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By C. B. Auel

THE subject of this paper involves the crux of the industrial safety problem. It is not overstating the fact to say that "a plant can be made as safe as the management and the workers want it to be;" if such desire is not in evidence and it is not possible to maintain interest in the work of safety, there can be practically no headway beyond the first few steps. These first steps may be said to embrace simply the mechanical or equivalent guarding of tools and equipment and may be taken in a more or less perfunctory manner; but, it has been estimated, they will not effect a reduction of more than 25 to 35 per cent. in the accidents likely to occur in an unguarded plant. The question therefore may be pertinently asked, "Whose interest is meant in the title of this paper, employers', employees?, or both?" It has been repeatedly stated that no safety work of any importance can be carried on: in a plant unless the employer believes in the value of such work. Such statements are true, but have become threadbare with constant repetition and the public is led to believe, that employers differ from ordinary human beings, that their sympathy for their fellowmen has become dulled, and they can be awakened to a sense of the fitness of things with respect to safety, health, sanitation, working hours, etc. only by legislation. There will undoubtedly be found an employer, now and again, who measures down to such specification; but the speaker, in a number of years of close contact with large employers (and his experience has been duplicated by many others) has found that the employers are usually far in advance of the general public in matters affecting the welfare of their employees, including their safety, and not from a selfish viewpoint, but from the humanitarian, economic, etc. If, at times, there is an apparent lack of headway in the solution of some problem connected with employees' welfare, it is not so much due to indifference or a failure to be awake, on the part of the employer, as it is to a lack of knowledge of the way in which to proceed to its successful accomplishment. Further, employers are, only human and cannot follow. every one of the innumerable matters connected with an industry down to their minutest details; they must delegate certain individuals as their representatives, clothing them with the necessary authority to act. These representatives should be looked upon as the Management in their respective fields and the

Jan 6, 1925

By Boyd Guthrie, J. D. Lankford

A progress report on the oil-shale and shale-oil processing research program at the U. s. Bureau of Mines Oil-Shale Demonstration Plant. Legislation providing for the program and aims are briefly noted. The remoteness and rugged nature of the terrain at the plant site are important factors in construction and operations. Large-scale units now in operation are the crushing plant and two 40-ton N-T-U retorts. These are described in detail. Under construction are several retorting pilot plants and a 200 bbl per day refinery. The refineiy incorporates several types of thermal operation, three-stage low-temperature acid treating, doctor sweetening and rerunning. Data are presented on typical N-T-U retort runs. Yields of 90 to loo pct of assay are realized on 30 gal to the ton shale with a retort cycle time of 18 hr. Data also are presented showing a comparison of a Mid-Continent petroleum and N-T-U shale oil. This comparison indicates that shale oil has a high pour point, low API gravity, and contains about 0.8 pct sulphur and 2 pct nitrogen. The naphtha fraction contains 3 pct tar acids, 9 pct tar bases and jo pct olefins. The problems involved in refining shale oil into usable products are discussed in detail. Introduction The Bureau of Mines oil-shale program now under way at Rifle, Colo., was begun in July 1944 under the provisions of the Synthetic Liquid Fuels Act, which was passed in the spring of that year under the sponsorship of Senator Joseph C. O'Ma-honey of Wyoming and Congressman Jennings Randolph of West Virginia, aided by Michael W. Straus, former Assistant Secretary of the Interior, and others. The oil-shale plant is only a part of the Office of Synthetic Liquid Fuels, Bureau of Mines, which has under way projects to develop synthetic liquid fuels from coal and other solid materials at Pittsburgh and Bruceton, Pa., Morgantown, W. Va., Louisiana, Mo., as well as the Petroleum and Oil-Shale Experiment Station at Laramie, Wyo., and the oil-shale demonstration plant at Rifle. The oil-shale program is entirely experimental. It is not intended that oil will be produced in great quantities. Production will be limited to the volume obtained from plant-scale experimental operations, which will be kept to the minimum size needed to develop techniques and processes and to demonstrate costs. After the passage of the enabling act in the summer of 1944 a survey of the oil-shale resources of the Nation was made to determine the most suitable general area in which to establish the demonstration plant. The most suitable area was found to be in the Rifle-De Bequearea in Garfield County, western Colorado. Bureau of Mines field parties covered this entire area thoroughly

