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By FRABK HERVEY PETTINGELL

THE stock exchange and its functions is about as well understood by the average individual as the fourth dimension. What is a stock exchange? Divested of the rules and regulations by which it is governed, and the facilities it provides for the convenient handling of securities, it would be in its nude state nothing more or less than a meeting place for brokers. The stock exchange in America dates back to 1752, when a group of merchants of New York established a meeting place at the foot of Broad Street for the purpose of dealing in meal and slaves. The first definite orgarization, however, had its beginning in 1792 when 24 New York brokers signed an agreement not to buy or sell public stock for less than one quarter per cent. commission. From this small group has grown by gradual degrees, the greatest organized security market in the world, namely, the New York Stock Exchange. At the present time there are 27 stock exchanges in the United States and 5 in Canada. Based on the volume of business transacted, the Los Angeles Stock Exchange ranks 6th among them. This is attributable to the fact that strictly speaking Los Angeles has never been a stock exchange town, like some other large cities. Take for instance San Francisco, which supported one stock exchange from 1862 to .1882 and has since supported two. No city, by the way, should tolerate two stock exchanges at the same time. It is an economic folly and a senseless duplication that can be compared with rival telephone companies or competing street railway systems, paralleling each other's lines and always leads to trouble and confusion, and sooner or later one or the other falls by the wayside. While Los Angeles has had stock exchanges of one kind or another since 1896, none of them attracted much attention until 1899 when the present exchange was organized and it did not get well under way until along in 1906.

Jan 1, 1925

By Richard Paul Seelig

The following review covers published information on pressing of metal powders at room temperature. Only those operations are considered which occur between the time the powder is filled into the cavity and the compact is ejected from the die. Thus, this review does not concern hot pressing, coining or sizing feed or flow problems, commercial presses nor designs. It was also necessary to disregard to a large extent the effect of pressing on subsequent operations and on properties after sintering. 'The pressing operation is considered independently in its function to compact loose metal powder into useful shapes which can subsequently be handled. There are some comments by the writer in connection with a few of the findings quoted in the literature in order to stimulate thought and discussion. The selection of references quoted in the text is in some cases arbitrary although an attempt was made to favor papers containing novel ideas, techniques or results which mag stimulate future research. In order to enable the reader to check further into the subjects mentioned, the original, rather extensive, bibliography is appended even though not all the references are touched on in the printed version of this review. The equipment used by various workers, for example a die design created by Bridgman,22 is very interesting. 'The die insert has a conical external surface. The vertical pressure exerted on the punch transmits itself to the die which in turn is pushed harder into its tapered retainer. Thus, the higher the pressure exerted on the punch, the higher also the pressure exerted inwards on the die inserts. Inasmuch as this pressure counteracts the internal pressure from the compact the two stresses balance each other so that it is possible to obtain tremendous pressures without breaking the die. The die collar was made from an oil hardening tool steel, heat treated to a tensile strength of some 300,000 psi. The die was closed at the bottom by a plug made from special tool steels. Bridgman found that there is no steel which will withstand a com-pressive stress of 700,000 psi without continuous slow flow or immediate fracture. Therefore, the only material suitable for use in the pressing punch was sintered carbide. In view of the ingenious design it was possible to use special tool steel as die material. Jones22 raises the question whether this method of pressing has practical application in powder metallurgy. Although these tremendous pressures cannot readily be utilized without many special precautions, the tapered die and retainer idea is believed to be useful even for lower pressures. Bridgman, himself," alls attention to the fact that the properties

Jan 1, 1947

By Richard Paul Seelig

The following review covers published information on pressing of metal powders at room temperature. Only those operations are considered which occur between the time the powder is filled into the cavity and the compact is ejected from the die. Thus, this review does not concern hot pressing, coining or sizing feed or flow problems, commercial presses nor designs. It was also necessary to disregard to a large extent the effect of pressing on subsequent operations and on properties after sintering. 'The pressing operation is considered independently in its function to compact loose metal powder into useful shapes which can subsequently be handled. There are some comments by the writer in connection with a few of the findings quoted in the literature in order to stimulate thought and discussion. The selection of references quoted in the text is in some cases arbitrary although an attempt was made to favor papers containing novel ideas, techniques or results which mag stimulate future research. In order to enable the reader to check further into the subjects mentioned, the original, rather extensive, bibliography is appended even though not all the references are touched on in the printed version of this review. The equipment used by various workers, for example a die design created by Bridgman,22 is very interesting. 'The die insert has a conical external surface. The vertical pressure exerted on the punch transmits itself to the die which in turn is pushed harder into its tapered retainer. Thus, the higher the pressure exerted on the punch, the higher also the pressure exerted inwards on the die inserts. Inasmuch as this pressure counteracts the internal pressure from the compact the two stresses balance each other so that it is possible to obtain tremendous pressures without breaking the die. The die collar was made from an oil hardening tool steel, heat treated to a tensile strength of some 300,000 psi. The die was closed at the bottom by a plug made from special tool steels. Bridgman found that there is no steel which will withstand a com-pressive stress of 700,000 psi without continuous slow flow or immediate fracture. Therefore, the only material suitable for use in the pressing punch was sintered carbide. In view of the ingenious design it was possible to use special tool steel as die material. Jones22 raises the question whether this method of pressing has practical application in powder metallurgy. Although these tremendous pressures cannot readily be utilized without many special precautions, the tapered die and retainer idea is believed to be useful even for lower pressures. Bridgman, himself," alls attention to the fact that the properties

