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By W. D. Robertson, A. S. Tetelman

The technique of decorating dislocations was employed to investigate deformation and fracture resulting from Precipitation of hydrogen in Fe-3 pet Si single crystals. It is shown that cracks are produced on (100) planes inside crystals, as a consequence of the precipitation of hydrogen gas, either when crystals are quenched from a hydrogen atmosphere at elevated temperatures or cathodically charged with hydrogen at room temperature. Plastic deformation in the vicinity of cracks, observed as arrays of decorated dislocations, is in conformity with the calculated stress distribution about a crack containing an internal pressure, and the observations provide information permitting a detailed analysis of the mechanics of crack growth. The fracture characteristics of crystals containing internal cracks were evaluated at 25o and -196°C and the results are related to the mechanism of hydrogen embrittlement in terms of the growth of preexisting cracks. HYDROGEN in bee iron or steel produces two characteristic changes in mechanical properties: I), a decrease in ductility (macroscopic strain at fracture) that depends on temperature and strain rate, and 2), spontaneous fracture under static load that depends on time and apparent stress. Resolution of these phenomena into the microscopic processes that combine to produce the macroscopic effects is especially difficult in the Fe-H system in which the active component cannot be directly observed and only maintained in equilibrium with great difficulty in the temperature and pressure range in which embrittlement phenomena appear. As a result of these complications, verification of the numerous hypotheses'-5 that have been proposed to explain the microscopic mechanism of embrittlement depends on self-consistency with measured changes in macroscopic properties that are averaged over the volume of a specimen. It is obviously important to obtain a more direct evaluation of the microscopic processes that combine to produce embrittlement. Accordingly, the present investigation was designed to identify and observe, as directly as possible, the microscopic effects of introducting hydrogen into a bee crystal. It was concluded from a previous investigation6 of X-ray line broadening, produced by introducing hydrogen into pure iron at room temperature, that the only effect that could be associated with the introduction of hydrogen was plastic deformation; in particular, dilation of the lattice was not observed, within ± 0.01 pet, and no evidence was found that could be interpreted to support the idea7'* that hydrogen occupies tetrahedral interstitial sites in the iron lattice. The absence of lattice dilation is consistent with the extremely small solubility of hydrogen in bee iron9,10 (0.015 at. pet at 900oC and 1 atm pressure), and the evidence of plastic deformation is consistent with the fact that hydrogen, introduced by cathodic charging, eliminates the carbon yield point.11-13 Following this investigation, the immediate problem was to devise a method by which plastic deformation could be observed directly. The technique employed by Hibbard and Dunn14 to observe the movement of dislocations during bending and subsequent polygonization of Fe-3 pet Si single crystals was adopted and modified for the present purpose to include the observation of dislocation arrays in the volume of the crystal, and their association with the fracture process. EXPERIMENTAL PROCEDURE Single crystals of a high purity Fe-3 pet Si alloy, containing 0.007 pet C, were grown in vacuum by

Jan 1, 1962

Discussion of the paper of M. E. Lormbardi,. presented at the New York meeting, February, 1915, and printed in Bulletin No. 9S, February, 1915, pp. 209 to 215. I. N. KNAPP, Ardmore, Pa.-Some years ago I made a swinging spider to carry a string of casing in a way somewhat similar to that described in this paper. The ground I tried it in was too soft for its successful operation. The spider had a central one-flange bushing to carry the slips. Under this flange and on top of the spider was a properly protected ball runway, or ball bearing, which permitted rotating the casing when it was in place and supported by the slips.

