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By Ralph Monaghan, Arthur Youmans

General principles of scintillation counter-type instruments for radioactivity logging are discussed and the various possible causes for instability are examined. It is shown how instrumentation problems are solved. Means are discussed for minimizing drift and instability due to "fatigue" of the photomultiplier tube and neutron activation of the crystals. INTRODUCTION Neutron and gamma-ray logs made with logging instruments employing scintillation counters are now routinely available from most of the logging service companies. The superior characteristics of scintillation counters by comparison with older types of detectors promises to bring about important improvements in quantitative interpretation of radioactivity logs. Moreover, new types of logs can be made with scintillation counters which are not possible with other detectors. But in spite of the obvious superiority of these counters with respect to efficiency, speed, and versatility, they suffer from a number of inherent difficulties and weak- nesses. Unless these inherent diffi-culties are fully recognized and satisfactorily overcome by sound engineering of the associated instrumentation, scintillation counter logs are particularly likely to exhibit drift and instability of sensitivity. This defect in logs when they are intended for quantitative interpretation is intolerable and more than outweighs any advantages over the older type of instrumentation when the latter is operating correctly. SCINTILLATION COUNTER OPERATION In general all radioactivity logging instruments consist of a detector sensitive to gamma radiation or to neutron radiation coming from the strata. This radioactivity is either due to naturally decaying radioactive elements in the rock, radioactivity induced in the rock by a neutron source in the instrument, or scattering by the rock of neutrons or gamma rays coming from a source in the instrument. In the scintillation counter the gamma radiation or neutron radiation reacts with the scintillation phosphor to produce light pulses. These light pulses are then converted to amplified electrical pulses by the multiplier phototube. Basically the problem of making a good scintillation counter logging instrument is to make the radiation sensitivity of the system as nearly constant as possible. The size of each scintillation counter pulse is dependent on the energy of the individual quantum of radiation being detected. In normal radiation logging, gamma rays of all energies, up to some maximum value, reach the detector. If a suitable scintillator is used, such as a sodium iodide crystal, each gamma ray produces a number of photons proportional to the energy absorbed by the crystal from the impinging radiation. The light flashes are detected by means of a photo-multiplier tube which contains not only a photo-sensitive cathode from which photoelectrons are collected, but also an amplifier, called an electron multiplier, built inside the photomultiplier tube; the electron multiplier usually has about 10 stages, having an over-all gain of perhaps 500,000. In an ordinary gamma-ray log one wishes to detect all gamma rays down to the lowest possible energy; therefore, one wishes only to reject the "noise" pulses which are invariably present due to thermal emission of electrons from the photo-cathode of the photomultiplier. In other radioactivity logs it may be desired to measure the radiation within a particular energy band, or above

Jan 1, 1958

By Cyril Wells, Robert F. Mehl

The purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2o C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made2. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsenl that variations as great as 30' C. exist in the reported data on the A3 temperatures in iron-carbon alloys. Fortunately, the Aa temperature in pure iron is now known to be 910" C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato5 on both hypoeutectoid and hyper-eutectoid steels. Esser made a dilatometric and magnetic study of iron and iron-carbon alloys containing 0.06 to 0.86 per cent C, for which a high purity is claimed. Presumably the electrolytic iron was reasonably pure, but the alloys contained considerable impurities, on the average totaling 0.35 per

Jan 1, 1937

By R. E. Zimmerman, Shiou-Chuan Sun

An evaluation of the mechanism surrounding the froth flotation of coarse coal and mineral particles as a result of experiments conducted at The Pennsylvania State College. Maximum size ranges for both bituminous and anthracite coals were established as well as the factors affecting the floating of coarse particles.

