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By E. A. Kaarsberg

The electron photomicrographs shown in this paper are of samples of the A.P.I. Reference Clay Minerals Montmorillonite No. 27 and Kaolinite No. 4 and of a shale from Spraberry Oilfield in Texas. These samples are part of a larger collection whose physical properties, composition and internal structure were previously studied by ultra-sonic and X-ray methods. ' Elastic anistropy was indicated in the montmorillonite and shale samples by sound velocity measurements parallel and perpendicular to the bedding. In the montmorillonite the velocities parallel and perpendicular to the bedding were 2.12 and 1.92 km/sec respectively, a difference of about 11%; in the shale the same velocity measurements were 4.18 and 3.75 km/sec, a difference again of about 11%. Within the bedding plane the sound velocity was also found to be independent of direction. The electron photomicrographs of the montmorillonite sample, which are shown in Fig. l(a) and (b), clearly indicate the preferred orientation of the mica-like clay particles parallel to the bedding. In Fig. 2(a) and (b) similar orientation in the shale sample can be seen although not quite as clearly. This is probably because, in addition to the clays illite and chlorite, the shale sample contains grains of quartz, calcite and dolomite which do not as readily show an alignment pattern as the clays do. This suggests that the elastic anisotropy of these two samples is derived from a preferred alignment of component mineral grains which are themselves elastically anisotropic. The bulk elastic properties of these two samples therefore appear to be much like those of mica. Velocity measurements were made on the kaolinite sample in three directions at right angles because no bedding could be discerned in it. The values ob-

Jan 1, 1967

By Franklin H. Wilson

COPPER base alloys containing various amounts of aluminum and silicon are of considerable commercial interest. In particular the alloy containing 7 pct aluminum and 2 pct silicon shows an attractive combination of high strength with excellent machinability. Since there is no evidence in the literature that this ternary system has been studied since the recognition by Smith1 and Anderson2 in 1939 of the kappa phase of the binary copper-silicon system, the determination of the equilibrium phase relationships in the copper corner of the ternary diagram has been undertaken to provide a fundamental basis for understanding the behavior of these alloys. Phase boundaries have been determined by the micrographic examination of quenched samples while points on the liquidus surface have been obtained by thermal analysis. The results, of sufficient precision to serve their major purpose of providing a guide for the control of the manufacture of alloys in the region covered, are presented in a series of both isothermal and vertical sections of the diagram. ALLOYS STUDIED For a rough survey of the copper corner of this ternary system the compositions listed in Table I (Series A) were employed. The results of examinations of these alloys indicated that the compositions listed in Table 2 (Series B) would further clarify regions of greater complexity. All alloys were prepared as 1200 g heats, the copper being melted under charcoal, and then first silicon and then aluminum were added. An [ ] excess of 0.05 pct silicon was allowed to cover deoxidation losses. Two small bars 5/8 by 1 ¼ by 1 ¼ in. were cast using Durville type casting equipment. Analyses were made on all alloys using material which was hot-rolled at 800 or 850°C and annealed 17 hr at 650°C. All analyses were found to be within 0.05 pct of the nominal composition. Since the precision of analysis is not much better than this, the points of both isothermal sections and vertical sections at fixed aluminum and silicon contents have been plotted at the compositions indicated by the nominal composition.

Jan 1, 1948

By W. C. Winegard, W. J. Bratina

Internal friction characteristics and temperature dependence of the torsion modulus for iodide zirconium containing 2.4 pct Hf were investigated, using a low frequency pendulum technique. The internal friction curve consists of a background which increases as the temperature increases, a maximum at 860°C apparently a background due to the al-lotropic transformation, a maximum due to grain boundary relaxation with an associated heat of activation of 58,000 cal per mol, and an anomaly below 350°C which may be associated with a precipitation perphenomenon, Oxygen in below small amounts reduces the grain boundary maximum substantially. The variation of the torsion modulus at 20°C was found to be 3450 Kg per mm2 for the zirconium used in the present work. IT is well known that small amounts of certain solutes materially affect the ductility of zirconium. Lely and Hamburger,&apos; as early as 1914, found that high purity zirconium exhibited a remarkable ductility, while Fast&apos; has shown that oxygen and nitrogen can cause substantia1 embrittlement. Treco" has recently demonstrated that the ductility decreases sharply with the oxygen content, and that 2 atomic pct O2 embrittles zirconium to such an extent that cold working is impossible. The marked decrease in ductility is difficult to understand in view of the fact that Domagala and McPherson4 report the solid solubility of oxygen in zirconium to be 29 atomic pct at 500 °C. Another metal which behaves much the same as zirconium in this respect is titanium. Pratt et al." investigated the internal friction characteristics of titanium and the effect of oxygen on the internal friction values. It is evident that internal friction measurements are of value for studying grain boundary segregation, as shown by Pratt et al. for oxygen in titanium, by Pearson for oxygen in copper, and by Maringer and Schwope for oxygen in molybdenum. With this in view, the internal friction characteristics of zirconium and the qualitative effect of oxygen on the grain boundary relaxation phenomenon were investigated. Materials and Experimental Procedure The zirconium used in the present work was supplied by the Foote Mineral Co. in the form of wire 0.05 in. diam. The analysis supplied by the manufacturer indicates the amount of hafnium as 2.4 pct, less than 0.01 pct O less than 0.01 pct N,, less than 0.02 pct H,, and less than 0.001 pct C. Additional spectro-graphic analysis indicates the other main impurities as follows: 0.01 pct Fe, 0.05 pct Si, 0.008 pct Cu, <0.005 pct W, <0.001 pct Al, <0.05 pct Mg, <0.001 pct Ni, <0.02 pct Ca, and <0.01 pct Ti. Microscopic examination of the material in the as received condition revealed very fine grains with numerous twins. Specimens were annealed either in situ in the internal friction apparatus or in evacuated silica tubes in an auxiliary furnace. When the specimens were annealed in the auxiliary furnace, they were wrapped in identical zirconium wire to prevent contamination by the container. Metallographic sections were taken in all cases. Some were taken from the specimens used for internal friction measurements after completion of the experiments, while others were taken from control specimens at intermediate stages of the experiments. lnternal friction values were obtained by measuring the free decay of a low frequency torsion pendulum (1 cycle per sec), the suspension of which was