Jan 5, 1915

By Graham Bright

Metal mines were developed long before coal mines and the early lighting of underground workings was effected by torches and candles. The early coal mines were outcrop workings and little trouble was experienced from gas, but as the mines became deeper and shaft mines were opened it became apparent that an open-fame lamp was exceedingly dangerous where gas occurred. No satisfactory way of lighting gaseous coal mines was found until Sir Humphrey Davy brought out his famous safety lamp in 1815. The introduction of the Davy lamp was a great step forward but it was unsatisfactory from a light standpoint because the gauze absorbed a large percentage of the light given out by the flame. Clanny corrected this by the introduction of a cylindrical glass lens, which not only permitted a free distribution of the light from the flame but added greatly to the safety by eliminating the possibility of the flame coming in contact with the gauze and by protecting the flame against air currents. A very complete story of the flame safety lamp since its inception is given in the U. S. Bureau of Mines Bulletin No. 227, by J. W. Paul, I;. C. Ilsley and E. J. Gleim, published in 1924. A little more recent publication, known as Safety in Mines Research Board Paper No. 4, entitled "The Light Power of Flame Safety Lamps," by R. V. Wheeler and D. W. Woodhead, was published in England in 1927. The flame safety lamp was the only lamp available for gaseous mines for about 100 years. Although the incandescent electric lamp has been in use over 50 years, it was not found safe to use this lamp from wired circuits in gaseous locations. The storage battery was advocated shortly after the development of the incandescent lamp but until the introduction of the tungsten filament in the miniature mine-lamp bulb, the battery lamp was not a real possibility because of the excessive weight of the battery necessary to produce a sufficient amount of light. The actual development of the electric-battery type of lamp took place largely between 1910 and 1915. In England and Europe, the developmenb was almost entirely along the

Jan 1, 1936

By Graham Bright

Metal mines were developed long before coal mines and the early lighting of underground workings was effected by torches and candles. The early coal mines were outcrop workings and little trouble was experienced from gas, but as the mines became deeper and shaft mines were opened it became apparent that an open-fame lamp was exceedingly dangerous where gas occurred. No satisfactory way of lighting gaseous coal mines was found until Sir Humphrey Davy brought out his famous safety lamp in 1815. The introduction of the Davy lamp was a great step forward but it was unsatisfactory from a light standpoint because the gauze absorbed a large percentage of the light given out by the flame. Clanny corrected this by the introduction of a cylindrical glass lens, which not only permitted a free distribution of the light from the flame but added greatly to the safety by eliminating the possibility of the flame coming in contact with the gauze and by protecting the flame against air currents. A very complete story of the flame safety lamp since its inception is given in the U. S. Bureau of Mines Bulletin No. 227, by J. W. Paul, I;. C. Ilsley and E. J. Gleim, published in 1924. A little more recent publication, known as Safety in Mines Research Board Paper No. 4, entitled "The Light Power of Flame Safety Lamps," by R. V. Wheeler and D. W. Woodhead, was published in England in 1927. The flame safety lamp was the only lamp available for gaseous mines for about 100 years. Although the incandescent electric lamp has been in use over 50 years, it was not found safe to use this lamp from wired circuits in gaseous locations. The storage battery was advocated shortly after the development of the incandescent lamp but until the introduction of the tungsten filament in the miniature mine-lamp bulb, the battery lamp was not a real possibility because of the excessive weight of the battery necessary to produce a sufficient amount of light. The actual development of the electric-battery type of lamp took place largely between 1910 and 1915. In England and Europe, the developmenb was almost entirely along the

Jan 1, 1936

By E. F. Adkins, R. W. Douglas

The variation of the spectral emissivity of osmium and ruthenium with temperature can be expressed by the following relations: DURING a study of the sintering characteristics of osmium and ruthenium, discrepancies in the previously accepted melting points of the metals were noted. The melting temperatures had not been measured at the time of the work, but were estimated in the literature as 2700°C for osmium and 2450°C for ruthenium.' A recent investigation by Baird2 has shown the melting temperatures of osmium and ruthenium are 3000" and 2250° C, respectively. In the present work, osmium bars sintered at temperatures as high as 2900° C showed no evidence of melting, whereas ruthenium showed definite evidence of melting at temperatures as low as 2250°C. In view of the apparent discrepancies, the melting temperatures of both metals were determined. The spectral emissivities of both metals were determined as an aid to studies of the sintering characteristics of these metals. MATERIALS AND PROCEDURES The materials used in these studies were metal powders supplied by Englehard Industries, Inc., through the courtesy of The International Nickel Co. Analytical data from three laboratories, although not in complete agreement as to the purity of the material or the major impurity elements, indicated that the maximum impurity levels were 0.5 and 1.0 wt pct in osmium and ruthenium, respectively. The metal powders were pressed to 1/4 by 1/4 by 6-in. bars at 20Tsi using carbon tetrachloride as a lubricant. The pressed bars were presintered 1 hr at 1200°C after heating 1 hr at 400°C. The presintered densities of the several bars of the metals ranged from 65 to 80 pct of ideal density. Specimens were self-resistance heated in a vacuum sintering bell. Temperatures were measured with an L&N, disappearing filament optical pyrometer. True temperatures were read at the base of an 0.30-in.-diam, 0.150-in. deep hole drilled into the center of a presintered bar. Apparent temperatures were read from the surface of the bar adjacent to the hole. MELTING POINT DETERMINATION The melting temperature of the metals was determined as the temperature at which a slight additional increase in current through the specimen resulted in a reduced temperature at the base of the hole. The apparent reduction in temperature is a result of the liquid metal filling the hole, thus altering the black-body conditions. The melting points of osmium and ruthenium, based on three deter-