Jan 1, 1947

By Orville R. Lyons

DISCUSSION Judson S. Hubbard (The Humphreys Investment Co., Denver)—In this very interesting paper several brief references are made to the Humphreys spiral, a device used for cleaning fine coal. In Table I, Plants 76 and 77, data are given on spiral performance treating Raton and Trinidad coal. The fine coal, as fed to the spiral in these instances, is actually a table middling, hence the more easily treated material was previously removed and a large number of particles were present which were difficult to clean. Mr. W. M. Bertholf of the Colorado Fuel and Iron Co. presented a paper in February, 1946, Cleaning Table Middlings from a Coal Washery with the Humphreys Spiral Concentrator, from which I quote: "In considering the results of our tests it should be noted that the feed was our table middling, and that any real separation is a 'moral victory' as there is little material that could properly be called coal and practically no heavy rock, the consequences being that previous attempts to clean the middling have not at all been successful." Referring again to Table I, Plants 72, 73, 74, and 75, these data were obtained by Yancey and Geer and others and presented at the February 1950 Meeting, AIME, in a paper entitled Laboratory Performance Tests of the Humphreys Spiral as a Cleaner of Fine Coal. Results shown for those tests involve all particles from 8 mesh through the colloids, which admittedly is not an ideal situation for spiral feed if much refuse is contained in the —80 mesh or —100 mesh size range. As an illustration of the effect of treating too broad a size range, let us consider Plant No. 75, Kentucky No. 9 seam. Spiral feed was 8 mesh x 0. Now had this been 8x100 mesh the percentage of misplaced material would have been 8.0 pct instead of the reported 15.26 pct. Similar comparisons can be made on the other data presented with respect to the spiral. Other types of equipment show a similar trend in that whenever too fine a size is treated in a given unit process the percentage of misplaced material increases. Since the spiral is working near the finer end of the size range, it will sometimes be advantageous to treat the entire range of —8 mesh material rather than to deslime and make a fair showing on, say, the +80 or + I00 mesh. Desliming is subsequently done in any case in the dewatering or thickening operation. Results obtained by spiraling any given coal depend on factors too numerous and complex to discuss here, but there are strong indications that proper preparation of feed to the spiral can improve results obtained on some of the raw coals tested. This is clearly pointed out at the end of the aforementioned paper by Yancey and Geer. "The spiral is an extremely simple device which involves no moving parts and is constructed almost entirely of unmachined castings. Since it is such an uncomplicated mechanism, operation is simple and virtually foolproof. These characteristics, which go far toward insuring low cost operation, are attractive attributes in any coal cleaning unit." Certain equipment used in conjunction with the spiral has resulted in a decrease in the percentage of misplaced material, notably in actual practice the launder screen which is used to remove objectionable high ash fines from a spiral-washed coal product. Private correspondence with the U. S. Bureau of Mines has intimated that an additional yield of coal is possible by flotation of the spiral middling. Possible future improvements and developments may result from other methods now under consideration. Finally, some compromise must be made between the best metallurgical performance and the best practical or economical results. Mr. Lyons emphasizes in his summary this objective of overall economy in selection of equipment. G. B. Walker (American Cyanamid Co., Stamford, Conn.)—I had the pleasure of reviewing the draft of this paper and my curiosity was aroused by the data given for Tromp plants, in that all of the examples shown appeared to be 2-product separations, whereas all the Tromp plants with which I am familiar have been 3-product units. The data given for plants No. 101 and 102 appear to be taken from Tromp's brochure on his process and represent the results obtained at the Dominale plant in Holland which was operated for many years by Mr. Tromp. The plant, which was designed to treat 58 tons per hr, was sampled while treating 35 tons per hr of 3Y4x-in. coal. Example 101 appears to conform to what would result if the middling product were calculated into the refuse product, while Example 102 represents the calculation of the middling into the coal product. It is believed that Examples 103 and 104 represent the operation of the Willem-Sophie Mine in Holland recalculated on the same basis. In checking the English examples given by numbers 14, 15, 16, and 17, the same procedure seems to have been followed. These results have, apparently, been taken from an article in Colliery Engineering in August 1941, describing the initial operation of the Williamthorpe Colliery of the Hardwick Colliery Co. Two vessels are employed in this plant, one to treat soft coal and one to treat hard coal. Example No. 14 presents the results that could be obtained from the soft coal bath if the middling were calculated into the refuse, and Example 15 the results when the middling is calculated into the coal. Examples 16 and 17 represent the same expedient in the case of the hard coal bath. Of interest to this discussion is the fact that during the past year the Simon-Carves Engineering Co. in England has installed in the Williamthorpe plant their new "Sim-Car" medium cleaning system which is based on magnetic extraction and control and which is licensed under the Heavy-Media Separation Processes patents by the American Zinc, Lead and Smelting Co. This system has been described in the December 1951, issue of Colliery Engineering. It is reported that since the Williamthorpe Colliery was changed from the Tromp system of medium cleaning to the Magneto-Motive method of medium control the opera-