Jan 1, 1957

By C. G. Bieber, R. F. Decker

The effects of minor constituents on the malleability of nickel alloys are described. These effects are related to the atomic diameter, valence, and position on the Periodic Table. The basic methods for removal or neutralization of deleterious elements are then reviewed. Finally, practical methods for melting nickel alloys are described in detail and related to minor constituent control. L HE first malleable nickel was produced by Fleit-man in about 1870 by the addition of manganese and magnesium to the molten metal to counteract the harmful effects of sulfur. Merica and Waltenbergl explained the mechanism by which these elements accomplished the desired result. They showed that sulfur in concentrations in excess of about 0.005 pct produced films of a brittle low melting eutectic of nickel-nickel sulfide which completely surrounded the grains. When manganese was added to molten nickel it reacted with the sulfur to form manganese sulfide which precipitated as widely scattered globules in the grain boundaries. The further addition of small amounts of magnesium converted the sulfur to a very stable sulfide of magnesium which was relatively insoluble in both the liauid and solid states and therefore occurred as finely divided particles within the grains where it had relatively little detrimental effect upon the malleability of nickel or its alloys. The practice of treating nickel with manganese and magnesium came to be called "deoxidation" and was employed without appreciable modification for the commercial production of wrought nickel and high nickel alloys (in this paper—50 pct or more nickel) until about 1930 even though the results were never entirely satisfactory. At that time a more extensive study was made of the effects of minor constituents on malleability and metallurgical quality. The results, small portions of which have been published,2-4 are presented here with other pertinent data. EFFECTS OF MINOR CONSTITUENTS UPON NICKEL Systematic additions were made of 0.5 pct or less of each of most of the elements of the periodic ta- ble. It was established in this study that some minor constituents other than manganese and magnesium were extremely influential. The malleability, as evaluated by the reduction of area in tension tests, depended roughly on temperature as shown in Fig. 1. Four temperature zones are of interest; the cold malleable zone (up to about 1000° F), the red short zone from roughly 1000° to 1500&apos; F, the hot malleable zone around 2000° F and the incipient melting zone. Most of the malleability problems are associated with the red short zone and the discussion will concern this mainly. The reduction of area in normal tensile tests on high-purity nickel (see curve A of Fig. 1) appeared to have no

Jan 1, 1962

By J. F. Butler

Boron nitride, BN, has been identified in boron low-carbon steels by means of light microscopy, electron microscopy and diffraction, and chemical analysis. This boron nitride is responsible for strain aging suppression in these steels through the removal of nitrogen from solution; however, small oxidizing potentials which result in deboronization In the austenitic temperature range also result in boron nitride decomposition and the subsequent occurrence of nitrogen strain aging. THE addition of boron to low-carbon steels is an effective means of eliminating the detrimental effects of strain aging;&apos;,&apos; however, the mechanism by which boron suppresses strain aging has not been established. In studying the effect of heat treatment on the strain aging of boron low-carbon steels, Butler3 found that no detectable nitrogen was present in the ferrite solid solution after various heat treatments even though the total nitrogen analyses of the steels were 0.003 pct N. Apparently the function of boron in suppressing strain aging is the removal of nitrogen from solution to form a relatively stable second phase. A clue to the identity of this phase was found by Speight4 who extracted from an aluminum-killed boron steel an acid insoluble residue which contained boron and nitrogen in proportions corresponding to the compound, BN. Shyne and Morgan5 found that the addition of nitrogen to a hardenable boron steel lowered its hardenability in a manner which suggest-d the presence of nucleating particles (presumably BN) even at high austenitizing temperatures. Although this indirect evidence for the presence of boron nitride in boron steels has been found, the compound was not identified metallographically as a separate phase in these steels. Because boron has an affinity for oxygen comparable to that of silicon,5 boron steels must be thoroughly killed with aluminum in order to prevent the reaction of boron with oxygen.7 The affinity of boron for oxygen also is demonstrated through the ease of deboronization of a boron steel in an oxidizing atmosphere. Digges, Irish, and Carwile8 found that a mixture of wet natural gas and air caused both deboronixation and decarburization of a boron steel at 1900°F. The boron content rose at the surface of the steel due to the formation of boron oxide. Shyne and Morgan9 encountered deboronization at much lower oxygen potentials; loss of boron occurred in steels treated at 1750o F under argon purified to 0.0014 pct 0, even though decarburization did not occur. Boron oxide, B2O3, is much more stable than the nitride, BN, as is indicated by the standard free energies of formation at 980oC: -235 kcal per mol of B2O3 (liquid) and -28 kcal per mol of BN (crystal). It is evident that the oxygen potential must be kept low in the presence of BN in order to prevent its decomposition and the subsequent formation of B2O3&apos; The purpose of the work described in this paper was to identify the nitride phase responsible for the removal of nitrogen from solution and to study its stability under oxidizing conditions. IDENTIFICATION OF BN In order to identify the phase containing boron and nitrogen, several alloys high in boron and nitrogen were made up in a small vacuum furnace. In alloys 3 and 4, Table I, electrolytic iron was used as a charge material. Boron additions were made in the form of 18 pct B ferro-boron after the iron was molten. In the case of alloy 3, the charge was solidified at this point; for alloy 4, nitrogen at 1 atm pressure was admitted over the melt before it was