Jan 1, 1949

By R. M. Brick

Segregation can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-I2 per cent Si alloys. The phasial condition implicitly described above—solidification over a range of temperatures with a compositional difference between solid and liquid—is found in nearly all solid solutions or combinations of solid solutions and eutec-tics, Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually deter-minable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be described first because it is an essential part of the picture. Coring Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus I, 3, 7 and solidus 2, 5, 8, and where the vertical I, 4: 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. Ib) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1945

By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

By A. William Johnson

It was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that .will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomo-geneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot be obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yield information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most importarlt types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in 3 gold-lead

Jan 1, 1942

By A. William Johnson

It was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that .will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomo-geneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot be obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yield information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most importarlt types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in 3 gold-lead

Jan 1, 1942

By James H. Courtright, Kenyon Richard

L. H. Hart (Chief Geologist, American Smelting & Refining Co.)— Because of a widely recognized association between breccia pipes of one form or another and many important copper deposits, conditions under which breccia pipes develop have been of great scientific interest for many years. Since these phenomena first attracted attention, many theories have been advanced to explain their origin. This is not unexpected, since it is likely that they have been formed by and under a wide range of conditions. Moreover, the entire subject is confused by the fact that the term brec-cia pipe is applied to a wide variety of occurrences. To discuss any part of the subject intelligently, therefore, it is necessary to start with definitions of the terms used. In their discussion of the Toquepala deposit, Richard and Courtright have carefully defined the terms they have used in their presentation of a very logical geological history of Toquepala breccias. This is a real contribution, as there is no reference in the literature known to the writer where the history of a series of breccia pipe epochs, confined essentially within one channelway, may be read with the degree of certainty that appears to be possible at Toquepala. Although the following comments are intended primarily to emphasize points brought out in the article by Richard and Courtright, certan subsequent detailed mapping by Hollister and Houston7 within the main central mineralized area of the Toquepala deposits not only supports most of Richard's and Courtright's con- clusions but also contributes additional facts that strengthen and broaden the whole concept of the origin of the Toquepala breccia pipes. In detailed mapping by Hollister and Houston,' the most significant feature disclosed is a well developed system of concentric fracturing in rocks peripheral to the main breccia pipe throughout an arc of 300°, interrupted only by the late dacite agglomerate in the north quadrant. Although Richard and Courtright noted that such fractures were developed in the southern and southeastern areas, continuity in the east and west quadrants is established by consistent orientation of the stronger set of fractures and joints. The existence of these structural weakness trends is emphasized by the emplacement of dike-like phenomena in and along members of this fracture system. Richard and Courtright described one of these dikes in the southeast quadrant. They referred to it as a ring-dike, composed of dacite porphyry. This suggests an apparent structural control of at least a part of the dacite porphyry intrusion by features related to the Toquepala breccia pipe center. This raises a perplexing question, since the dacite porphyry intrusion had been presumed to antedate breccia pipe activity. However, if this ring-dike is related to the breccia pipe center, it may indicate that some part of the dacite porphyry intrusion advanced in a manner resulting in an intensely localized stress center, which produced the concentrically arranged fracture system. The ring-dike would then appear to be evidence strongly sug-

Jan 1, 1959

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 W. A. Ver Wiebe

The year 1939 in Kansas, with a production of 57,944,300 bbl. from 19,669 wells, shows a slight recession from the peak of oil production reached the previous year, when slightly over 59,000,000 bbl. of oil was marketed. The previous peak had been reached in 1917 with 45,451,000 bbl. marketed. Another still earlier peak had been reached in 1904, when slightly less than 5,000,000 bbl. was produced and sold. The production of gas probably reached a new peak during 1939 with a total of over 69 billion cubic feet. Between the peak of the year 1908, when over 80 billion cu. ft. was produced, and that of 1939 the production dropped to 16 billion cu. ft., in the year 1921. During the year 1458 wells were drilled. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or recompleted in a different geological horizon. Nearly 75 per cent (1029) of the total number of wells were completed as commercial oil wells (824 in western and 205 in eastern Kansas). The commercial gas wells completed number 71, of which 24 are in eastern Kansas and 47 in western Kansas. The remaining completions include 154 dry holes in eastern and 204 dry holes in western Kansas. Based on daily potential capacity the new discoveries of the year accounted for a cumulative initial production of 264,000 bbl. in eastern and 1,158,827 bbl. in western Kansas. It is interesting in this connection to note that the number of wells completed in the state rose gradually to a first peak in 1904, when 2782 were drilled. The number dropped off rapidly to 368 three years later, but rose to the second and highest peak in 1918, when 4671 wells were completed. In the period between 1904 and 1912 more gas wells than oil wells were completed. Between the high peak of 1918 and the somewhat lower peak of 1937, the low point was reached during 1931 with the completion of only 470 wells. In the matter of new pools discovered, Kansas again ranks high. The exact number depends somewhat upon the interpretation of a "new" area—whether it should be called a new pool or a long extension of an older pool. In some places this determination cannot be made until more wells are drilled within the area. Therefore, the figures given

