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By J. D. Alexander, W. L. Martin, J. N. Dew

This paper presents data obtained using a flood-pot technique to determine the fuel available and the corresponding theoretical air requirements for in situ combustion of crude oils. Since the technique is relatively quick and easy, it is a practical and convenient tool for evaluating reservoirs as fireflood prospects. It is also a research tool which facilitates systematic study of the variables affecting fuel availability and corresponding air requirements. The understanding of these variables is of prime importance to those concerned with the technical and economic development of in situ combustion as an oil-recovery process. The experimental results show conclusively that the fuel available for in situ combustion is not a constant but, rather, varies with crude-oil characteristics, porous-medium type, oil saturation, air flux and time-temperature relationships. Thus, the fuel availability for specified field applications should be determined using actual reservoir crude and core material and the process conditions expected during in situ combustion in the reservoir. INTRODUCTION In situ combustion is a thermal process for recovering crude oil from reservoirs. The thermal energy released during the combustion of a small amount of the oil in place aids in the displacement of the remaining oil. Numerous articles have been published describing the in situ combustion process giving detailed results of laboratory and field experiments.10 In order to engineer an in situ combustion project, a number of important factors must be considered and determined. These factors include: (1) the amount of fuel consumed per unit of reservoir volume swept by the combustion zone, (2) the composition of the fuel consumed, (3) the amount of air required to consume this fuel, (4) the portion of the reservoir swept by the combustion zone, (5) the appropriate air-injection rates and pressures, (6) the amount of oil that will be recovered, (7) the rate of oil production and (8) the operating costs. Nelson and McNiell1 recently have described a procedure which utilizes laboratory combustion-tube data as a basis for the calculation of some of these design factors. Various authors have attempted to describe the in situ combustion process mathematically, and considerable progress has been made. Analytical solutions to the problem of heat transfer from a moving combustion front have been obtained for linear and radial systems."-' All of the published results involve the assumptions that: (1) fuel concentration is constant throughout the reservoir, or that fuel concentration is inversely proportional to the velocity of the front for a given rate of oxygen consumption; and (2) the fuel reacts instantaneously with injected oxygen, while liberating a constant amount of heat per unit weight of fuel at all temperatures. It seems both desirable and reasonable to test the validity of these assumptions experimentally. This paper presents laboratory data which were obtained by means of a "fire flood-pot" method for determining fuel availability and composition, and the corresponding theoretical air requirements for in situ combustion of crude oils under variable conditions. The mechanics of the method are similar to a conventional tube-run experiment.' The important differences involve the size of the reservoir model used and the method for providing the experimental environment. The new method subjects conventionally-sized core samples or unconsolidated sands to a programmed environmental sequence similar to that experienced by a similar volume of rock during the approach and passage of a combustion front in a long tube or in an oil reservoir undergoing in situ combustion. Restored-state samples can also be used. The small samples and relatively simple techniques involved allow an experiment to be set up, run and calculated in about three 8-hour days. This is a considerable improvement over long-combustion-tube techniques which can require several days to run and several more work days to set up and calculate. All the runs presented were run at 40-psig injection pressure. Pressure was not considered as a variable for these experiments, since we previously had found that it had only a small effect on fuel availability up to 600 psig.APPARATUS AND MATERIALS APPARATUS The fire flood-pot apparatus consists of a consolidated

By R. Taggart, D. H. Polonis, J. C. McMillan

Thin foil electron microscopy techniques have been used to study the micros tructure of a Ti- 7.5 wt pct vanadium alloy in the quenched and aged cond_itions. Selected area diffraction has identified a (1011) twinning mode accompanying the martens ite t9.an.sfo?rn~ation. Precipitation of the 0 phase during the aging of quenched alloys has been obsevced to occuv in the form of plates and needles with preferential growth along the (1120) direction in the a' matrix. In the present work, the micro structures of quenched and aged alloys of the 0 isomorphous Ti-V system have been investigated by means of thin-foil electron-microscopy techniques. Most of the previous studies of martensitic phases in titanium-base alloys have utilized optical microscopy and X-ray diffraction techniques. The application of transmission electron microscopy is more recent, and only a few such studies have been reported.1-5 This paper is concerned particularly with the crystallographic nature of substructures formed in the martensitic a' plates. The early stages of aging or tempering have also been examined to determine the modes of precipitation from the martensitic solid solutions. Such information is essential in studying strengthening mechanisms and in determining the feasibility of high-strength rnartensitic alloys based on titanium. Liu and Margolin6 reported several types of substructures within the martensitic plates of quenched Ti-Mn alloys. It was later suggested by Liu7 that the structure of martensitic plates might be very complex and not single crystals as normally assumed. The sub-markings could not be identified with the two possible habit-plane orientations {334}ß and {344}ß, and it was not positively determined whether they are associated with mechanical twinning. The recent studies by Armitage5 on titanium martensites in a variety of commercial alloys have indicated that twinning does not generally accompany the transformation. This observation is in accordance with the Mackenzie and Bowles model for the transformation in pure titanium8 which suggests that twinning is not to be expected. However, a number of other recent investigators have reported twinlike substructures in the martensitic plates of several titanium systems including commercia1 titanium,2,3 Ti-Cu,5,9 Ti-Ta,1 and the commercial alloy Ti-8A1-1Mo-1V. Blackburn* has reported that the structure of quenched Ti-8A1-1Mo-1V depends on the prior solution temperature. He identified two types of martensitic structures, one of which is described as a heavily faulted hcp or twinned fcc structure and the other an hcp structure with a high internal dislocation density. The latter type exhibited some twinning with a (1011) twin plane. EXPERIMENTAL PROCEDURES AND RESULTS The alloy used in the present work was a 7.5 wt pct V alloy that was prepared by conventional arc-melting techniques. This alloy composition was selected