Jan 1, 1962

James W. Neill, Pasadena, Cal. (communication to the Secretary*):—Professor Hofnlan's paper brings the art up to date. As I was one of the pioneers in this business, I beg to give the following incomplete data regarding my efforts in this line. In the year 1883, while I was in charge of the smelting-operations at Mine La Motte, Mo., there mas at the concentrator an unusually large protluction of a middle product, locally called " iron," which carried considerable values in nickel and cobalt, and which it was desirable, for this reason, to treat by itself. The works could not spare a furnace for the purpose; and to handle this product I improvised a " roast-hearth " from an old " lead-hearth." This was a small cast-iron furnace of the uslial construction, about 2 by 4 ft. in dimensions, with a hollon- cast-iron back, through which the wind circulated before entering the tuyeres. I had a cast-iron grate made to fit this hearth, and placed it tlush with the lip, or apron, and above the tuybres. On this grate, which had round holes about 0.25 in. in diameter, and a total surface of about 20 by 40 in., I roasted the nickeliferous pyrite product; starting the fire with kindling, then adding charcoal, and then gradually feeding the sulphides with a shovel, so as to cover the fire, choke down blow-holes, and get an even bed. Blast at a pressure of 3 or 4 oz. was supplied by a Can-blower. When a cake of roasted material had formed, it was removed with a steel bar, or fork, to the lip of the furnace, and thence into a wheel-barrow. The fine material which had renlained unmelted, but very hot, on top of the cake would promptly ignite when the cake was broken up and removed. The fire would then be covered with fresh material and

Jan 1, 1911

By Ernest Gayford

When the United States Government started buying gold at varying prices per ounce, set by the President and the Treasury Department, the gold miner found himself facing new conditions, as gold became a commodity with a fluctuating market price. While it was self-evident that the miner was to receive more for his gold than the old established price of $20.67 per ounce, there was an element of uncertainty, which made it difficult, and perhaps dangerous, to decide to invest his time and money to produce gold, especially if the profit would represent only the difference between $20.67 an ounce and the new price as set from day to day by the Government. When, however, on Jan. 30, 1934, the United States went off the gold standard, the price of newly mined gold being rather definitely set at $35 per ounce, with some assurance that the price would be maintained at or near this figure for a long time to come, the gold miner was justified in revaluing his property on the basis of the new price, and the prospector was offered inducement to spend his time and energies hunting for new mines, or going back to old locations previously abandoned as of doubtful value. It is interesting to see what this new price means to the producer of newly mined gold, and how much of the increase is passed on to the producer. It will be found that, as with the base metals, the nearer he can get to producing a finished product himself the greater his reward will be; the net returns for bullion being necessarily higher than for the same amount of gold shipped in concentrates to the smelter. Bullion can be shipped to the United States mints or Government assay offices under the following terms and conditions. An affidavit must accompany the shipment, stating, among other things: 1. The source of the gold; whether ore, tailings or placer. 2. The tons of ore, tailings or cubic yards of gravel from which the shipment was recovered.