Jan 5, 1950

By W. M. Albrecht, W. D. Klopp, R. I. Jaffee, B. G. Koehl

Kinetic studies were made of the reactions of tantalum with oxygen, nitrogen, and air at 400o to 1500°C. The tantalum-oxygen reaction is linear from 500° to 1250°C. The tantalum-nitrogen reaction follows a cubic rate law at 400° to 700°C and a parabolic rate law at 800" to 1475°C. The reaction behavior in air is initially parabolic followed by a transition to linear behavior. In the search for high-temperature materials, considerable interest is being shown in the refractory metal, tantalum. It is the third highest melting metal with a melting point of 2996°C. Also, tantalum has excellent ductility, making it one of the most workable refractory metals. In considering high-temperature applications of tantalum, the oxidation kinetics of the metal must be known. Such information also serves as a basis for the development of corrosion resistant tantalum-base alloys. Therefore, this study was made to investigate the reaction of tantalum with air, nitrogen, and oxygen. LITERATURE Several oxides of tantalum have been reported. The pentoxide, Taz05, is the only oxide of tantalum whose identity has been established. A high-temperature modification, aTa2Os, has been reported by several investigators.1-4 A low-temperature phase, ßTa2O5, undergoes an allotropic transformation at 1320o to 1350oC. 5-8 Four other oxides of tantalum have been reported. The oxides TaO2, TaO, and Ta4O have been reported by schonberg.9 A suboxide Ta2O, was observed by Wasilewski 6. However, the presence of oxides lower than Ta2O5 is questioned by Lagergren and Magneli.7 In oxidation studies, vermilyeal0 and Peterson, et al.,12 reported one possible phase intermediate between Ta and Ta2O5. Only Ta2O5 was formed in the tantalum air reaction, as reported by Michae1.l3 Several studies have been made on the kinetics of the tantalum-oxygen reaction. vermilyeal4 investigated the range 50° to 300°C and found that the rate of growth of a thin adherent oxide film could be described by the Cabrera-Mott theory. Gulbransen and Andrew15,18 studied the reaction kinetics of tantalum in oxygen pressure of 1/10 atm at 250° to 450°C. At all temperatures the reaction followed the parabolic rate law for periods up to two hours. The oxidation behavior in the range 500" to 1000°C was found to be linear at oxygen pressures of 0.2 to 600 psi according to Peterson. et al.l1 At very low pressures (1 x 10-3 to 2 X lo-' mm of Hg) Gebhardt and seghezzi17 reported linear oxidation at 800° to 1500°C. The reaction of tantalum with air is similar to the reaction with oxygen. Studies have been made by Waber, et a1.,12 and Michae1.l3 Two nitrides of tantalum, TaN and Ta2N are known. Their structures have been determined by Brauer and Zapp 18,19 The tantalum-nitrogen reaction kinetics have been investigated by Gulbransen and Andrews. 15, 16 The reaction follows the parabolic rate law at 500° to 850°C at a nitrogen pressure of 1/10 ,atm. At the same temperature, the tantalum-nitrogen reaction is much slower than the tantalum-oxygen reaction. EXPERIMENTAL TECHNIQUES Material— The material used in this study was high-purity, electron-beam-melted tantalum obtained from the Temescal Metallurgical Corp. The hardness of the as received ingot was 76 Vhn. The analysis of the material is given in Table I. Methods—Cylindrical specimens of tantalum approximately 0.9 cm in diam and 0.5 cm in length

Jan 1, 1962

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 M. E. Wadsworth, T. L. MacKay