Jan 1, 1968

By Leo Tarasov

MAGNETIC torque studies of ferromagnetic single crystals have been carried out in a number of laboratories during the last decade1,2 and some work has been reported on polycrystalline material showing preferred orientation. Goss3 used the method extensively in developing electrical sheet with desirable magnetic properties, but he used it as a control rather than as a means of studying the texture. Bozorth4 made a quantitative correlation of a torque curve he obtained from some cold-rolled iron with the texture as determined from X-rays, but did not extend his studies beyond the one specimen. Other studies, which have been reported from time to time 1.5 have also been incomplete in the sense that no effort was made to study a whole series of samples, differing only in degree of cold reduction, or in the annealing temperature, in order to ascertain the effect of such treatments on the texture as revealed by torque measurements. It is the purpose of this investigation to make such a study, mainly in order to see how useful the method can be made when used under favorable circumstances and to find what kind of a correlation can be expected between magnetic and X-ray studies of texture. Before proceeding further, it is desirable to say a little about single crystals, so as to make clear the concepts involved in magnetic torque measurements.

Jan 1, 1939

By M. Yokoi, K. Yoshida, T. Ishihara

The solubility of aluminum in cryolite melts has been determined by measuring the weight loss of aluminum submerged in melts contained in closed silicon nitride crucibles. The solubility in pure cryolite has also been checked with radioactive isotopes. The solubility decreases with increasing A1203 concentration, decreasing temperature, and decreasing cryolite ratio. The change of aluminum solubility in pure cryolite with the activity controlled by using Al-Ag and A2-Cu alloys supported the assumption that aluminum would dissolve in the form of monovalent ions according to the reaction 2AI + A1' —3 A1'. DURING the electrolytic production of aluminum, the electrodeposited metal redissolves in the bath in some form and is subsequently oxidized back to the former ionic state. This dissolution is believed to cause a decrease in current efficiency. Reported data on the solubility of aluminum in cryolite melts are scattered. The mechanism of the dissolution has not yet been determined, although certain tentative interpretations have been proposed. Many previous studies were performed under different test conditions. Studies were performed in open Systems and closed systems,'o and some were apparently not given sufficient time to Saturate." The solubility can be determined either analytically or gravimetrically. The analytical determination involves measurement of hydrogen gas evolved when frozen cryolite bath saturated with aluminum is treated with sodium hydroxide or hydrochloric acid. The gravimetric determination, adopted by many investigators,'-37'3>14 involves measurement of weight loss of the metal after equilibration with a known amount of salt. It appears that the former technique yields much smaller values of solubility than the latter technique. This large difference in results strongly suggests that the dissolved metal in the cryolite melt is no longer in the metallic state. In the present study, the solubility was determined by the gravimetric technique at various activities of aluminum using A1-Ag and Al-Cu alloys. An attempt was also made to determine the ionic (or atomic) state of the dissolved metal from the solubility data. 1) EXPERIMENTAL Apparatus. Preliminary tests demonstrated that silicon nitride was suitable as a container material since it is compatible to both the fluoride melts and molten aluminum. Crucibles were made from silicon powder nitrided with Nz gas at 1600°C. The good compatibility between crucible and melts is due to the near perfect nitrogenation of silicon. Only small amounts of silicon were found in the aluminum metal after the experiments. The crucible dimensions were 90 mm inside height, 38 mm ID, 105 mm outside height, and 50 mm OD. Close-fitting lids made of silicon nitride were also prepared. The crucible was placed in a close-fitting graphite crucible heated by a vertical Kanthal furnace, Fig. l. The lid and crucible are fastened tightly together by the condensation of vaporized bath in the narrow gap between them. The temperature was measured in the wall of the graphite crucible and controlled within * 5°C. The temperature difference between the measuring point and the interior of the melts was initially determined. Materials. The materials used were: Greenland cryolite (impurities CaF,, 0.5 pct; AlzO3, 0.2 pct; high-purity aluminum metal (purity 99.99 pct); A1203 and AlF, (provided by Nippon Light Metal Co., Ltd); reagent-grade NaF and CaF2; and 99.9+ pct Ag and Cu. Powdered reagents were carefully dried before use. A1-Ag and A1-Cu alloys were prepared before the experiments; their composition was checked by analysis

