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By S. M. Brisbane

THE life of refractory linings in rotary cement kilns can be shortened by uneven or inadequate support of the kiln and its shell and by variations in the conditions of operation. Alteration of these factors may, according to their nature, bring about mechanical deterioration of the lining or promote chemical attack. Chemical attack has been described elsewhere.1-4 The distortion of cement kilns has been discussed in a general manner by Rochow,6 ho indicates the amount of distortion which may occur in an unlined shell, and by Rosenblad: who states that the deformations of the shell are greatest above the trunnions. The present article indicates the extent of the distortion of a kiln to an oval shape in certain selected positions and the deviation from a straight line of the kiln along its length between two supports. The cement kiln is a long, hollow, rotating cylinder consisting of steel plates which may be either welded or riveted together. This shell is supported on tires, frequently 60 ft apart, which roll on trunnions. The large mass of the kiln causes distortion of its cross-section; it becomes slightly oval, i.e., diameters lengthen as they become horizontal and shorten as they become vertical. There is also a tendency for the shell to bow between supporting tires; this bowing may be upwards or downwards depending on the position of the weight forces and the supports. The extent of the deviations from the ideal kiln shape was investigated. Observations described in this paper were made on the shell of the clinkering zone between the first and second tires of two of the kilns at the Geelong works of Australian Portland Cement Pty. Ltd. The kilns were both 400 ft long and 10 ft diam with a welded enlarged burning zone 11 ft 6 in. diam. The shell was fabricated from mild steel and in this section its thickness was 1 in. It was lined with 41/2 in. of chemically bonded magnesite-chrome bricks which were jointed with mild steel plates. The kilns operate on a 4 pct slope and the speed may be varied between 0.75 and 1.68 rpm. The wet process is used; kilns are coal fired and are fitted with integral coolers. Temperatures within the kiln are difficult to determine with any accuracy because of the absence of black body conditions, but surface temperatures are probably in the range 1420° to 1470°C. Average shell .temperatures at the two positions at which the deformation studies were made were 370°C and 355"C respectively. Methods: In determining the ellipticity it was necessary to measure the lengths of the vertical and horizontal diameters while the kiln was in operation; data obtained from a stationary kiln would not have the same practical significance. For this purpose the four points V, W, X, and Y at the ends of two mutually perpendicular diameters were marked on one kiln. The point X is shown in Fig. 1. For the measurement of the length of the vertical diameter a vertical column, to which a horizontally aligned telescope was attached, was placed 10 ft from the kiln. The telescope could be racked up and down in a vertical plane. Two sets of readings were taken, one set when each of the points V, W, X, and Y was at its maximum height above the

Jan 1, 1957

By E. A. Jones

THE Southeast Missouri division of the St. Joseph Lead Co. normally hauls and hoists over 5 million tons of lead ore each year. This ore is mined in the stopes and headings of 20 mines, hauled to a main line system, see above, and transported up to 6.4 miles to ore-hoisting shafts. Average haulage distance is 2.16 miles. A few years ago a distinguished mining engineer visiting this area for the first time remarked, "You do not have a mining problem; yours is a haulage problem." Its relative importance may be gaged by the fact that mine haulage represents about 25 pct of the total cost of mining ore, the most costly single underground operation. The Southeast Missouri lead belt is a mining district located about 65 miles south of St. Louis. This district is roughly 6 miles wide and 10 miles long. The ore horizon lies about 400 ft below the surface where most of the ore is mined from flat-lying beds of dolomitic limestone. This paper deals with the central part of the district, namely, that portion which contains a group of interconnected mines all in a central haulage system, serving four hoisting shafts. The two major hoisting operations are carried out at Federal No. 17 shaft and Leadwood No. 12 shaft. No. 17 accounted for about 70 pct of the ore hoisted in the district during 1950, averaging about 14,000 tons per operating day. The underground dumping and skip-pocket system at this shaft is similar to those of the other shafts except that it has two rotary dumps. The other ore-hoisting shafts have only one. It might be mentioned that waste rock is hoisted at still other shafts, hauled off, and dumped on the surface by trucks. The hoisting shafts are on a connected system of about 200 miles of underground 24-in. gage main line railroad. There is also the Bonne Terre system, with its own ore-hoisting shaft, which consists of 13.5 miles of 24-in. gage main line, located in the extreme north portion of the lead belt area. Smaller outlying mines such as Doe Run No. 12 and Hayden Creek operate on trackless or shuttle car haulage. In addition to the system of main line haulage, each contributing mine group has its own extensive system of stope or heading railroad. Trackless mining is making considerable headway in the Lead-wood and Desloge mines. Here the shovel loads into a shuttle car which in turn dumps into mine cars spotted on the main line track system. When the merits of underground haulage and surface transportation are compared, it must be remembered that in early days there were many individual

