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By Byron Bird

WHILE Mr. Fahrenwald has been working on the fundamentals of ore-dressing, in Idaho, the Northwest Experiment Station of the U. S. Bureau of Mines, in cooperation with the University of Washington, has been studying the corresponding fundamentals for the closely-allied subject of coal-washing. In this work many of the principles outlined in Mr. Fahrenwald's paper have been touched on, one important exception being that phase of his studies where conditions were approximated between those existing on a table and those existing in a hindered-settling classifier. During the past three years this work has been given over almost exclusively to a study of coal-tabling to devise better methods of cleaning fine sizes of coal, particularly the coals of the Northwest, which are very difficult to wash. One important result of this study thus far has been the development of a satisfactory hindered-settling coal classifier, now in use in several commercial plants. Recently table stratifica-tion has been the subject for study. This latter phase of the work with coal,. as well as the earlier portion dealing with hindered-settling classification, has in a measure paralleled Mr. Fahrenwald's work with ore. Without going into details about the results of the coal experiments, I shall merely say that, from a quali-tative standpoint, they are, in general, concordant with Mr. Fahrenwald's, but that from a quantitative stand-point the results, particularly those with, table strati-fication, are somewhat different. These differences may disappear as the work progresses-Mr. Fahrenwald is further ahead with his experiments than we are at the Northwest Station-but if not, the disparity would not be surprising, and indeed would be what one might reasonably expect when investigators work on two very dissimilar materials and use different apparatus and methods of study. However, this- mention of our coal-washing experiments is made only in passing. A principle of general application that may be estab-lished from Mr. Fahrenwald's paper is that different types of stratification should be used in successive' gravity-concentration processes to. obtain best results.

Jan 3, 1927

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 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 metal 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 microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) 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 metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 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. Scheil4 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 Bedworth5 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.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß' phase, homogeneous between

Jan 1, 1947

By Luis Toron, Salvador Cortes-Obregon

THE Oaxaca coal fields, shown in Fig. 1, are located in the Alta Mixteca region in the states of Oaxaca, Puebla, and Guerrero. Known outcrops are scattered over 3125 square miles. It is probable that further exploration will reveal a more extensive area of deposits. The region is of great importance to Mexico, as at present the only sources of coal are the fields near the U. S. border. Steel mills are also located in the North, and finished products must travel 600 to 800 miles to the area of consumption in central Mexico. The oaxaca coal, only 120 miles south of Mexico, D.F., lies close to several iron ore deposits. If this

Jan 1, 1955

By L. S. Darken

IT has been known for sometime that in an ionic lattice, such as that of Ag2S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulfide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulfide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall1 support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffusion proposed by several authors, most recently by Birchenall and Mehl.2 This theory has, however, also been questioned3.4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however, Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz,5 who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a similar mechanism, whatever it may be, at a greater or lesser rate, thus giving rise