Jan 1, 1969

By C. A. Hartnagel

The year 1944 marks the eightieth anniversary of the discovery of petroleum by drilling in New York State. It was in 1864 that a half dozen shallow wells were drilled at Limestone in Cattaraugus County, in a region that now forms the northern extension of the 82,000-acre Bradford pool. These early wells found oil, but not in paying quantities. They did, however, attract attention to the district and were a factor in the development of the still active Bradford pool of Pennsylvania and New York. During 1943, the production of petroleum in New York amounted to 5,029,000 bbl. This represents a decrease over the previous year, in which 5,421,000 bbl. was produced. The flush production for the New York fields occurred in the early eighties shortly after the discovery of oil in the Richburg pool of Allegany County. During the flush period, production was in excess of five million barrels annually. By 1887, however, the output had decreased to an amount only slightly more than two million barrels, and through the early years of the present century the annual total was often less than one million barrels. Flooding of the oil sands for increasing productioil was made legal in 1919, and in 1927 the output once more reached the two million mark. Two years later it had increased to over three million barrels. In Table r is shown production since 1935, in which year for the first time the output under flooding methods was in excess of four million barrels. From this table, it is evident that oil production in New 'I'ork is rather well stabilized, and since most of the oil is obtained by the flooding, or water-drive, method, with little or no prospect of discovery of new oil territory, rapid changes in yield from year to year are not to be expected. In thickness, the oil sands have a maximum of about 50 ft., and by means oi flooding may produce 10 to 12 thousand barrels an acre and proportional amounts for thinner sands. In some cases, floods have been developed in sands only 12 ft. thick. Under good flooding conditions a yield of 2000 bbl. an acre is about the lower limit at which oil can bc produced at the present price of $3.00 a barrel. The average cost for the physical development ol a lease, not including the cost ol the lease itself, is $5000 an acre. Since several months must intervene before the flood begins to act on the oil wells, and a year or more is required to bring thc wells to maximum daily production, it is evident that a considerable interval occurs before maximum returns are realized. Once a flood is developed and the wells

Jan 1, 1944

By C. A. Hartnagel

The year 1944 marks the eightieth anniversary of the discovery of petroleum by drilling in New York State. It was in 1864 that a half dozen shallow wells were drilled at Limestone in Cattaraugus County, in a region that now forms the northern extension of the 82,000-acre Bradford pool. These early wells found oil, but not in paying quantities. They did, however, attract attention to the district and were a factor in the development of the still active Bradford pool of Pennsylvania and New York. During 1943, the production of petroleum in New York amounted to 5,029,000 bbl. This represents a decrease over the previous year, in which 5,421,000 bbl. was produced. The flush production for the New York fields occurred in the early eighties shortly after the discovery of oil in the Richburg pool of Allegany County. During the flush period, production was in excess of five million barrels annually. By 1887, however, the output had decreased to an amount only slightly more than two million barrels, and through the early years of the present century the annual total was often less than one million barrels. Flooding of the oil sands for increasing productioil was made legal in 1919, and in 1927 the output once more reached the two million mark. Two years later it had increased to over three million barrels. In Table r is shown production since 1935, in which year for the first time the output under flooding methods was in excess of four million barrels. From this table, it is evident that oil production in New 'I'ork is rather well stabilized, and since most of the oil is obtained by the flooding, or water-drive, method, with little or no prospect of discovery of new oil territory, rapid changes in yield from year to year are not to be expected. In thickness, the oil sands have a maximum of about 50 ft., and by means oi flooding may produce 10 to 12 thousand barrels an acre and proportional amounts for thinner sands. In some cases, floods have been developed in sands only 12 ft. thick. Under good flooding conditions a yield of 2000 bbl. an acre is about the lower limit at which oil can bc produced at the present price of $3.00 a barrel. The average cost for the physical development ol a lease, not including the cost ol the lease itself, is $5000 an acre. Since several months must intervene before the flood begins to act on the oil wells, and a year or more is required to bring thc wells to maximum daily production, it is evident that a considerable interval occurs before maximum returns are realized. Once a flood is developed and the wells

Jan 1, 1944

By J. E. Owen

EXPERIMENTS on twenty-six drilling muds were carried out in an effort to establish a correlation between the apparent viscosity values for these muds as obtained with the Marsh funnel and the Stormer viscometer. This required a calibration of both instruments in which the density of the calibrating liquids was taken into account. Corresponding to the Marsh-funnel viscosity values that were obtained at 1500 c.c. in, 1 qt. out, equivalent Stormer viscosity values were obtained at a Stormer cylinder test speed of approximately 1100 r.p.m. Further, a linear relation between the logarithms of the Stormer cylinder test speed and the resulting apparent viscosity was found to exist for the muds tested for 200 to 1000 r.p.m. The significance of the slope of this linear relationship is discussed as it applies to the field use of drilling muds. It was concluded that Marsh-funnel viscosity measurements are expressible in absolute units that may be correlated with Stormer viscosity measurements, provided these are made in the manner described in the paper. INTRODUCTION The Marsh funnel is used almost universally to determine the viscosity of drilling muds in the field. The Stormer viscometer is commonly used to determine the viscosity of drilling muds in the laboratory. With the Marsh funnel, the time required for one quart of mud to flow out of the funnel originally filled with 1500 c.c. is often taken as the measurement of viscosity. With the Stormer instrument, drilling mud is tested at a cylinder speed of 600 r.p.m. and by means of calibration data the apparent viscosity is expressed in absolute units. Neither of these instruments is an absolute viscometer, and apparent viscosities obtained with either are influenced by the arbitrarily standardized conditions under which the measurements are made. It is disconcerting to the man in the field to be told that laboratory measurements of the viscosities of a group of muds differ widely, when he has already observed that they have identical viscosities when tested in the Marsh funnel. Drilling muds are not perfect fluids, therefore it is not surprising to find a lack of correlation between the apparent viscosity of a mud as determined with the Marsh funnel and that determined with the Stormer viscometer. The work described here was undertaken to develop a correlation between Marsh-funnel and Stormer viscosity measurements. To a considerable degree this has been accomplished. This study has resulted not only in a better understanding of the two viscosity instruments and the data obtainable from them, but has given considerable information regarding the viscosity characteristics of drilling muds. EXPERIMENTAL PROCEDURE Calibration of Harsh Funnel and Stormer Viscometer The first step in the experimental procedure was the calibration of the Marsh funnel and the Stormer viscometer with