Sintered UO, samples were leached in sulfuric acid solutions of various concentrations. A pressurized system was used so that it was possible to investigate the kinetics of the reaction to 270°C with oxygen overpressures as high as 900 psi. The rate was observed to be a function of the concentration of hydrogen ions and directly proportional to the partial pressure of oxygen. Evidences are presented which indicate that a UO2 surface site reacts with a molecule of water to form a hydroxyl complex which in turn can dissociate with the characteristics of a weak acid. A rate determining step has been proposed which involves the reaction between an oxygen molecule and the hydroxyl complex on the surface of UO,. ThE 2 principal methods for uranium dissolution are carbonate and acid leaching. The sulfuric acid leach is the more popular and is used for the treatment of the majority of the ores of Africa, Canada, and the United States. Low recoveries in basic leach circuits led investigators at the University of British columbia1 to study leaching of uranium ores in pressurized vessels. Early in the study of dissolution of uranium it was found that only uranium in the hexava-lent state could be leached in acid or basic circuits. Therefore, the use of oxygen over-pressure in an autoclave offered an interesting approach to solving the low recovery problems of carbonate leaching. UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. A pressurized system was used to provide a means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The mechanism for the dissolution of UO2 should be similar for any of the uraninite type minerals. At the present all of the kinetic studies that have been conducted have been in carbonate media. Peters and Halpern2 carried out a kinetic study of the leaching of pitchblende. Their specimens were pitchblende ores selected on the basis of high grade and homogeneity. Pearson and wadsworth3 conducted a kinetic study of the dissolution of UO2 in carbonate solutions with results very similar to those obtained by Peters and Halpern. EXPERIMENTAL The UO2 as received* was found by spectroscopic *Mallinckrodt reagent, supplied by the Atomic Energy Commission. analysis to have a purity of 99.94 pct 0.03. It was ground in a mechanical agate mortar and screened through a 400-mesh sieve. Thin flat disks of UO2 were prepared by pressing the sized powder in a specially constructed die at a total pressure of approximately 25 tons per sq in. The pressed disks were approximately 0.25 cm thick, 1.6 cm diam, and 3.5 g in weight. As pressed, the samples were approximately 65 pct of theoretical density. It was essential that a binder such as poly-vinyl alcohol be added before pressing to prevent formation of cracks when fired. It was found by trial and error that pressed disks sintered close to 1870°C in a hydrogen atmosphere, reach densities between 91 and 91.5 pct of the theoretical density. At this density the samples had no measurable porosity based upon a 2-hr emersion in boiling water. An X-ray examination of these sintered UO2 disks showed them to be identical with the original UO2 received. Reaction of UO2 with the alundum furnace core was prevented by placing molybdenum between the samples and the core according to the method of Corwin and Eyerly.4 Leaching studies were carried out in a specially designed autoclave, the details of which have been presented e1sewhere.6 The main features of the equipment as applied to a kinetic study are: 1) solution samples may be removed during the course of a single run; and 2) temperature and agitation are carefully controlled. Two-ml samples removed from the autoclave during the course of a run were analyzed for U3O8 content with a Beckman model DK-2 spectrophotometer by the method of

Jan 1, 1959

By A. H. Daane, R. L. Myklebust

The yttrium-manganese system has been investigated by thermal, metallographic, and X-ray diffraction methods. There are three intermetallic compounds present: YMn2 which melts congruently, YMn4, which undergoes syntectic decomposition, and YMn,, which undergoes peritectic decomposition. The compound YMn4 is ferromagnetic at room temperature with a Curie temperature of 214°C. There are eutectics at 25.2, 60.9, and 82.0 wt pct Mn which melt at 878°, 1100°, and 1075°C, respectively. Crys-tallographic data are given for YMn4, and YMn12 . The terminal solid solubilities are low. In a general program of study of yttrium metal in this laboratory some alloy systems of this metal with elements of the first transition period have been examined. This work was originally instigated by experiences in cladding yttrium with jackets of some protective metals such as Inconel for high-temperature service in air.' In some cases a low-melting phase was observed to form between the Inconel and the yttrium resulting in failure of the samples. In characterizing this reaction, a survey was made of the systems of yttrium with chromium, manganese, iron and nickel,, and it was found that a eutectic was formed between these metals and yttrium on the yttrium-rich side of the system. This present study of the Y-Mn system was carried out to examine in more detail the alloying nature of yttrium, and to correlate trends that have been observed in previous related studies. It was observed by Voge13 that in the systems of lanthanum, cerium, and praseodymium with each of the metals in the first transition series, the tendency to form compounds diminished in the order nickel, cobalt, and iron while no compounds were formed with manganese, chromium, or titanium. Beaudry and Daane4 observed a similar behavior in the systems of yttrium with some members of the first transition series except that the tendency for compound formation was greater. Both the Y-Ti5 and Y-Cra systems consist of simple eutectics, while in the Y-Fe,7 Y-CO, and Y-Ni4 systems, there are four, eight, and nine compounds, respectively. In addition to the above trends, the similar atomic radii and electronegativities of yttrium and thorium invite a comparison between their alloying behaviors with a common element such as manganese. In crys- tallographic studies, Florio et al.' have identified three intermediate phases in this system which are ThMn2, Th6Mn23, and ThMn,,. Gschneidner and Waber10 have examined published information on alloy systems of the rare-earth metals and have correlated this information with current alloying theory. From their study, they predicted that the Y-Mn system would contain one intermetallic compound. On the basis of this prediction, the trend in the alloying behavior of yttrium with the elements of the first transition series and the alloying behavior of thorium with manganese, one might expect from one to three intermetallic compounds to form in the Y-Mn system. A consideration of Hume-Rothery's rules of alloying based on size-factor, electronegativity, and valency suggested a small terminal solubility and possible compound formation. The present study was undertaken to confirm these predictions of low terminal solid solubility and compound formation and to establish the general alloying behavior of yttrium with manganese. EXPERIMENTAL Materials. The manganese used in this investigation was obtained from the Foote Mineral Co. as electrolytic plates of 99.9 pct stated purity; the yttrium metal was prepared in this laboratory. Table I gives the analyses of these materials. For the solubility studies at the yttrium-rich end of the alloy system, distilled yttrium, whose major impurity was 200 ppm Ti, was used. Preparation of Alloys. The alloys were formed by comelting the two metals in an are-melting furnace under an atmosphere of argon. The buttons thus formed were inverted and remelted three to five times to promote homogeneity. Due to the high vapor pressure of manganese, it was assumed that the weight lost during are-melting was all manganese. This assumption was based on the very good agreement observed between calculated compositions and chemical analyses of several alloys. The compositions of the dilute alloys used for solid solu-