Jan 1, 1935

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 R. C. Gifkins

R. C. Gifkins (CSIRO)—In this paper evidence is put forward to support the idea of grain boundary shearing in aluminum at 4.2°K and the phenomenon is explained in terms of a low-temperature "equicohesive temperature". It is stated that these findings show that grain boundary shear cannot be ruled out in any situation by temperature arguments alone. We believe, from our own recent study of "apparent grain boundary sliding'' at temperatures below 0.45 Tm, that it can be ruled out on temperature arguments alone.45 Our experiments were made principally with magnesium and a Ms-A1 alloy ("Magnox A12"). Careful examination of offsets of marker lines or steps at grain boundaries produced by deformation at room temperature (-0.3 Tm) showed many of these to result from curvature over narrow zones along the grain boundaries. A significant residuum did, however, appear as a sharp offset or step. It was found that the mean value of this step rose to a small value during the first 0.5 to 1 pct strain and then remained at this level with further strain. Moreover, exactly the same values were obtained (at the same stress) at 75°C instead of 21°C. That is, in this range of temperature the "apparent sliding" was not temperature-sensitive. At 125°C and above there was sliding which increased with strain and which was temperature-dependent. When this temperature-dependent sliding was used to calculate the sliding to be expected at room temperature, this underestimated the "apparent sliding" by a factor of 104. The conclusion drawn is that the "apparent sliding" consists of shear localized in a zone of a width measured perhaps in microns, whereas it seems that true sliding occurs on the boundary surface.46 A model for such localized shear has been developed in general terms, following a similar model of Urie and Wain.47 Other strong evidence for low-temper- ature sliding has been based on the offsets of marker lines consisting of a substructure seen using the electron microscope to resolve these.48 We have repeated this work and found that the effects can be accounted for in terms of cracks in an oxide film which is produced when the substructure is etched up; these cracks form over zones of shear rather than at actual interfaces. However, in aluminum at room temperature (-0.3 Tm) there is no "apparent sliding" which is optically detectable. We suggest that, when the temperature is much lower (and possibly the rate of strain higher, too), as in the experiments of Chin et al., then aluminum behaves like magnesium at room temperature, and a narrow zone of shear develops to accommodate differences in strain across the grain boundary. Such a zone could well give rise to triple-point cracks. It is hoped to investigate these suggestions further. B. Y. Chin, W. F. Hosford, Jr., and W. A. Backofen (authors' reply)—It is interesting to have Dr. Gif-kin's comments, although it is somewhat difficult to reply in detail without the reference containing the work that he describes. Apparently though, he does find a low-temperature temperature-independent sliding that would seem to be related to the observations reported here. Perhaps some of the difficulty has semantic origins, growing out of the distinction between ('true sliding" and "apparent sliding".

Jan 1, 1965

By George D. Graffin

The first use of graphite is lost in the mists of time. It was used by primitive man to make drawings on the walls of caves and by the Egyptians to decorate pottery. As early as 1400 A.D. graphite crucibles were being made in the Haffnerzell district of Bavaria. Through the Middle Ages graphite was confused with other minerals, especially galena and molybdenite. Two common names that are still used for the mineral are "Plumbago," meaning leadlike, and "Black Lead." The latter name implied that graphite is either composed of lead or at least contains a large percentage of it. Gessner is credited with having recognized it as a separate mineral in 1565, but its composition was not determined until 1779, when Scheele demonstrated that graphite oxidized to carbon dioxide, thus proving its carbon constitution. In 1789, Werner named it "graphite" from the Greek word "graphein," meaning to write. The United States has long relied on foreign countries for its graphite supplies. This reliance has been due more to the lack of suitable domestic graphites than to any particular preference for buying minerals overseas. Ceylon (now Sri Lanka) graphites were imported as early as 1820, and Madagascar graphites have been imported since the properties on that island were opened up about a hundred years later. Mexico has long supplied the United States with most of its requirements for amorphous graphite. Physical Properties and Classification Graphite is found in laminated, flaky aggregates disseminated in schistose rocks. It also occurs in veins and exhibits a foliated or fibrous structure. Graphite is a black lustrous mineral that crystallizes in the hexagonal system, with rhombohedral symmetry. The crystals have tabular form and are six-sided; the faces are commonly striated. The flakes have perfect basal cleavage and are opaque. When well crystallized, the flakes have a black metallic luster while the amorphous material is black and earthy, with a microcrystalline compactness. The flakes feel greasy. Graphite is an excellent conductor of heat and electricity. It melts at approximately 3500°C and sublimes at about 4500°C. It is combustible in the presence of oxygen between 620° and 670°C, but is stable and chemically inert at ordinary temperatures.