Jan 1, 1948

By C. B. Alcock, R. G. Hudson

Sulfur pressure measurements above FeS in equilibrium with iron have been carried out by the Knudsen orifice method. A comparison is made of the weight loss of the cell per unit time obtained in the above experiments, that calculated from Richardson and Alcock's measurements of the S2 pressure above FeS in equilibrium with iron, and the dissociation constant for diatomic sulfur from spectroscopic and thermal data. EXTENSIVE equilibrium measurements have been made to determine the sulfur potentials of a great many systems of metallurgical interest.' In order to confirm their reliability, to supply data which may be of use in further thermodynamic calculations, and to establish the reliability of the Knudsen orifice in obtaining accurate thermodynamic values at high temperatures, the present investigation on the pressure of the gaseous species above FeS in equilibrium with iron has been carried out. The Knudsen orifice method has been used for these pressure measurements. Experimental The apparatus and general technique for this investigation are the same as that reported for the determination of the vapor pressure of silver.' To reduce the residual gas pressure in the evacuated chamber, a titanium getter, maintained at run temperature, was introducbed. Several types of Knudsen cells were used—platinum, zircon, and fused silica. The orifice in the zircon cell was fashioned with a small diamond wheel. The same precautions were used in this investigation as were employed in the work on Mo2S2.3 The FeS-Fe mixture was prepared by heating a sample of pure FeS,, supplied by K. K. Kelley of the Bureau of Mines, with excess iron powder, cp grade, obtained from the Fisher Scientific Co. These two substances were heated in a closed Armco iron crucible at 960°C, held in a vacuum of less than 10" mm Hg for 24 hr. The mass was then removed from the cell and ground in an agate mortar. In this form it was charged to the various Knudsen cells. Heating the Knudsen cell for an additional two days was sufficient to obtain constant rates of weight loss of the cell. The data obtained in this investigation are recorded in Table I. To establish whether or not a sulfide of iron is volatile at these temperatures, 0.7646 g of the FeS-Fe mixture, described above and containing 69.2 pet Fe, was placed in the zircon Knudsen cell. Run Nos. 103 to 109 were performed on it. After the completion of these runs, the total amount of iron left in the cell was obtained by chemical analysis. It contained 0.537 g Fe, compared to 0.529 g in the original charge. Thus, there was an apparent gain in iron of 1.5 pet. This is attributed to unknown experimental error, and the conclusion is that no sulfide of iron is volatile. The vapor pressure of pure iron4 is about one thousandth that of the sulfur pressure' at these temperatures. The vapor pressure of iron inside the Knudsen cell will be almost exactly that of pure iron, since in the iron-rich phase the percentage of sulfur is of the order of 0.025 pet.At this low percentage of sulfur Henry's law is probably obeyed by the sulfur. Thus, the iron will obey Raoult's law. In any event, the vapor pressure of iron will be lower than that of pure iron and, since the vapor pressure of pure iron is negligible compared to the pressure of sulfur, the weight loss of the cell due to the vaporization of iron should be negligible. Since neither iron nor FeS is volatile to an appreciable extent, the total weight loss of the cell must be due to the vaporization of sulfur. Discussion and Calculations On the assumption that S, is the only gaseous species present in appreciable quantity, its pressure

Jan 1, 1957

By Ralph Hultgren

IN solid solutions atoms of differing sizes occupy the same crystalline lattice, requiring that some of them be compressed and others expanded. The energy involved has been called misfit strain energy and is an important concept of crystal chemistry. If the atomic sizes and elastic constants of interatomic bonds are known, the misfit energy may be calculated,' provided certain simplifying assumptions are allowable. Usually, isotropic crystals are assumed and interatomic distances are taken to be the statistical average determined from X-ray diffraction. Such calculations yield values of the misfit energy of the order of 1 or 2 kcal per atom in alloys such as Au-Cu at compositions of 50 atomic pct. However, evidence has accumulated in recent times that atoms change their sizes with composition of alloys, implying electronic rearrangement of the bonds. The size changes have been found particularly by application of the X-ray method developed by Warren, Averbach, and Roberts.' Thus, Averbach, Flinn, and Cohen3 determined radii in Au-Cu alloys. Oriani4 showed that these new radii led to a calculated misfit energy in disordered AuCu, which was decreased from the values calculated by the usual theory more than twenty-fold, to only 80 cal per g atom. Thermodynamic calculations from the phase diagram5 also show misfit energy to be no more than a few hundred calories per g atom in this alloy. The question of what electronic rearrangements are possible therefore becomes compelling in estimating misfit energy. In the following pages the results of certain calculations on the AuCu tetragonal superlattice are submitted. Conclusions drawn from these should be applicable in large degree to disordered solid solutions. As in all ordered states, bonding distances in the superlattice are individually known, rather than being merely average distances as found from lattice constants of disordered states. Moreover, only the Au-Au and Cu-Cu distances are strained; the elastic constants of these are known in the elementary state. In the usual calculation it is necessary to assume elastic constants for Au-Cu bonds. Misfit energy has thus been calculable without the need of many simplifying assumptions usually made. It is still assumed that equilibrium bond lengths and elastic properties of the bonds are the same in the alloy as in the pure metals. As previously discussed, this is probably not correct. Also assumed is that the bonds are not affected by strain of neighboring bonds. A calculation of Young's modulus from compressibility data shows this to be far from true; extensive electronic rearrangements take place. It would seem that misfit energy cannot be calculated from elasticity data for the elements. The usual methods may, however, give an upper limit which is often much higher than the true value. The question of electronic rearrangement is, of course, a complex one. Pauling's theory gives a simple, approximate treatment of the relation between type of bond and bond distance. This has been applied with some success to the Au-Cu system, as will be shown in a later section. Misfit Energy in Au-Cu Alloys Hume-Rothery and Raynor6 discuss the Au-CU system as a type example of strain energy. The gold atom is 12.8 pct larger in diameter than the copper atom, near the size factor limit beyond which solid solubility is severely restricted. They therefore consider the misfit energy to be large, a conclusion for which they believe they find evidence in the phase diagram. Gold and copper are completely miscible in the solid state, but the alloy has a minimum melting point at an intermediate composition. From this Hume-Rothery and Raynor conclude that the strain energy is nearly large enough to prevent miscibility; the phase diagram tends toward a eutec-tic type. In Ag-Cu, which has almost identical size relationships, solid miscibility is quite limited; whereas in Au-Ag, where atomic sizes are nearly the same, there is complete miscibility without a minimum in the melting point. From their arguments the heat of formation of Au-Cu would be expected to be endothermic or only slightly exothermic, that of Ag-Cu to be endothermic, and that of Au-Ag to be exothermic. Deviations, from Ve-gard's law of additivity of atomic radii support these conclusions, since Au-Cu and Ag-Cu both have pronounced positive deviations, and Au-Ag has a negative deviation. Nevertheless, Au-Cu alloys form exothermically; indeed, considerably more exothermically than Au-Ag, Table I. Hence, strain energy must be much less important in this case than Hume-Rothery and Raynor have supposed.