Jan 1, 1962

By Francis Collins, E. R. Brownscombe

A study has been made of the material balance-fluid flow method of estimating reserves and degree of water drive from pressure and production history data. By considering the effect of random pressure errors it is shown that in a particular example a standard deviation of three and one-half pounds in each of ten pressure survey? permits the determination of the reserves with a standard deviation of 8 per cent and the water drive with a standard deviation of 15 per cent, assuming that certain basic geologic data are correct. It is believed that this method of estimating reserves and water drive is useful and reliable in a number of cases. The method is particularly valuable when reservoir pressure data are accurate within a very few pounds, but may also be applied with less accurate pressure data if a relatively large reservoir pressure decline occurs early in the life of the field, as for example in an under-saturated oil field. INTRODUCTION A knowledge of the magnitude of reserves and degree of water drive present in any newly discovered petroleum reservoir is necessary to early application of proper production practices. A number of investigators have contributed to methods of relating reserves, degree of water drive, and production and pressure history. 1-8 Three types of problems of increasing complexity may be mentioned. If a reservoir is known to have no water drive. and if the ratio of the volume of the reservoir occupied by gas to the volume of the reservoir occupied by oil (which ratio permits fixing the overall compressibility of the reservoir) is known, then only one further extensive reservoir property remains to be determined, namely the magnitude of the reserves. A straightforward application of material balance considerations will permit this determination. The problem becomes very much more difficult if we wish to determine not only the magnitude of the reserves but also the magnitude of water drive, if any, which is present. In principle, a combination of material balance and fluid flow considerations will permit this evaluation. Finally, if neither the magnitude of reserves, the degree of water drive, nor the ratio of oil to gas present in the reservoir is known and it is desired to determine all three of these variables, the problem could in principle be solved by a fluid flow-material balance analysis which determines the overall compressibility of the reservoir at various points in its history. The change in compressibility with pressure would provide a means of determining the ratio of gas to liquid present, since the compressibilities of gas and liquid vary differently with pressure variation. However, in practice this problem is probably so difficult as to defy solution in terms of basic data precision apt to be available.&apos; It is the purpose of this discussion to illustrate the second case, which involves the determination of two unknown variables, single phase reserves and degree of water drive, from pressure and production history and fluid property data, and to study the precision with which these unknowns can be determined in this manner in a particular case. Although an electric analyzer developed by Bruce as used in making the calculations to be described, numerical methods necessary in carrying out the process have been devised and have been applied for this purpose. Schilthuis,&apos; for example, developed a comprehensive equation for the material balance in a reservoir. He combined this with a simplified water drive equation, assuming that the ratio of free gas to oil was fixed by geological data and that a period of constant pressure operation at constant rate of production was available to determine the constant for his water drive equation. On this basis he was able to compute the reserves and predict the future pressure history of the reservoir. Hurst developed a generalized equation permitting the calculation of the water drive by unsteady state expansion from a finite aquifer. He showed in a specific case how the water influx calculated by his equation, using basic geologic and reservoir data to fix the constants, matched the water influx required by material balance considerations. Old3 illustrated the simultaneous use of Schilthuis&apos; material balance equation and Hurst&apos;s fluid flow equation for the determination of the magnitude of reserves and a water drive parameter from pressure and production history. He used this method to calculate the future pressure history of the reservoir under assumed operating conditions. As a basis for determining reserves, Old assumed a value for his water drive parameter and calculated a set of values for the reserves, using the initial reservoir pressure and each successive measured pressure. The sum of the absolute values of the deviations of the resulting reserve numbers from their mean value was taken as a criterion of the closeness of fit to the experimental data possible with the water drive parameter assumed. New values of the water drive parameter were then assumed and new sets of the reserves calculated until a set of reserves numbers having a minimum deviation from the average was established. The average value of- the re-