Jan 1, 1940

By R. M. Waterstrat

The phase VPt has been reported to have a crystal structure of the B19 (AuCd) type at low temperatures.''' A recent investigation3 has indicated that this phase forms by an ordering reaction from the disordered fcc Pt(V) solid solution which is stable at high temperatures. olander4 has shown that there exists a close structural relationship between the orthorhombic B19 structure and a fcc structure possessing the L1 , (CuAu) type of atomic ordering. One may derive the B19 structure by a shear-like displacement of the atoms in the (002) plane of the ordered fcc lattice along the (010) direction through a distance equal to one eighth of the unit cell dimension, see Fig. 1, followed by an orthorhombic distor; tion of the cube axes such that a = 2.693A. h = 4.413A. and c =4.767A (estimated uncertainty 0.005A). Filings of this phase were produced by grinding a VPt alloy having the B19 structure with a diamond dental grinding disc. When these filings were subjected to X-ray diffraction examination, a pattern of a severely cold-worked fcc structure was obtained. higher solution temperature used (1200 C) or to a much lower oxygen pressure than he reported, due to transfer through many bends and tubes in his complicated apparatus. An interesting observation was made when an oxygen addition was attempted in a cylindrical sample of columbium in the cold worked condition rather than in the annealed condition. The interior of the sample re-crystallized during the oxygen addition at 900°C. The periphery, however. (1 mm) did not recrystallize. A similar sample without oxygen recrystallized throughout the entire cross section. It appears that the re-crystallization is hindered by interstitial oxygen. Presumably, the interior recrystallized before appreciable oxygen could diffuse into the core. This work was supported by the United States Atomic Energy Commission. When the filings were annealed in a high vacuum furnace for 15 min at 110O0C, however. they returned to the B19 structure perhaps as a result of reordering. Subsequent less-severe cold-working of these filings by grinding in a hardened steel mortar and pestle at room temperature produced a transformation into a cold-worked L1, structure which was slightly tetragonal. Thus it appears that the degree of deformation may influence the final structure. Considerable line-broadening was observed in X-ray diffraction patterns obtained from the cold-worked filings and therefore no attempt was made to obtain accurate lattice parameters. Vacuum annealing treatments at 1100'C intended

Jan 1, 1970

By W. A. Ver Wiebe

The year 1939 in Kansas, with a production of 57,944,300 bbl. from 19,669 wells, shows a slight recession from the peak of oil production reached the previous year, when slightly over 59,000,000 bbl. of oil was marketed. The previous peak had been reached in 1917 with 45,451,000 bbl. marketed. Another still earlier peak had been reached in 1904, when slightly less than 5,000,000 bbl. was produced and sold. The production of gas probably reached a new peak during 1939 with a total of over 69 billion cubic feet. Between the peak of the year 1908, when over 80 billion cu. ft. was produced, and that of 1939 the production dropped to 16 billion cu. ft., in the year 1921. During the year 1458 wells were drilled. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or recompleted in a different geological horizon. Nearly 75 per cent (1029) of the total number of wells were completed as commercial oil wells (824 in western and 205 in eastern Kansas). The commercial gas wells completed number 71, of which 24 are in eastern Kansas and 47 in western Kansas. The remaining completions include 154 dry holes in eastern and 204 dry holes in western Kansas. Based on daily potential capacity the new discoveries of the year accounted for a cumulative initial production of 264,000 bbl. in eastern and 1,158,827 bbl. in western Kansas. It is interesting in this connection to note that the number of wells completed in the state rose gradually to a first peak in 1904, when 2782 were drilled. The number dropped off rapidly to 368 three years later, but rose to the second and highest peak in 1918, when 4671 wells were completed. In the period between 1904 and 1912 more gas wells than oil wells were completed. Between the high peak of 1918 and the somewhat lower peak of 1937, the low point was reached during 1931 with the completion of only 470 wells. In the matter of new pools discovered, Kansas again ranks high. The exact number depends somewhat upon the interpretation of a "new" area—whether it should be called a new pool or a long extension of an older pool. In some places this determination cannot be made until more wells are drilled within the area. Therefore, the figures given