Jan 1, 1958

By Rollin Farmin

Rock pressure against the supports for underground workings in certain mines becomes sufficiently severe to crush sound timbers. The cost of maintenance of these mines increases critically as the workings are extended. "Heavy ground " and "swell-jng ground" are terms commonly applied to a condition of excessive pressure from the wall rock. Defined for the purposes of this paper, "heavy ground" delivers gravi-tative pressure on the supports of a mint opening; "swelling ground" delivers pressure arising from expansion of the wall rock. Mining problems created by heavy ground have been studied extensively by mining engineers, as in the recent Symposium on Block caving.' A parallel study of rock bursts2 attacks the field of ground that ruptures under strain. The problem of swelling ground, which has received less current attention, is the subject of this paper. An ExaMPLe of Swelling Ground Severe cases of swelling ground are found in the gougy shear zones in mines along the western Sierra Nevada, where the veins are accompanied by faults through altered serpentine, schist and slate. For example, along troublesome stretches in the ldaho Maryland mine, Grass Valley, California, swelling ground continues to crush drift timbers, with diminishing intensity, for 3 to 10 years after entry. During this period, from five to nine generations of crushed timber sets must be replaced and a large additional tonnage of scaly rock and wet gouge must be removed from the drift to make room for this succession of new timbers. After "the squeeze has been taken out of the ground" the timbers will stand for years, until they collapse from decay. Heaving of floor and footwall along drifts develops soon after the timber sets are placed and frequent grading down of the track is necessary to keep it serviceable and to maintain headroom. If sills are placed under the drift posts, the sets break more quickly and the track becomes impassable at once. When the floor is left Open? and the bottoms of posts and stulls are pencil-pointed, the scaly ground of the fault zone swells up around the timbers (Fig. I) instead of breaking them (Fig. 2). A foot or two of this encroaching ground is trimmed from the floor and lower sides of the drift several times before complete retimbering is necessary. when a set of timber fai1s under the Pressure of swelling ground, there is no immediate fall of timber and broken rock to fill the drift, as is customary in heavy, caving ground. Instead, ground swelling from sides, top and bottom gradually closes the opening, over a period of weeks or months, and no especial hazard to workmen is present while they have room to walk through the narrowing drift. Most