Jan 1, 1953

By Orville R. Lyons

DISCUSSION Judson S. Hubbard (The Humphreys Investment Co., Denver)—In this very interesting paper several brief references are made to the Humphreys spiral, a device used for cleaning fine coal. In Table I, Plants 76 and 77, data are given on spiral performance treating Raton and Trinidad coal. The fine coal, as fed to the spiral in these instances, is actually a table middling, hence the more easily treated material was previously removed and a large number of particles were present which were difficult to clean. Mr. W. M. Bertholf of the Colorado Fuel and Iron Co. presented a paper in February, 1946, Cleaning Table Middlings from a Coal Washery with the Humphreys Spiral Concentrator, from which I quote: "In considering the results of our tests it should be noted that the feed was our table middling, and that any real separation is a 'moral victory' as there is little material that could properly be called coal and practically no heavy rock, the consequences being that previous attempts to clean the middling have not at all been successful." Referring again to Table I, Plants 72, 73, 74, and 75, these data were obtained by Yancey and Geer and others and presented at the February 1950 Meeting, AIME, in a paper entitled Laboratory Performance Tests of the Humphreys Spiral as a Cleaner of Fine Coal. Results shown for those tests involve all particles from 8 mesh through the colloids, which admittedly is not an ideal situation for spiral feed if much refuse is contained in the —80 mesh or —100 mesh size range. As an illustration of the effect of treating too broad a size range, let us consider Plant No. 75, Kentucky No. 9 seam. Spiral feed was 8 mesh x 0. Now had this been 8x100 mesh the percentage of misplaced material would have been 8.0 pct instead of the reported 15.26 pct. Similar comparisons can be made on the other data presented with respect to the spiral. Other types of equipment show a similar trend in that whenever too fine a size is treated in a given unit process the percentage of misplaced material increases. Since the spiral is working near the finer end of the size range, it will sometimes be advantageous to treat the entire range of —8 mesh material rather than to deslime and make a fair showing on, say, the +80 or + I00 mesh. Desliming is subsequently done in any case in the dewatering or thickening operation. Results obtained by spiraling any given coal depend on factors too numerous and complex to discuss here, but there are strong indications that proper preparation of feed to the spiral can improve results obtained on some of the raw coals tested. This is clearly pointed out at the end of the aforementioned paper by Yancey and Geer. "The spiral is an extremely simple device which involves no moving parts and is constructed almost entirely of unmachined castings. Since it is such an uncomplicated mechanism, operation is simple and virtually foolproof. These characteristics, which go far toward insuring low cost operation, are attractive attributes in any coal cleaning unit." Certain equipment used in conjunction with the spiral has resulted in a decrease in the percentage of misplaced material, notably in actual practice the launder screen which is used to remove objectionable high ash fines from a spiral-washed coal product. Private correspondence with the U. S. Bureau of Mines has intimated that an additional yield of coal is possible by flotation of the spiral middling. Possible future improvements and developments may result from other methods now under consideration. Finally, some compromise must be made between the best metallurgical performance and the best practical or economical results. Mr. Lyons emphasizes in his summary this objective of overall economy in selection of equipment. G. B. Walker (American Cyanamid Co., Stamford, Conn.)—I had the pleasure of reviewing the draft of this paper and my curiosity was aroused by the data given for Tromp plants, in that all of the examples shown appeared to be 2-product separations, whereas all the Tromp plants with which I am familiar have been 3-product units. The data given for plants No. 101 and 102 appear to be taken from Tromp's brochure on his process and represent the results obtained at the Dominale plant in Holland which was operated for many years by Mr. Tromp. The plant, which was designed to treat 58 tons per hr, was sampled while treating 35 tons per hr of 3Y4x-in. coal. Example 101 appears to conform to what would result if the middling product were calculated into the refuse product, while Example 102 represents the calculation of the middling into the coal product. It is believed that Examples 103 and 104 represent the operation of the Willem-Sophie Mine in Holland recalculated on the same basis. In checking the English examples given by numbers 14, 15, 16, and 17, the same procedure seems to have been followed. These results have, apparently, been taken from an article in Colliery Engineering in August 1941, describing the initial operation of the Williamthorpe Colliery of the Hardwick Colliery Co. Two vessels are employed in this plant, one to treat soft coal and one to treat hard coal. Example No. 14 presents the results that could be obtained from the soft coal bath if the middling were calculated into the refuse, and Example 15 the results when the middling is calculated into the coal. Examples 16 and 17 represent the same expedient in the case of the hard coal bath. Of interest to this discussion is the fact that during the past year the Simon-Carves Engineering Co. in England has installed in the Williamthorpe plant their new "Sim-Car" medium cleaning system which is based on magnetic extraction and control and which is licensed under the Heavy-Media Separation Processes patents by the American Zinc, Lead and Smelting Co. This system has been described in the December 1951, issue of Colliery Engineering. It is reported that since the Williamthorpe Colliery was changed from the Tromp system of medium cleaning to the Magneto-Motive method of medium control the opera-

Jan 1, 1953

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally. Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan," show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision, using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.' However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: 3_____________________ fB = 9.20.vV.vn. (n-1).(n+2)/8 [I] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsym-metric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system of one degree of freedom can be applied: fP = -1/2-vE/m [2] Here fp is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: t, = 2/f = nvm/E [3] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson7 1831) P = /4 D2-pL-g-h + D.y sin a [4] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, PL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of the liquid in cm, y the surface tension in dynes per cm and a the supporting angles or the one required to insure equilibrium, a being smaller than the contact angle 0. Although demonstrated by Poisson, it has not