Jan 1, 1954

By Rex W. Woods

The clue history of performance of a highly volatile type oil reservoir which is now greater than 80 per cent depleted is presented. The reservoir is at a depth of approximately 8,200 ft and includes an area greater than 7,500 acres. The reservoir has been exploited by 10 wells which to date have yielded about 10,880,000 bbl of stock tank oil by pressure depletion. Reservoir pressure has declined from an original of 5,000 psi to approximately 1,450 psi. Produced gas/oil ratio has increased from 3,200 to 23,000 cu ft/bbl with a corresponriing increase in APl gravity of the stock tank oil from 440 to 620 . Pressure and fluid data are given for different stages of depletion. INTRODUCTION In papers by Sloan,' and Cook, Spencer and Bo-browski,' properties of highly volatile type reservoir oil were discussed in detail and methods were presented for predicting performance of reservoirs containing this type of fluid. The purpose of this paper is to present performance history of a highly volatile type oil reservoir designated as Reservoir A which has been produced by pressure depletion and field separation without processing of gas GEOLOGY The reterence field which includes Reservoir A is a structural feature north of a trend of major folding along a northeast-southwest axis. In the area of development, the structure has the appearance of a dome with formation dip of three to four degrees, but structural relations between the reference field and the axis of major folding to the south have not been determined. No faulting within the field is evident. Oil and gas productive sands have been found at depths of 7,000 ft to 10,000 ft in a columnar section of Mio-Oligocene age. The sand bodies in the section are lenticular and usually continuity of sand is limited to a small area. Sand A which forms Reservoir A at a depth of 8,200 ft, however, has exceptional continuous development in the reference field. Fig. 1 shows an isopachous map of net oil sand for Reservoir A. Net thickness of oil sand at producing wells ranges from 14 to 34 ft with an average of 22 ft. Pinch-out of sand has been shown by drilling in the southwest part of the field, but extent of the reservoir on the northwest and northeast parts of the field is indicated only by thinning of the sand. The vertical oil column between the highest and lowest producing well in the reservoir is 339 ft. No water-oil contact has been found within the reservoir. As interpreted from the isopachous map, the reservoir includes about 8,900 acres with an average net sand thickness of 12 ft. Because of limited data on extent of the reservoir, the isopachous map permits only an approximation of sand volume in the reservoir. DEVELOPMENT AND PRODUCTION Reservoir A was discovered during 1938 and was developed with eight wells to the end of 1942. One well was completed during 1946 and the tenth well in the reservoir was completed during 1951. Three of the original wells and the last completion have produced from Sand A only. Six wells have produced from Sand A through the casing side of dual completions. Initial producing rates of the original wells ranged from 800 to 1,000 BOPD. Production history for the reservoir is shown in Fig. 2. Production of the reservoir was begun during 1940 and in May, 1952, peak production from seven wells was 5,300 BOPD. At the end of March, 1954. cumulative production was 10.880,000

Jan 1, 1956

By Irving Cadoff, Kurt Komarek, Edward Miller

THE lead-telluride phase diagram as compiled by ansen' has one intermetallic compound, PbTe, with solid-solubility limits extending from 22 to 45 wt pct Te (31.4 to 57.1 at. pct). Pelzel2 redetermined the solubility limits on the lead-rich side of the compound by measuring the relative areas of the two phases in samples annealed in the liquid + compound region, and obtained data that agreed with that of Hansen. Recent studies of the semiconducting properties of PbTe3 however, have indicated that addition of either lead or tellurium to PbTe does not produce samples having carrier concentrations greater than about 10 19 cm-3. Assuming that each impurity atom results in one ionized charge carrier, this carrier concentration corresponds to a solubility range of less than 0.04 at. pct. Fritts and Karrar4 have also observed two phases in samples containing from 0.15 to 3.0 pct excess Pb. To resolve the discrepancy between these data, the solid solubility limits of the compound PbTe were reinvestigated, using several other techniques. Ten 25-g samples with compositions of 1/2, 1, 3, 5, and 10 wt pct excess Pb and Te and two 100-g samples of 15 and 65 wt pct Te were prepared, sealed in evacuated quartz capsules, and melted at 950oC. The 1 pct excess Pb and Te and the 15 and 65 wt pct Te alloys were homogenized for 96 hr at 450°C; the remaining specimens were annealed 50°C below the solidus temperature reported in Hansen. The specimens were polished and etched with dilute HNO,. All the samples were two phase, the second phase appearing at grain boundaries or as spheroidized inclusions in the grains. In the case of the tellurium rich specimens, the second phase could be identified as a eutectic. Debye-Scherrer powder diffraction patterns of the i, 1, 3, 5, and 10 pct excess samples were obtained using CuKa filtered radiation. The films were indexed as the B1 or NaCl structure. The calculated lattice parameter of PbTe was the same for all the specimens, with an average of a0 = 6.460 ± 0.0005A. Lines due to excess lead or tellurium were very faint but could be clearly seen in all the films. The relative areas of the two phases in the 15 and 65 wt pct Te samples were corrected for the differences in density of Pb, Te, and PbTe, and taken as proportional to the relative volumes of the two phases. The corrected relative volumes agreed with a phase diagram having negligible solubility of both lead and tellurium in lead tellurium. The density of the two specimens was obtained to give a third independent determination of the phase limits. The specimens were broken into small pieces to eliminate any internal porosity, and adherent air bubbles were removed by vigorous shaking under water for several hours. The density of lead (11.34 g per cm3) and of tellurium (6.25 g per cm3) was taken from the International Critical Tables and that of stoichiometric PbTe (8.25 g per cm3) calculated from the lattice parameter. For the 15 wt pct Te samples, the density assuming no solubility was calculated to be 9.89 g per cm3; the observed density was 9.86 g per cm8. For the 65 wt pct Te alloy, the density calculated for the case of no solubility was 7.24 g per cm3; the measured density wag 7.22 g per cm3. These results are consistent with those of planimetry and X-ray. SUMMARY Data have been presented which show that the solid solubility of both lead and tellurium in PbTe is