Jan 1, 1946

By L.W. Eastwood, Arthur E. Bousu, C. T. Eddy

The recrystallization and grain-growth phenomena of cold-worked metals have considerable industrial importance because of their role in the fabrication of metals. For this reason, and because of the general academic interest in the subject, these processes have received considerable attention since the time of J. E. Stead's paper1 on The Crystalline Structure of Iron and Steel. There are considerable differences of opinion regarding the theory of recrystallization and grain growth and also differences in the observation of the modus operandi of the processes themselves. The value of many of the existing quantitative data on grain growth is decreased by the failure to distinguish between the grain sizes just after complete recrystallization and those resulting from coalescence. For this reason also, the value of the diagrams of stable grain sizes, like those produced by Bass and Glocker2 and Czochralski3, is lessened in so far as an interpretation of the facts of recrystallization is concerned. It is hoped that the data presentcd in this paper will help to clarify and to simplify the facts relating to recrystallization, and at the same time will show that some of the present-day conceptions are untenable. A paper on the theory of recrystallization, with additional data, will be completed in the near future by the writers. Since the literature on the subject has been adequately and frequently reviewed, the only referenccs to it in this paper will be those necessary in the discussion of the data presented.

Jan 1, 1935

By Arthur E. Bousu, C. T. Eddy, L. W. Eastwood

The recrystallization and grain-growth phenomena of cold-worked metals have considerable industrial importance because of their role in the fabrication of metals. For this reason, and because of the general academic interest in the subject, these processes have received considerable attention since the time of J. E. Stead's paper1 on The Crystalline Structure of Iron and Steel. There are considerable differences of opinion regarding the theory of recrystallization and grain growth and also differences in the observation of the modus operandi of the processes themselves. The value of many of the existing quantitative data on grain growth is decreased by the failure to distinguish between the grain sizes just after complete recrystallization and those resulting from coalescence. For this reason also, the value of the diagrams of stable grain sizes, like those produced by Bass and Glocker2 and Czochralski3, is lessened in so far as an interpretation of the facts of recrystallization is concerned. It is hoped that the data presentcd in this paper will help to clarify and to simplify the facts relating to recrystallization, and at the same time will show that some of the present-day conceptions are untenable. A paper on the theory of recrystallization, with additional data, will be completed in the near future by the writers. Since the literature on the subject has been adequately and frequently reviewed, the only referenccs to it in this paper will be those necessary in the discussion of the data presented.