Jan 1, 1941

By Harry Perry

In the United States the state mining laws enacted in the late 1800s were the first laws to recognize that an employer had a responsibility to provide the employee a place to work that met at least some minimum safety standards. The coal mining industry was also the first major industry in the United States to be regulated in 1952 by federal safety laws, although federal inspectors had the right-of-entry as early as 1941. Within recent years, however, the Congress has enacted a number of federal safety regulations for a variety of industries, such as the Aviation Act (1958), National Traffic and Motor Vehicle Act (1966), National Gas Pipeline Act (1968), and Radiation Control for Health and Safety Act (1968). The fatality and injury experiences of the mining industry in the United States, while at a significantly higher rate than for industry as a whole, showed a continuous improvement until the last decade or two-at which time the rate leveled off. Although fatality and injury rates in foreign countries have been generally lower than in the United States, further improvement in those countries also has been difficult to achieve in recent years. It appears, therefore, that some major change in mining laws, combined with a radical improvement in mining technology and a more effective labor-management safety program, will be needed if further reductions are to be achieved in fatality and injury rates. At the same time, there is a growing awareness by society that an employee's place of work, where he spends nearly half of his waking hours, should be made as safe as possible. As increased consideration is given to means for achieving greater safety in all industrial situations, it is becoming apparent that more is required than merely providing physical safeguards on tools and machines. Rigorous, strictly enforced safety standards are useful, but more important is the desire of labor and management to make certain that industrial accidents are prevented. The pressure to achieve increased productivity, and thus receive higher wages, can be a significant deterrent to safe working practices. The temptation can be great to "take a chance" or "cut a corner" in order to speed up production. Public concern over all types of industrial safety in the United States was reflected by the introduction of a number of general occupational health and safety bills in Congress for the first time in 1968. While no legislation resulted, the hearings revealed that, although there were differences in how standards should be set and who should administer them, there was agreement on the need for adequate laws. Since the mining industry has been subject to safety standards longer than other industries, it is not surprising that advanced safety concepts for mining are being explored by the industry and the enforcing agencies. More complete and sophisticated accident reporting is being planned that will reveal the

Jan 1, 1976

By David A. Thomas, David N. French

The lrnrdness of WC crystals has been measured with the Knoop indenter at loads of 100 and 500 g on the (0001) and (1070) planes. The hardness as tneasitred on the basal plane is 2400 kg per sq mm and shows little anisotropy. The hardness on the prism plane, however, shows a marked orientation dependence, with a low value of 1000 kg -per sq mm when the long axis of the Knoop indenter is oriented parallel to the c axis and a high value of 2400 kg per sq mm when the indenter is perpendicular to the c axis. Slip lines (Ire observed surrounding the microhardness indentations and they show slip on (1010) planes, probably in [0001] and (1120) directions. This slip behavior can be explained by the crystal structure of TVC, which is simple hexagonal with a c/a ralio of 0.976. The hardness anisotropy call be explained by [0001]{1010} and (1130) {10l0] slii) and the resolved shear-stress analysis of Daniels and Dunn. HARDNESS anisotropy is a well-known phenomenon and has been reported for many metals, with both cubic and hexagonal structure.1-6 For hexagonal tungsten carbide, WC, a wide range of hardness values is reported in the literature. For example, Schwarzkopf and Kieffer7 give a hardness of 2400 kg per sq mm and report a value of 2500 kg per sq mm by Hinnüber. Foster and coworkerss give the average Knoop microhardness as 1307 kg per sq mm with a maximum value of 2105 kg per sq mm. Although these values and the structure of WC suggest the likelihood of hardness anisotropy, no such measurements have been made. We first detected a large apparent hardness anisotropy in WC crystals about 75 p large, in over-sintered cemented tungsten carbide. Prominent slip lines also occurred around many indentations. This report presents further observations and interpretations of hardness anisotropy and slip in WC crystals obtained from Kennametal, Inc. Both Knoop and diamond pyramid indenters were used on a Wilson microhardness tester with loads of 100 and 500 g. EXPERIMENTAL RESULTS The carbide crystals tended to be triangular plates parallel to the (0001) basal plane of the hexagonal structure. The side faces were parallel to the ( 1010) prism planes. Specimens were mounted approximately parallel to these two types of faces and metallographically polished. Laue back-reflection X-ray patterns were used to orient the specimens, which werethen ground to within ±1 deg of the (0001) and (1010) planes. The Knoop hardness values measured on the basal plane are plotted in Fig. 1. There is only a small anisotropy, with a hardness range of 2240 to 2510 kg per sq mm. The additional points at angles from 52.5 to 67.5 deg confirm the sharp minimum hardness at 60-deg intervals, consistent with the sixfold hexagonal symmetry. The average hardness of all values obtained on the basal plane is 2400 kg per sq mm. While the basal plane shows only slight anisotropy, the (1010) plane exhibits marked hardness anisotropy, from 1000 to 2400 kg per sq mm. Fig. 2 shows the hardness as a function of the angle between the long axis of the indenter and the hexagonal c axis, the [0001] direction. The minimum and maximum occur when the indenter is oriented parallel and perpendicular to the [0001] direction, respectively. The anisotropy of the prism plane is contrary to that reported for hexagonal zinc and hard- However, the basal-plane anisotropy is similar to these two metals.1'2 To check the accuracy and reproducibility of the measurements, a series of fifteen impressions was made at 100-g load in the same orientation in the same area of the specimen surface. The average for all was 2040 kg per sq mm, with a range of 1950 to 2130 kg per sq mm, giving an accuracy of about ± 5 pct. Thus the slight anisotropy on the basal plane is almost within experimental error. Fig. 3 shows slip lines around the Knoop indentations on the basal plane. The slip traces are in directions of the type (1130). The presence of slip steps on the basal plane indicates that the slip direction lies out of the (0001) plane. Because WC has a c/a ratio of 0.976,' the shortest slip vector is [0001], which suggests slip systems of the type [0001] (1010). Fig. 4 shows slip lines around the Knoop intentations on the (1010) plane. These slip lines are inconsistent with [0001] slip but can be