Jan 1, 1953

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally. Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan," show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision, using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.' However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: 3_____________________ fB = 9.20.vV.vn. (n-1).(n+2)/8 [I] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsym-metric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system of one degree of freedom can be applied: fP = -1/2-vE/m [2] Here fp is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: t, = 2/f = nvm/E [3] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson7 1831) P = /4 D2-pL-g-h + D.y sin a [4] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, PL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of the liquid in cm, y the surface tension in dynes per cm and a the supporting angles or the one required to insure equilibrium, a being smaller than the contact angle 0. Although demonstrated by Poisson, it has not

Jan 1, 1953

By B. L. Averba

THE determination of retained austenite by X-ray diffraction uses the following relationship:"" Pa = constant . RVaA (8) [1] where: P is the diffracted power from phase a; R, the calculated intensity factor; A, the absorption correction; 8, the diffraction angle; and Va, the irradiated volume of phase a For a flat sample making a glancing angle + with the incident beam the absorption correction is calculated as: * 1 sin (28 - 4) A .= 1 [2] µ sin, (28 — 4) + sin 4 where µ is the linear absorption coefficient. Beu3 has proposed that the computed absorption correction be combined with the constant and that the experimental observation of the absorption correction used in the original method be eliminated. This procedure is permissible only if: 1—There is no preferred orientation in the sample, and 2—The geometric requirements have been met precisely. If these conditions are not met the validity of the determination is questionable. Unfortunately the necessary conditions must be tested experimentally for each determination, and this is done most easily by observing whether the apparent absorption has the form of Eq. 2. In practice it may be convenient to plot P/R vs the parameter sin (2? — )[sin (28 — +) + sin +] to obtain straight lines for the ap- parent absorption correction. Deviations from straight lines indicate either that the sample has not been positioned correctly or that the relative intensities are incorrect. Geiger counter spectrometer methods also have been used successfully for retained austenite determinations. In the usual spectrometer arrangement the sample makes equal angles with the incident and diffracted beams (8 = ); thus the absorption correction is simply 1/2µ and independent of 8. The retained austenite is then easily calculated from integrated intensity measurements on austenite and martensite lines. If the austenite content is not too low and if excessive fluorescence is not encountered it is possible to use filtered radiation and a recording spectrometer. The integrated intensities are then proportional to the areas of the diffraction peaks. For lower austenite contents the following technique was used: A bent quartz monochromator and a Geiger counter spectrometer are employed. The monochromatic radiation is focused on the front slit, and the counter slit is made broad enough to include the entire line. A series of readings are taken in the vicinity of the diffraction peak. The highest reading includes the diffraction line plus background. The background is obtained from the average of several readings on each side of the peak. The integrated intensity is obtained by subtraction. CrK, and FeKa have been used for such determinations. This technique has been found to be as sensitive and as accurate as the photographic methods. In the spectrometer methods the ratio austenite/ martensite may be obtained from readings on austenite and martensite lines and the application of Eq. 1. It is also possible to use external standards and to obtain the austenite contents from measurements on the austenite lines alone. The small correction for carbides then becomes unnecessary. The best standards are probably samples with known

Jan 1, 1954

By E. P. Abrahamson

The effect of transition element binary solid solution additions upon the re crystallization temperature of nickel has been investigated. All additions raised the re crystallization temperature. Both the rate of change of re crystallization temperature with at. pet solute and the limit of initial linearity are found to correlate with the free atom ground state outer electron configuration of the solute element. A comparison of all of the correlations for the transition elements studied has yielded a set of empirical relations, which allows the prediction of the effect of dilute binary transition elements on the recrystallization temperature of other transition elements. The work of Abrahamson, et al.1-7 on dilute binary solution alloys indicated a correlation between the free atom ground state electron configuration of the solute and both the brittle-ductile transition and re-crystallization temperature. Further, it has been shown3,4 that the limit of initial linearity may also be correlated with the solute electron configuration. Since previous studies have dealt with bee and hexagonal base elements, this study is made to note what effect, if any, the fee base structure might have. Nickel also serves to give a solvent configuration which will allow the comparison of all of the transition element solvents. Olsen8 has studied the effect of some trace elements upon the recrystallization of nickel. He included only Ti, Zr, W, Mn, and Co of the transition elements. The differences in change of recrystallization temperature were attributed to the solute atom size and to the solubility of the solute in nickel. PROCEDURE All alloys were made using 99.9 + pet Ni with 0.003 C, 0.015 Fe, 0.007 0, and 0.0007 H. The solute elements were 99.9 + pet pure. According to the published binary phase diagrams9 and metallo-graphic examinations at X750, all solute elements were in solid solution. The alloys were arc melted and remelted four times in the form of cubic 200-g buttons under an argon atmosphere. They were then hot forged at 800oC to 0.750 in. diam, machined to 0.60 in., vacuum annealed for 1 hr at 700°c, swaged to 0.40 in. and annealed at 700oC for 1 hr in vacuum. The grain size was checked and found to be 77 * 20 grains per sq mm. The specimens were then swaged to 0.187 in., yielding 76 ± 1 pet cold work. All alloys were then chemically analyzed for the solute addition. The interstitial contents remained at the values of the starting material when checked on random alloy specimens. The swaged rod was cut into 8.25 in. lengths and heat treated in a gradient furnace for 1 hr. The gradient was maintained at 250" to 850°C over an eight inch length, recorded by twelve thermocouples. Control was ± 3oC, accomplished at the hot end. The recrystallization was determined metallo-graphically over the entire specimen. The criterion chosen was that point on the specimen showing the first recrystallized grain at a constant magnification, X200. Specimens were repeated, and the agreement was found to be generally ± 3oC.