Jan 1, 1961

By A. Rosenzweig, M. M. Karnowsky

The generalized binary diagram of the Au-Sn-Pb system is presented. The chief characteristic is the pseudobinary between lead and AuSn. On the high-gold side of the pseudobinary, four reaction isotherms were found at 363°, 274°, 225°, and 204°C. On the low-gold side of the pseudobinary, three reaction isotherms at 277°, 205°, and 176°C were found. A vertical section from the eutectic solder composition to gold was developed from the isothermal sections generated. METALLURGICAL problems arising from the intentional or accidental formation of Au-Sn-Pb alloys in soldering applications have indicated a need for information on the phase equilibria in this ternary system. The literature indicates that a complete diagram presenting this information has not been prepared. Even the recent excellent work by prince' entitled "The Au-Pb-Sn Ternary System" actually extends only to the AuSn or 50 at. pct Au range. There are more events in the 50 to 100 at. pct Au than in the less than 50 at. pct range. This article by Prince furnished much guidance in preparing this report. Initial efforts with the isopleth from the eutectic solder composition 61.9 wt pct Sn-38.1 wt pct Pb and 0 to 90 wt pct Au indicated that extensions of the work to the whole of the diagram (even if in less detail) were necessary to understand this system. In undertaking the construction of such a diagram, this study used differential thermal analyses (DTA) and metallography with verification and identification of phases by electron microprobe analyses. EXPERIMENTAL PROCEDURE The procedure began with the development of a cell which would be unreactive with lead, tin, and gold, retain its strength to 1100°C, exclude oxygen, and also furnish a suitable well for insertion and protection of a thermocouple to monitor temperature changes in the material. Such a cell would make it possible to reuse the sample should a repetition of determination be desired. Fig. 1 is a photograph of two such quartz cells as finally developed. The specimens have been run many times. The cell is made up of an inner sample bucket and an outer capsule with a thermocouple well which the sample surrounds. The DTA unit was an assembly devised from available instrumentation. The sample holder was a 3-in.-long cylinder of nickel, 2 1/2 in. in diam, fitted securely in a vertical tube furnace. Two holes 7/8 in. in diam were symmetrically located to receive the quartz cells. A dummy cell with nickel powder was used as the reference. The absolute temperature was recorded with a Pt/Pt 10-pct Rh thermocouple with an automatic Kaye ice bath compensator. (Calibration indicated the compensator to be accurate to better than ±0.5° over the 100° to 1000°C range.) The absolute temperature was measured in the sample and recorded on an L&N mul-tirange recorder with a full-scale display of 1 mv and automatic ranging of 99 mv. The differential signal between the sample temperature and the reference temperature was amplified with an L&N microvolt amplifier and recorded on an L&N Speedomax G recorder. Since two charts were obtained, the chart speeds were equalized and each event was noted on the differential chart, and the temperature at that time was obtained from the temperature record.

Jan 1, 1969

By W. A. Anderson, F. N. Rhines, W. A. Johnson

The rate of the high-temperature oxidation of pure copper has been measured repeatedly by numerous investigators. It appears to be generally agreed: (I) that at constant temperature, after the initial stages of oxidation have been passed and the scale has attained a substantial depth, the film thickness increases in proportion to the square root of the time of oxidation; and (2) that for any given period of oxidation the logarithm of the square of the film thickness is proportional to the reciprocal of the absolute temperature of oxidation.' These relationships are explained upon the basis that the rate of diffusion of copper to the external surface of the film is the controlling factor in establishing the rate of growth. Extensive studies have been devoted also to the mechanism and rates of the early stages of oxidation. There is thus available a reasonably well established theory of the oxidation of pure copper upon which to construct an explanation of the more complex oxidation of copper alloys. Few general principles have as yet emerged from the chaos of observations that have been reported in the field of the oxidation of alloys.2 It is evident, however, that the copper alloys may be divided into two main groups, whose oxidation characteristics are distinguish- able. The first group, composed of the alloys with the noble metals, forms substantially pure copper oxide scales; the alloying element is concentrated within the residual metal, and sometimes particles of almost pure noble metal are found in the scales completely surrounded by copper oxide. In the second group, composed of the alloys of copper with the baser metals, the alloying element appears as an oxide in the scale, often in greater concentration than in the alloy itself and sometimes to the exclusion of copper oxide. The oxide scales of the latter class have been found to be made up of one, two, and sometimes more distinguishable layers of which the innermost is often metallic in character, composed of particles of the oxide of the alloying element embedded in essentially pure copper and known as the subscale or zone of internal oxidation. The need for a thorough quantitative study of these modes of oxidation is evident. Since it is apparent that several mechanisms must be cooperating to produce the complex oxide scales found on copper alloys, the analysis of the process into its several simple operations should prove instructive. Fortunately, it is possible experimentally to produce internal oxidation in the absence of an external scale; this permits the isolation and intensive study of one of the steps in the oxidation process. In the present research the rates of internal oxidation of an extensive series of dilute solid solution alloys of copper have been measured and a theory has been developed to predict the observed