Jan 1, 1962

By D. C. Hilty, W. Crafts

J. Chipman—It has been my privilege to discuss this work with the authors on several occasions and to observe at first hand the experimental methods employed. I wish, therefore, to emphasize certain points which they have mentioned only briefly with regard to the experimental techniques. The rotating induction furnace as here employed interposes liquid metal between slag and refractory thus preventing the two nonmetallic parts of the system from reaching equilibrium with one another. It is therefore impossible for the metallic phase to be completely in equilibrium with both the slag and the crucible. The metal also acts as a partially permeable membrane allowing certain components, including oxygen, to diffuse from slag to crucible. This transfer results in building up on the face of the crucible a layer of material whose composition is in part dependent on that of the bath. Reactions between the layer and the solid refractory are slow, as evidenced by the rather good life of the crucible. Hence it seems probable that the layer is more nearly in equilibrium with the metal than with the underlying crucible material and that, once it is established under a bath of a given composition, its further reactions with that bath are slow. Additions to slag or bath may be followed by changes in the layer; and time must be allowed for virtual completion of such changes, before it can be assumed that slag and metal are in equilibrium. We may judge from the results reported that, in general, this was the case and that the data represent at least quite close approximations to slag-metal equilibrium. Data on deoxidation and on oxygen solubility are no better than the analytical methods employed. The vacuum fusion method as used by the authors seems entirely adequate for the samples analyzed. I have had frequent occasion to compare results with their laboratory, always with very satisfactory agreement. The determination of aluminum at very low concentrations is perhaps an even more difficult procedure. Here also the colorimetric method used has been worked out with great care and is undoubtedly the most dependable method available. The discrepancy between observed and calculated deoxidation or solubility lines is not to be explained as the result of experimental errors, either in the sampling or analysis of the metal. Nor is it to be blamed upon inaccuracies in the several kinds of indirect data upon which the calculated results were based. It is true that both the observed and the calculated lines admit of some uncertainty as to their exact locations, but the uncertainties are small compared to the wide gap which separates the two lines. The authors have pointed out the real cause of the discrepancy. In all of their experiments the solid phase was not Al2O3 but a mixed oxide containing iron and aluminum. This suggests an extension of the calculated values to include equilibrium with the spinel FeO . A12O3. The free energies of FeO and A12O3 are known, that of the spinel is not. However, it cannot differ greatly from that of its component oxides for even in the more stable spinel, chromite, the free energy of formation from the oxides is less than 10,000 cal. For purposes of calculation we shall call this free energy X and solve for values of X lying between zero and 10,000 cal. The other data required are taken from the forthcoming revision of "Basic Open Hearth Steelmaking" and are given in the following equations in which underlined symbols indicate elements dissolved in liquid steel and the standard concentrations are 1 pct. ?F° at 1600°C, cal ?LA = 2 Al + 3 O; + 107,200 FeO = Fe + 0; + 5,460 FeO + A12O3 = Fe + 2A1 + 4 0; + 112,660 — X The corresponding equilibrium concentrations are shown in fig. 21. The line marked A12O3 corresponds to the first equation, those marked FeO . AL2O3 correspond to the last, with X = 0, 5000 and 10,000 cal, respectively. The two upper lines represent the data of Hilty and Crafts and of Wentrup and Hieber. The points are the observations of Hilty and Crafts in the presence of 0.50 pct Mn.