Jan 1, 1962

By N. A. Gokcen, S. Fujishiro

THE pressures of Mn(g) in equilibrium with Mn7C3 and graphite have been measured by McCabe and Hudson' and Butler, McCabe, and paxton2 by means of graphite, zirconia, and Ta-Mo Knudsen cells. The details of corrections in their measurements were somewhat different from those of the authors;3'4 hence, further independent results at higher temperatures seemed to be warranted. The stoichiom-etry of Mn7C3 in equilibrium with graphite and its stability up to the vicinity of 1373 °K have been satisfactorily established by Kuo and persson5 (See also Hansen and Anderko).' The method of investigation has been described elsewhere in detail.3'4 The carbide was prepared in the manner described by McCabe and Hudson. In order to avoid possible reactions with refractory oxides, only graphite cells were used for the effusion experiments. The authors' results are the runs M-1, M-2 and M-3 listed in Table I, together with those of McCabe and co-workers. The heat capacity, c;, of Mn7C3 is not known; therefore McCable et al. plotted their data as log P vs 1/T and the results were only expressed first' as, and later2 as logP=- -14220+6.06 without further thermodynamic calculations. However, it is possible to estimate closely the necessary heat capacity as follows: When H; - &98 of CrC, or MnO, is plotted vs x, corresponding to various compounds, with temperature as the parameter, it is seen that the relationship is represented by a line of very small curvature. This relationship is also followed by other compounds which do not exhibit solid state phase transformations. In view of the fact that chromium and manganese have the atomic numbers of 24 and 25 respectively, it is reasonable to assume that H; - H;ae vs x for MnC, follows the same type of lines as those for CrC, for which adequate data are available.7 Similar correlations appear to be valid for oxides of two neighboring metals for which reliable data are available. The procedure is thus to move the lines for CrC, vertically (parallel to the axis of HT - H298) until they coincide with the points for MnC1/3, the only carbide of manganese whose H; - HO298 has been

Jan 1, 1963

By E. T. Turkdogan, J. H. Swisher

bi the fivst part of the paper results ave given on the rate of decarburization of Fe-C melts ln CO2-CO atmospheres at 1580°C. The rate -controlling step is believed to he that irvlloluing dissociation of curbotz dioxide on the suvfuce of the melt. 4 genevral reaction mechanistm is poslnlated jor gels-t11eta1 veactions oc-curit~g on the surface of iron coutcotamncited with chemi-sovbed osygesL. Oxygen the present work on decavbuvization of liquid iron and previous studies on the kinetics of nitrogen absorption and desorplion are discussed in terms of the postulated mechanism, ManY of the early studies of rate of decarburization of liquid steel were of an exploratory nature and laboratory exppriments carried out pertained to open-hearth or oxygen steelmaking processes. References to previous work on this subject may be found in a literature survey made by Ward. Using more sophisticated experimental techniques, several investigators have recently studied the kinetics of decarburization of molten Fe-C alloys in oxygen-bearing gases. For example, Baker et al2.' reported their findings on the rate of decarburization of liquid iron, levitated by an electromagnetic field, in carbon dioxide-carbon monoxide-helium atmospheres. In these levitation experiments the samples used were small in size, e.g., -0.6-cm-diam spheres weighing -0.7 g, and the rates were measured for decarburization from about 5 to 1 pct C at 1660°C. The rates obtained under their experimental conditions were considered to be controlled primarily by gaseous diffusion through the boundary layer at the surface of the levitated melt. Parlee and coworkers3 measured the rate of absorption of carbon monoxide in liquid iron. The rates were found to follow first-order reaction kinetics, yielding a reaction velocity or a mass transfer coefficient in the range 0.2 to 0.4 cm per min. The coefficient was found to decrease with increasing carbon content of the melt. These investigators attributed the observed rates to the transfer of carbon or oxygen through the diffusion boundary layer adjacent to the surface of the melt. In the work to be reported in this paper, an attempt has been made to study the kinetics of gas-metal surface reactions involved in the decarburization of liquid iron. EXPERIMENTAL The experiments consisted of melting 80-g samples from an Fe-1 pct C master alloy in an induction furnace and decarburizing in controlled CO2-CO mixtures at 1 atm pressure and 1580°C. The master alloy was prepared by adding graphite to electrolytic "Plastiron" melted in racuo. None of the impurities in the master alloy exceeded 0.005 pct. The reacting gases were dried by passage through columns of anhydrone; in addition, CO2 impurity in carbon monoxide was removed by passage through a column of ascarite. A schematic diagram of the apparatus is shown in Fig. 1. A 1.25-in.-diam recrys-tallized alumina crucible containing the sample was placed inside a 3-in.-diam quartz reaction tube, all of which was surrounded by an induction coil. A 450-kcps induction generator was used as the power source. Water-cooled brass flanges, which contained the gas inlet, gas exit, and sight port, were sealed to the top of the reaction tube with epoxy resin. The reacting gases were metered with capillary flowmeters and passed through a platinum wire-wound alumina preheating tube, 0.25 in. ID and 11 in. long. The gases were preheated to about 1300°C. A disappearing-filament optical pyrometer was used to measure the melt temperature. The pyrometer was initially calibrated against a Pt-6 pct Rh/Pt-30 pct Rh thermocouple. The temperature was controlled to within +10°C by manually adjusting the power input to the induction coil. In a typical experiment, an 80-g sample of the master alloy was melted in a CO2-CO atmosphere having pcO2/pco = 0.02 and flowing at 1 liter per min. A negligible amount of carbon was lost and no significant reduction of alumina from the crucible occurred during melting, e.g., 0.005 pct Al in the metal. After reaching the experimental temperature of 1580°C, the gas composition was changed to that desired for a particular series of decarburization experiments. The duration of the transient period for obtaining the desired gas composition at the surface of the melt was about 20 sec . The flow rate of the reacting gas was maintained at 1 liter per min. After a predetermined reaction time, the power to the furnace was turned off. During freezing, which took about 10 sec, the amount of gas evolution was not sufficient to result in a significant loss of carbon. The samples were analyzed for carbon by combustion and in a few cases they were analyzed for oxygen by the vacuum-fusion method. RESULTS A marked increase in the rate of decarburization of iron with increasing pcO2/pco ratio in the gas stream is demonstrated by the experimental results given in Figs. 2 and 3 for pco2/pco ratios from 0.033 to 4.0. In one series of experiments, denoted by filled triangles in Fig. 2, the reacting gas was diluted with argon (48 vol pct) resulting in a slower rate of decarburization. Samples from two series of experiments with pco2/pco = 0.033 and pco2/pco = 0.10 (with argon dilufion) were analyzed for oxygen. In these Samples the oxygen content increased with reaction time