Jan 1, 1942

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. E. Donath

Application of the coal hydrogenation process for the production of chemicals is described. It has been estimated that a plant to produce 31,090 bbl per day of chemicals and fuels would cost $326,- 000,000. These products would consist of 6.1 pct by weight tar acids, 50.8 pct aroma tics, 16.4 pct LPG, and 26.7 pct gasoline. THE coal hydrogenation process is well known as a means for the production of liquid fuels from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aro-matics and of tar acids and tar bases. The relative amounts of heavy and middle oil—boiling above and below, e.g., 325°C—can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.' Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydrogen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catchpot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1953

By Edward F. Winter, C. E. Ruoff

A silicon solid-state array image scanner is described. This paper deals with structural and performance properties of the array which basically consists of PIN photo and gating diodes, and low capacitance isolation diodes. Each chip of the array is composed of an 8 by 9 matrix of photo detector cells; each cell contains one each of the three diode types mentioned. This x-y matrix is read a column at a time with an access delay of approximately 100 nsec per column. It is designed to detect the presence or absence of illumination within 10-mil diam image spots located on a 15- by 15-mil grid. Radiant power level of an illuminated spot is low; of interest is the range around I uw with a of 8400g Structural improvements to the original array which will result THE purpose of this paper is to describe the results of a solid state scanner exploratory development activity. The scanner is intended to sense the presence or absence of low-level illumination falling upon a matrix of 10-mil wide squares arranged on a 15- by 15-mil x-y grid pattern. The light of interest has a wavelength of 8400, characteristic of radiation emitted from a GaAs lasing diode. This wavelength matches well the spectral absorption of silicon,' thus the well-developed silicon processing technology can be applied to fabricating large integrated arrays of PIN photocells to sense the radiation. The illumination state of the cells of the array is read, one column at a time, by addressing a drive line of the particular column in question and examining the state of those sense lines which are orthogonal to the drive Lines of in greater sensitivity at various wavelengths, both above and below 8400Å, and in greater speed are presented. These include variations in diffusion depth, resistivity of N and P regions, isolation techniques, and packaging. Trade-offs between access speed, cycle frequency, and sensitivity are discussed. A packaging approach to achieving an array composed of several chips is described. Requirements on this package are: 1) maintenance of 15- by 15-mil pitch of the light sensitive cell position, therefore positional accuracy of mounted 8 by 9 cell photo detector chips; 2) maintenance of inherent high array speed even though signal levels are low through high density close proximity mounting of monolithic sense amplifier circuitry. the array. One bank of N sense amplifiers is required, where N is the number of photodiode cells in each column of the array. CELL AND CHI" STRUCTURE A photograph of a single monolithic cell is shown in Fig. 1. Each cell is composed of three junctions, an isolation junction, a logic or blocking diode junction, and a photodiode junction; all of these junctions are connected electrically by a common N region. An electrical schematic of four cells of the array is shown in Fig. 2 with the associated driver and sense amplifier circuits in block diagram form. Note the common cathode configuration of the three diodes of each cell. Fig. 3, a diagram of the cell vertical struc ture, illustrates how the electrical configuration of

Jan 1, 1970

By Rollin E. Hook, Attwell M. Adair

The response of CrzO3 and C~304 to various heat treatments was studied in are-melted iodide chromizim over the temperature range 1000" to 1750°C. These oxides, which are present as impurity phases in this material, were identified by X-ray diffraction teclzniques which were supplemented by optical metallop-aphy. As a function of increasing temperature, Crs04 is first observable in samples annealed at 1300°C and coexists with Cr2O3 (the low-temperature oxide) over a temperature range exceeding 200°C. As the temperature decreases, Cr3O4 dissolves with the concomitant precipttation of Cr2Y2. Both oxides precipitate predominantly at pain boundaries. The reactions which occur are involved with at least ternary equilibria, possibly due to iron which is present as an impurity in arc-melted iodide chromium. HILTY, Forgeng, and Folkman' reported in their investigation of the Fe-Cr-0 system that Cr3O4 (with about 8 pct Fe substituted for chromium) is a primary phase found in alloys with 9 or more pct Cr. They reported that this phase is stable only at high temperatures and that below the liquidus Cr3O4 is disproportionated into Cr2O3 and chromium-rich metal for both Fe-Cr-O alloys and in oxygen saturated pure chromium. Further, they proposed that CrsO4 forms by a peritectic reaction between Cr2O3 and the liquid. On the other hand, Hook, Garrett, and Adair2 found in their investigation of impurity phases formed in "pure" chromium (material consolidated from iodide chromium crystals) that Cr3O4 forms intergranularly and is stable as low as 1500°C which is 375OC below the melting point of chromium. The purpose of the research described herein is to determine the temperature range of stability of Cr3O4, and to show the nature of its decomposition. This further investigation indicates that Cr3O4 undoubtedly occurs in this material as low as 1300°C. The chromium studied was consolidated and fabricated from iodide chromium crystals (ICr-5) and contained Fe r 135 ppm, Si = 20 to 100 ppm, and 0 = 35 to 137 ppm. A complete chemical analysis is given elsewhere.' Annealing was conducted in 1 atm of purified helium and all samples were rapidly cooled (-200°C per sec) by withdrawing them from the furnace hot zone under a high flow rate of helium. The details of the electrolytic-etching technique and electrolytic-digestion techniques for preparation of insoluble residues for X-ray examination are given elsewhere also.' EXPERIMENTAL RESULTS The Starting Material. The as-swaged rod (final swaging done at 900°C) had a wrought grain structure and contained a dispersion of CrzO3 inclusions of maximum particle size of about 2 or 3 p, Fig. 1. The microstructure also contained a dispersed