Jan 1, 1940

By R. M. Brick

SEGREGATION can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming. steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-12 per cent Si alloys. The phasial condition implicitly described above-solidification over a range of temperatures with a compositional difference between solid. and liquid-is found in nearly all solid solutions or combinations of solid solutions and eutectics. Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually determinable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be. described first because it is an essential part of the picture. CORING Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus 1, 3, 7 and solidus 2, 5, 8, and where the vertical 1, 4, 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. 1b) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1944

By Ralph E. Esarey, Robert G. Reno

DriLLing activity and prospecting for oil and gas increascd in Indiana in 1941 over the previous year. The greater part of the drilling and development continued to centralize in the Indiana portion of the Interior Coal Basin, in the southwestern part of the state, but other parts of the state were not neglected. Many wildcat wells were drilled, including a series of core tests through the mantle of drift on the southern flank of the Michigan Basin. These core tests have been followed by several unsuccessful production tests. Production tests were made also along the axis of the Logansport-Kankakec branch of the Cincinnati Arch. In all, 411 field locations and 141 wildcat wells were completed in Indiana during 1941; that is, a total of 552 wells, an increase of 3 2 wells over the previous year. The field tests resulted in 260 oil wells, 57 gas wells, and 94 dry holes; wildcats included 16 oil wells, 3 gas wells and 122 dry holes. At the end of the year, 53 field wells and 34 wildcats were drilling. Gibson and Posey Counties led the state, with 154 and 155 wells drilled, respectively. However, 125 wells produced oil in Gibson County, while 98 produced oil in Posey County. Twenty-five per cent of all wells drilled were wildcat; II per cent of these produced oil and 5 per cent produced gas. Grifin field continued to lead in drilling activity, with 157 successful wells and 20 dry holes (including important wells defining the field). Production is found in five pay zones (Tar Springs, Waltersburg, Elwren, Aux Vases and McClosky). It produced a major part of Indiana's estimated 7,200,000 bbl. of oil during the year. Heusler field, Posey County, expanded with 11 oil ells and 4 dry holes in the Waltersburg and Tar Springs. Vienna field, Posey County, completed four oil producers in the Mansfield sandstone, between 1200 and 1250 ft. The College field, discovered late in 1940, received three oil producers and two dry holes in the Aux Vases. Two new fields were discovered in Posey County during the year: Lamott pool, in the Tar Springs, at 1950 ft., had initial production of 55 bbl. on discovery. One producer and one dry hole have been drilled since. Mt. Vernon pool found saturation in both the Waltersburg and Cypress formations. The discovery well tested about 1000 bbl. per day; it tested the McClosky at 2764 ft. Seven producers have been drilled since the October discovery. Welborne-Switch pool found oil in the Cypress sand at approximately 2500 ft., with an initial production of 33 bbl. One more well in the area proved a dry hole. Gibson County had the following discoveries in 1941: The Patoka field was opened by a McClosky producer of 300 bbl. Another producing well has been drilled. An attempt was made to extend the Illinois Mt. Carmel field into Gibson County, Ind., and one producer of 24 bbl, was completed on the Indiana side. A dry hole has since been drilled, one location south. One small well was completed in the Mans. field at 1105 ft. in sec. 31, T.2 S., R.12 W., Gibson County promising a new field