Jan 1, 1949

By E. R. Brownscombe, Francis Collins

A study has been made of the material balance-fluid flow method of estimating reserves and degree of water drive from pressure and production history data. By considering the effect of random pressure errors it is shown that in a particular example a standard deviation of three and one-half pounds in each of ten pressure survey? permits the determination of the reserves with a standard deviation of 8 per cent and the water drive with a standard deviation of 15 per cent, assuming that certain basic geologic data are correct. It is believed that this method of estimating reserves and water drive is useful and reliable in a number of cases. The method is particularly valuable when reservoir pressure data are accurate within a very few pounds, but may also be applied with less accurate pressure data if a relatively large reservoir pressure decline occurs early in the life of the field, as for example in an under-saturated oil field. INTRODUCTION A knowledge of the magnitude of reserves and degree of water drive present in any newly discovered petroleum reservoir is necessary to early application of proper production practices. A number of investigators have contributed to methods of relating reserves, degree of water drive, and production and pressure history. 1-8 Three types of problems of increasing complexity may be mentioned. If a reservoir is known to have no water drive. and if the ratio of the volume of the reservoir occupied by gas to the volume of the reservoir occupied by oil (which ratio permits fixing the overall compressibility of the reservoir) is known, then only one further extensive reservoir property remains to be determined, namely the magnitude of the reserves. A straightforward application of material balance considerations will permit this determination. The problem becomes very much more difficult if we wish to determine not only the magnitude of the reserves but also the magnitude of water drive, if any, which is present. In principle, a combination of material balance and fluid flow considerations will permit this evaluation. Finally, if neither the magnitude of reserves, the degree of water drive, nor the ratio of oil to gas present in the reservoir is known and it is desired to determine all three of these variables, the problem could in principle be solved by a fluid flow-material balance analysis which determines the overall compressibility of the reservoir at various points in its history. The change in compressibility with pressure would provide a means of determining the ratio of gas to liquid present, since the compressibilities of gas and liquid vary differently with pressure variation. However, in practice this problem is probably so difficult as to defy solution in terms of basic data precision apt to be available.&apos; It is the purpose of this discussion to illustrate the second case, which involves the determination of two unknown variables, single phase reserves and degree of water drive, from pressure and production history and fluid property data, and to study the precision with which these unknowns can be determined in this manner in a particular case. Although an electric analyzer developed by Bruce as used in making the calculations to be described, numerical methods necessary in carrying out the process have been devised and have been applied for this purpose. Schilthuis,&apos; for example, developed a comprehensive equation for the material balance in a reservoir. He combined this with a simplified water drive equation, assuming that the ratio of free gas to oil was fixed by geological data and that a period of constant pressure operation at constant rate of production was available to determine the constant for his water drive equation. On this basis he was able to compute the reserves and predict the future pressure history of the reservoir. Hurst developed a generalized equation permitting the calculation of the water drive by unsteady state expansion from a finite aquifer. He showed in a specific case how the water influx calculated by his equation, using basic geologic and reservoir data to fix the constants, matched the water influx required by material balance considerations. Old3 illustrated the simultaneous use of Schilthuis&apos; material balance equation and Hurst&apos;s fluid flow equation for the determination of the magnitude of reserves and a water drive parameter from pressure and production history. He used this method to calculate the future pressure history of the reservoir under assumed operating conditions. As a basis for determining reserves, Old assumed a value for his water drive parameter and calculated a set of values for the reserves, using the initial reservoir pressure and each successive measured pressure. The sum of the absolute values of the deviations of the resulting reserve numbers from their mean value was taken as a criterion of the closeness of fit to the experimental data possible with the water drive parameter assumed. New values of the water drive parameter were then assumed and new sets of the reserves calculated until a set of reserves numbers having a minimum deviation from the average was established. The average value of- the re-

Jan 1, 1949

By J. E. Hanafee, G. J. London

MANY studies of the deformation behavior of materials under a superimposed hydrostatic pressure have shown that materials brittle at ambient pressure behave in a ductile manner under pressure. Thus, with a metal such as beryllium which possesses relatively low ductility, but otherwise exhibits quite useful physical and mechanical properties, hydrostatic pressure may be particularly useful for both forming beryllium shapes and studying its deformation behavior. In fact, it has been found1"4 that polycrystal-line beryllium in both ingot and powder form appears to behave in a more ductile manner on a macroscopic level in a hydrostatic pressure environment, and it has been suggested2 that this is due to activating a new slip mode. Furthermore, Andrews and Radcliffe5 have found pressure induced nonbasal dislocation activity in hot pressed beryllium. Recently6 it has been shown in "c-axis" compression tests under hydro-static pressures up to 28 kbars that the shear stress needed to cause slip with a Burgers vector out of the basal plane (pyramidal slip) does not change with increasing pressure in beryllium with a purity of some 99.5 pct. This material is equivalent or more pure than the beryllium used in the previous pressure studies. Thus, it appears, as suggested by Inoue et al.,3 that the hydrostatic pressure affects the fracture stress rather than the stress necessary to activate pyramidal slip in beryllium. However, in "c-axis" pressure tests on high purity 12 zone pass beryllium (˜50 ppm total impurities) the macroscopic compression stress needed to cause pyramidal slip was considerably lower than that at ambient pressure.6 It has further been shown that alloying beryllium with nickel and copper in the range 2-5 wt pct also favors the occurrence of pyramidal slip in "c-axis" compression tests,7&apos;8 while lower amounts of nickel and copper do not have significant effects. In the present study the combined effect of hydrostatic pressure and alloying high purity beryllium on the shear stress needed to cause pyramidal slip has been ascertained. A 2.5 wt pct Cu alloy was selected as the first alloy to study as this level of copper did favor pyramidal slip at room pressure. A high purity (12 zone pass) single crystal of beryllium 0.3 by 0.1 by 0.1 in. was cut and polished by an orientation and lapping technique8 so that the top and bottom compression surfaces were parallel and within 3 min of arc to the (0001) plane and the sides parallel to the {l010} and {ll20} planes. In these compression specimens, therefore, the resolved shear stress was nearly zero on both the basal and prism planes, and slip was restricted to pyramidal systems. Analysis of slip traces on the two lateral surfaces served to accurately identify the active slip planes.6&apos;9 The pressure unit was a modified piston-cylinder device fitted with a manganin transducer coil arrangement which continuously monitored and recorded the hydro-static pressure. The load on the specimen was measured by a strain gage load cell which operated entirely within the pressure chamber. This load cell was calibrated before and after each pressure cycle at room pressure in situ and the calibration did not vary more than ±1 pet. These techniques and devices have been previously described in more detail.6 Successively higher compressive stresses were applied to the single crystal under a superimposed hydrostatic pressure until fracture occurred. The strain rate was (4.5 ± 2.0) x 10-6 sec-1 and the average rate of pressure application and release was approximately 0.3 kbars per min. As the load on the specimen was applied by the piston which was used to increase the hydrostatic pressure, the pressure increased during the compression test. This increase ranged from 0.0 to 0.8 kbars, and the maximum hydrostatic pressures are quoted in Fig. 1. The lateral surfaces of the specimen were examined in a light microscope after each pressurization/stress cycle so that the stress at the onset of {1122} pyramidal slip could be ascertained. Post compression height measurements allowed the plastic strain in the specimen to be evaluated to within 0.03 pct. The resulting compression stress-plastic strain curve is shown in Fig. 1 with results of a "c-axis" test on a similar Be-2.5 wt pct Cu single