Jan 1, 1964

By S. J. Rothman, L. T. Lloyd

S. J. Rothman and L. T. Lloyd (Argonne National Laboratory)— Hagel's paperz0 discusses the question of the mechanism for self-diffusion in bcc transition metals. Recent work21"23 has led us to agree with him in reabandoning the ring mechanism in favor of a defect mechanism, most likely vacancies. On the other hand, we think that Hagel's attempt to group together all self-diffusion in bcc transition metals is wrong. We prefer the scheme of Peart, Graham, and omlin," who separate them into two groups. One group contains the anomalously behaved metals P titanium,', y uranium, and perhaps zirconim.' The other group contains a iron," this alloy was held at 1800°C for 2 hr before quenching, its structure was all a. B. C. Giessen, I. Rump, and N. J. Grant (Authors' reply)—We very much appreciate the discussion by Deardorff and Kato regarding the a to /3 transformation temperature of hafnium. In the W-Hf program, as well as in a current study of the system Cr-Hf, standard precautions were exercised against contamination, including vacua of less than 10"5 mm Hg and a weight control check of all specimens to insure an impurity rise of less than 100 ppm. Following receipt of the above discussion, a revision was made in the annealing process. Arc-cast specimens were etched with a 10 pct HF-90 pct HNO solution until 1 mm of surface, including a possible oxide film, was removed. Annealing was done in a hafnium container which provided a long diffusion path for gaseous contaminants. Finally, the heat treating time was shortened. Structural changes were noted to occur quite slowly. A 99.5 at. pct Hf alloy showed 70 pct /3 after 30 min at 1700°C and was 100 pct /3 after 10 min at 1715°C. After 24 hr at 1740C, the alloy was found to be 10 pct/3. This change is due to contamination; it was estimated that it corresponds to an increase of 60°C in the transformation temperature over a 24 hr period. The corresponding change in 30 rnin would be slight. Using the same hafnium as in the above publication, and three new alloys at 98, 99, and 99.5 at. pct Hf, the transformation temperature was indicated to be 1715" 15°C. Since this hafnium contained 4.4 at. pct Zr, a correction of 40 5C, based on an assumed approximately linear transformation temperature curve, must be made for pure hafnium. This yields a value of 1755 20°C in good agreement with Deardorff and Kato's value. Because the slope of the boundary is small, this permits a good extrapolation, and we regard the W-Hf alloys as well suited to check the Hf transformation temperature. niobirn,'' and molybdenum,22 whose activation energies correlate with the melting temperature and whose Do values follow Zener's predictions.28 We have no quarrel with Hagel's placing chromium into the second group; we disagree with his interpreting our data to make uranium fit into that group. Hagel considers that the measurements of self-diffusion in uranium below about 950°C represent combined volume and grain boundary diffusion. This contention is based on the curvature of the penetration plot for our 891°C run,4 which also has a nearly straight line plot of log c vs x. Hagel has extrapolated these characteristics to our 803.5C run and fitted his Arrhenius plot for self-diffusion in y uranium to our four highest temperature points only. We think this is wrong for the following reasons.

Jan 1, 1963

By F. M. Stewart, F. H. Callaway, R. E. Gladfelter

In this paper oil initially in place is calculated by the various methods commonly used for analysis of water drive fields using data available as time progresses. Rate and pressure are predicted by means of the same methods using data available at the end of two years' history. These predictions are then compared with subsequent performance permitting an evaluation of the methods, which are Modified Schilthuis, Simplified Hurst, van Everdingen et al (1952), and the Electric Analyzer. INTRODUCTION Several variations of the material balance equation, differing in the term used to evaluate water influx, are in common use for estimating oil in place, predicting rate and volume of water influx, and forecasting producing rates and reservoir pressure in water drive reservoirs. The electric analyzer with an electrical network set up to simulate the oil reservoir and aquifer and their contained fluids may be used for the same purpose. Examples of the application of one or another of these methods have appeared in the literature. The accuracy and reliability of the material balance for calculating oil in place have been covered.' However, there have been few articles in which more than one method has been applied to an actual field allowing a comparison. It is felt that a field example, simple in nature, where the Modified Schilthuis, Simplified Hurst, van Everdingen et al (1952), and the Electric Analyzer have been applied would be of benefit in providing an evaluation of these methods as to their comparative usefulness and reliability in calculating initial oil in place and predicting performance. The Torchlight Tensleep reservoir is a small field in a large aquifer. The reservoir oil is greatly under-saturated, having a bubble point of only 55 psi and 2 cu ft/bbl of gas in solution. Changes in the reservoir volume factor in the range of pressures encountered are small, meaning little error in converting production to reservoir conditions. The pressure has declined from 1,618 psi initially to 137 psi during the first four and one-half years. Water production has been negligible. For Torchlight, the material balance equation as discussed later is considerably simplified by the omission of terms having to do with free gas. Thus with simpler equations, less variables to consider, the large pressure drop, the absence of a gas phase, and rapid pressure-rate adjustments, which mean an unusual amount of history in a short time, the reservoir appears suitable for comparing the methods listed above. GENERAL INFORMATION ON THE FIELD The Torchlight field is located on the eastern side of the Big Horn Basin, Big Horn County, Wyo., approximately 3 miles east of the town of Basin. The Tensleep reservoir was discovered in September, 1947. It lies at a depth of about 3,000 ft and produces oil of 35" API gravity. A total of five wells have been completed in the Tensleep, but only four are now producing. The reservoir is well defined in areal extent in that a total of 13 wells have penetrated the Ten-