Jan 1, 1965

D. B. DOWLING,* Ottawa, Ont.-I do not propose to start any argument, but really there is a comeback to what Mr. Coste says.1 Geography is probably not geology, but geology is geography. You cannot regard structure as geography on the surface, but it is geology as soon as you get under the surface. In Canada, it is quite true that they went too close to the Rocky Mountains. When boring in the foothills, as Mr. Coste says, they were too close to the mountains where they got into a faulted area, and if there had been storage, it probably would have lost a good deal of the oil. The situation in the Calgary field is one that might be interpreted in many ways, but in front f the foothills there is a very deep syncline. The gas and oil that is recovered on the edge of the, foothills is of such a nature that we must assume that it is not the pure crude oil. It seems to be somewhat refined, or a condensation product. The solution, or at least the argument that appeals to me, is that as the deeper part of that basin is, say, 6000 ft. below sea level, there must have been some breaking up of the oil on account of pressure and of the heat, and we are getting gas, traveling up toward the surface in the foothills; and as it comes up, it probably condenses again, and is caught in folds on the edge of the syncline so that we have a natural condensing machine there. The oil is not found on the eastern side of the folds, it is found on the western side. On the eastern side and on the summit there is a little light oil, gasoline, we will say, blowing into the well once in a while; now that looks like a natural condensation of the gas and a storage behind the summit.

Jan 5, 1919

By W. L. Fourney

This paper describes a number of model tests conducted in Plexiglas models to investigate the phenomenon of fracture pressurization. The models were examined with high speed photography while being subjected to explosive loading. At the same time pressure transducers were used to record the pressure in the borehole as a function of time and also along the path of the propagating fracture to measure the pressure at various locations along the fracture as a function of time. Both propellants and explosives were used to charge the borehole. Air as well as fluid filled boreholes were needed to provide a variety of pressure rise rates. On some tests eddy current displacement gauges measured crack opening displacements as a function of time. As a final check high speed photographs taken during the event were used to visually ascertain the location of the fracture at any given time.

Jan 1, 1984

By G. E. Keller, G. D. Coe

Several methods have been devised for rapid determination of sulfur in coal using a high-temperature combustion furnace. The fundamental principles of the various methods are similar but the techniques vary widely. The method described herein is no different in principle from some of its predecessors but varies considerably in technique. Originally devised to overcome the low-accuracy criticism leveled against the others, the tube-furnace method has proved successful for limited applications. Work is being done to widen the applicability of the technique. Subsequent to the work of A. Vita1 in 1920, a number of investigators have published data dealing with the rapid determination of sulfur in coal using a high-temperature combustion furnace.2-5 These, together with several unpublished methods, involve wide differences in technique although they are all similar in principle. Investigation of typical details of procedure showed that poor precision or accuracy could be attributed to one or more of the following: 1) inadequate quantity of sample to be representative, 2) a delivery tube temperature too low to confine condensation to a washable area of the tube, 3) no provision for back washing the delivery tube, 4) incomplete absorption of the sulfur compounds due to inadequate bubbler, and 5) the false assumption that all of the sulfur is evolved as sulfur dixoide. The method herein discussed is no different in principle from some of its predecessors; the differences are in technique. Although the method is rapid—a determination can be completed in 5 min— accuracy has riot been sacrificed in order to achieve speed. MATERIALS AND EXPERIMENTAL WORK Fig. 1 shows the arrangement of the equipment. A metered volume of oxygen is passed through calcium chloride for removal of moisture, then through Ascarite for removal of carbon dioxide, and thence through a glass tee to the feed end of the combustion tube. Connected to the side arm of the glass tee is a rubber tube that is closed with a pinch clamp during combustion of a sample. The products of combustion are expelled through a Vycor bubbler, the end of which is submerged 3 cm below the surface of a 1 pct hydrogen peroxide solution contained in a 300 ml high-form beaker. At the completion of the 4-min combustion period the contents of the beaker are titrated to a yellow end point, using a methyl red indicator, with 0.05 N sodium hydroxide (or sodium tetraborate). The pinch clamp on the tube leading from the tee in the oxygen line is then opened and mouth suction applied to draw the hydrogen peroxide up into the bubbler past the ell, almost to the rubber tube connecting the bubbler to the combustion tube. This washing of the bubbler is repeated until no further acid reaction with the indicator is obtained. The hydrogen peroxide-sul-furic acid solution is then titrated to the final yellow end point. Test work conducted at the Robena Laboratory disclosed the following critical conditions that had important bearing on the precision of the method: Weight of Sample: Several series of tests wherein the sample weight ranged from 0.1 to 0.5 g of -60 mesh coal showed that the lowest variance (standard deviation squared) resulted from the use of 0.5-g samples; the variance was slightly greater when 0.3-g samples were used, and with less than a 0.3-g sample weight the variance increased rapidly with decrease in weight. Although the use of a 0.5-g sample invariably resulted in a very slight explosion as soon as the sample entered the hot zone of the combustion tube, this did not detract from the precision of the method. Temperatures: Mott and Wilkinson5 found that a combination of low temperature (1250°C) and low oxygen flow rate (less than 700 ml per min) tended to give high results due to formation of oxides of nitrogen. Although the method herein employs a much higher oxygen rate than 700 ml per min, as an additional precaution to assure accurate results, 1315°C (2400° F) is recommended as the most desirable furnace temperature. The temperature of the elbow of the bubbler should be at least 75°C to minimize condensation