Jan 1, 1942

By W. A. Backofen

THE texture of cold-drawn copper wire has been described most often as a composite of [Ill] and [loo] directions aligned parallel to the wire axis.' Hibbard2 suggested that sufficient reduction will result in a single [111] texture and reported that after a reduction in area of 96.4 pct, such a texture was nearly obtained. Other work3-4 has shown that recrystallization within the temperature range of 300" to 1000°C does not alter the texture established by cold-drawing. In general, however, the texture of cold-drawn end annealed copper wire is not as well defined as the deformation texture. In the work reported here it was found that the double-fiber, deformation texture persists even after a reduction in area of 97.3 pct, and after recrystallization the texture is practically all [l00]. The wire used in this work was prepared in the following way. A 3/4-in. diam length of annealed OFHC copper was cold-drawn to a diameter of 1/8 in., a reduction in area of 97.3 pct. Each step in the drawing operation brought about a reduction in area that varied from 6 to 10 pct. Short lengths of this wire were etched in a 50-pct solution of nitric acid to a diameter of approximately 0.01 in. The texture of the cold-drawn specimens was determined with the conventional X-ray transmission diffraction technique using filtered copper radiation. The X-ray beam was directed perpendicularly to the wire axis and the diffraction rings were recorded on a flat film. Fig. la is typical of the photo-grams obtained and reveals that the cold-drawing schedule described above introduces a distinct, double-fiber texture with both [Ill] and [l00] directions aligned parallel to the wire axis. Supplementary measurements with a Geiger-Mueller counter of the intensity of reflection from (111) planes showed that the [111] component was much more predominant than the [l00]. Additional specimens of the drawn and etched wire were annealed in a salt bath at temperatures from 300" to 450°C. The texture of the recrystal-lized wire was studied with the same technique applied to the cold-drawn wire. Fig. lb is an X-ray photogram of a specimen annealed for 1 ½ at 300°C and is typical of those obtained from re-crystallized specimens. The photogram shows that recrystallization of this material is accompanied by the almost complete elimination of the [111] component of the deformation texture. A pronounced strengthening of the [100] component was evident from intensity measurements with a Geiger-Mueller counter. In summary, the deformation texture of cold-drawn OFHC copper wire, after a reduction in area of 97.3 pct, may still be described as a composite of [Ill] and [loo] directions aligned parallel to the wire axis. Recrystallization of such wire at temperatures from 300" to 450°C introduces a texture which consists almost entirely of a [loo] alignment. Acknowledgment Sidney Rolle of the Scomet Engineering Co. generously supplied the OFHC copper used in this work. References 'C. S. Barrett: Structure of Metals. p. 382 (1943) New York. McGraw-Hill Book Co. 2 W. R. Hibbard, Jr.: Trans. AIME (1949) -185, p. 598; Journal of Metals (Sept. 1949) TN 19E. 3 P. 422 of ref. 1. 'E. Schmid and G. Wasserman: Ztsch. Physik (1926) 40, p. 451.

Jan 1, 1952

By Robert G. Reno, Ralph E. Esarey

DriLLing activity and prospecting for oil and gas increascd in Indiana in 1941 over the previous year. The greater part of the drilling and development continued to centralize in the Indiana portion of the Interior Coal Basin, in the southwestern part of the state, but other parts of the state were not neglected. Many wildcat wells were drilled, including a series of core tests through the mantle of drift on the southern flank of the Michigan Basin. These core tests have been followed by several unsuccessful production tests. Production tests were made also along the axis of the Logansport-Kankakec branch of the Cincinnati Arch. In all, 411 field locations and 141 wildcat wells were completed in Indiana during 1941; that is, a total of 552 wells, an increase of 3 2 wells over the previous year. The field tests resulted in 260 oil wells, 57 gas wells, and 94 dry holes; wildcats included 16 oil wells, 3 gas wells and 122 dry holes. At the end of the year, 53 field wells and 34 wildcats were drilling. Gibson and Posey Counties led the state, with 154 and 155 wells drilled, respectively. However, 125 wells produced oil in Gibson County, while 98 produced oil in Posey County. Twenty-five per cent of all wells drilled were wildcat; II per cent of these produced oil and 5 per cent produced gas. Grifin field continued to lead in drilling activity, with 157 successful wells and 20 dry holes (including important wells defining the field). Production is found in five pay zones (Tar Springs, Waltersburg, Elwren, Aux Vases and McClosky). It produced a major part of Indiana's estimated 7,200,000 bbl. of oil during the year. Heusler field, Posey County, expanded with 11 oil ells and 4 dry holes in the Waltersburg and Tar Springs. Vienna field, Posey County, completed four oil producers in the Mansfield sandstone, between 1200 and 1250 ft. The College field, discovered late in 1940, received three oil producers and two dry holes in the Aux Vases. Two new fields were discovered in Posey County during the year: Lamott pool, in the Tar Springs, at 1950 ft., had initial production of 55 bbl. on discovery. One producer and one dry hole have been drilled since. Mt. Vernon pool found saturation in both the Waltersburg and Cypress formations. The discovery well tested about 1000 bbl. per day; it tested the McClosky at 2764 ft. Seven producers have been drilled since the October discovery. Welborne-Switch pool found oil in the Cypress sand at approximately 2500 ft., with an initial production of 33 bbl. One more well in the area proved a dry hole. Gibson County had the following discoveries in 1941: The Patoka field was opened by a McClosky producer of 300 bbl. Another producing well has been drilled. An attempt was made to extend the Illinois Mt. Carmel field into Gibson County, Ind., and one producer of 24 bbl, was completed on the Indiana side. A dry hole has since been drilled, one location south. One small well was completed in the Mans. field at 1105 ft. in sec. 31, T.2 S., R.12 W., Gibson County promising a new field