Jan 1, 1955

By P. A. Beck, A. Merlini

Quantitative texture determinations were made for rolled and for rolled and annealed strips of 3, 6, and 10 pct Zn brasses. The main components of the rolling texture gradually shift over a wide composition range from the orientation characteristic of copper to that of 70-30 brass. At least the main features of the corresponding gradual changes in the annealing texture may be accounted for qualitatively on the basis of the oriented growth theory of annealing textures. All the oriented nucleation-type theories are notably less successful in accounting for the observed textures. EARLIER investigations by von Goeler and Sachs,' Dahl and Pawlek,' and Brick, Martin, and Angier" suggested that the annealing texture of copper is more sensitive to the addition of solute elements than the rolling texture. It was reported3 that the cube texture changes over into a brass-type recrys-tallization texture on addition of about 1 pct Zn, while the deformation texture changes only at about 5 pct Zn. Such behavior would be difficult to reconcile with any theory of annealing texture formation that relates the annealing texture to the deformation texture. In particular, the oriented growth theory of the cube texture" is based on a certain orientation relationship between the cube texture and the main components of the deformation texture which could not be reconciled with the reported behavior of low brasses. It was, therefore, of interest to re-examine these textures by means of the quantitative methods now available. The deformation and annealing textures of rolled a brasses with approximately 3, 6, and 10 pct Zn have been determined in terms of (111) and (200) pole figures. Experimental Methods The chemical analyses of the Cu-Zn alloys of commercial purity used in the present work are given in Table I. Chill-cast bars of the tabulated compositions were rolled and annealed according to the following schedule: I—rolling from 1.2 to 1.02 in. thickness, 15 pct reduction area, annealing 15 min at 450°C; 2— rolling from 1.02 to 0.867 in. thickness, 15 pct reduction area, annealing 15 min at 450°C; 3—rolling from 0.867 to 0.600 in. thickness, 31 pct reduction area, annealing 2 hr at 540°C; 4—rolling from 0.600 to 0.400 in. thickness, 33 pct reduction area, annealing 2 hr at 480°C. In the final straight rolling of 96.25 pct reduction area, the strips were reversed end to end after each pass. The final annealing temperature was determined for each alloy by annealing specimens of the cold-rolled strips in salt bath for 5 min at varying temperatures. The results of the hardness measurements are given in Fig. 1, where the final annealing temperature used for each alloy in determining the annealing texture is indicated by a cross.

Jan 1, 1956

By E. C. Truesdale, Gerald Edmunds

A few years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.&apos; During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. Table 1.—Typical Analyses Percentnge by Weight Sum of Zinc Fe, Ib1 Fe Cd 1A1 cd Special High Grade*.......... 0.007b 0.005b 0.005b none O.OIOb C.P. (chemically pure)......... < 0.0002 0.0005c 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 637). b Maximum. &apos; Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson&apos;s1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned &apos; to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By E. A. Gulbransen, J. W. Hickman

INTRODUCTION DURING the past two decades considerable progress has been made in the art of manufacturing heater alloys. The conventional iron-chromium-nickel alloys have been improved by the addition of small quantities of other elements. Up to the present time, to our knowledge, there has not appeared a systematic study of these alloys where the newer tools of investigation have been brought to bear on the problem. It is not yet clear what roles the additional elements play in increasing life time in usage. As a first approximation one might guess that elements such as manganese, silicon, zirconium, calcium and aluminum would aid in the formation of a protective film on the alloy surface, thus retarding the oxidation rate and increasing lifetime. If these additional elements do form protective oxides in the outer surface of the oxide film, it may be possible to identify them by means of reflection electron diffraction. It is also possible that the additional elements may not diffuse to the surface but may remain at the interface between the oxide and the metal. Then, too, the major elements in the alloys undoubtedly form oxides which are stratified on the surface. If the minor elements concentrate in a layer in contact with the substrate where they undergo oxidation and if this oxide film offers resistance to the diffusion of iron, chromium and nickel ions, then the lifetime of the heater element might be expected to increase. It is also possible that preferential reduction in the diffusion rates of the several ions may occur to such a degree that oxides may form in the body of the film and on the outer surface which are different from those that would normally form if the additional elements were not present. The use of transmisson electron diffraction may aid us in interpreting these phenomena. Up to the present time all of the factors which influence the lifetime of a given heater element are not definitely known. Among these are: (I) The rate of oxidation of the alloy. This may be dependent upon the composition and the physical state of the alloy. (2) The stability of the structure of the coating which forms. Transitions from one structure to another or solid phase reactions resulting in a change of composition may occur. The tendency of the film to adhere to the substrate when heated and cooled successively will be important. (3) The evaporation of various constituents from the alloy such as the removal of carbon by oxygen in a decarburization reaction. With these possibilities in view, an electron diffraction study of the oxides occurring on six different nickel-chromium alloys was undertaken with the hope that the results of this study could be correlated with oxidation rate studies as determined by means of the vacuum microbalance method1 and with