Jan 1, 1961

By N. J. Grant, F. B. Cuff

DURING a recent investigation of high-purity aluminum,' evidence was found for grain-boundary sliding and migration at room temperature. The investigation was concerned primarily with an electron-microscopic study of a fine (approximately 1 micron) network that appeared on the surface of chemically polished aluminum. The nature of the network will not be discussed since it serves only as markers showing relative displacements in this instance. The pertinent observation, shown in Fig. 1, was made on a flat tensile specimen which had been strained about 8 pct at room temperature. As can be seen in this electron micrograph, a grain boundary has undergone a certain amount of sliding. The reason for the existence of the two differently appearing networks is given in the foregoing reference. For present purposes, however, the transition region can be disregarded. A close study of this picture reveals that in addi- tion to sliding there is a narrow band adjacent to and above the grain boundary. Fig. 2 is a schematic drawing showing the essential features of this band.

Jan 1, 1959

By Nicholas T. Camicia

A career in the coal mining industry today offers students one of the most interesting and challenging opportunities available in the industrialized world. As reserves of other fossil fuels dwindle in face of the world's demand for energy, it has become apparent that coal, once the king of energy sources, must be relied upon again as the major fuel for powering industrial growth in developed and developing nations. Centuries of coal supplies lie beneath the earth's surface, assuring the world of a steady, plentiful supply of energy until science and technology can produce a way to harness and efficiently use renewable sources, such as solar. The need to increase our use of coal during the last two decades of the 20th century is reason enough to believe that the future growth of the coal industry is assured. A major impediment to that growth might be backward national public policies that could restrict the full utilization of our coal reserves. These policies could result from overregulation and a failure of the public to recognize that coal use, with proper techno- logical safeguards, is compatible with our society's environmental-quality objectives. Communication of this problem and its solution is a major undertaking of the coal industry in the 1980s. At the end of the 1970s, the American coal industry was producing approximately 635 Mt/a (700 million stpy) of coal. To meet the nation's projected energy needs by 1985, the annual tonnage must be doubled. A similar scenario is predicted for the rest of the world. Such growth in the modern international business world will require huge additional amounts of capital, equipment, and people who know how to wisely raise and apply the capital; use the equipment productively; and deal with the many community, public, and governmental problems such expansion will create. Whether a student's interest is in actual mining operations, business administration, engineering, finance, law, industrial relations, marketing

Jan 1, 1981

By H. Biloni

A metallographic study of solute segregation produced during controlled solidification of Sn-Pb alloys has previously been reported.' It was found that the growth conditions which produced well-developed cellular substructures led to severe segregation, and even at solute concentrations of 0.2 wt pct Pb regions of a lead-rich phase were formed at the junctions of cell boundaries (nodes). Similar sample preparation and etching techniques have now been applied to several tin alloys at more dilute concentrations. The crystals were solidified uni-directionally under less-severe growth conditions so that the predominant interface structure was composed of two-dimensional cells.* Binary alloys with lead, using 9.999 pct Sn as a solvent, and ternary alloys with lead and bismuth or lead and antimony, using zone-refined tin as a solvent, were examined. The liquid was decanted from the growing crystals in all cases to reveal the interface structure and ensure that two-dimensional cells were being formed. However, since interference may arise from a liquid layer that clings to the interface during decanting,3 an examination of the segregation pattern was always made behind the interface. In all cases, the structure within the bulk of a crystal at greater than 1 cm behind the decanted interface was substantially the same as that nearer the interface. Representative photomicrographs of the dilute Sn-Pb alloy are shown in Figs. 1, 2, and 3. Most observations are similar to those of the previous investigation. For example, the solute concentration at the cell walls is higher than in the intercellular regions; where cell boundaries meet, the segregation is enhanced; the macromosaic or stria-tion substructure and grain boundaries show enhanced segregation; there is also a depletion of solute at cell walls near a striation boundary, as Spittle et a1.4 have observed at decanted interfaces. Not all these observations can be seen in the photos shown since attention has been focused on a special feature; as evident in the photomicrographs, cer-