Jan 1, 1942

By M. H. Caron

THE most outstanding property of ammonia liquors, used in the ammonia leaching process is their very limited ability to dissolve all compounds present in reduced ore except nickel and cobalt. Although they do have such a high degree of purity, even the smallest amounts of impurities contaminate the precipitate of basic nickel carbonate that may be obtained from pregnant liquors by straight distillation. Figures have been given in a separate paper regarding the extent of such contamination. The product of straight distillation is likely to contain small amounts of Fe, Mn, MgO and SiO2 as well as some sulphate and sulphide. The sulphur can be readily eliminated by calcination of the product at the proper temperature and MgO and SiO2 by reduction and melting of the metal with a suitable flux. After such treatment the metal is relatively pure, and the iron and manganese content will be very small. The cobalt content, however, may vary considerably, depending upon the ore treated. The metal obtained from pure true garni-erite ores usually has only a small cobalt content of less than 1 pct. Metal obtained from medium grade iron-rich nickel ores may show cobalt values from 2 to 3 pct, and the alloy obtained from laterite is likely to contain as much as 10 pct cobalt. By proper treatment a good deal of cobalt may be recovered from lateritic nickeliferous iron ores, and cobalt will become the major constituent of the pregnant liquor if asbolan ores or similar products are treated. The pregnant liquor of "run of mine" nickel ores may have a pinkish shade, indicating the presence of cobalt. It is evident that from such liquors the metals should be recovered separately. Even if cobalt is present in only very small amounts, it would probably be economically justifiable to recover both metals as pure as possible if a suitable process could be devised. The author has made investigations along this line and has patented some processes adapted to the treatment of this type of solutions. Selective Dissolution of Nickel from Basic Nickel Carbonate Containing Some Cobalt: Basic nickel carbonate obtained from true garnierite ores by straight distillation of the pregnant liquors, always contains some cobalt as well as the normal impurities. In. order to improve the quality of the nickel product and to recover most of the cobalt, the following process has been devised. By using liquors with a low CO2 to NH3 ratio, nickel can be redis-solved preferentially to cobalt. It is not a sharp and clean separation but a selective one, for the bulk of the nickel may be redissolved with a small amount of cobalt, and a small residue may hold the bulk of the cobalt. The greatly increased cobalt content of the residue is indicated by a pronounced olive green color, in contrast with the light green color of pure basic nickel carbonate. The following example is given from Dutch patent No. 52788, Klasse 40a. 43 granted June 17, 1942: The original precipitate contained about 0.55 pct cobalt calculated on total nickel + cobalt. Eight hundred and fifty grams of the basic nickel carbonate were redissolved in leach liquor containing 7.12 pct NH3 and 2.12 pct CO2. The weight of the dry residue was about 3.5 pct of the original weight. By analysis it was found that the residue contained: Fe 1.93 pct, Co 6.01 pct, Ni 34.87 pct and also a certain amount of silica. The clear filtered blue liquor was distilled and the precipitate of basic nickel carbonate from this analyzed: Fe 0.008 pct, Co 0.0146 pct, Ni 42.37 pct. It is obvious that this product is considerably more pure, since calculation shows that about 94 pct of the original cobalt remained in the residue. Cobalt and nickel can be recovered by further