Jan 1, 1948

By S. S. Solomons, V. H. Tillmann, L. Smaniotto

INTRODUCTION The Zinc Corporation, Limited and New Broken Hill Consolidated Limited (ZC/NBHC) mines are situated at Broken Hill, New South Wales, Australia (refer Fig. 1). Both companies are wholly owned subsidiaries of Australian Mining and Smelting Limited (AM&S). Annual production from both mines is 2.3 million tonnes of lead, silver and zinc ore mined by a variety of underground methods. From 1911 to 1968, conventional overhand cut and fill stoping (both open and square set timber) was used almost exclusively, though some trials with shrinkage and sublevel stoping were undertaken. The trial stopes used short holes in conparison with today&apos;s sublevel open stopes. Mechanised cut and fill methods with regular rockbolt support were introduced in the early 1960&apos;s and undercut and fill stoping replaced square set timber stoping for pillar extraction in the late 1960&apos;s. Since 1968, increasing emphasis has been placed on longhole open stoping (LHOS) although some areas of the orebodies are comrnrnitted to the abovemehtioned methods since existing stope development makes it impracticable to change. In 1979, approximately half the total production was mined by LHDS and it is expected that the LHOS proportion will increase in the future. A vertical crater retreat method of longhole mining has also been successfully introduced to replace the undercut and fill stoping of some pillars and it is expected that this stoping method will be used in some future primary ore extraction. This paper reviews the progress of LHOS technology at ZC/NBHC with emphasis on the stope planning and design process and the importance of rock mechanics applications. The objective has been to maximise the primary extraction of the orebody giving due consideration to stability and safety. This has led to the design of a novel sloped wall longhole stoping method which should eliminate the formation of pillars by mining the orebody in a "continuous" manner incorporating a sloped sand interface between the blocks of ore being mined and the previously mined sandfilled stope. The expected results include the complete extract of the orebody without the formation of pillars and with minimal dilution of ore with sandfill. The evolution of the method can be best illustrated by following the mining progress of the relatively new Southern &apos;B1 Lode orebody at the NBHC mine. GEOLOGY Southern &apos;8&apos; Lode is the southern extension of the &apos;Bt Lode orebody, which is currently being mined further to the north in ZC/NBHC (refer Fig. 2). The ore block being developed and stoped extends for a vertical height of 90 metres from No. 17 level down to approximately ten metres above No. 19 level. The ore minerals are sphalerite and galena with the zinc:lead ratio averaging approximately 3:l with a minor amount of silver associated with the galena. There is a sharp contact between the ore and the country rock on the footwall and keel, while the hanging wall gradates into medium and low grade material. The gangue is primarily quartz together with garnet, biotite, feldspar, gahnite, sericite and minor apatite. In various horizons within the orebody, grey feldspar, quartz and garnet pegmatites occur as stratiform layers. The ore and country rock are competent with some inconpetent boundaries.

Jan 1, 1981

By Fred H. Poettmann, A. L. Benham

correlation of waters and identification of mixtures of two and three waters is important in secondary recovery evaluation studies and studies involving underground movement of waters. The importance of such studies suggests the need for a method to correlate a great number of water analyses to accurately identify and improve the understanding of mixtures of waters. Geochemical analyses of waters furnish a quantitative measure of each of the ions present in a water. Table L shows a portion of the data on many oilfield water analysis report forms in use today. Under "parts per million" are listed the quantitative amounts of each ion in milligrams per liter. Following the work of Stabler&apos; and Palmer", some laboratories have reported additional data to indicate the reaction capacity, or reacting value of each ion. Table I lists data under two subheads for the "reacting value". Under the first subhead, the reacting value is reported in gram equivalents per million, hereinafter called equivalents per million. This value is determined by multiplying milligrams per liter of the ion by a factor equal to the reciprocal of the equivalent weight of the ion. Under the second subhead (per cent) is listed the percentage of each ion based on the total equivalents per million. Sodium is not usually an analyzed value in routine analyses, but is determined by the difference between total negative equivalent per million values and the sum of all of positive ion values for which analyses were made. This difference is reported as sodium, hereafter labelled "sodium". On this basis, the subtotals of the equivalent per million and per cent reacting values of the positive and negative ions are equal. CORRELATION OF WATER ANALYSES DATA Previously reported methods for correlating oilfield waters have used part of the data in Table 1, and can be classified into two categories. Correlation by Chemical Character Correlation methods using the chemical character of waters, as represented by the per cent reacting values of the ionic constituents, have been used by Palmer2 and Tickell. These methods have the limitation of neglecting the ionic concentration of the waters. This limitation can be serious in areas where waters have the same chemical character, but differ in concentration. Correlation by Concentration of the Ionic Constituents The Reistle&apos; and the Stiff methods use the ionic concentration in parts per million and equivalents per million. These methods are effective in differentiating waters of similar chemical character and varying concentration, as in the highly saline waters of the Mid-Continent area. These methods have the disadvantage that they correlate waters by comparing many graphs of individual water analyses to determine the similarity to, or the variance from "type" waters. PROPOSED METHOD OF CORRELATING WATER ANALYSES DATA Correlation graphs presented in Fig. 1 represent water analyses data as points to facilitate the correlation of waters. The graph on the left of Fig. 1 is a plot of per cent reacting value of magnesium vs calcium. The right