Jan 1, 1968

By J. W. Matousek, C. S. Samis

me thermodynamic properties of the components in the Cu-Ni-S ternary system have been studied by measuring the H2S/H2 ratios in a gas phase equilibrated with the molten matte at 1200°C. The measured sulficr potentials have been extended by extrapolation and combtned with previously published data to permit the thermodynamic analysis of the ternary system by integration techniques. A simplifying assumption of ideality in the Ni3Sz-CuS pseudobinary has been made. SINCE copper and nickel metals were first extracted from their sulfide ores the interaction between the two metals and sulfur has been of industrial and theoretical interest. The processes developed to extract copper and nickel have been reported periodically in the literature. The theoretical studies on the Cu-Ni-S ternary have been restricted to problems directly associated with production. It is only within recent years that the binary systems related to this ternary have been analyzed thermodynamically and mathematical devices developed to permit a corresponding treatment of the ternary system. In 1910 an investigation of the role of nickel in Cu-Ni-Fe-S mattes was reported,' It was concluded from this work that nickel is not an element replacing iron in mattes, but rather that Cu-Ni alloys behave as a single metal during the matte converting operation. The laws which govern the converting of Cu-Ni alloys were found to be the same laws as those that govern the conventional converting of copper alone. Although considerable information has been reported on the theoretical aspects of copper smelting, little data is available on the smelting of Cu-Ni ores except for phase diagrams and process descriptions. The available information on the Cu-Fe-S ternary and related systems prior to 1953 has been summarized by Ruddle.2 Since Ruddle's publication, Rosenqvist and coworkers have completed phase equilibria investigations of the Fe-S, Co-S, and Ni-S binaries,3 the Fe-S-O ternary,4 and the Cu-Fe-S-O quaternary.4 An extensive investigation of the Cu-Fe-S ternary system at smelting temperatures has been made by Krivsky and Schuhmann.5 At these temperatures, the Cu-Fe-S system is very similar to the Cu-Ni-S ternary with respect to the location of the single-phase and two-phase liquid matte regions. In the former, however, the area of immiscibility is more extensive and the region of liquid matte-liquid metal-solid metal equilibria is much more extensive. Krivsky and Schumann observed that the Cu2S-FeS pseudobinary system is, for practical purposes, an ideal mixture. This investigation has served as a valuable guide in analyzing the Cu-Ni-S ternary. EXPERIMENTAL The experimental procedure employed in this investigation was the conventional technique of equilibration of the sulfide matte with gaseous mixtures of hydrogen and hydrogen sulfide at 1200°C. The thermodynamic properties of sulfur (S2) in the gas phase are determined by means of Eq. [I] and the activity of sulfur in the matte by Eq. [2].

Jan 1, 1963

By C. A. Heiland

WITH seventeen papers submitted. and thirteen presented in three sessions, the geophysicists had a most successful meeting at New York in February. The first paper on Monday morning dealt with the location of a diabase dike near Chapel Hill, N. C., by magnetic and resistivity methods. The magnetic indications were pronounced directly over the dike. whereas the anomalies of apparent resistivity were less distinct and displaced away from the dike. In the second paper, Professor Keys reported on the results obtained with four different methods of depth calculation on known portions of the Falconbridge

Jan 1, 1937

By Felix Edgar Wormser

JUST as the ancients used the products of their crude mining endeavors to fashion tools with which to make digging easier, so today mining enterprises are dependent upon the very metals they mine for the efficient conduct of mining and metallurgical operations. In fact, the outlet afforded by the production of minerals in the United States is no mean market for the nonferrous metals. I believe that mine managers frequently lose sight of the opportunity they have to select from competitive products those which will help the market for their own metal output. For example, some years ago a large lead mine used storage-battery locomotives for its haulage, common practice, of course, throughout the United States. These particular locomotives, however, were powered not with the ordinary lead storage battery but by a competitive battery product made from an imported metal. After studying this situation, the manager saw how he could help himself by purchasing a product made from his own mineral output, and in his next order turned tip the use of the lead storage battery.