Jan 1, 1965

By R. H. Kolb

A long term project at Shell Development Co.'s Exploration and Production Research Laboratory has been the improvement of the accuracy and the ease of BHP measurements. As a result of these efforts, two complete and separate systems have now been built for the automatic logging of BHP variations. The first of these is a small-diameter instrument suitable for running through production tubing on a single-conductor well cable. During the development of this instrument, as much emphasis was placed on providing a high degree of usable sensitivity and repeatable accuracy as on obtaining the advantages of surface recording. The second system combines the benefits of automatic, unattended recording with the convenience of a permanently installed Maihak BHP transmitter.' THE CABLE INSTRUMENT For many years the standard instrument for BHP determination has been the wireline-operated Amerada recording pressure gauge or one of several other similar devices. This gauge records on a small clock-driven chart carried within the instrument, and although relatively precise readings from the chart are possible, they are difficult to ob-tain. a Both the maximum recording time and the resolution of the time measurements are limited by chart size, and when a slow clock is required for long tests, the precision of the time measurement is often inadequate. Since it is impossible to determine the data being recorded until the gauge has been returned to the surface, wasted time often results when a test is protracted beyond the necessary time or when it is terminated too soon and must be re-run. Clock stoppage or other malfunctions which would be immediately apparent with surface recording remains undetected with down-hole recording; the test is continued for its full term with a consequent loss in production time. As new uses for subsurface pressure data evolved, the shortcomings of the wireline instrument became increasingly apparent, and the concurrent development of a surface-recording pressure gauge and the associated high-pressure well cable service unit' was undertaken. Description of the Instrument Because of its ready availability and advanced degree of development, the Amerada bourdon-tube element was chosen as the basic pressure-sensing device. This element converts a given pressure into a proportional angular displacement of its output shaft, and a suitable telemetering system was designed to measure accurately the extent of this displacement and to transmit the measurement to the surface and record it. The telemetering system furnishes a digital record printed on paper tape by an adding machine-type printer. The present arrangement provides a resolution of one part in 42,000 over the angular equivalent of full-scale deflection, giving a usable sensitivity of better than 0.0025 per cent of full scale. An additional refinement simultaneously records on the tape the time or the depth of the measurement, also in digital form. When the instrument is placed in operation, an adjustable programer can be set to initiate a read-out cycle automatically at selected time intervals. When subsurface pressures are changing rapidly, readings may be recorded as frequently as once every 10 seconds; when pressures are more nearly stabilized, the period between readings may be extended to as much as 30 minutes. Because the instrument is surface-powered as well as surface-recording, the maximum period of continuous logging is (for all prac. tical purposes) unlimited. The subsurface instrument is a tubular tool, 1 1/4-in. in diameter and 6.5 ft in length, operating on 12,000 ft of conventional 3/16-in. IHO logging cable. The transmitting section, mounted above the bourdon-tube element in place of the regular recording mechanism, contains no fragile vacuum tubes or temperature-sensitive transistors. This unit has been laboratory-tested to 1 0,000 psi and 300°F and has performed dependably during a number of field operations. The down-hole transmitting arrangement can be fitted to any standard Amerada pressure element, regardless of range and with no modification of the element itself. Calibration To obtain a repeatability commensurate with the sensitivity and resolution of the instrument, it was necessary to develop a special calibrating technique. The manufacturers of the Amerada recording pressure gauge claim an accuracy of only 0.25 per cent of full scale, which is a realistic figure for normal calibrating and operating procedures. An exhaustive investigation was made of the errors inherent in the bourdon-tube element, itself, independent

By John W. Tieman

Coal is a term applied to vegetable matter (trees, grasses, etc.) which was subjected to heat and pressure through geologic ages. This resulted in a change in both the physical and chemical properties. Because its chemical composition is variable, geologists classify coal as a heterogeneous mineral rather than a homogeneous mineral. Peat represents the initial, unconsolidated stage in the development of coal. This coalification continues with time and the application of temperature and pressure to lignite, subbituminous, bituminous, and anthracite toward the theoretical graphite end member. PHYSICAL PROPERTIES OF COAL The physical properties are concerned with the characteristics of coal in its natural state, or prior to its end use as a fuel. For example, the hardness and grindability of coal determine the maintenance cost for coal mining, handling, and pulverizing equipment; the specific gravity of coal and its associated minerals determines the coal preparation technique used in a cleaning plant as well as the capacity of coal bins, boats and size of cargo, and other coal storage facilities. The physical properties are, of course, dependent on the chemical constituents of coal, and all properties are interrelated. Specific Gravity The specific gravity (sp gr) of a solid is the ratio of the weight of a cubic foot of the solid to the weight of a cubic foot of water. The specific gravity of pure coal has been reported to range between 1.23 to 1.72 and increases with the change in rank from lignite to anthracite. This means that it is 1.23 to 1.72 times heavier than water.