Jan 1, 1951

By J. D. A. Morrow

TO my mind the National Bituminous Coal Act so far has proved one of the unhappiest experiences that has ever befallen the bituminous coal operators of the United States. Viewed in the light of its ugly consequences everyone should recognize this measure for what it is -a weird thing as unreal as a page from "Alice in Wonderland." Indeed it might be another stanza to the tale of the Walrus and the Carpenter, with the coal operators in the role of the unfortunate oysters who were taken on that memorable ramble. It is time that coal producers open their eyes, jerk themselves out of any lingering hypnotic optimism about the price-fixing provisions of this law, demand the repeal of these corroding clauses, and then set about remedying as best they can the disastrous effects of this retromingent scheme to regulate the coal business.

Jan 1, 1939

By R. J. S. Brown, B. W. Ganison

A new logging method has been developed, based on measurement of the nuclear magnetism of formation fluids. The nuclear magnetism log (NML) is the only log that responds solely to formation fluids. It operates equally well in both oil-base and water-base muds and in empty holes, and can be used in all kinds of formations except strongly magnetic ones. Two separate NML measurements can be made, one of which provides a continuous formation fluid curve. This fluid curve is called the free fluid log (FFL) and is believed to indicate a minimum effective porosity in most formations. The FFL not only delineates fluid-containing zones, but provides an excellent correlation curve that can be obtained under conditions where conventional correlation logs are ineffective. Preliminary tests indicate that the second kind of NML measurement may help distinguish oil and water zones and provide information concerning permeability and wettability. (The FFL itself appears to provide some information on permeability.) The second kind of NML measurement requires stopping the logging tool for a short time opposite a zone of interest and taking more extensive NML data that can be displayed as nuclear magnetic relaxation curves. In some instances, oil and water saturations for the region immediately adjacent to the borehole can be read from these relaxation curves. INTRODUCTION In 1946, Bloch, Hansen and Packard and Purcell, Torrey and Pound3 independently announced the successful demonstration of the phenomenon of nuclear magnetic resonance. During the past 13 years, there have been many applications of nuclear magnetic resonance, including applications to the study of chemical structure and to the measurement of magnetic field strengths. Preliminary experiments on the feasibility of using nuclear magnetism measurements in well logging were made independently by California Research Corp. and Varian Assoc., the Varian work being sponsored by the Byron Jackson Tools, Inc. Since then a cooperative research program on nuclear magnetism logging has been carried out by the Byron Jackson Div. and Research Center of Borg-Warner Corp., and California Research Corp., subsidiary of Standard Oil Co. of California. The use of nuclear magnetism in well logging is of special interest because it offers a way of making direct measurements on the hydrogen in the formation fluids and not on the rock matrix. Within the past 1 1/2 years, successful measurements have been made with a research model logging tool in wells in California, Tex as, Utah, Louisiana and Wyoming. NUCLEAR MAGNETISM SIGNALS Polarization, Relaxation and Precession Many atomic nuclei possess magnetic moments and spins; that is, they are similar in some respects to bar-magnet and gyroscope combinations. Molecules and their nuclei are subject to thermal motion, which has a scrambling effect, tending to leave as many nuclear spins oriented in any one direction as in any other. However, if a magnetic field is applied, the magnetic nuclei tend to align in the direction of the field. The scrambling and aligning forces compete with each other, with the result that a few more spins are oriented parallel to the field than in other directions. This gives a net magnetization, or polarization, which is directly proportional to the strength of the applied magnetic field (aligning influence) and inversely proportional to the absolute temperature (scrambling influence). When the magnetic field in, or temperature of, a liquid sample containing protons is changed, the new equilibrium value of proton polarization is not established immediately but requires an amount of time which depends on the nature of the hydrogen-containing materials. The process of approaching the equilibrium value of polarization is called relaxation.'.' Polarization is a vector quantity, and the components parallel to and perpendicular to the magnetic field must be considered separately. Relaxation of the component parallel to the field is called "thermal relaxation", or "longitudinal relaxation", and the corresponding time for this component of non-equilibrium polarization to decay by a factor of e (natural log base) is denoted T. The relaxation of the perpendicular component is called "transverse relaxation", and the corresponding relaxation time is denoted T,. The potential energy of a magnet in a uniform field depends on the angle the magnet makes with the field; therefore, a change of the component of net polarization parallel to the magnetic field involves an exchange of energy between the spin system and the thermal motion of the molecules, leading to the term thermal relaxation for the relaxation of this component. Suppose we subject a sample to a strong magnetic field at right angles to the earth's field for a time greater than TI. A polarization, thus, is established at right an-