Jan 1, 1970

By B. M. Larsen

Attempting to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic" and "macroscopic," depending on whether the variations in concentration of solutes or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also untlerly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all sepregation effects. Undercooling and Nuclei Formation It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus temperature. In practical terms this means that the nuclei number illcreases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. Temperature Gradients and Heat Dissipation during Freezing Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period. Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1945

By C. Baldwin Sawyer

During the last half century, much time has been devoted to investigations of the effect of nitrogen on the physical properties of steel, but in all discussions of results there is considerable doubt as to the accuracy and interpretation of analyses. No conclusions concerning the effects of nitrogen on the physical properties of steel can be more reliable than the methods used for determining the quantities of nitrogen present. The work described in this paper endeavors to establish some additional conditions required by the customary distillation method for reliable and nccurate determinations. Results by a combustion method of analysis for total nitrogen content are presented; these indicate that all of the nitrogen in steel, exclusive of that contained in blowholes, may be determined by the distillation method. Based on these more sound and more reliable analyses, results havc been obtained that bear on the following divisions of the general subject, nitrogen in steel: Nitrification of steel by melting in nitrogen, nitrification of steel by heating in ammonia, decomposition of nitrified steel by heating, and thermal analysis of nitrified steel. Consideration of Two Methods of Analysis and Some Results The details of the distillation and combustion methods are chemical in character and of little interest to most readers. They are therefore described in an appendix. The distillation method is essentially that described by Hurum and Fay1 and was generally used throughout this work. It is capable of the greatest accuracy and all results given are significant to the last, figure. Where analyses do not check, the samples

Jan 1, 1923

By C. Baldwin Sawyer

During the last half century, much time has been devoted to investigations of the effect of nitrogen on the physical properties of steel, but in all discussions of results there is considerable doubt as to the accuracy and interpretation of analyses. No conclusions concerning the effects of nitrogen on the physical properties of steel can be more reliable than the methods used for determining the quantities of nitrogen present. The work described in this paper endeavors to establish some additional conditions required by the customary distillation method for reliable and nccurate determinations. Results by a combustion method of analysis for total nitrogen content are presented; these indicate that all of the nitrogen in steel, exclusive of that contained in blowholes, may be determined by the distillation method. Based on these more sound and more reliable analyses, results havc been obtained that bear on the following divisions of the general subject, nitrogen in steel: Nitrification of steel by melting in nitrogen, nitrification of steel by heating in ammonia, decomposition of nitrified steel by heating, and thermal analysis of nitrified steel. Consideration of Two Methods of Analysis and Some Results The details of the distillation and combustion methods are chemical in character and of little interest to most readers. They are therefore described in an appendix. The distillation method is essentially that described by Hurum and Fay1 and was generally used throughout this work. It is capable of the greatest accuracy and all results given are significant to the last, figure. Where analyses do not check, the samples