Jan 1, 1981

By S. G. Proctor, D. L. Baaso, W. V. Conner

A double crucible system was developed for I-g scale plutonium reductions. The equipment consists of an inner MgO crucible, an outer MgO crucible, and a stainless steel pressure vessel. The reduction charge is PIaced in the inner crucible and the annulus between the inner and outer crucibles is filled with a mixture of calcium and iodine. The exothermic reaction between the calcium and iodine in the annulus supplies the heat required for complete reaction of the reduction charge ana' good metal coalescence. Metal yields of 80 to 85 ,pct were obtained from I-g scale reductions and yields as high as 97.5 pct were obtained from 0.5-g scale reductions. The system was used to reduce charges containing as little as 0.1 g of Pu resulting in metal yields up to 90 Pct. THIN metal foils of highly enriched plutonium isotopes are used as targets for cross section and other measurements. The isotopes are separated in the calutrons at Oak Ridge and are very expensive to prepare. Often, only 1 or 2 g of material are available thereby emphasizing the need for a method of preparing these small quantities of metal. Procedures for 1-g scale plutonium reductions have been described, but these procedures require elaborate or expensive equipment. For example, the procedure described by Anselin et al.1 requires an inert atmosphere glovebox and induction heating equipment. The procedure described by Baker2 also uses induction heating equipment to obtain the recommended heating rates and liner temperatures. Baker's procedure also requires high purity PuF4 with very little PuO2 present. The procedure described in this paper resulted from a search for a simple and inexpensive method for making 1-g scale plutonium reductions. EXPERIMENTAL Equipment. The equipment required for the double crucible system consists of a pressure vessel, two MgO crucibles, a MgO crucible lid, and a resistance-heated, vertical crucible furnace. The crucibles were slip cast from high purity MgO and were supplied by the Coors Porcelain Co. and the Norton Co. The pressure vessel and lid were fabricated from 316 stainless steel. Materials. The PuF4 used for this study was obtained from the P1utoniu:m Metal Production Department at Rocky Flats. The PuF4 was prepared in a con- tinuous hydrofluorinator by reacting Pu02 with HF at 650°C. The isotopic composition of the plutonium was approximately 93 pct 239PU, 6 pct 240PU, and 0.5 pct 241PU. Some of this PuF, contained less than 1 pct Pu02 (Batch No. 6 and 7), while other batches contained up to 15 pct Pu02 (Batch No. 3). The chemical analyses of all the PuF4 used for this study is given in Table I. The calcium was 99 pct pure, AEC grade, and only that fraction which would pass through a 20 mesh screen was used. The I2 was USP grade re-sublimed I2 which was ground before being used. Procedure. Various charge compositions and methods for loading the double crucible system were tested. The optimum conditions for 1-g scale reductions are described below. The double crucible system was loaded as shown in Fig. 1. The outer crucible was placed in the pressure vessel and the annulus between them was filled with MgO sand. The inner crucible was placed in the outer crucible, supported by a layer of MgO sand in the bottom of the outer crucible. A mixture of 5.2 g of Ca and 25 g of I2 was placed in the annulas between the two crucibles. The upper portion of the annulas was filled with MgO sand. Next, a layer of a mixture of calcium and I, equal to 20 wt pct of the calcium and I2 used in the main charge was placed in the bottom of the inner crucible. The PuF, to be reduced was mixed with a 30 pct excess of calcium and 1 mole of I2 per mole of Pu and this mixture was placed in the inner crucible. The charge was topped with a layer of a mixture of calcium and I2 equal to 20 wt pct of the calcium and I2 used in the main charge. The pressure vessel was sealed with a flat copper gasket and was purged by alternately evacuating and filling with argon. The purge valve was closed and the vessel was placed in a vertical crucible furnace which was preheated to 950°C. The furnace was turned off after 20 min of heating and the vessel allowed to cool. Experience has shown that. this amount of heating is sufficient to assure complete reaction of the charge. RESULTS AND DISCUSSION The double crucible system has been used to produce plutonium metal on a 0.1- to 1-g scale. Reduction

Jan 1, 1970

By John Chapman, J. C. Vaughan

Although a considerable amount of practical importance attaches to systems involving gases and molten metals, little is known regarding the effects of alloy elements upon the solubility of gases in liquid iron. The solubilities of hydrogen1 and nitrogen2,3 in pure liquid iron arc known and it has been shown that small amounts of silicon and aluminum3 exert only a small effect upon the solubility of nitrogen but greatly increase its rate of solution. This paper presents the results of a study of the solubility of nitrogen, at pressures approximately one atmosphere, in molten iron containing up to 15.8 per cent silicon. EXPEBIMENTAL METHOD There are two general methods by which the solubility of a gas in a molten metal may be determined. In the first, which Sievertsl employed, the gas is measured from a burette into the enclosure containing the metal and the amount absorbed is found by subtracting from the total volume that of the dead space in the container. The second method, which was used successfully for pure liquid iron, is to expose the molten metal to the gas until absorption ceases, then to solidify and analyze the metal. In either method the stirring produced by inductive heating prevents the development of a stagnant layer at the metal surface and ensures actual attainment of equilibrium. Obviously the second method is accurate only when the saturated metal is capable of solidifying without gas evolution. Since the rate of solution of nitrogen in iron is increased by the presence of silicon, it was to be expected that the rate of evolution would be correspondingly increased and for this reason the first method was selected. A sketch of the furnace is shown in Fig. 1. A small high-frequency coil having 17 turns fitted closely around a fused silica tube, 2 in. in diameter, in which was placed, on a bed of 60-mesh alumina sand, an

Jan 1, 1940

By J. C. Vaughan, John Chapman

Although a considerable amount of practical importance attaches to systems involving gases and molten metals, little is known regarding the effects of alloy elements upon the solubility of gases in liquid iron. The solubilities of hydrogen1 and nitrogen2,3 in pure liquid iron arc known and it has been shown that small amounts of silicon and aluminum3 exert only a small effect upon the solubility of nitrogen but greatly increase its rate of solution. This paper presents the results of a study of the solubility of nitrogen, at pressures approximately one atmosphere, in molten iron containing up to 15.8 per cent silicon. EXPEBIMENTAL METHOD There are two general methods by which the solubility of a gas in a molten metal may be determined. In the first, which Sievertsl employed, the gas is measured from a burette into the enclosure containing the metal and the amount absorbed is found by subtracting from the total volume that of the dead space in the container. The second method, which was used successfully for pure liquid iron, is to expose the molten metal to the gas until absorption ceases, then to solidify and analyze the metal. In either method the stirring produced by inductive heating prevents the development of a stagnant layer at the metal surface and ensures actual attainment of equilibrium. Obviously the second method is accurate only when the saturated metal is capable of solidifying without gas evolution. Since the rate of solution of nitrogen in iron is increased by the presence of silicon, it was to be expected that the rate of evolution would be correspondingly increased and for this reason the first method was selected. A sketch of the furnace is shown in Fig. 1. A small high-frequency coil having 17 turns fitted closely around a fused silica tube, 2 in. in diameter, in which was placed, on a bed of 60-mesh alumina sand, an

Jan 1, 1940