Jan 1, 1935

By L. M. Pidgeon, K. T. Aust

There has been considerable interest in the possible use of titanium in magnesium alloys.' Zirconium has shown some promise in this connection2 and its general similarity with titanium suggests that the latter might act in a similar manner. A literature survey revealed that quantitative data on the Mg-Ti system was unavailable. Several patents3 have claimed that titanium additions from 0.2 to 4 pct to magnesium alloys were possible, but no mention was made as to the form in which the titanium existed in the alloy. Kro114 succeeded in introducing only traces of titanium into magnesium by bubbling TiCl4 through the metal under argon or by reacting it with sodium titanium fluoride. The application of theoretical data given by Carapella5 based on Hume-Rothery's principles, involving atomic size factor, crystal structure, valency and the electro-chemical factor, suggests that a Mg-Ti alloy is a favorable case, and the system appeared to warrant experimental examination. Experimental Procedure and Results THERMAL ANALYSIS If titanium is appreciably soluble in magnesium, a change in the melting point of the magnesium might be detectable using standard cooling curve methods. Magnesium was melted in graphite crucibles under an argon atmosphere, the assembly being enclosed in a silica tube. Graphite thermocouple protection tubes served also to stir the melts. The apparatus was very similar to Fig 1, with the addition of a refractory and baffle system to prevent undue heat losses from the top of the crucible. Chromel-alumel thermocouples were calibrated using Al of 99.97 pct purity. Dominion Magnesium Limited sup- plied redistilled high purity magnesium of the analysis given above. Titanium was added in three different forms: 1. Titanium powder —100 mesh, from the Titanium Alloy Manufacturing Co., Niagara Falls, N. Y. 2. Sheet titanium from the U.S. Bureau of Mines, produced by Mg reduction of TiCl4. 3. Magnesium —50 pct titanium master alloy from Metal Hydrides Inc., Beverly, Mass. The melting point of the high purity magnesium used was measured experimentally as 651.0°C. More than a dozen tests were conducted using titanium from the three sources referred to above, in calculated additions up to 20 pct titanium, at temperatures between the melting point and 1000°C and holding periods up to 6 hr. In no case was evidence obtained of solubility of titanium in magnesium, using inverse-rate and time-temperature curves. The melting point of the magnesium was unchanged within the accuracy of measurement, namely -+0.5°C; and no other thermal arrests were detected. Metallographic investigation of the thermal analysis billets indicated that the titanium additions were apparently mechanically entrapped in the magnesium in segregated areas. Consequently, these samples were not analyzed for titanium. The master alloy proved to be a mechanical mixture of titanium particles in a magne- sium matrix. These results indicated that the titanium solubility, if such existed, could not be obtained by the usual thermal methods. X RAY DIFFRACTION INVESTIGATION In an effort to detect solubility of titanium in magnesium, samples were investigated using both the Debye-Scherrer and the Focusing Back-Reflection methods. Filings from samples of the thermal analysis billets and from pure magnesium were annealed in argon one hour at 350°C to relieve mechanical strain. Measurements made of the interplanar spacings showed no difference between the Mg-Ti samples and pure magnesium. The interplanar spacings could be measured to within 0.0002A, and the greatest variation found was 0.0004A, in the back-reflection method. The diffraction lines for magnesium were not shifted by the titanium additions indicating that the solid solubility of titanium in magnesium is of a very low order—less than 0.5 pct. From both diffraction methods, a d or interplanar spacing of 0.817A was obtained for the redistilled high purity magnesium. This latter value is not given in the standard X ray diffraction cards for magnesium metal or vacuum distilled magnesium. Theoretical calculations for a close-packed hexagonal space lattice for magnesium indicate that the planes {2134) should give a line which was found. The relative intensity for this reflection at 0.817A is slightly less than that at 0.870k for magnesium. SOLUBILITY OF TITANIUM IN LIQUID MAGNESIUM The Mg-Mn system was examined by Grogan and Haughton6 who were

Jan 1, 1950

By John D. Ridge, Betty S. Moriwaki

One of the most profound economic forces operating on a global scale is the movement of metals, ores, and concentrates from one country to another. A single shipment can pass through a series of ports and leave a flow map looking like some psychological nightmare. Statistical tracing often proves as difficult. How much did one given country send to another? Does the word ton represent the same thing to all people? What part did free ports and transshipment play? Where did the metal finally stop traveling and enter fabrication? The amount of mineral produced in the form of concentrate and as refined metal can be tracked down in the Minerals Yearbook of the U. S. Bureau of Mines. Quantities imported by the U. S. can also be found in that publication. But the Yearbook will not tell what happened to the metals that did not find its way to the U. S. Even after a study of supplementary literature, such as the USBM Mineral Trade Notes and the publications of the International Tin Study Group and of other private and public organizations, the picture remains vague at best.

Jan 5, 1955

By G. W. Brock

Experiments in the form of aging of overstrained tension specimens and elevated temperature tension testing, have been carried out on recrystallized arc-cast molybdenum. The aging behavior of molybdenum was found to be strongly dependent on the degree of plastic strain present in the lattice: the reason for this being the low solid solubility for the common interstitial elements in molybdenum. GEORGE W. BROCK, formerly Research Associate, Department of Theoretical and Applied Mechanics, University of Illinois, Urbana, III., is Research Associate, Department of Engineering Sciences, IBM Research Center, Yorktown Heights, N. Y. Manuscript submitted January 19, 1961. IMD THE term strain aging is familiar in connection with the recovery of the yield point in mild steel after tensile overstraining, and there are other instances where it is known to exert an appreciable effect on mechanical properties. For example, steel exhibits a greater tensile strength at mildly elevated temperatures than at room temperature and serrated stress-strain flow curves occur under certain conditions. It has been known for a number of years that the phenomenon of strain aging is directly connected with the presence of carbon and nitrogen in the lattice; and extremely small amounts of either element are sufficient to produce the effect. In this study, the aging behavior of overstrained tensile specimens of recrystallized molybdenum has