Jan 1, 1923

By V. S. Gupt, W. H. Somerton

Rock may undergo great changes in physical properties when heated to high temperatures and then cooled, The temperature and intensity of reactions causing rock alterntiorl.s can he controlled by introducing certain chemicals during heat treament. Three typical outcrop sandsone samples were saturuted with common salt solutions, then heated to several maximum temperatures. After cooling, it was found that per-rrreuhilities had increased much more for salt-saturated samples than for samples not saturated with salt but heated to the same temperatures. This was only true, however. for samples heated above the melting points of the particrrlar salts. Potassium chloritle was particularly effective with Bandera sandstone. Samples saturated with potassium chlorirlr. solution and heated to 900C showed an 11-fold increa.se in perrrieahility. Samples without potasrirdrn chloritle but heated to the .same temperature. showed only a 2.7-jold incresre in permecahility. In application, it seems possible that injecting chemicalc into the formations from a wellbore followed by applying intensive borehole heating might promote reactions which would greatly improve permeability of the formalions. INTRODUCTION Great changes in the physical properties of rocks which have been heated to temperatures in the range of 600 to 800C have been reported earlier. Permeability increases of 50 per cent, and equivalent decreases in sonic velocity and breaking strength have been observed. Although there might be some suppression of certain reactions responsiblc for these changes when rock samples are heated under simulated reservoir pressure conditions. recent work has shown that these are more than offset by the increased importance of other reactions at high pressures. The reactions considered responsible for alteration of rock properties by heating include differential thermal expansion. dehydration, phase changes and dissociation of mineral constituents. Ceramists have long known that temperatures at which reactions occur can be raised or lowered by the presence of certain impurities in the sys. tcnl. Thus the possibility exists that by saturating rocks with appropriate solutions. desired reactions might be accelerated and unwanted reactions might be suppressec! when the rock is heated. Purpose of the present work was to investigate the effects of several common salts on the thermal alteration of sandstones. Types of reactions which might occur are reviewed and the findings of a number of thernlochemical alteration tests are presented. THEKMOCHEMICAL ALTERATION OF SANDSTONE MINERALS The most abundant constituent of most sandstones is quartz. Quartz can exist in at least eight different forms, but in the temperature range of immediate interest (to 900C) only two forms are of importance—alpha quartz below 573C and beta quartz above this temperature. Although the alpha-beta inversion of quartz is very important in thermal alteration of rocks. it is not particularly important here because the inversion temperature cannot be changed significantly by the presence of impurities or by the application of pressure. The transition temperature of quartz to tridynlite is 867C. but the transition is very sluggish. Tridymite is considered to be a metastable transition phase between two stable phases: quartz?cristobalite. However. the transition temperature for tridymite to cristobalite is 1,470C.4 The quartz-tridymite-cristobalite transition can be accelerated substantially by the presence of fluxing agents. Finely divided calcium, magnesium and titanium oxides accelerate the conversion while A12O may retard it. A Mixture of NaCl and CsCl reduces the temperature for cristobalite formation by as much as 420°C. Feldspars constitute the second most important mineral in sandstones. The melting points of feldspars range between 1,000 and 1,700°C depending upon the variety. No information available indicated any important role of fluxing agents in the thermal alteration of this group of minerals. Carbonate minerals are subject to dissociation at temperatures within the range of the present investigation. The dissociation of magnesite can start at a temperature of 373°C, but the reaction is sluggish and might not occur untll a temperature of 500°C or ,higher is reached. Dolomite dissociates in two stages at 500°C and 890°C, whereas calcite dissociation temperature is about 885C. Because CO2 is released in the dissociation of carbonates, ail such reactions are somewhat dependent upon CO2 partial pressure. In the absence of CO: in the surrounding atmosphere, the dissociation of calcite starts at 500°C.However. when 1 atm of CO surrounds the sample, the dissociation does not start until 900C. The other carbonates are apparently much less sensitive to a change in partial pressure of CO2. The aragonite calcite transformation can occur an!. where within the temperature range of 357 to 488°C. depending upon the presence of impurities such as barium. strontium. lead and perhaps zinc. The differential thermal analysis (DTA) curves of both magnesitc and dolomite vary with the presence of &apos;impuritics. The presence of iron in particular seems to affect the magnesitc DTA curve

Jan 1, 1966

By Malcolm F. Hawkes, Robert F. Mehl

THE rate of isothermal transformation of austenite to pearlite depends upon the rate of nucleation, N, and the rate of growth, G, of pearlite in austenite.1.2 Values of N are given in terms of the number of nuclei forming in unit time per unit grain boundary area of unreacted austenite; values of G are given in terms of the linear rate of radial growth. Variations in the isothermal rate with temperature result from variation of -N and G with temperature. Depth of hardening of a steel depends fundamentally upon values of N and G; changes in carbon and alloy content effect changes in N and G and thus affect depth of hardening. Quantitative studies are available on N and G for the formation of pearlite in plain carbon eutectoid steels.3 Systematic studies in this field are necessary if the phenomena are to be well enough known to furnish. a proper basis for full rationalization and for theory. Accordingly, the studies are continuing, both with respect to the effect of alloying elements upon the values of N and G in the formation of pearlite, and to the values of N and G for the formation of ferrite in hypoeutectoid steels. The present paper is the first relating to the effect of alloying elements upon the values of N and G for pearlite. It offers special interest since cobalt is known to have an anomalous effect upon the rate of formation of pearlite, accelerating it, whereas all other elements retard it.&apos; It will be shown that cobalt increases both N and G for pearlite and that this effect is inherent in the Fe-Co-C system and not dependent upon factors relating to austenite heterogeneity nor upon any recognizable adventitious factor. Inasmuch as the rate of diffusion of carbon in austenite and the interlamellar spacing of pearlite are variables related to G and possibly to N (in a manner not yet certain), measurements of the "effect of cobalt upon them are also reported here. In the course of the work, measurements were made on the effect of cobalt upon the martensite temperature and these are given. COBALT AS AN ALLOYING ELEMENT IN STEEL PROPERTIES OF COBALT Cobalt resembles iron more closely than does any other chemical element. Its atomic number is 27, hence it is the element immediately following iron in the periodic system. The two differ in atomic structure only in the fact that cobalt contains seven electrons instead of six in the third, or transition, level of the third shell. The next shell, which is the

Jan 1, 1947

By Ralph K. Foster

During five underground mine fires which occurred in Arizona during 1980 and 1981, sealing the fire area became necessary. To minimize leakage into the fire area, ventilation control measures were instituted to balance pressure across the bulkheads. Problems en- countered in sealing the fire areas and measures taken to improve these conditions are discussed. The routing of the ventilation and ventilation control to en- sure the workers&apos; safety were also important considerations in reopening the mines. The use of continuous CO monitors is discussed. One important consideration was the condition of the fire, and chromatographic analysis was used to establish this. Graphs comparing the Trickett ratio, carbon monoxide, carbon dioxide, and oxygen concentrations are given. The Trickett ratio was useful but needed to be augmented by the comparison of CO, C02, and 02. Problems with getting good samples from sealed areas and recommended procedures that were developed during these fires are discussed.