Jan 1, 1935

By C. W. Chen

MARTENSITE transformations in ß Cu-Al alloys have been studied by Greninger1 and other investigators. According to Greninger, the parent phase ß1 an ordered body-centered-cubic structure obtained from ß phase by suppressing the eutectoid decomposition, transforms into an ordered hexagonal-close-packed phase in composition containing 12.9 to 14.7 pct Al. The M, temperature decreases with increasing aluminum content; for the alloy containing 14.5 pct Al, for example, the ß1??' transformation occurs below room temperature. More recently, Kurjumow2 studied the transformation in ß Cu-Al alloys with the addition of nickel. His report stimulated new interest in the subject due to the observation of completely reversible transformation without hysteresis in the transformation temperature ranging from 10° to —10°C. In the present paper some characteristics are described of the transformation of Cu-Al-Ni alloys that were partly studied by Kurjumow. Experimental Procedure High purity copper (99.999 pct) and aluminum (99.99 pct) and electrolytic nickel were used in the preparation, by the Bridgman technique, of single crystal specimens which contained aluminum and nickel of 14.5 and 0.5 to 3.0 pct, respectively. Polished surfaces were prepared mechanically. Specimens were then chemically etched to remove distorted material, homogenized at 1000°C for several hours, and quenched drastically to room temperature in a 10 pct NaOH bath to produce the parent phase ß1. The transformation was studied under a microscope and, in some cases, recorded by means of motion pictures. A device similar to that designed by Greninger and Mooradian3 was used to cool and reheat the specimens. Results and Discussion When the specimens were cooled below room temperature, the ß1 to ?' transformation began at 10°C with the appearance of ?' crystals In relief, Fig. la. As the specimen temperature dropped further, the transformation continued, either by the growth of the ?' crystals, with the ß1 — ?' interface moving into the ß1 phase, Fig. 1c and 1d, or by the formation of new ?' crystals, Fig. 1b. As a consequence of the former process, banded structure is observed as a common feature of the low temperature phase. According to the theory of the formation of martensite by Wechsler, Lieberman, and Read,' the bands of ?' phase are probably twin-related, as is the case in the diffusionless phase change of In-T1 alloys,5 but this was not revealed by X-ray tech- niques. New ?' crystals, in needle form, often emerged suddenly across the ?' bands during the transformation. These acicular crystals then grew, both in length and in width, see Fig. 2a through 2d. The transformation on cooling is completed at about -35°C. Upon heating, the reverse transformation started at —10° C, in a manner nearly opposite to the transformation on cooling, and completed at 35°C. There was no noticeable change in the transformation temperature when the nickel content was varied within the limits previously mentioned. Through control of the specimen temperature, the transformation can be started, stopped, or reversed at will. This phenomenon has frequently been observed in the martensite transformation of many nonferrous alloy systems. Other systems are Au-Cd6 and In-Tl.5 ow-- ever, in the latter systems, the transformation is accomplished by single interface motion if the specimen composition is homogeneous and the temperature gradient in the specimen is uniform and sharp, whereas in the Cu-Al-Ni specimens, only multiple interface transformation is observed. The speed of the interface motion appears to be a functionof the rate of temperature change and the temperature gradient across the specimen length. In one case, in which the temperature increased at the rate of 10°C per min and there was no temperature gradient along the specimen axis, the speed of the disappearance of a ?' plate was determined, by the study of the motion pictures made, to be 26 µ per sec. Quench markings were observed on the polished surfaces of specimens. The markings were grouped into one or more sets of different orientations, and were parallel in each set. The ?' plates formed in subsequent transformation were parallel to the markings, indicating that the ?' plates and the quench markings had the same geometric relation-ship to the ß1 matrix. The quench markings on two intersecting surfaces of a specimen were therefore used in the determination of the habit plane of transformation, by the trace method suggested by Barrett.' Results obtained from five sets of markings in three specimens indicate that the habit plane is an irrational plane about 2" from one of the {221} planes. This is very close to the habit plane (3" from 221 planes) of ß Cu-Al alloys containing more than 13.0 pct Al.1 The martensite transformation of Cu-Al-Ni alloys is reproducible. No sluggishness was found between consecutive transformation cycles, although a slight difference in the distribution pattern of the ?' plates was observed, compare Figs. Id and 2d. The transformation can be strain-induced. This characteristic has been tested by a simple method. When a specimen was elastically strained slowly in a vise, ?' plates were gradually produced in the same fashion as during transformation on cooling, This test was done at room temperature, and thus above the M,

Jan 1, 1958

By J. W. Evans

ONE possible method for the separation of hafnium from zirconium is by the vapor phase oxidation of the purified mixed chlorides. An important factor for success depends on the difference in free energies of the following reactions: ZrCl(g) + O2 = ZrO2(s) + 2C12 [1] HfCl4(g) + O2 = HfO2(s) + 2C12. [2] Prakash and Sundaram1 have calculated these values from certain data and carried out experimental work with partial success. However, their free energy values for reaction 2 diverge rather widely from other data which are presented here. The possibility of successful separation is briefly considered in the light of these alternative values. Table I shows the free energy values (?F°) for reactions 1 and 2 derived from the recent compilation of data on oxides and chlorides by Glassner.2 The corresponding values of Prakash and Sundaram for the same temperatures are also shown. The alternative values to those of Prakash and Sundaram for reaction 2 are substantially confirmed by the data of Kubaschewski and Evans" and Cough-lin' on heats of formation, entropies, and heats of vaporization. In spite of the considerable uncertainty in the hafnium data it is reasonable to suppose that the oxide-chloride free energy difference for two such chemically similar elements would not be very far apart. These figures indicate clearly that the oxidation of hafnium chloride is appreciable at all temperatures. Nevertheless, there is a significant difference between the values for reactions 1 and 2