Jan 1, 1962

By H. J. Wasson, E. B. Hopkins

Throughout 1928, production of oil from Venezuela steadily increased, and at the close of the year, the output was at the rate of nearly 400,000 bbl. a day. The total for the year was approximately 106,500,000 bbl., representing an increase of about 66 per cent. over the 63,000,000 bbl. produced in 1927. Venezuela now stands next to the United States as the second largest oil-producing country in the world; and there is abundant evidence to suggest that this relationship will endure for a number of years. Reserves were notably increased in the Lake shore fields, and the potential output of the Maracaibo Basin is much greater than the current production. In spite of this, the percentage of production increase was comparatively moderate, and the rate of this increase continued to fall off slightly, as has been the case for the last three years. This does not suggest that further annual increases in Venezuelan output will not materialize; only that the rate of these increases appears to be on the decline, and that with every succeeding year the future tendency will be in the direction of a stabilized level of output. The following table shows the production trend of the country since 1925: 1925 increase over 1924, 132 per cent. 1926 increase over 1925, 80 per cent. 1927 increase over 1926, 75 per cent. 1928 increase over 1927, 66 per cent. Many factors will work to prevent a reversal of this trend, but the principal ones are strong ownership in large-acreage units, and the probable indisposition of the world market to absorb a more rapidly increasing Venezuelan output at prices profitable to the producers. The distress oil element is not a factor in Venezuela; also, any unforeseen jump, such as results in the United States from the discovery of a Seminole or a deep sand at Long Beach, or Santa Fe Springs, is impossible in Venezuela, on account of lack of means for transporting a sudden surplus of oil, and the slowness with which additional transportation equipment in the form of shallow-draft tankers can be obtained.

Jan 1, 1929

By Tony B. Szwilski

A short study has been made of the underground mining potential in the Plains region, the Province of Alberta, Canada. Particular reference is made to the possible application of longwall mining: Presently underground mining is limited to small scale room-and- pillar methods. The problems anticipated with large scale mining at shallow depths (30 m) are examined. Production factors based upon longwall retreat mining utilizing shield supports are also considered.

Jan 1, 1981

By G. R. Fritterer

Investigators in the field of temperature measurement have long sought a thermoelectric couple fulfilling the following requirements: 1. It should be useful up to and including high industrial temperatures; i. e., 1000 to 1800 C. 2. Its thermoelectric variation with temperature should be linear and be maintained after heating to high temperatures for long periods of time. 3. It should be reproducible; i. e., different couples of the same elements should have similar calibration curves. 4. Its thermoelectric power should be large so as to allow the industrial use of rugged recording instruments. 5. Chemical reactions with, and physical changes within the elements of the couple should not alter its calibration. No thermocouple proposed to date exhibits simultaneously all of these characteristics, whereas the couple about to be described fulfills all requirements to a satisfactory degree. New Thermoelectric Materials A thorough survey of the literature on thermoelectricity revealed that present-day thermocouples could not meet the specifications mentioned above because their thermoelements are metallic. Metals have a marked tendency to deteriorate chemically and their melting points limit their use to low temperatures. Refractory substances, however, are usually resistant to chemical attack and are quite stable at high temperatures. Hence a survey of refractory substances having thermoelectric possibilities was made. One class of thermocouples considered was that in which carbon and a carbide of some metal or nonmetal were the thermoelements. Previous investigators neglected to study this field but certain recommendations were made by them for the use of couples in which carbon served as one element. These proposals are listed in Table 1. The couples suggested are unsatisfactory because of their low thermoelectric powers, the low melting points of their metallic elements, etc. The