Jan 1, 1975

By Carl Henrich

Jan 1, 1893

By Benjamin S. Lindsey, James Norman

BARITE (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some kinds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to 100 per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaSO4, 11.11 per cent Si02, and 2.85 per cent R203. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder ,was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of nonmetallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is separated. LABORATORY FLOTATION WORK Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coe1 for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1941

By R. F. Mehl, W. Batz, C. Wells

L. S. Darken—It is indeed gratifying to find that the results of the two different methods here reported are in substantial agreement with each other and with the earlier work1 of two of the authors. Dr. R. P. Smith, of our laboratory, has been conducting some experiments at 1000°C to determine the diffusivity of carbon in austenite by a third method— the steady state method. This work, which will soon be reported, is far enough advanced that we can say it is in substantial agreement with that of the present authors. The only disparity which might be considered significant is in the high-carbon region, where we find that the diffusivity rises a little less steeply than indicated in fig. 8. F. E. Harris—The authors have presented an impressive arrangement of data concerning the diffusion of carbon in austenite. Of particular interest is the compilation, table IV, which is repeated in col. B of table V for direct comparison with values (col. A. table V) from a formulation using a single Q value of 31,000 cal as the activation energy for diffusion. This comparatively simple formulation has been used quite successfully in the practical application of calculating the carbon added (or removed) through the face in carburizing and decarburizing experiments, where the face concentrations are held quite constant for known times and temperatures. Literally hundreds of tests have been so checked where the computed and experimental values have varied by less than 5 pct. For higher temperatures, where proper carburizing data are hard to obtain, the diffusion couple is treated as a decarburization of the high-concentration bar and as a carburization of the low-carbon member. The analysis has been limited to a maximum of 1.40 wt pct carbon. The agreement between cols. A and B in table V may be considered fair, if a liberal viewpoint is taken. The use of a diffusion couple has one serious drawback, in that comparatively small amounts of carbon pass through planes of concentration close to those of the initial high-carbon and low-carbon members, and hence small errors become important. In addition to the sensitivity at these high and low concentrations.

Jan 1, 1951

By Benjamin S. Lindsey, James Norman

BARITE (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some kinds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to 100 per cent through 325mesh. The crude rock with which all test work was done assayed 85.1 per cent BaSO4, 11.11 per cent Si02, and 2.85 per cent R2O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.1 The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of nonmetallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is separated. LABORATORY FLOTATION WORK Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coe1 for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1941

By W. A. Tiller, J. D. Harrison

HOT pressing of powder particles has gained importance recently, since it affords a method in which high densities are rapidly attained. In a recent study on hot pressing of alumina powders, Mangsen, Lam-bertson, and Best1 have shown within the limits of their experiment, the validity the rate equation for densification in hot pressing, originally proposed by Murray, Livey, and Williams.2 i.e., where D = fraction of theoretical density, t = time, P = pressure and 77 is the viscosity, all in appropriate units. This equation was derived from earlier work of Shuttleworth and Mackenzie3 which is based on the closing of spherical pores under the action of surface tension. The integrated form of this equation yields a straight-line relation between log (1 - D) and t. Such conditions were found by Felten4 to be true only after extended periods of pressing. In an endeavor to quantitatively evaluate the exactitude of this equation in the initial sintering stage, i.e., prior to sealing of the pores, spherical anti-