By Frank J. Anderson

IN the cement region of the Lehigh Valley, a difference of 2 to 3 pct in CaCO3 can make or break a new quarry development, and experience of the Dragon Cement Co. has shown that values of calcium carbonate, as reported from churn drill samples, have been increased as much as 6 pct on the average when the same area was diamond drilled. This calcium carbonate increase consequently lowered the values for silica, iron, and alumina, and made these sections much more attractive. Since 1950, the Dragon Cement Co. Inc. has been engaged in extensive diamond drilling in the local limestone of the Northampton, Pa., region, known as the Jacksonburg formation, and in the Lebanon, Pa., region in the Annville limestone, both of Ordovician age.

Jan 12, 1954

By B. C. Woodfine

WHEREAS it is generally assumed that the highest temperature at which temper brittle-ness takes place is about 625°C, 1,2,3 Jaffe, Buffum, and coworkers have referred in several recent papers45,6,7 to the occurrence of temper brittleness in an SAE 3140 steel at 650" and 675°C. Their re- sults show that a considerable increase in transition

Jan 1, 1955

By S. J. Im

Bupyung Silver Mines daily treats average 14 tons of concentrates containing 9,000 g Ag per ton. Bupyung Silver Refinery uses Merrill Crowe process to recover the silver from the leach solution containing 1.0 g/l Ag; Series of experiments were carried out to recover the silver from the solution by means of direct electrowinning in place of Merrill Crowe process. The recovery of the silver was 99% when the cell voltage and the retention time were 1.9 v and 3.0 hours, respectively. Power consumption was 3.2 Kwh/kg of Ag. It was found that impurity buildup was not significant during the recycling. The direct operating cost for the electrowinning was evaluated to be $ 0.35/kg of Ag.

Jan 1, 1984

By H. M. Conger

Kaiser Steel Corporation's Eagle Mountain mine is located in the Colorado Desert, 60 miles east of Indio, California. Iron concentrates from the mine are shipped by rail 164 miles to the' Company's steel mill at Fontana, and also to Longbeach, California for export. Temperatures are typical of the lower desert ranging from a high of 120 degrees in the summer to a low of 25 degrees in the winter. The average, annual rainfall of about two inches comes mainly as cloudbursts during the summer months. From its inception, the Eagle Mountain mine has had the problem: of breaking its mine rock. Practices followed from 1949 until 1962 were very costly, did not produce uniformly good fragmentation, and were incapable of sustaining, high production. During this period, every conventional type of explosive was tried and found to be unsatisfactory for one reason or another.

Jan 11, 1965

By A. Steiner, E. Miller, K. L. Komarek

Equations have been derived to calculate the chemical potentials of the components of liquid binary alloys from liquidus and enthalpy data. The equations are applicable to systems with intermetal-lic compounds of limited solid solubility. The liquidus curve of the Mg-Sn system was accurately redetermined, and the melting point of the compound Mg2Sn was found to be 770.5° * 0.3°C. The thermo-dynamic properties of the liquid alloys were calcu -lated from the liquidus data. The activity of tin shows both positive and negative deviations from Raoult&apos;s law and the relative integral entropy is positive. THE phase boundaries in an equilibrium phase diagram are functions of the thermodynamic properties of the coexisting phases. Specifically, the shape of the liquidus curve near an intermediate compound is determined by the properties of the compound and the liquid phase. Hauffe and wagnerl have derived an equation for the chemical potential differences (ui) of the liquid alloys near the congruent melting point when the heat of fusion of the compound and the liquidus curve are known. In their derivation the temperature dependence of the ui value was neglected, and liquid of stoichio-metric composition was chosen as the reference state. To obtain chemical potentials over the ntire composition range of the phase diagram with the pure components as the reference state, equations have been derived which incorporate the temperature dependence of the chemical potentials. Such a thermodynamic analysis can be carried out when the liquidus curve and the enthalpy values are known. The equations have been applied to the redetermined liquidus curve of the Mg-Sn system to obtain the thermodynamic properties of liquid Mg-Sn alloys. The Mg-Sn phase diagram has been studied by various investigators and the results have been compiled and critically assessed by Hansen.2 Preliminary thermal analyses showed that the basic features of the diagram were correct. The system has one congruent melting compound, Mg2Sn, two eutectics, and some solid solubility of tin in magnesium. However, the published liquidus temperatures show considerable scatter. In order to perform an accurate thermodynamic analysis, the liquidus curve between the magnesium-rich and tin-rich eutectic compositions was therefore redetermined by careful thermal analysis using highest-purity starting materials. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd, Toronto, Canada) had a purity of 99.99+ pct with the following impurities (in ppm): 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu, <10 Fe; tin (Cominco Products, Spokane, Wash.) contained 99.999+ pct Sn. The graphite crucibles were machined from graphite rods (United Carbon Products Corp., Bay City, Mich.) which had an average total ash content of less than 30 ppm. All the graphite parts were baked out in vacuum at 950" to 1000°C for a minimum of 24 hr to remove volatile organic materials. The graphite crucibles (3 in. long, 1-5/8 in. OD, 1-3/8 in. ID) were tightly closed with a threaded cover (1/2 in. thick) which had a central thermocouple well (2-1/4 in. long, 5/16 in. OD, 3/16 in. ID). Cover and thermocouple well were machined from one piece of graphite. A thin sheath of quartz was inserted in the well to protect the thermocouple

