such a "balanced" tension-compression cycle yields a ductility considerably higher than that present after prestraining in tension only. The results of these tests can be correlated with those of an investigation on the effects of prestraining in compression.~ As also shown in Fig I, the ductility in subsequent tensile tests decreased with com- pression, at a rate considerably slower than that after prestraining in tension. The above discussed testing conditions can be considered as special cases of a general straining cycle, consisting of first, straining in tension by an amount el, subsequently straining in compression by an amount e2, and finally determining the retained &apos;ductility, e,, in a tensile test. Prestraining in tension is then represented by el > o and e2 = o. Prestraining in compression is given by e~ = o and e~ < o. Balanced cyclic straining is defined by the condition el > o and cz = — 61. In order to obtain further information on the effects of straining cycles consisting of tension and subsequent compression, further tests were made, varying both the tension strain, el, and the compression strain, e2, within extreme limits; el varied between 0.06 and 0.28 and e2 between — 0.008 and —0.h approximately. Apparently, such tests have not been previously performed. They revealed phenomena which have not been recognized to date, The results of the investigation are herewith reported, without attempting to correlate them with internal processes within the metal structure. However, in order to assist in an analysis of this type, the results have been represented in various manners. In addition, further test data on the effects of prestraining by compression were provided by using specimens of various contours (notched specimens) in the sub-

Jan 1, 1949

By J. R. Long, T. R. Graham, R. S. Dean

FOLLOWING the development of elec¬trolytic manganese production by the Bureau of Mines, an extensive program was planned to study the character of this high-purity product and its possible utilization in various alloy combinations. Previous work reported in the literature concerning alloys containing substantial amounts of manganese dealt largely with material prepared from relatively impure grades of the metal, and in many instances the impurities thus introduced did not permit true evaluation of manganese as an alloying element. One phase of the Bureau&apos;s program included a general review of the system and the establishment of the physical properties of copper-manganese-zinc alloys, using electrolytic manganese, and with particular emphasis directed to com¬positions within the alpha solid solution area. A number of reports of the work on alloys in this system, giving specific data concerning the equilibrium system and some of its alloys, have already been published. One study1 established the alpha solid solution area at various temperature levels and composition ranges up to 50 pct manganese. Other investigation reports presented the properties of selected alloys; namely, a 65 pct copper, 10 pct manganese, 25 pct zinc alloys&apos; a sensibly white manganese brass composed of 70 pct copper, 20 pct manganese, 10 pct zinc,3 and a series of alloys with a constant copper content of 60 pct and 5 to 25 pct manganese, balance zinc.4 In these reports tensile properties as influenced by cold-working and subsequent annealing were given in detail. Additional data are now available on other alloys of the alpha region up to 50 pct manganese, and these, together with previously published information, are sufficiently complete to establish the relationship between properties and composition for this portion of the ternary system. The present report is a summary of the tensile properties of wrought alloys in the form of sheet and rod stock. The summary is necessarily limited to data for only one condition of cold-work and a single annealing temperature, since a complete exposition of all the data available would be too extensive for this presentation. Nevertheless, it is possible to make a reasonable approximation of the tensile properties in other conditions of cold-working and annealing by a correlation of the data previously presented on specific alloys and the data given here.

Jan 1, 1947

For the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS NEW YORK, N. Y. PHILIP N. MOORE ST. Louis, Mo. FIRST VICE-PRESIDENT C. W. GOODALE BUTTE, MONT. TREASURER GEORGE D. BARRON NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 1, 1919