By D. H. Gray, G. Bergamini, I. Fatt

A method developed by soil scientists for measuring permeability anisotropy of soils has been adapted for use in studies of sandstone permeability aniso-tmpy. Studies on Berea and Bandera sandstone show that permeability of these materials decreases upon application of simulated overburden pressure. Permeability reduction of Berea and Grubb sandstone cores subjected to simulated overburden pressure is shown to be a function of the ratio of radial to axial stress. INTRODUCTION The effects of mechanical stress on reservoir rock parameters are now generally accepted as being important in reservoir engineering calculations. In several oil fields the unique behavior of the reservoir has been attributed to the influence of overburden pressure or internal fluid pressure on rock permeability or fluid content. l Although the gross effects of overburden pressure on permeability, porosity, waterflood efficiency, electrical resistance and sonic velocity have now been established,3-9 there are some very interesting, and perhaps important, details of rock behavior under stress that have not heretofore been studied. In this paper we will show that permeability anistropy of several sandstones is a function of overburden pressure. We will also show that permeability reduction of cylindrical samples of two sandstones, when subjected to mechanical stress, is a function of the ratio of radial to axial stress. Most studies of overburden pressure effects made in the past have attempted to duplicate reservoir conditions by applying hydrostatic external pressure on all surfaces of the sample. Assuming perfect elasticity, that is, no viscoelastic flow during geological time, reservoir rock in situ cannot be under hydrostatic stress as is apparent from the value of 0.25 for Poisson&apos;s ratio for most rock. In the absence of tectonic forces the horizontal stress component If there are directional permeability effects, as has been reported from field and laboratory studies, l0,11 then one would expect hydrostatic stress as used in the laboratory to give a different permeability reduction from that occurring under reservoir stress conditions. The influence of stress on directional permeability was measured by a modification of the method first described by Maasland and Kirkham for use on soil samples.12 Their method permits calculation of the permeabilities along each of the three mutually perpendicular axes of a cubic sample. The modification reported in this paper extends the method to observing these permeabilities when the sample is under hydrostatic stress. The Hassler sleeve type of core holder is satisfactory for studying overburden pressure effects on permeability if a known force is applied to the end plugs. Wyble6 used a sleeve core holder but did not load the end plugs. In this paper we combine sleeve pressure and axial force to give permeability changes which we believe are close to those occurring in reservoirs when reservoir pressure changes. The combination of sleeve pressure and axial force assumes, however, that the sleeve pressure simulates both vertical stress and horizontal stress in one direction. METHOD PERMEABILITY ANISOTROPY The Maasland and Kirkhaml2 method of measuring permeability anisotropy uses a cube of porous material which is Open On three faces and has discs with a Center hole for an air inlet cemented to the other three mutually perpendicular faces (Fig. 1). The rate at which air pressure falls in a bottle of known volume, and pressure slightly above atmospheric, when the bottle discharges through each disc, is

By J. P. Myers, A. H. Flagg, E. S. Mardock, J. L. P. Campbell, J. M. Terry

The development process for the use of radioactive tracers as a means of locating zones of permeability is discussed. The general techniques for the safe handling of radioactive materials is given as developed by the Lane-Wells Co. and Well Surveys, Inc. The prob1em and. successes with tracers in waterflood systetns, oil and gas injection profiles, fracture sand tracing, squeeze (ement tracing. lost circulution, and cement top localion are discussed and illustrated. INTRODUCTION The exact location of the permeable zones lying within the productive horizon has been a major problem faced by the petroleum engineer for decades, and it has been a problem which has seldom been solved with certainty. Reservoir engineers usually have to incorporate a question mark in their estimates of future reservoir performance because of blanks in the core data. Although the use of radioactivity or electrical logs for the estimation of porosity has been of great assistance in furnishing a record for the reservoir engineer, this application of logging data has not completely solved the problem. In short, the industry needs an in-situ well surveying method which can locate and estimate the permeability of the zones existing within a given pay section. The initial development work with radioactive tracers has been towards filling the need for permeability information. Progress to date permits the location of permeable zones with a qualitative estimate of their relative importance with respect to permeability. The calibration of the method is still incomplete. but present development work on tracer preparations, borehole effect correction factors, and instrument limitations give a promise of quantitative "permeability profiles" in the near future. The development work on the radioactive tracer method discussed here began several years ago in the laboratories of Well Surveys, Inc., in Tulsa. At the outset of this work, three approaches to the problem were visualized as follows: 1. A fluid carrying a soluble, chemically inert, gamma ray emitting isotope is pumped down the borehole and out into the permeable zones of the formation. The greater gamma activity of the permeable zones thus permits them to be differentiated from the impermeable zones which contain no active tracer. It was found difficult to obtain a tracer material which was chemically inert. Absorption to some degree was noted in all experiments. Also, it proved impossible to hold the tracer near the horehole where it could be logged. 2. A fluid carrying a soluble, gamma ray emitting isotope is pumped down the borehole into the permeable formations. In contrast with proposal 1, above. the tracer is chemically active with the fluids and materials in the pore spaces of the permeable zones. The permeable zones are thus indicated by their higher radioactivity level. The main difficulty in this proposal was finding a tracer material which would not be absorbed by shale as well as in the permeable porosity. Very little field work was done with this system. 3. Radioactive particles suspended within the injection fluid are pumped down the well. As the fluid enters the permeable formations, the radioactive particles are filtered out on borehole wall. The permeable zones are differentiated from the impermeable by the gamma ray activity deposited on the formation wall.

Jan 1, 1956