Jan 1, 1962

By J. M. Steininger

The mechanism of flotation of sphalerite with sulthydryl compounds of different acidities has been interpreted in terms of chemisorption of unionized collector molecules on hydroxylated zinc surface sites. At a constant collector concentration of 1.5 x 10 -4 M, the upper pH limit of flotation has been found to be directly and closely related to the negative logarithm of the collector acidity constant, pKa The experimental results indicate that flotation is prevented when about 95% of the collector is ionized. At low pH, collector adsorption decreases because of the reduction in number of hydroxylated zinc surface sites. These two effects explain why sphalerite does not float with the more acidic sulfhydryl compounds. Typical anionic collectors for sulfide minerals are short chain xanthates or dithiophosphates which are nearly completely ionized in the generally alka- line flotation circuits.1,2 Flotation mechanisms have therefore been usually interpreted in terms of ionic collector adsorption and competition with ionic depressants of the same sign as the collector. A few attempts have been made, however, to consider adsorption of neutral collector molecules. Contact angle measurements obtained by Wark and cox3 have been interpreted by Cook and Nixon4 as representing adsorption of the free acid molecules on sulfide minerals such as pyrite, galena, chalcopyrite, and sphalerite. Cook and Nixon tried to show that the free acid concentration of the collector was substantially constant along the curves relating collector addition and minimum pH for bubble adherence. However, in a review of the subject,5 Sutherland presented new data on the flotation of pyrite with mercaptobenzothiazole which did not support the hypothesis of constant concentration of either collector ions or collector free molecules. He further showed that, with the assumption of constant occupation of surface sites, both theories lead to relations between pH and collector addition having similar mathematical expressions. In fact, with the more likely assumption of variable occupation of surface sites which results in more complex relationships, it appears impossible to

Jan 1, 1968

By Franklin Bache

THERE seems to be in the public mind, and even in the minds of some coal-operators not experienced in mines subject to dust-explosions, a feeling that there has been something mysterious at the bottom of a number of recent American colliery-explosions. It has been declared in cases of accidents in mines regarded as particularly well equipped, in which every preventive precaution was said to have been taken, that the explosions were incomprehensible, and resulted from causes beyond the present knowledge of the practical coal-operator. But it is safe to say that no explosion has taken place which could not be explained by reasons well understood by most operators. The LT. S. Geological Survey Test Laboratory, recently inaugurated at Pittsburg for the reported purpose of investigating scientifically the matter of explosions in mines, will discover no new explanation of explosions. It call, however, co-ordinate the previous investigations of similar boards in England and on the Continent; and it may do a vast amount of good by promulgating widely, and in a form comprehensible by the most unlettered miner, certain facts and obvious deductions that cannot but have an effect in reducing the number and extent of the mine-disasters which, in the last few years, have been so terrible in frequency and magnitude. The only possible sources of explosions of any magnitude in coal-mines are : (1) explosives stored in quantity in the mine; (2) gases generated or liberated in the mine; and (3) coal-dust. Combinations of any of the three may, of course, take part in the result. The danger of any great loss of life from stored explosives alone is very remote. The simplest ordinary precaution forbids the presence, in one place underground, of any considerable quantity of explosives, and it would require an