Jan 1, 1933

GEO. F. COMSTOCK,* Niagara Falls, N. Y. (written discussion?).¬A study of this paper raises a question on which it is hoped Mr. Stork will throw more light; that is, why does an oxygen content generated on poor melting conditions have a deleterious effect on the properties of the iron, while an oxygen content generated by the oxidation of steel scrap in the cupola is beneficial to the strength and chilling ability? In each case the oxygen is absorbed at the same time and place in the process of melting and it is by no means clear why the superiority of semisteel should be assigned solely to its oxygen absorption, when oxygen absorbed without the steel addition is admitted to be injurious. It is not apparent why oxygen caused to be absorbed by the steel addition should not pro-duce the effects of burning, sluggishness, slag inclusions, gas occlusions, etc., the same as oxygen absorbed by the iron in the cupola for any other reason, and it would seen that other factors to which he has not given sufficient emphasis must enter into the author's results. To an impartial reader of this paper, who was most favorably inclined toward J. E. Johnson, Jr.'s theory of the improvement of cast iron by oxygen, the discrepancy in the author's reasoning or statements is difficult to accept, and it is hoped that an explanation will appear in the final discussion.

Jan 11, 1919

By S. P. Sharples

Having occasion a few weeks ago to investigate the subject of black band iron ore in West Virginia, I was surprised at being met at the outset with a denial of its existence. One gentleman went. so far as to offer one hundred dollars an acre for any land in West Virginia that contained a seam or vein of even a single foot in thickness, and when shown the ore he acknowledged that it was genuine, but declared it had been imported. That black band does occur in West Virginia is to-day well known to a number of persons. There is a seam on the Gauley River of about a foot in thickness of good ore, which I understand Mr. Lewis and others are making preparations to work. The great trouble with black band ores as heretofore found in this country has been their limited extent. At Fort Washington, for instance, they had a very fine show ing of ore, but it soon gave out. It has also been asserted that the black band ores of the Western Coal Measures were worthless in the furnace, and Fort Washington has been pointed out as an example of the fate of any one who should undertake to work them. But they have been successfully worked at Youngstown and in other parts of' Ohio, and I am assured by old furnace-men from Ohio that there is not the slightest difficulty in. working them if properly managed. The deposits to which I wish to call the attention of the Institute,

Jan 1, 1882

By B. F. Fackenthal

One of the practical questions presented to the blast-furnace manager, with regard to which little help can be obtained from existing technical literature, is the manner of filling and blowing-in. This operation is often performed according, more or less, to traditions which have come down from earlier practice, and which, if not positively detrimental when followed with the large modern furnace, may at least be greatly improved, just as the running of the furnace itself, while in blast, has been improved. It is not necessary, as many of the old furnace-men believed, to make a lot of white or silver-gray iron at the start, or to spend many weeks, or months even, in bringing the furnace to its normal burden. It has seemed to me that the publication of carefully-recorded data of practice on this point may be interesting to the members of the Institute engaged in the management of blast-furnaces. The enlarged blast-furnace at the Durham Iron Works, Riegelsville, Pa., owned by Messrs. Cooper & Hewitt, of New York City, was first put in blast February 21, 1876, since which time it has made seven blasts, and is now running on the eighth. A description of the furnace-plant, together with a record of the fifth blast, was given in my paper read at the Chattanooga meeting, May, 1885 (Transactions, xiv., 130). After some of the early blasts the furnace-lines underwent considerable change, and I have thought best to accompany this paper with drawings showing the lines and the tuyere-arrangement (see Plates I. and II.), and to give also the following summary of the conditions and results of each blast. During the first and second blasts no coke was used, and the furnace ran very irregularly, showing a constant tendency to scaffold, which was attributed, in great part, to the small hearth and other defective lines. The large proportion of air required at this furnace is accounted for by the fact that the engines are defective, and do not deliver into the furnace the amount of air indicated by the pistondisplacement.