Jan 1, 1964

By Martin A. Mayers

Five-sixths of all the coal that is mined in the United States is burned, without previous treatment other than screening, for the production of heat and power, so that its value is fixed by its suitability for this purpose. Nevertheless, the characteristics of individual coals that determine their fitness for use in particular pieces of combustion equipment are not yet well known. This condition is due not only to the small extent of our knowledge concerning coal itself, but also to our comparative ignorance of the nature of the combustion process. The following paper is an analysis of the combustion process as it occurs in industrial furnaces, based largely on the results of laboratory research on combustion rates. From this analysis it is possible to determine the characteristics of the fuel that limit the capacity of a given piece of combustion equipment. Limitations imposed by other factors than the attainable speed of combustion will not be considered, since they are subject to a different type of analysis involving the balancing of maintenance costs against fixed charges. In order to observe the relations among the various factors that affect the speed of combustion, representative particles of fuel will be followed through two types of furnaces. A pulverized-coal furnace will be considered first, because the independence of the individual particles facilitates the analysis of the effect of furnace conditions. The second example will be a grate-fired furnace in which ignition of the fuel takes place on the underfeed principle. This includes both underfeed and chain grate stokers, (8)† but does not include hand-fired furnaces and some overfeed stokers. The furnace will be considered to be large enough, the temperature high enough, and enough air provided, to burn the fuel completely, without, for the moment, specifying these quantities more completely. Furnaces Burning Pulverized Coal In a pulverized-coal furnace, the fuel particle is carried, in a stream of air, into the furnace, where it is subjected to radiation from the flame and from the hot walls of the furnace. The increase of particle tempera-

Jan 1, 1936

By H. W. Page

Petroleum requirements since V-J day have been appreciably higher than predicted. Foreign operations now exceed maximum wartime levels by about 14 per cent. Domestic operations since V-J day have averaged 92 Per cent of the wartime peak. In spite of maximum foreign refinery runs, large exports of all products, except residual fuel oil, are necessary to meet foreign demand. During the next few years it is expected that foreign operations will continue at capacity, including new installations, but that, because of increases in foreign demand, exports will continue at about their present level. Domestic operations will increase during this period and crude production probably will exceed maximum efficient rates. Even after 10 years some exports probably will be required, but eventually these will be supplanted by increased output of foreign refineries, except for small tributary exports. The increase in domestic requirements will exceed the decline in exports. Unless findings of crude oil exceed present expectations, the increasing demand will be met by increased imports and synthetic methods-—such as the Hydrocarbon Synthesis Process for conversion of natural gas and coal to gasoline and distillates. Catalytic cracking installations will increase as crude availability decreases. This will help to meet the increasing demand for gasoline but will intensify the domestic shortage of residual fuel oil. Eventually larger imports will be required to satisfy the demand for this product. Introduction Under the pressure of the wartime period, there was time only occasionaly to look ahead in anticipation of what the postwar era held for the petroleum industry. Perhaps the general expectation was that a rather pronounced decline in the level of industry petroleum operations would take place shortly after the end of the war, with the impact felt mainly on the economy of the United States- It is of interest now, nine months after V-J day, to take inventory of the near-term situation and see what significant forces are at work. With this as a starting point, it should be possible to engage in something more satisfactory than pure speculation concerning trends in the immediate future and 10 to 20 years ahead. Present and Near-term Situation During the nine-month period following V-J day, foreign crude oil production and rebery operations have actually increased the These activities were at maximum capacity on V-J day but the continuation of drilling programs, the completion of new and rehabilitated refineries and of transportation facilities during the Past nine months have increased the foreign capacity. This added capacity has been fully utilized. Foreign crude oil production in May 1946 is about 14 per cent higher than during July 1945 and refining operations some 12 per cent higher&apos; During the same period there has been a falling off in similar activities within the