Aug 1, 1909

By Henry Leidheiser, Melvin C. Jr. Hobson

The rate of formation of the intermetallic compound, indium antimonide, at the interface between iudium and antimony at 100°C is greatly increased when a composite electrode of indium electrode -posited on antimony is made the cathode in an electrolytic cell. The amount of indium antimonide formed during electrolytic treatment at constant potential appeared to he proportional to the square root of time, but the scatter of the data, particularly at long times, makes it impossible to state this conclzlsi1:ely. The rate constant for the electrochemical synthesis was estimated to he 1.5 x 10-12 sq cm per sec. A similar- set of experiments was conducted in the absence of an applied potential but under otherwise similar conditions. The rate constant lor the thermal synthesis was less than 2 x 10-14 sq cm per, sec, at least two orders of magnitude less than obtained during electrolytic treatment. In a series of electrochemical studies it was observed that intermetallic compounds formed on the surface of polarized electrodes.1'2 The possibility of using this technique for the electrochemical preparation of intermetallic compounds was investigated and subsequently applied to the synthesis of the semiconducting III-V compounds. Gallium antimonide, indium arsenide. indium antimonide, and indium bismuthide were successfully formed by electrodepositing the Group III element from a boiling acid solution onto an electrode made of the Group V element. The following kinetic studies were undertaken on indium antimonide to obtain quantitative information on the rate of formation of this representative III-V compound under a potential gradient. EXPERIMENTAL The electrolytic cell for these experiments was a modified, three-neck, round-bottom, 500-ml distillation flask. Sealed into the side of the flask was a Luggin probe which monitored the surface of the working electrode and extended out of the flask to a small reservoir containing a saturated calomel electrode. The counter electrode was platinum. The three electrodes were connected to a Wenking po-tentiostat which maintained a preselected constant potential near the surface of the working electrode with reference to a saturated calomel electrode. All potentials noted in this paper are with reference to a saturated calomel electrode at 45° ± 5°C. The potential and the current were both monitored using Sargent Model MR recorders. The antimony electrodes were cast in graphite molds to form spheres about 15 mm in diameter with a shank 6 mm in diameter and 10 mm long. A heavy copper wire (12B & S gage) was soldered to this shank. Collodion was applied for protection to the shank and the connecting part of the copper lead. A snug-fitting O-ring was slipped over the shank and the electrode was then fitted into a teflon holder such that only the spherical portion was exposed. The electrode surfaces were cleaned and chemically polished prior to assembly and introduction into the electrolyte by etching in a modified CP-4 solution (50 parts glacial acetic acid, 10 parts concentrated nitric acid, 2 parts 48 pct hydrofluoric acid). The electrolyte was 10-2 M In+3 in 1 MH2So4 and its temperature was held constant by refluxing. The reflux condenser was open to the atmosphere and no temperature correction was made for changes in barometric pressure. The indium concentration in the electrolyte was checked from time to time by the analytical method outlined below for the determination of the amount of indium antimonide formed electrochemically. A schematic of the recorded potential is shown in Fig. 1. At point A the antimony electrode was introduced into the cell and the open-circuit potential recorded. At point B the potentiostat, preset at the desired potential, was switched on. It was switched off at point C and the potential fell to the open-circuit value of the electrodeposited indium. The

Jan 1, 1965

By Robert I. Kingman

SUFFICIENT testing has been performed with the Dutch State Mines Cyclone for thickening and desliming flotation feed at the concentrator of the National Lead Co., Tahawus, N. Y., to prove its application for this work. It is the purpose of this article to present some of the test results, operational details and advantages of cyclone thickening and classification. The metallurgy of the mill operation was described by Frank R. Milliken, assistant manager of the titanium division.l The present flowsheet for the recovery of ilmenite consists in grinding the crushing plant product in four open-end rod mills in closed circuit with mechanically vibrating screens to approximately -20 mesh. The screen undersize is treated in Crockett magnetic separators which produce three products: magnetic concentrate, nonmagnetic tailing containing ilmenite and gangue, and a Crockett slime overflow. The non- magnetic tailing is classified into eight sizer spigots products and a classifier overflow. The spigot sand products are tabled separately to produce a rough ilmenite concentrate, a middling product and a tailing. The table middlings are returned to Crockett feed. The table concentrate is dewatered and dried and further concentrated on Wetherill magnetic separators to produce the finished ilmenite concentrate.

Jan 8, 1950

By W. H. Bassett

THE ease and value of the application of spectrum analysis to industrial chemistry appears to be appreciated in few of the large works laboratories of this country. For 8 years, this analysis has been of great value to the authors in both analytical and metallurgical work. To the analyst the complete qualitative analysis of an unknown alloy, revealed by a spectrogram, is a sure basis for the planning of the most direct and rapid method of attack. As the determination of each element proceeds, the purity of precipitates may be checked as often as desired. The spectrograph proves invaluable in the recognition of impurities, the separation of which would entail a lengthy and difficult procedure, or when the weight of an unknown is less than is necessary to complete the desired determinations. A few hundredths of a gram will usually suffice for spectrographic analysis. In the separation of the rarer elements, the spectrograph will show, with precision, the point where each step has been successful. In zinc of certain classes, indium, gallium, and germanium have been isolated in this way; the presence of antimony in lake coppers has been proved; and bismuth has been detected in zinc and in alloys where the presence of a few thousandths of a per cent. would be harmful. An antimony precipitate in a delicate determination may contain a considerable proportion of tin or arsenic, both of which will be revealed. The spectrograph is consequently important to the metallurgist as well as to the analyst.

Jan 2, 1922