Jan 1, 1890

By R. W. Fountain, M. Korchynsky

The precipitation phenomena occurring in cobalt-tantalum alloys have been investigated in the temperature range frm 500" to 1050°C by correlating the results of metallographic, X-ray, micro-and macrohardness, and electrical resistivity studies. The property andmacrohardness,changes were found to depend on 1) general precipitation, and 2) lamellar precipitation. Two new intermetallic phases have been identified: 1) a Co3Ta, a metastable ordered face-centered-cubic compound, and 2) a stable ß Co3Ta phase of hexagonal structure. In addition, the previously reported Co2Ta phase was found to exist in two allotropic modifications: the hexagonal MgZn,-type and the cubic MgCu2-type Laves phases. SINCE a large variety of structures can result as a consequence of the decomposition of a solid solution, predictions on the nature of property changes are difficult, if not impossible, to make. For any rational attempt to correlate properties and structures of a precipitation-hardenable alloy, a detailed understanding of the kinetics of decomposition and morphology of phase separation, as well as knowledge of phase relationships, appears to be prerequisite. Information of this type has been accumulated in the past for many alloy systems, both of theoretical and pastforpractical importance.1,2 Although the presence of intermetallic compounds has been reported in cobalt-base alloys,3 the amount of published information on precipitation-hardenable cobalt-base systems is very limited. A survey of the binary phase diagrams of cobalt indicates that cobalt-tantalum alloys might be of interest as typical of other cobalt-base systems in which Laves phases of the A,B type can be precipitated from solid solution. The present work has been undertaken, therefore, to study the kinetics and morphology of the precipitation reaction in this system and to establish a base for a correlation between the structural aspects and properties in this class of alloys. PREVIOUS WORK The only available phase diagram of the cobalt-tantalum system is based on the work of Koster and Mulfinger. According to these authors, the maximum solubility of tantalum in cobalt is about 13 pct (at 1275°C) and. less than 7 pct at room temperature. Tantalum additions lower the temperature of allotropic transformation of cobalt (about 420°C), and at 7 pct Ta, the high-temperature face-centered-cubic modification (ß cobalt) is retained at room temperature. The precipitating phase was originally designated as Co5Ta2 compound (55.2 pct Ta, about 1550°C melting point), but subsequent investigations by wallbaum5" identified this constituent as the A,B-type Laves phase. Wallbaum's data indicate that there are two modifications of this intermetallic compound: one richer in cobalt (Co2.2 Tao.8)of the hexagonal MgNi, type; and another of a higher tantalum content (Co2Ta) of the cubic MgCu, type. On the other hand, Elliott7 found that the cobalt-rich alloy (CO2.10,Tao.~l) was predominantly the cubic MgCu, type at 800°C and a mixture of both the MgCu2 and the hexagonal MgZn,-type Laves phases at 1000°C. At 1200°C, Elliott found only the MgZn, type while at 1400°C, he observed only the MgCu2 type. At the stoichiometric composition, Co2Ta, Elliott reported only the cubic MgCu2-type Laves phase in the temperature range of 600oto 1600°C. The precipitation of the cobalt-tantalum intermetallic compound is accompanied by a marked increase in hardness. According to Koster's4 data, the Brinell hardness of an 8 pct Ta-Co alloy increases from 230 to 340 upon short-time aging at 800°C. EXPERIMENTAL PROCEDURE The binary cobalt-tantalum alloys investigated contained 5, 10, and 15 pct Ta. The range of tantalum additions was thus slightly broader than the reported minimum and maximum solid solubility limits of tantalum in cobalt (7 and 13 pct, respectively)4 The alloys were vacuum-induction melted in a magnesia crucible using cobalt rondelles and technically pure tantalum sheet as raw materials. Deoxidation of the melt was accomplished with carbon, and the chemical analysis of the alloys is given in Table I. The effect of isothermal aging treatments on the progress of precipitation was studied on samples cut from cast ingots. These samples were solution treated for 2 hr at 1250°C and water-quenched. Aging was conducted in the temperature range from 500" to 1050°C for periods between 15 min and 1000 hr and followed by water-quenching. To prevent contamination from the atmosphere, all samples were sealed in evacuated Vycor or quartz tubes for heat-treatments. For solution treatment, argon at 0.2 atmospheric pressure was introduced prior to sealing of the capsule to prevent collapse at high temperature, and titanium sponge was placed at one end of the capsule to act as a getter. MACROHARDNESS The effect of aging on Vickers hardness (Dph) of

Jan 1, 1960