Jan 1, 1982

By John F. Elliott, Robert D. Pehlke

The rate of reaction of nitrogen with liquid iron and with binary alloys of iron and Al, Cb, Cr, Ni, O, S, Si, and W were measured. The surface active elements, oxygen and sulfur, decrease the rate markedly. The other alloying elements have very little effect on the rate except when they function as deoxidizers, The rates of absorption and de-sorption were found to be equal. Several possible reaction mechanisms which may control the rate are considered. In order to describe completely the behavior of nitrogen in steelmaking processes, the mechanisms of mass transfer between the gaseous and liquid phases, nitrogen and iron, respectively, must be understood. A kinetic study to determine the nature of these mass transfer processes was undertaken, and the results of that investigation are presented in this paper. Specifically, the study was directed toward determining the influence of alloying elements on the rates at which pure nitrogen gas at constant pressure is absorbed and desorbed by liquid iron solutions: A previous paper1 reported measurements of the equilibrium solubility of nitrogen in liquid binary iron alloys. The experimental data are presented and discussed first and then several possible rate limiting mechanisms are considered. PREVIOUS RESEARCH The results of several investigations on the rate of absorption of nitrogen by liquid iron and iron alloys have been reported.2-14 There is little agreement on the rate coefficients among these studies because of the influence of geometry on the experimental system and of the purity of the liquid iron. The rate was found to be influenced by alloying content for the binary liquid iron systems: Fe-Al,2 Fe-C,4,6 Fe-Cr,4,5,8 Fe-Mn,5 Fe-Ni,5,8 Fe-O,9,10 Fe-O,9,10 and Fe-Si.2,6,7,11 Several investigators12"15 have reported that the rate of nitrogen absorption is increased in a reducing gas mixture and decreased in an oxidizing atmosphere. A mechanism for the retardation by oxygen of the absorption of nitrogen has been described by Naeser18 as the formation of an iron oxide film at the gas-metal interface. The film slows the absorption rate until it disolves in the metal, thus permitting nitrogen to enter the liquid iron. Karwat17 discussed the influence of oxygen in terms of the formation of gaseous molecules of nitrous oxide which represent a higher energy form than the nitrogen and oxygen or the oxidizing gas and consequently constitute an energy barrier for the process. Fischer and Hoffmann10 showed that the oxygen markedly reduces the rate of absorption of nitrogen, the rate constant being one order of magnitude smaller in liquid iron containing 0.15 to 0.24 pct 0 as compared to that in melts containing 0.001 to 0.02 pct 0. Although Chipman and Murphy2 reported that the rate of absorption of nitrogen in liquid iron was essentially independent of temperature, Eklund3 found that the rate increases strongly with increasing temperature as did Kootz4 and Saito.5,6 Karnaukhov and Morozov7 also reported a large temperature coefficient, but related it to increased stirring at higher power inputs in an inductively heated system. All of the authors above have treated their results assuming that the reaction is diffusion controlled, that the surface reaction is in equilibrium with nitrogen gas, and that a "first order" reaction takes place. Karnaukhov and Morozov7 and Humbert; who studied the rate of absorption in a closed system by observing pressure changes in the system as a function of time, concluded that their results best fit a diffusion-type analysis. This was further verified by von Bogdandy, Dick, and stranski18 and Fischer and Hoffmann10 who found the initial rate of

Jan 1, 1963

By W. Luyken, E. Bierbrauer

A number of articles have been published, notably those by R. S. Handy, R. T. Hancock and A. P. Watt in Engineering and Mining Journal, dealing with the calculations involved in ore dressing. These publications demonstrate both the importance of the subject and the lack of success in developing a generally recognized method for comparing enrichment effects. Considering that we may wish to compare enrichment results on similar or dissimilar ores, that we may desire to make the comparison on the basis of either the absolute or the economical efficiency, and that the number of factors upon which the result depends is large, the question arises whether it is possible to set up a positive method for such calculations. In the following pages it is our aim to show that a sure, complete and successful way to overcome existing difficulties has been found. Graphical Analysis of Ore-dressing Processes The following is from Truscott&apos;s Text Book of Ore Dressing (London, 1923): x = assay of ore treated (feed). y = assay value of the concentrate. 2 = assay value of the tailing. a = weight of feed. 6 = weight of concentrate. c = weight of tailing. C = fractional concentration = = . a y - z K = ratio of concentration = 1/c a/b = y-z/x-z 2 B = fractional recovery = 9 = C y/x (3) 100R = percentage recovery. Copt. = theoretically best concentration. 100 — Copt = waste in the feed.