Jan 1, 1959

ALASKA Established November 19, 1947 Regular meetings fourth Monday of each month except June, July, and August Theodore A Loftus, Chairman John C Boswell, Vice-Chairman Patrick H O'Neill, Secretary-Treasurer Box 1034, Fairbanks, Alaska District Vice-Chairmen Robert L Thorne, Juneau, Alaska Alfred J Lomen, Jr , Nome, Alaska Donald G. Wilcox, Anchorage, Alaska

Jan 1, 1952

By Luther Wagoner

Having given in a former paper1 the results of assays of sea-water, bay-mud, dredgings from San Francisco bay, etc., and believing it might be interesting to extend the work to include some deep-sea dredgings, I procured from the Smithsonian Institution six samples taken by the U. S. steamer Albatross, and marked as follows: Depth in No. station. Locality. Latitude. Longitude. Fathoms. 1. 2103. Off Delaware bay. 38' 47' 20" N., 72o 37' W., 1,091. 2. 2265 to Between Chesapeake 35° 37' N., 74O to 75O W., 49 to 70. 2297. bay and Hatteras. 3. 2420. Off Chesapeake bay. 37' 03' 20" N., 74O 31' 40" W., 104. 4. 2528. East of Georges 41° 47' N., 65o 37' 30" W., 677. bank. 5. 2572. SE. of Georges bank. 40° 29' N., 66O 041 W., 1,769. 6. 2681 South of Nantucket. 39' 43' N., 70' 29' W., 990. The above samples were assayed by the cyanide-method, described in my former paper (p. 807), about 30 g. of sample being used, and the following results were obtained: Value in Milligrams Per Metric Ton. No. Station. Gold. Silver. 1. 2103. 145 1,014 2. 2265 to 2297. 44 304 3. 2420. 15 353 4. 2628. 267 1,963 5. 2572. 125 377 6. 2681. 66 414 No. 4, Station 2528, consisting of red clay and volcanic ash, mas re-assayed ; 35 g. was roasted at a low heat for one hour and weighed 34.05 g. after roasting; the color was changed to a deep brick-red; and when assayed by the cyanide-method

Jan 1, 1908

By E. M. Tory, P. T. Shannon

An analysis of batch and continuous thickening in terms of the movement of planes of constant concentration (i.e. continuity waves) is presented. Use of solids flux as a primary variable greatly facilitates the analysis and clarifies the relationship between batch and continuous thickening. An "ideal" slurry is defined as one whose settling rate is a function only of the local solids concentration. An analysis of continuous thickening of this ideal slurry in an ideal thickener explains many aspects of the steady — and unsteady — state behavior of real slurries, such as the main features of a thickener's "solids profile" (including the break attributed to rake action), the sudden appearance at abnormally high feed rates of a zone of constant concentration and the velocity with which it rises, and the effect of detention time at constant weight of sludge per unit area. Where deviations exist, they are explained in terms of the batch settling behavior of real slurries. The purpose of this paper is to interpret continuous thickening phenomena in terms of batch settling behavior. Both types of thickening may be considered as the process of propagating concentration changes, due to the downward movement of the solids, from the bottom of the settling vessel upward through the slurry.' These concentration changes may be either finite or infinitesimal as in the case of the propagation of a continuous concentration gradient. The slurry itself may be moving downward as in the case of continuous thickening. The downward velocity of the slurry may be such that the concentration changes being propagated up from below remain stationary relative to the thickener walls. This is the case for steady-state thickening. It seems appropriate to analyze continuous thickening in terms of the movement of planes of constant concentration. This has already been done for batch settling."3 Although our main interest is in real slurries, there are certain aspects of both types of settling which can be deduced from a theoretical analysis of highly idealized systems. To this end, an "ideal slurry" is defined as one for which the dimensionless settling rate at any point is a function only of the local solids concentration.1,2 An "ideal thickener" is one in which there is no radial variation in either the solids concentration or in the downward component of slurry velocity. The underflow outlet is a point sink. It is to be expected that the behavior of non-ideal systems will deviate in some measure from theoretical results. However, the same characteristics which cause deviations in continuous thickening should be evident in batch settling, permitting a rational explanation of the former in terms of the latter. PREDICTED RESULTS FOR AN IDEAL SLURRY IN AN IDEAL CONTINUOUS THICKENER General Theory: In continuous thickening, the downward solids flux (mass/area-time) relative to the thickener, G, results from two different

Jan 1, 1967

By Stuart St. Clair

EARLY in 1936, when the American Petroleum Institute issued -J "American Petroleum Industry," which was a survey of the current position of the petroleum industry, and its future outlook, and the figures for petroleum requirements .for 1950 and 1960 were widely publicized by the several oil journals, the impression was given that the petroleum- industry must be nearing maturity and would by 1950 have passed the high' point of its obligations to business progress in the United States.`' Let -us look at the figures which might conduce, this thought. Referring to p. 32 of the report, the total indicated crude-oil requirements in 1940 are 1,099,000,000 bbl-; for 1950, the peak, 1,109,800,000 bbl.; for 1960 a decline to 1,071,020,000 bbl. This downward trend, then established, is probably expected to continue. And this in the face of a crude production in 1935 of 993,942,000 bbl., 38,858,000 bbl.

Jan 1, 1936