Jan 1, 1951

By J. E. Dorn, L. A. Shepard

LOW and Gensamer' demonstrated a number of years ago that the yield point phenomenon in mild steels was associated with the presence of fer-rite soluble carbon or nitrogen. More recently the yield phenomenon in body-centered-cubic metals containing interstitials was rationalized by Cottrell' in terms of a simple dislocation model. Interstitial atoms interact with dislocations in two ways; they cause not only local expansions but induce local tetragonality in the lattice. Consequently, interstitial~ interact with the hydrostatic tension and shear components of the stress about dislocations. They tend to migrate toward the expanded regions of edge dislocations and to assume sites that relieve the shear stresses of screw dislocations. Thus, a dislocation saturated with solute atoms constitutes a lower free energy state than that obtained when the dislocation threads through the average composition regions of the matrix. A greater stress will be required to separate the dislocation from its atmosphere than to move the dislocation through the matrix. This factor gives rise to the upper yield stress, which is required to unleash a series of dislocations in a localized region. This local yielding is propagated across the specimen to form a thin band of plastically deformed material known as a Lueder's band, making an angle of about 45" to the stress axis. Once the band has formed, deformation continues at the lower yield stress by the spreading of the Lueder's band in the direction of the applied stress. Undoubtedly the spreading of Lueder's bands at the lower yield stress is accomplished by the high stress concentrations at the band fronts, which serve to induce continued unlocking of new dislocations in advance of the migrating band fronts. Cottrell and Bilby have shown that the dependence of the yield point on temperature can be deduced by assuming that thermal fluctuations aid the stress in unlocking small dislocation loops from their solute atmospheres. Once a loop that exceeds a critical size has been nucleated, the entire locked diqlocation is released and can migrate. Fisher4 simplified this analysis by assuming that the locking forces were short range, so that if the dislocation loop were displaced only one Burgers vector from its atmosphere, it would be unlocked. Applying his model to the special case of delayed yielding under a constant stress of the order of the upper yield strength, he demonstrated that the delay time 7 for yielding should depend on stress and temperature according to where A and B are constants, G is the shear modulus, and u and T are the resolved shear stress and absolute temperature, respectively. Cottrell and Bilby, Fisher, and Fisher and Rogers' have shown that the above deductions are at least in qualitative harmony with the experimental facts. A number of investigators5-0 have shown that the yield point phenomenon can also be induced in sub-stitutional alloys of face-centered-cubic metals. In general such yield points are not as pronounced as those encountered in body-centered-cubic metals containing interstitials. The yield point phenomenon in these materials is usually enhanced by prestrain-ing at low temperatures and aging at intermediate temperatures. Undoubtedly the yield point phenomenon induced by strain aging substitutional alloys also results from locking of dislocations. But the locking of dislocations in substitutional alloys of face-centered-cubic metals differs somewhat from interstitial locking of dislocations in body-centered-cubic metals. Substitutional elements in face-centered-cubic lattices cause only radial displacements of the adjacent lattice points. Consequently, only the edge components of dislocations can be locked by the mechanism suggested by Cottrell. Additional locking, however, can be obtained by the Suzuki mcchanism.10 In face-centered-cubic metals, dislocations exhibit lower energies when they are present in the

Jan 1, 1957

By Leonard L. Melton, Calvin D. Saunders

The design and performance of many operations common to the petroleum industry depend upon the unique properties of a class of materials known as non-Newtonian fluids. The art of measuring and describing these properties, called rheology, has fallen far behind the field applica-tion of these fluids in this industry. Empirical methods are still employed although theoretically sound methods of analysis are now available. This paper illustrates a completely general method of analysis of the rheological properties of non-Newtonian fluids which id independent of the type of viscometer employed and also the rheological type of fluid encountered except those of a thixo-tropic or rheopectic nature. Values of the rheological properties of a fluid obtained using this method of analysis are based upon an absolute scale of measurement, eliminating the necessity of employ-jng arbitrary concepts of the flow properties of non-Newtonian fluids, The fundamental nature of this method of analysis is further demonstrated by evaluating the precision with which measurements have been made of these rheological properties by employing a dimensionless criteric: —the Fanning friction factor-Reynolds number correlation. INTRODUCTION Non-Newtonian fluids are not new in the petroleum industry. Particular properties of non-Newtonian materials have been recognized and used to advantage in drilling fluids and have found excellent application in the hydraulic fracturing process.'.' While usage of these fluids is not new in this industry, the art of measuring and describing their rheological properties is still in its infancy. This is reflected in the accepted method of evaluating drilling fluids, API RP 29, (1950), which recommends a one point "viscosity" measurement. These shortcomings are recognized by various groups in the industry and more adequate methods have been prposed.3,4 The efforts Of these people are to be commended; but, at the same time, the limitations of their method of analysis and viscometer must be appreciated. This method Of analysis is applicable Only to Bingham plastic fluids as is pointed out early in their articles. The consistency of a Bingham plastic fluid must also lie within the range of the viscometer which is also well defined by the author. It is believed that the apparent simplicity of this method of analysis and the utility Of Operation Of their viscometer will soon make the terms non-Newtonian fluid and Bingham plastic fluid synonymous as used in this industry; a tendency which has already been encountered. Application of this method of analysis to a non-Newtonian fluid other than a Bingham plastic can lead to erroneous results. The field of rheology has long been hampered by the adherence to arbitrary concepts of Of of the flow properties Of non-Newtonian fluids. This has resulted in the design and operation of viscometers so as to fulfill these concepts rather than following the more logical method of analyzing experimental data so as to yield a fundamental truth. completely Bingham proposed the concept Of plastic flow and yield asu rement. data presented by Buckingham could hardly be interpreted so as to substantiate this theory; but rather succeeded in establishing the fact that compliance with this flow concept could never be realized in the capillary tube vis-cometer.5 Bingham, in reply, sug-gested "Rather than complicate our formula, it would seem to me a much better plan to so change the conditions of flow that the formula will be linear... Reiner0 stated .This plan has been followed by me in collaboration with Miss Riwlin. . . . From the present paper (Reiner and Riwlin, 1929) it will be seen that it is possible to choose the conditions of flow so that the formula based on Bingham's law of plastic flow remains linear. This is realized in the rotation viscometer," Thus, a viscometer, with design and operation based on the Reiner and Riwlin equation for plastic flow, is restricted to a specific range of flow