Jan 1, 1947

By Martin A. Mayers

Five-sixths of all the coal that is mined in the United States is burned, without previous treatment other than screening, for the production of heat and power, so that its value is fixed by its suitability for this purpose. Nevertheless, the characteristics of individual coals that determine their fitness for use in particular pieces of combustion equipment are not yet well known. This condition is due not only to the small extent of our knowledge concerning coal itself, but also to our comparative ignorance of the nature of the combustion process. The following paper is an analysis of the combustion process as it occurs in industrial furnaces, based largely on the results of laboratory research on combustion rates. From this analysis it is possible to determine the characteristics of the fuel that limit the capacity of a given piece of combustion equipment. Limitations imposed by other factors than the attainable speed of combustion will not be considered, since they are subject to a different type of analysis involving the balancing of maintenance costs against fixed charges. In order to observe the relations among the various factors that affect the speed of combustion, representative particles of fuel will be followed through two types of furnaces. A pulverized-coal furnace will be considered first, because the independence of the individual particles facilitates the analysis of the effect of furnace conditions. The second example will be a grate-fired furnace in which ignition of the fuel takes place on the underfeed principle. This includes both underfeed and chain grate stokers, (8)† but does not include hand-fired furnaces and some overfeed stokers. The furnace will be considered to be large enough, the temperature high enough, and enough air provided, to burn the fuel completely, without, for the moment, specifying these quantities more completely. Furnaces Burning Pulverized Coal In a pulverized-coal furnace, the fuel particle is carried, in a stream of air, into the furnace, where it is subjected to radiation from the flame and from the hot walls of the furnace. The increase of particle tempera-

Jan 1, 1936

By H. W. Page

Petroleum requirements since V-J day have been appreciably higher than predicted. Foreign operations now exceed maximum wartime levels by about 14 per cent. Domestic operations since V-J day have averaged 92 Per cent of the wartime peak. In spite of maximum foreign refinery runs, large exports of all products, except residual fuel oil, are necessary to meet foreign demand. During the next few years it is expected that foreign operations will continue at capacity, including new installations, but that, because of increases in foreign demand, exports will continue at about their present level. Domestic operations will increase during this period and crude production probably will exceed maximum efficient rates. Even after 10 years some exports probably will be required, but eventually these will be supplanted by increased output of foreign refineries, except for small tributary exports. The increase in domestic requirements will exceed the decline in exports. Unless findings of crude oil exceed present expectations, the increasing demand will be met by increased imports and synthetic methods-—such as the Hydrocarbon Synthesis Process for conversion of natural gas and coal to gasoline and distillates. Catalytic cracking installations will increase as crude availability decreases. This will help to meet the increasing demand for gasoline but will intensify the domestic shortage of residual fuel oil. Eventually larger imports will be required to satisfy the demand for this product. Introduction Under the pressure of the wartime period, there was time only occasionaly to look ahead in anticipation of what the postwar era held for the petroleum industry. Perhaps the general expectation was that a rather pronounced decline in the level of industry petroleum operations would take place shortly after the end of the war, with the impact felt mainly on the economy of the United States- It is of interest now, nine months after V-J day, to take inventory of the near-term situation and see what significant forces are at work. With this as a starting point, it should be possible to engage in something more satisfactory than pure speculation concerning trends in the immediate future and 10 to 20 years ahead. Present and Near-term Situation During the nine-month period following V-J day, foreign crude oil production and rebery operations have actually increased the These activities were at maximum capacity on V-J day but the continuation of drilling programs, the completion of new and rehabilitated refineries and of transportation facilities during the Past nine months have increased the foreign capacity. This added capacity has been fully utilized. Foreign crude oil production in May 1946 is about 14 per cent higher than during July 1945 and refining operations some 12 per cent higher&apos; During the same period there has been a falling off in similar activities within the

Jan 1, 1947