Jan 1, 1930

By H. R. Deeth, C. J. Koenig

ABOUT ten years ago nepheline syenite was introduced to the ceramic industry and the material has now found application in the various branches of the industry, namely, as a vitrifying agent in white-wares and as a source of alumina and alkalies in glasses, glazes, and porcelain enamels. Spence1 described the early mining and processing developments regarding this material. Since the time of his article many research papers have appeared relating to the usage of nepheline syenite but little has been published relative to subsequent mining and processing methods. A complete indexed review of the literature was issued recently by Ohio State University.2 Since "Lakefield" nepheline syenite from Blue Mountain, Ontario (Fig I); is the only commercial ceramic-grade nepheline syenite now being marketed on this continent, discussion is limited to this operation carried on by American Nepheline Limited, Lakefield, Ont., and its subsidiary in the United States, American Nepheline Corp. at Rochester, N. Y. THE DEPOSIT Blue Mountain is a long ridge rising to an elevation of about 350 ft at its highest point above the surrounding country and extending for about six miles in a northeasterly direction across Methuen township, Peterborough County. The rock of the Blue Mountain central alkaline intrusive is fine grained, light colored and of even granitic texture. The solidified mass consists predominately of the minerals albite, nepheline and microcline in order of abundance. The average mineralogical composition for the deposit obtained by a study of 112 samples taken regularly over the whole formation is as follows:3 [VOLUMETRIC MINERAL PER CENT Albite54 Microcline20 Nepheline22 Muscovite2 Mafics2 (Biotite, hastingsite, magnetite) Total100] The mineral nepheline (or nephelite) belongs to the feldspathoid group but is lower in silica content than are the feldspars. It is a silicate of soda, potash, and alumina (NaKAl2O32SiO2). Its presence with albite (Na2O A1203 6SiO2) and microcline (K20 A12O3 6SiO2) gives the Blue Mountain deposit an alkali content of 15 pct and an alumina content of approximately 24 pct. While this huge alkaline mass is somewhat variable mineralogically, it has a uniform chemical composition. When the iron, mostly in the form of magnetite, is removed during processing, a remarkably uniform finished product is obtained. Geological surveying has disclosed many million tons of nepheline syenite in the Blue Mountain deposit. Diamond drilling in the area where mining is now being carried out indicates a block of about one million tons.

Jan 1, 1947

By P. P. Gregory

Natural petroleum gas occurring in the oil-bearing reservoirs is found to exist either as free gas associated with the oil and/or in solution in the oil. In some virgin fields practically no free gas is encountered under the reservoir conditions of pressure and temperature, although in other fields a considerable section of the "pay" horizon is occupied by free gas. In other words, a given oil field may or may not have a gas cap before the exploitation takes place. However, when the reservoir pressure is reduced to a point below the critical saturation pressure by withdrawals of fluids from the producing formation, the gas dissolved in the oil inevitably begins to come out of solution and becomes free gas. Under the controlled methods of production and drilling, a portion of this gas is produced with the oil to the surface and a portion of it remains within the reservoir to accumulate at higher structural levels toward which it migrates by virtue of its low specific gravity. The rate of growth of a gas cap in a given structure depends primarily upon the rate of decline in the reservoir pressure. If the rate of pressure decline is rapid, the gas cap likewise will grow rapidly. On the other hand, shrinkage in the gas-cap area was noted in some fields in which reservoir pressures wereincreasing. Determination of Gas-oil Contact and Thickness of Gas Cap The gas-oil contact can be conveniently located in the process of drilling a well and by electrical logging. However, very little can be found in the petroleum literature concerning methods of predetermining gas-oil contacts in producing reservoirs. Therefore, the writer feels justified in describing briefly a simple, workable, and inexpensive method of determining gas-oil contacts and outlining the limits of gas-cap areas in a field where such knowledge may be essential for efficient production and development operations. The method involves the determination of the following data: (I) Structural data, such as the depth or elevation of the top&apos; of "pay" horizon; (2) reservoir pressures; (3) tubing and casing pressures at the well head; (4) static oil-pressure gradient; (5) static gas-pressure gradient. These data can be secured with a minimum of expense, inasmuch as the

Jan 1, 1938

By H. R. Skewes

IN the course of small seale experiments on the electrodeposition, of copper, extremely brittle deposits were obtained from electrolytes prepared by leaching calcined chalcopyrite with aqueous sulfuric acid. It was not possible to strip the metal without fracture after it had been deposited from such electrolytes onto smooth oiled copper sheets, the usual plant procedure for the production of so-called starting sheets. The embrittlement did not occur with electrolytes made either by leaching the calcine with water or by treating an acid leachate to remove iron as hydrous ferric oxide. The electrolytes which produced brittle deposits were found to contain molybdenum in concentrations of 10 to 25 mg per 1, whereas those which produced ductile deposits contained <0.5 mg per 1. Synthetic electrolytes having the composition: Cu", 40 gpl; Fe", 0.5 to 1.0 gpl; Fe3+, 0.5 to 1.0 gpl; and H,SO,, 10 to 50 gpl, were prepared from reagent-grade salts; by adding ammonium molybdate, the embrittling effect of the higher concentrations of molybdenum (VI) was strikingly confirmed. The brittle deposits contained up to 0.03 pct Mo. The importance of oxidation state of the molybdenum was demonstrated when the electrolyte containing it was circulated continuously through a bed of fine copper metal during deposi- tion. Under these reducing conditions, the cathode deposit was ductile and molybdenum could not be detected. Molybdenum has not been recognized as one of the metals causing embrittlement of copper nor is it listed among the usual impurities. In most elec-trowinning plants there is a purification step which removes iron from the leachate before electrolysis. In these cases molybdenum would be coprecipitated with hydrous ferric oxide. In the case of the large leaching plant at Chuquicamata, Chile, where the leachate is reported to contain considerable molybdenum, it would be reduced to a lower oxidation state during removal of chlorine by means of cement copper. This may explain why the embrittling effect of molybdenum has not been reported previously. Moreover, in copper refining plants where soluble anodes have been prepared by a high temperature smelting process, it is most unlikely that any molybdenum would remain with the copper, whereas the calcines in this work were prepared in a fluidized bed reactor at a temperature not exceeding 720°C. Acknowledgment This work is part of an investigation on the roasting and extraction of copper from sulfide ores sponsored jointly by Mt. Morgan Ltd., Queensland, and the Mt. Lyell Mining and Railway Co. Ltd., Tasmania.

Jan 1, 1958