Jan 1, 1958

By John R. Anderson, Michael B. Bever

CARBON may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,1 the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. EARLIER DATA The solubility of carbon in molten pure copper is about 0.0001 pct at 1100 °C and 0.0004 pct at 1475°C.1 Various authors2-6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range 1217° to 1245°C. This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By R. I. Lahring, C. G. Inks

A surfactant waterflood, using a block copolymer of ethylene and propylene oxide (PLURONIC L64*), wa., started in 1956 in Kansas to determine the commercial feasibility of such a process. The production formation was the Bartlesville sand at a depth of 1,400 ft. Leares in the test area had attained both primary and secondary production peaks, and were on a normal decline when the tests were initiated. The injection wells were taking water at a reasonable pressure and none of the operating conditions were particularly unusual. The leases were selected primarily because of normal operating conditions, and not because of any serious problems demanding remedie>,. Oil production and water injection data were recorded during the 10-year test period, and their compilation indicates that the surfactant resulted in an increase of about 9 percent in secondary oil production. Other benefits derived from the surfactant injection were lower injection pressure that resulted in reduced power consumption and reduced erosion of the pumps; and lower calcium scale buildup. These fringe benefits more than offset the cost of the surfactant used. Introduction During the past several decades, considerable research has been carried out on secondary recovery of crude oil that remains in the producing formation despite the most efficient, current primary production practices. Methods are constantly sought of increasing recovery of oil, while at the same time improving the economic efficiency of operations. One method that has received intensive study over the years is the use of a surfactant as a waterflood additive. Laboratory tests show conclusively that dilute solutions of surfactants remove considerably more oil from uncon-solidated sand cores than does water alone.'- The loss of surfactant by adsorption at solid-liquid interfaces has caused serious doubt that surfactants can be used economically as waterflooding additives. This is especially true with anionic and cationic surfactants, and to a lesser extent with nonionic surfactants. This work was undertaken to determine the effectiveness in increasing oil production by injecting water containing small quantities of a nonionic surfactant. The surfactant selected was PLURONIC L64*, a block copolymer based on ethylene and propylene oxide, having the following structure The selection of the test site, a typical shoe-string sandstone type of field located at Batesville pool, Toronto District of Woodson County, Kans., was made because of its normal primary and secondary recovery operating conditions, and not because of any serious operating problems. When the tests were begun, the field was experiencing the customary post-peak production decline of a waterflood. Using for the tests a field that was on a normal production decline, while maintaining constant all variables other than the addition of the surfactant. was of varamount importance if success or failure was to be attributed to a particular cause. It was reasoned that if a surfactant was added to the injection waters and nothing else was done to influence the oil production or injection of water, the effects of the surfactant on the flood could be determined precisely. Production History The first well in the tested field was drilled in 1935. Gas repressurization began immediately, but it was not until Aug., 1938, that the major portion of the field was developed. During the period of repressurization, 1,700 MMcf of gas was injected. As can be seen from the curves of Fig. 1, the production peak from gas injection was attained in 1937 and a normal production decline followed. Early in 1942, water injection wells were drilled and injection of water Was initiated. The amount of water injected increased as more injection wells were drilled until a peak injection rate of 2,700 BID was reached in

Jan 1, 1969